JPWO2019240259A1 - Resin composition, sealing sheet and sealing body - Google Patents

Abstract

In the present invention, component (A): a modified polyolefin resin, component (B): a compound having a cyclic ether group, component (C): a tackifier having a softening point of 80 ° C. or higher, and component (D): heat. A resin composition containing a cationic polymerization initiator, a sealing sheet having an adhesive layer formed using this resin composition, and a seal in which an object to be sealed is sealed using the sealing sheet. It is a stationary body. According to the present invention, a resin composition having excellent film-forming property and sheet processability in a normal temperature environment, and an adhesive formed by using this resin composition, having a high storage elastic modulus after curing and excellent sealing property. A sealing sheet having a layer and a sealing body in which an object to be sealed is sealed using the sealing sheet are provided.

Description

The present invention relates to a resin composition having excellent film-forming properties and sheet processability in a room temperature environment, a sealing sheet having an adhesive layer having excellent sealing properties, and a sealing sheet formed by using this resin composition. The present invention relates to a sealing body in which a stopper is sealed using the sealing sheet.

In recent years, organic EL elements have been attracting attention as light emitting elements capable of high-luminance light emission by low-voltage direct current drive.
However, the organic EL element has a problem that the light emitting characteristics such as the light emitting brightness, the light emitting efficiency, and the light emitting uniformity tend to deteriorate with the passage of time.
It is considered that oxygen, moisture, etc. infiltrate into the organic EL element and deteriorate the electrodes and the organic layer as a cause of the problem of deterioration of the light emitting characteristics. Therefore, the organic EL element is sealed with a sealing material. However, it has been practiced to prevent the ingress of oxygen and water.
When sealing an organic EL element using a sealing material, it is necessary to embed a minute gap in the organic EL element. Therefore, conventionally, a sealing material having low viscosity and viscosity stability has been developed. I came.

For example, Patent Document 1 describes a resin composition containing a specific epoxy resin, a specific epoxy resin curing agent, a specific microcapsule, and a specific amount of filler, which is measured by an E-type viscometer at 25 ° C. , Compositions having a viscosity at 2.5 rpm of 0.5 to 50 Pa · s are described.
Patent Document 1 also describes that low viscosity and high moisture resistance of a cured product can be achieved at the same time by using a liquid epoxy resin and a liquid epoxy resin curing agent and adjusting the content of the filler. There is.

International Publication No. 2012/014499 (US2013 / 0128435 A1)

Since the composition described in Patent Document 1 has low viscosity and viscosity stability, it is excellent in coatability and sealability. However, since this composition has fluidity before the curing reaction, it is necessary to use a special coating device such as a dispenser when sealing the organic EL element, and the organic EL element or the like needs to be used. The manufacturing process of light emitting devices is complicated.
Therefore, it is excellent in film forming property and sheet processability in a normal temperature environment, it is possible to simplify the manufacturing process of a light emitting device such as an organic EL element, and it has a high storage elastic modulus after curing and is sufficiently sealed. There has been a demand for a resin composition capable of forming a sealing sheet having performance.

The present invention has been made in view of the above circumstances, and is a resin composition having excellent film-forming property and sheet processability in a normal temperature environment, and a storage elastic modulus after curing formed by using this resin composition. It is an object of the present invention to provide a sealing sheet having an adhesive layer having a high sealing property and excellent sealing property, and a sealing body in which an object to be sealed is sealed by using the sealing sheet.

As a result of diligent studies to solve the above problems, the present inventors have conducted diligent studies.
(I) A resin composition containing a modified polyolefin resin, a compound having a cyclic ether group, a tackifier having a softening point of 80 ° C. or higher, and a thermal cationic polymerization initiator can be used for film formation and sheet processing in a normal temperature environment. The sealing sheet having excellent properties and (ii) an adhesive layer formed by using this resin composition has a high storage elastic modulus after curing and is excellent in sealing properties.
The present invention has been completed.

Thus, according to the present invention, the following resin compositions [1] to [8], the sealing sheet of [9], and the sealing bodies of [10] and [11] are provided.

[1] A resin composition containing the following components (A), (B), (C), and (D).
Component (A): Modified polyolefin resin (B) Component: Compound having a cyclic ether group (C) Component: Adhesive-imparting agent having a softening point of 80 ° C. or higher (D) Component: Thermal cationic 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 oxylan 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 100 to 500 parts by mass with respect to 100 parts by mass of the component (A).
[5] The resin composition according to any one of [1] to [4], wherein the content of the component (C) is 1 to 200 parts by mass with respect to 100 parts by mass of the component (A).
[6] The resin composition according to any one of [1] to [5], wherein the content of the component (D) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (B). Stuff.

[7] The resin composition according to any one of [1] to [6], which further contains a silane coupling agent.
[8] The resin composition according to [7], wherein the content of the silane coupling agent is 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (A).

[9] A sealing sheet composed of two release films and an adhesive layer sandwiched between the two release films, wherein the adhesive layer is one of [1] to [8]. A sealing sheet formed by using the described resin composition.
[10] A sealed body in which the object to be sealed is sealed using the sealing sheet according to [9].
[11] The sealed body according to [10], wherein the object to be sealed is an electronic device.

According to the present invention, a resin composition having excellent film-forming property and sheet processability in a normal temperature environment, and an adhesive formed by using this resin composition, having a high storage elastic modulus after curing and excellent sealing property. A sealing sheet having a layer and a sealing body in which an object to be sealed is sealed using the sealing sheet are provided.

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

1) Resin composition The resin composition of the present invention contains the following components (A), (B), (C), and (D).
Component (A): Modified polyolefin resin (B) Component: Compound having a cyclic ether group (C) Component: Adhesive-imparting agent having a softening point of 80 ° C. or higher (D) Component: Thermal cationic polymerization initiator

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

The modified polyolefin resin is a polyolefin resin into which a functional group has been introduced. The modified polyolefin resin can be obtained, for example, by subjecting the polyolefin resin as a precursor to a modification treatment using a modifier.
The polyolefin resin refers to a polymer containing a repeating unit derived from an olefin-based monomer. The polyolefin resin may be a polymer consisting of only repeating units derived from an olefin-based monomer, or may be derived from a repeating unit derived from an olefin-based monomer and a monomer copolymerizable with the olefin-based monomer. It may be a polymer composed of the repeating unit of.

As the olefin-based monomer, α-olefin having 2 to 8 carbon atoms is preferable, ethylene, propylene, 1-butene, isobutylene, or 1-hexene is more preferable, and ethylene or propylene is further preferable.
These olefin-based monomers may be used alone or in combination of two or more.

Examples of the monomer copolymerizable with the olefin-based monomer include vinyl acetate, (meth) acrylic acid ester, and styrene. Here, "(meth) acrylic acid" represents acrylic acid or methacrylic acid (the same applies hereinafter).
As the monomer copolymerizable with these olefin-based monomers, one type can be used alone, or two or more types can be used in combination.

Examples of the polyolefin resin include ultra-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. Examples thereof include -propylene copolymer, olefin-based elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene- (meth) acrylic acid copolymer, and ethylene- (meth) acrylic acid ester copolymer. ..

The modifier used for the modification treatment of the polyolefin resin is a compound having a functional group in the molecule.
Functional groups include carboxyl group, carboxylic acid anhydride group, carboxylic acid 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, a carboxyl group, a carboxylic acid anhydride group, a carboxylic acid ester group, a hydroxyl group, an ammonium group, an amino group, an imide group, an isocyanate group and an alkoxysilyl group are preferable, and a carboxylic acid anhydride group and an alkoxysilyl group are more preferable. , A carboxylic acid anhydride group is particularly preferred.
The compound having a functional group may have two or more kinds of functional groups in the molecule.

Examples of the modified polyolefin-based resin include acid-modified polyolefin-based resins and silane-modified polyolefin-based resins. An acid-modified polyolefin resin is preferable from the viewpoint of obtaining more excellent effects of the present invention.

The acid-modified polyolefin-based resin refers to a polyolefin resin graft-modified with an acid. For example, a polyolefin resin is reacted with an unsaturated carboxylic acid to introduce a carboxyl group (graft modification). In the present specification, the acid includes the concept of an acid anhydride, the unsaturated carboxylic acid includes the concept of an unsaturated carboxylic acid anhydride, and the carboxyl group refers to the concept of a carboxylic acid anhydride group. It includes.

As unsaturated carboxylic acids to react with polyolefin resin, maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, Examples thereof include aconitic acid anhydride, norbornene dicarboxylic acid anhydride, tetrahydrophthalic acid anhydride and the like.
These can be used alone or in combination of two or more. Among these, maleic anhydride is preferable because it is easy to obtain a resin composition having excellent sheet processability and a cured product of the resin composition having excellent adhesive strength.

The amount of the unsaturated carboxylic acid to be reacted with the polyolefin resin is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, and further preferably 0.2 to 0.2 parts by mass with respect to 100 parts by mass of the polyolefin resin. 1 part by mass. The resin composition containing the acid-modified polyolefin-based resin thus obtained is likely to have an excellent cured product due to its adhesive strength.

As the acid-modified polyolefin resin, a commercially available product can also be used. Examples of commercially available products include Admer (registered trademark) (manufactured by Mitsui Chemicals), Unistor (registered trademark) (manufactured by Mitsui Chemicals), BondyRam (manufactured by Polyram), orevac (registered trademark) (manufactured by ARKEMA), and the like. Modic (registered trademark) (manufactured by Mitsubishi Chemical Corporation) and the like can be mentioned.

The silane-modified polyolefin-based resin refers to a polyolefin resin graft-modified with an unsaturated silane compound. The silane-modified polyolefin-based resin has a structure in which an unsaturated silane compound as a side chain is graft-copolymerized with a polyolefin resin as a main chain. Examples thereof 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 preferable.

As the unsaturated silane compound to be reacted with the polyolefin resin, a vinylsilane compound is preferable. Examples of vinylsilane compounds include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltripentyroxysilane, vinyltriphenoxysilane, vinyltribenzyloxysilane, and vinyltri. Examples thereof include methylenedioxysilane, vinyltriethylenedioxysilane, vinylpropionyloxysilane, vinyltriacetoxysilane, vinyltricarboxysilane and the like.
These can be used alone or in combination of two or more.
As a condition for graft-polymerizing an unsaturated silane compound on a polyolefin resin as a main chain, a known conventional method of graft polymerization may be adopted.

The amount of the unsaturated silane compound to be reacted with the polyolefin resin is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass, and further preferably 0.5 to 0.5 parts by mass with respect to 100 parts by mass of the polyolefin resin. 5 parts by mass. The resin composition containing the silane-modified polyolefin-based resin thus obtained tends to obtain an excellent cured product due to the adhesive strength.

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

The modified polyolefin resin may 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).
Since the compound having a cyclic ether group has excellent compatibility with the component (A), by using this compound, a resin composition having excellent film forming property and sheet processability in a normal temperature environment, and water vapor blocking property can be used. A cured product of a resin composition having excellent properties can be obtained.
In the present specification, the normal temperature environment is an environment of 20 ° C. ± 15 ° C. (5-35 ° C.) (JIS Z 8703).

The compound having a cyclic ether group means a compound having at least one or more cyclic ether groups in the molecule.
Examples of the cyclic ether group include an oxylan group (epoxy group), an oxetane group (oxetanyl group), a tetrahydrofuryl group, a tetrahydropyranyl group and the like. Among these, it has an oxylan group or an oxetane group from the viewpoint that a resin composition having excellent film-forming property and sheet processability in a normal temperature environment and a cured product of the resin composition having excellent adhesive strength can be obtained. It is preferably a compound, and a compound having two or more oxylan groups or oxetane groups in the molecule is particularly preferable.

Examples of the compound having an oxylan group in the molecule include an aliphatic epoxy compound (excluding an alicyclic epoxy compound), an aromatic epoxy compound, and an alicyclic epoxy compound.
Examples of the aliphatic epoxy compound include monofunctional epoxy compounds such as glycidyl etherified products of aliphatic alcohols and glycidyl esters of alkylcarboxylic acids;
Examples thereof include polyglycidyl ethers 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.

Representative compounds 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, neopentyl glycol di. 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 polyol obtained by adding one or more alkylene oxides to glycidyl ether, which is a polyhydric alcohol such as diglycidyl ether, or aliphatic polyhydric alcohol, such as propylene glycol, trimethylolpropane, and glycerin. Polyglycidyl etherified, diglycidyl ester of aliphatic long chain dibasic acid;
Monoglycidyl ethers of aliphatic higher alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxide stearate, butyl epoxidized stearate, epoxidized polybutadiene;
Examples thereof include 2,4,6-tri (glycidyloxy) -1,3,5-triazine.

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 ( Above, 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 (all manufactured by Kyoeisha Chemical Co., Ltd.);
Adeka Glycyrrol ED-503, Adeka Glycyrrol ED-503G, Adeka Glycyrrol ED-506, Adeka Glycyrrol ED-523T, Adeka Resin EP-4088S, Adeka Resin EP-4088L, Adeka Resin EP-4080E (all manufactured by ADEKA);
Examples thereof include TEPIC-FL, TEPIC-PAS, and TEPIC-UC (all manufactured by Nissan Chemical Industries, Ltd.).

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

In addition, 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, On-Coat EX-1020, On-Coat EX-1030, On-Coat EX. -1040, On-Coat EX-1050, On-Coat EX-1051, On-Coat EX-1010, On-Coat EX-1011, On-Coat 1012 (all manufactured by Nagase ChemteX Corporation);
Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (all manufactured by Osaka Gas Chemical Co., Ltd.);
HP4032, HP4032D, HP4700 (all manufactured by DIC Corporation);
ESN-475V (above, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.);
JER (former Epicoat) YX8800 (manufactured by Mitsubishi Chemical Corporation);
Maproof G-0105SA, Maproof G-0130SP (above, manufactured by NOF CORPORATION);
Epicron N-665, Epicron HP-7200 (all manufactured by DIC Corporation);
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 (all manufactured by ADEKA Corporation);
TECHMORE VG-3101L (all manufactured by Printec Co., Ltd.) and the like can be mentioned.

The alicyclic epoxy compound includes a polyglycidyl etherified product of a polyhydric alcohol having at least one alicyclic structure, or cyclohexene oxide or cyclopentene obtained by epoxidizing a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. Examples include oxide-containing compounds.
Typical compounds of these alicyclic epoxy compounds are 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 (3,3) 4-epoxycyclohexyl) propane, dicyclopentadiene diepoxyside, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3 , 4-Epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pinenooxide, limonendioxide and the like.

A commercially available product can also be used as the alicyclic epoxy compound. Examples of commercially available products include celoxide 2021P, celoxide 2081, celoxide 2000, celoxide 3000 (all manufactured by Daicel Corporation) and the like.

Compounds having an oxetane group in the molecule include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 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) Bifunctional aliphatic oxetane compounds such as butane, 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, a commercially available product 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.);
Aron Oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-221, OXT-212 (all manufactured by Toagosei Co., Ltd.);
Examples thereof include Etanacol OXBP and OXTP (all manufactured by Ube Industries, Ltd.).

Among these compounds having a cyclic ether group, a cured product of a resin composition having excellent film forming property and sheet processability in a normal temperature environment and a cured product of a resin composition having excellent adhesive strength can be obtained. It is preferably liquid at 25 ° C. Further, it is preferable that the cyclic ether group is an oxylan 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, and 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 in the above range, a sealing material having 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 a 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 100 to 500 parts by mass, more preferably 110 to 450 parts by mass, and further preferably 120 to 400 parts by mass with respect to 100 parts by mass of the component (A). ..
By setting the content of the compound having a cyclic ether group in the above range, it becomes easy to obtain a cured product of a resin composition having a higher adhesive strength.

[Component (C): Adhesive-imparting agent with a softening point of 80 ° C. or higher]
The resin composition of the present invention contains a tackifier having a softening point of 80 ° C. or higher as the component (C).
By containing a tackifier having a softening point of 80 ° C. or higher, a resin composition having excellent film-forming properties in a normal temperature environment and adhesiveness in a high temperature environment can be obtained.
In the present specification, the high temperature environment is an environment of 40 to 80 ° C.
The softening point of the tackifier having a softening point of 80 ° C. or higher is preferably 80 to 150 ° C., more preferably 100 to 150 ° C., still more preferably 120 to 150 ° C. from the viewpoint of imparting excellent adhesiveness. ..

Examples of the tackifier having a softening point of 80 ° C. or higher include rosin-based resins such as rosin resin, rosin ester resin, and rosin-modified phenol resin; hydrogenated rosin-based resin obtained by hydrogenating these rosin-based resins;
Terpene resins such as terpene resins, aromatic-modified terpene resins, and terpene phenolic resins; hydrogenated terpene resins obtained by hydrogenating these terpene resins;
α-Methylstyrene monopolymerized resin, α-methylstyrene / styrene copolymer resin, styrene monomer / aliphatic monomer copolymer resin, styrene monomer / α-methylstyrene / aliphatic monomer copolymer Styrene-based resins such as resins, styrene-based monomer monopolymerized resins, styrene-based monomers / aromatic monomer copolymerized resins; hydride-based resins obtained by hydrogenating these styrene-based resins;
Examples thereof include a C9-based petroleum resin obtained by copolymerizing a C9 fraction such as inden and vinyl toluene produced by thermal decomposition of petroleum naphtha, and a hydride petroleum resin obtained from this C9-based petroleum resin.
Among these, a styrene-based resin is preferable, and a styrene-based monomer / aliphatic monomer copolymer-based resin is more preferable.
These tackifiers having a softening point of 80 ° C. or higher can be used alone or in combination of two or more.

As the tackifier having a softening point of 80 ° C. or higher, a commercially available product can also be used. Commercially available products include terpene resins such as YS resin PX, PXN series, Clearon (registered trademark) P series (manufactured by Yasuhara Chemical Co., Ltd.), Picolite A, C series (manufactured by PINOVA);
Aliphatic petroleum resins such as Quinton (registered trademark) 100 series (manufactured by Zeon Corporation);
Alicyclic petroleum resins such as Quinton (registered trademark) 1000 series (manufactured by Zeon Corporation);
Examples thereof include rosin or rosin 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 Industry Co., Ltd.).

The weight average molecular weight of the tackifier having a softening point of 80 ° C. or higher is preferably 100 to 10,000, more preferably 500 to 5,000, from the viewpoint of imparting excellent tackiness.

The content of the tackifier having a softening point of 80 ° C. or higher is preferably 1 to 200 parts by mass, more preferably 10 to 150 parts by mass with respect to 100 parts by mass of the component (A).
By setting the content of the tackifier having a softening point of 80 ° C. or higher within the above range, it becomes easy to obtain a resin composition having better film-forming property in a normal temperature environment and adhesiveness in a high temperature environment.

[Component (D): Thermal cationic polymerization initiator]
The resin composition of the present invention contains a thermal cationic polymerization initiator as the component (D).
The thermal cationic polymerization initiator is a compound capable of generating a cationic species that initiates polymerization by heating. The thermal cationic polymerization initiator is not particularly limited and is appropriately selected depending on the curing conditions and the type of the cationically polymerizable compound.

Examples of the thermal cationic polymerization initiator include sulnifoum salt-based compounds, quaternary ammonium salt-based compounds, phosphonium salt-based compounds, diazonium salt-based compounds, iodonium salt-based compounds, and the like. Among these, a sulnifoam salt-based compound or a quaternary ammonium salt-based compound is preferable, and a sulnifoam salt-based compound is more preferable, from the viewpoint that the sealing sheet can be cured at a low temperature.

Examples of the sulfonium salt-based compound include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroalcinate, tris (4-methoxyphenyl) sulfonium hexafluoroalcinate, and diphenyl (4-phenylthiophenyl). ) Sulfonium hexafluoroalcinate and the like can be mentioned.

A commercially available product can also be used as the sulfonium salt-based compound. Commercially available products include Adeca Opton SP-150, Adeca Opton SP-170, Adeca Opton CP-66, Adeca Opton CP-77 (all manufactured by Asahi Denka Co., Ltd.);
Sun Aid SI-60L, Sun Aid SI-80L, Sun Aid SI-100L, Sun Aid SI-B3A (all manufactured by Sanshin Chemical Co., Ltd.);
CYRACURE UVI-6974, CYRACURE UVI-6990 (all manufactured by Union Carbide);
UVI-508, UVI-509 (all manufactured by General Electric);
FC-508, FC-509 (all manufactured by Minnesota Mining and Manufacturing);
CD-1010, CD-1011 (all manufactured by Sirstmer);
Examples include CI series products (manufactured by Nippon Soda Co., Ltd.).

Examples of the quaternary ammonium salt compound include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium p-toluenesulfonate, and N, N-dimethyl-. N-benzylanilinium hexafluoroammonate, N, N-dimethyl-N-benzylanilinium tetrafluoroborate, N, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N, N-diethyl-N-benzyltrifluo Ammonium sulfonate, N, N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoroantimonate, N, N-diethyl-N- (4-methoxybenzyl) toluidinium hexafluoroantimonate and the like can be mentioned.

Examples of the phosphonium salt-based compound include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.

As the diazonium salt-based compound, commercially available products such as AMERICURE (manufactured by American Can) and ULTRASET (manufactured by Asahi Denka Co., Ltd.) can be used.

Examples of the iodonium salt compound include diphenyliodonium hexafluoroalcinate, bis (4-chlorophenyl) iodonium hexafluoroalcinate, bis (4-bromophenyl) iodonium hexafluoroalcinate, and phenyl (4-methoxyphenyl) iodonium hexafluoroarcinate. Nate and the like can be mentioned.

In addition, a commercially available product can also be used as the iodonium salt-based compound. Commercially available products include UV-9310C (manufactured by Toshiba Silicone), Photoinitiator 2074 (manufactured by Rhone-Poulenc), UVE series products (manufactured by General Electric), and FC series products (manufactured by Minnesota Mining and Manufacturing). Made) and the like.

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

The content of the thermal cationic polymerization initiator is usually 0.01 to 10 parts by mass, preferably 0.05 to 9 parts by mass, and more preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of the component (B). It is a mass part.
By setting the content of the thermal cationic polymerization initiator in the above range, it becomes easy to obtain a cured product of a resin composition having excellent curability and adhesive strength in a normal temperature environment.
Also, if the content of the thermal cationic polymerization initiator is too high. Sealing sheet formed using the obtained resin composition Since the storage elastic modulus at 23 ° C. before the thermosetting treatment is high, the adhesive strength of the cured product is low, the sealing property is inferior, and dark spots are generated. May not be able to be suppressed.

The resin composition of the present invention may contain components other than the above-mentioned component (A), component (B), component (C), and component (D).
Examples of the components other than the component (A), the component (B), the component (C), and the component (D) include a silane coupling agent and a solvent.

Examples of the silane coupling agent include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltri. 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, and vinyltris (2-methoxyethoxy) silane;
Epyl groups such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane Silane coupling agent with;
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-aminopropyl Asilane coupling agent having an amino group such as a hydrochloride of trimethoxysilane;
A silane coupling agent having a ureido group such as 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane;
Silane coupling agent having halogen atoms such as 3-chloropropyltrimethoxysilane and 3-chloropropyltriethoxysilane;
A silane coupling agent having a mercapto group such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane;
Silane coupling agent having a sulfide group such as bis (trimethoxysilylpropyl) tetrasulfide and bis (triethoxysilylpropyl) tetrasulfide;
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, and allyltrimethoxysilane;
Examples thereof include silane coupling agents having a hydroxyl group such as 3-hydroxypropyltrimethoxysilane and 3-hydroxypropyltriethoxysilane; and the like.
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 7 parts by mass with respect to 100 parts by mass of the component (A). 5 parts by mass.
By setting the content of the silane coupling agent in the above range, it becomes easy to obtain a cured product of a resin composition having better adhesive strength in a normal temperature and high temperature environment.

As the solvent, an aliphatic hydrocarbon solvent such as n-hexane and n-heptane;
Aromatic hydrocarbon solvents such as toluene and xylene;
Halogenated hydrocarbon solvents such as dichloromethane, ethylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, monochlorobenzene, etc.;
Alcohol-based solvents such as methanol, ethanol, propanol, butanol, and 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-based solvent such as ethyl cellosolve;
Ether-based 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 and the like.

In addition, the resin composition of the present invention may contain components other than the silane coupling agent and the solvent as long as the effects of the present invention are not impaired.
Examples of the components other than the silane coupling agent and the solvent include antistatic agents, stabilizers, antioxidants, plasticizers, lubricants, coloring pigments and the like. These contents may be appropriately determined according to 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) Encapsulation sheet The encapsulation sheet of the present invention is the following encapsulation sheet (α) or encapsulation sheet (β).
Sealing sheet (α): A sealing sheet composed of two release films and an adhesive layer sandwiched between the two release films, wherein the adhesive layer is the resin composition of the present invention. A sealing sheet formed by using.
Sealing sheet (β): A sealing sheet composed 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 has the resin composition of the present invention. A sealing sheet formed by using an object.
It should be noted that these sealing sheets represent a state before use, and when the sealing sheet of the present invention is used, the release film is usually peeled off.

The release film constituting the sealing sheet (α) functions as a support in the manufacturing process of the sealing sheet (α) and protects the adhesive layer until the sealing sheet (α) is used. Functions as a sheet.

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

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

The method for producing the sealing sheet (α) is not particularly limited. For example, the sealing sheet (α) can be produced by using the casting method.
When the sealing sheet (α) is produced by the casting method, the resin composition of the present invention is applied to the peeled layer surface of the peeling film by a known method, and the obtained coating film is dried. By doing so, an adhesive layer with a release film is produced, and then another release film is laminated on the adhesive layer to obtain a sealing sheet (α).

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

Examples of the method 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 storage elastic modulus of the sealing sheet before the thermosetting treatment at 23 ° C. is usually 0.1 to 50 MPa, preferably 0.5 to 5 MPa. When the storage elastic modulus at 23 ° C. before the thermosetting treatment is within the above range, excellent sheet workability can be maintained. The storage elastic modulus of the sealing sheet before the thermosetting treatment at 23 ° C. can be measured by the method described in Examples.

Since the adhesive layer of the sealing sheet (α) is formed by using the resin composition of the present invention, it has thermosetting property. The conditions for thermosetting the adhesive layer are not particularly limited.
The heating temperature is usually 80 to 200 ° C, preferably 90 to 150 ° C.
The heating time is usually 30 minutes to 12 hours, preferably 1 to 6 hours.

The thickness of the adhesive layer of the sealing sheet (α) is usually 5 to 25 μm, preferably 10 to 20 μm. The adhesive layer having a thickness within the above range is preferably 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 storage elastic modulus of the sealing sheet after the thermosetting treatment at 80 ° C. is usually 100 to 10,000 MPa, preferably 200 to 8,000 MPa.
Generally, the organic EL element is used in a temperature environment of -20 to 80 ° C. Therefore, a sealing sheet having a storage elastic modulus at 80 ° C. after the thermosetting treatment in the above range is excellent in sealing performance of a light emitting device such as an organic EL element under the above temperature environment. The storage elastic modulus of the sealing sheet after the thermosetting treatment at 80 ° C. can be measured by the method described in Examples.

The adhesive layer after the thermosetting treatment has excellent adhesive strength.
The adhesive strength of the adhesive layer after the thermosetting treatment is usually 1 to 25 N / 25 mm, preferably 2.5 to 25 N / when the 180 ° peeling test is performed under the conditions of a temperature of 23 ° C. and a relative humidity of 50%. It is 25 mm.
This 180 ° peeling test can be measured according to, for example, the method for measuring the adhesive strength described in JIS Z0237: 2009.

The water vapor permeability of the adhesive layer having a thickness of 50 μm after the thermosetting treatment is usually 0.1 to 200 g / m ² / day, preferably 0.1 to 150 g / m ² / day.
This water vapor permeability can be measured using a known gas permeability measuring device.

Examples of the release film and the adhesive layer constituting the sealing sheet (β) are the same as those shown as the release film and the adhesive layer constituting the sealing sheet (α), respectively.
The gas barrier film constituting the sealing sheet (γ) is not particularly limited as long as it is a film having a water vapor blocking property.

^{The gas barrier film preferably has a water vapor permeability of 0.1 g / m 2} / day or less in an environment of a temperature of 40 ° C. and a relative humidity of 90% (hereinafter, abbreviated as “90% RH”), and is 0. more preferably .05g ^/ m is 2 / day or less, still more preferably not more than 0.005 g ^/ m 2 / day.
When the water vapor transmittance of the gas barrier film in an environment of 40 ° C. and 90% RH is 0.1 g / m ² / day or less, oxygen and moisture are contained in the elements such as the organic EL element formed on the substrate. It is possible to effectively suppress the deterioration of the electrode and the organic layer due to the infiltration of such substances.
The transmittance of the gas barrier film such as water vapor can be measured using a known gas transmittance measuring device.

Examples of the gas barrier film include metal foil, thin film glass, resin film and the like. Among these, a resin film is preferable, and a gas barrier film having a base material and a gas barrier layer is more preferable.

Resin components constituting the base material include polyimide, polyamide, polyamideimide, polyphenylene ether, polyetherketone, polyetheretherketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyallylate, and acrylic resin. , Cycloolefin-based polymer, aromatic polymer, polyurethane-based polymer and the like.
The thickness of the base material is not particularly limited, but is preferably 0.5 to 500 μm, more preferably 1 to 200 μm, and further preferably 5 to 100 μm from the viewpoint of ease of handling.

The material of the gas barrier layer is not particularly limited as long as it can impart desired gas barrier properties. The gas barrier layer is obtained by subjecting a gas barrier layer made of an inorganic thin-film film, a gas barrier layer containing a gas barrier resin, and a layer containing a polymer compound (hereinafter, may be referred to as “polymer layer”) to a modification treatment. Gas barrier layer [In this case, the gas barrier layer does not mean only the region modified by ion injection treatment or the like, but means "a polymer layer containing the modified region". ] Etc. can be mentioned.
Among these, a gas barrier layer made of an inorganic thin-film film or a gas barrier layer obtained by modifying a polymer layer is preferable because a thin layer having 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 deposition film include a vapor deposition film of an inorganic compound or a metal.
As raw materials for vapor-deposited films of inorganic compounds, inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, tin oxide, and zinc oxide tin oxide;
Inorganic nitrides such as silicon nitride, aluminum nitride, and titanium nitride;
Inorganic carbides; Inorganic sulfides; Inorganic oxide nitrides such as silicon nitride;
Examples thereof include inorganic oxidative carbides; inorganic nitriding carbides; and inorganic oxidative carbides.
Examples of the raw material of the metal vapor deposition film include aluminum, magnesium, zinc, tin and the like.
These can be used alone or in combination of two or more.

Among these, an inorganic vapor deposition film made of an inorganic oxide, an inorganic nitride or a metal as a raw material is preferable from the viewpoint of gas barrier property, and further, an inorganic oxide or an inorganic nitride is used as a raw material from the viewpoint of colorless transparency. An inorganic vapor deposition film is preferable. Further, the inorganic vapor deposition film may be a single layer or a multilayer.

From the viewpoint of gas barrier property and handleability, the thickness of the inorganic vapor deposition 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 further preferably 40 nm or more and 200 nm or less.

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

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

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 further preferably 40 nm or more and 200 nm or less.

Examples of the method for forming the gas barrier layer containing the gas barrier resin include a method in which a solution for forming a gas barrier layer containing the gas barrier resin is applied onto a base material or another layer, and the obtained coating film is appropriately dried. ..

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

The polymer compounds used in the gas barrier layer in which the surface of the polymer layer is modified include silicon-containing polymer compounds, polyimide, polyamide, polyamideimide, polyphenylene ether, polyetherketone, polyetheretherketone, polyolefin, and polyester. , Polysulfone, polysulfone, polyethersulfone, 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, a silicon-containing polymer compound is preferable from the viewpoint of being able to form a gas barrier layer having more excellent gas barrier properties. Examples of the silicon-containing polymer compound include polysilazane-based compounds, polycarbosilane-based compounds, polysilane-based compounds, polyorganosiloxane-based compounds, poly (disylanilenphenylene) -based compounds, and poly (disylanilen-ethynylene) -based compounds. Can be mentioned. Of these, polysilazane compounds are preferable from the viewpoint that a gas barrier layer having excellent gas barrier properties can be formed even if the compound is thin. By subjecting the layer containing the polysilazane compound to a modification treatment, a layer having oxygen, nitrogen and silicon as main constituent atoms (silicon nitride layer) 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, equation (1)

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

In the above equation (1), n represents an arbitrary natural number.
Rx, Ry, and Rz are independently hydrogen atoms, alkyl groups having unsubstituted or substituents, cycloalkyl groups having unsubstituted or substituents, alkenyl groups having unsubstituted or substituents, unsubstituted or substituted, respectively. Represents a non-hydrolytable group such as an aryl group having a group or an alkylsilyl group.

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

The polysilazane compound having a repeating unit represented by the formula (1) is any of 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.

Further, in the present invention, a modified polysilazane can also be used as the polysilazane compound. Examples of the polysilazane modified product include JP-A-62-195024, JP-A-2-844437, JP-A-63-81122, JP-A-1-138108, and JP-A-2-175726. JP-A-5-238827, JP-A-5-238827, JP-A-6-122852, JP-A-6-306329, JP-A-6-299118, JP-A-9-313333, JP-A-9-31333 Examples thereof include those described in Japanese Patent Application Laid-Open No. 5-345826, Japanese Patent Application Laid-Open No. 4-63833, and the like.
Among these, as the polysilazane compound, perhydropolysilazane in which Rx, Ry, and Rz are all hydrogen atoms is preferable from the viewpoint of easy availability and the ability to form an ion-implanted layer having excellent gas barrier properties.
Further, as the polysilazane compound, a commercially available product commercially available as a glass coating material or the like can be used as it is.
The polysilazane compound 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 the object of the present invention is not impaired. As the other component, a component listed as a component other than the component (A), the component (B), the component (C), and the component (D) can be contained.
The content of the polymer compound in the polymer layer is preferably 50% by mass or more, more preferably 70% by mass or more, because a gas barrier layer having more excellent 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 in which a polymer compound is dissolved or dispersed in an organic solvent onto a base material or another layer by a known coating method, and drying the obtained coating film. be able to.

As the organic solvent, solvents other than the above-mentioned component (A), component (B), component (C), and component (D) 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 listed as the method for coating the resin composition can be used.
The method for drying the coating film is not particularly limited, and the methods listed as the method 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 the method 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 treatment 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 modifying a polymer layer by exposing the polymer layer to plasma. For example, plasma treatment can be performed according to the method described in Japanese Patent Application Laid-Open No. 2012-106421.
The ultraviolet irradiation treatment is a method of irradiating a polymer layer with ultraviolet rays to modify the polymer layer. For example, the ultraviolet modification treatment can be performed according to the method described in Japanese Patent Application Laid-Open No. 2013-226757.

Among these gas barrier layers, ions are implanted into the layer containing the silicon-containing polymer compound from the viewpoint of efficiently modifying the inside of the polymer layer without roughening the surface and forming a gas barrier layer having more excellent gas barrier properties. Those obtained by subjecting the treatment are preferable.

The ions to be injected into the polymer layer include ions of rare gases such as argon, helium, neon, krypton, and xenon;
Ions such as fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, sulfur;
Ions of alkane-based 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, rare gas ions such as argon, helium, neon, krypton, and xenon are preferable because ions can be injected more easily and a gas barrier layer having more excellent gas barrier properties can be formed.

The amount of ions injected can be appropriately determined according to the purpose of use of the gas barrier film (necessary gas barrier property, colorless transparency, etc.).

Examples of the method of injecting ions include a method of irradiating ions (ion beams) accelerated by an electric field, a method of injecting ions (plasma ions) in plasma, and the like. Above all, the latter method of implanting plasma ions (plasma ion implantation method) is preferable from the viewpoint that the target gas barrier layer can be easily formed.

In the plasma ion injection method, for example, plasma is generated in an atmosphere containing a plasma-generating gas such as a rare gas, and a negative high-voltage pulse is applied to the polymer layer to generate ions (cations) in the plasma. , Can be performed by injecting into the surface portion of the polymer layer. More specifically, the plasma ion implantation method can be carried out by the method described in the WO2010 / 107018 pamphlet and the like.

By ion implantation, the thickness of the region where ions are implanted can be controlled by the implantation conditions such as the type of ions, applied voltage, and processing time, depending on the thickness of the polymer layer and the purpose of use of the gas barrier film. It may be determined, but it is usually 10 nm or more and 400 nm or less.

The injection of ions can be confirmed by performing elemental analysis measurement in the vicinity of 10 nm from the surface of the polymer layer using X-ray photoelectron spectroscopy (XPS).

The method for producing the sealing sheet (β) is not particularly limited. For example, in the method for producing the sealing sheet (α) described above, the sealing sheet (β) can be produced by replacing one of the release films with a gas barrier film.
Further, after producing the sealing sheet (α), the sealing sheet (β) is produced by peeling off one of the release films and adhering the exposed adhesive layer and the gas barrier film. You can also. In this case, when the sealing sheet (α) has two release films having different release forces, it is preferable to release the release film having the smaller release force from the viewpoint of handleability.

As described above, the cured product of the adhesive layer of the sealing sheet of the present invention has excellent sealing properties. Therefore, the sealing sheet of the present invention is suitably used in optical applications such as a sealing material for light emitting devices such as organic EL elements.

3) Encapsulant In the encapsulant of the present invention, the object to be sealed is sealed by using the encapsulation sheet of the present invention.
"It is 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 to be sealed. It means to cover the object to be sealed by making it adhere to the material.
The encapsulant of the present invention includes, for example, a substrate, an element (object to be sealed) formed on the substrate, and a sealing material for encapsulating the element. Examples thereof include those in which the sealing material is derived from the adhesive layer of the sealing sheet of the present invention (cured product of the adhesive layer).

The substrate is not particularly limited, and various substrate materials can be used. In particular, it is preferable to use a substrate material having a high visible light transmittance. Further, a material having high blocking performance to block moisture and gas from the outside of the element and having excellent solvent resistance and weather resistance is preferable. 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, etc. Examples thereof include transparent plastics such as polystyrenes, polyarylates, polysulfones and polyolefins, and the gas barrier film described above.
The thickness of the substrate is not particularly limited, and can be appropriately selected in consideration of the light transmittance and the performance of blocking the inside and outside of the element.

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

The method for producing the sealed body of the present invention is not particularly limited.
For example, in the case of the configuration of the sealing sheet (α) of the present invention, one release film of the sealing sheet (α) is removed, a gas barrier film is attached to the exposed adhesive layer, and then the other release film is peeled off. By removing the film and attaching the adhesive layer on the object to be sealed, the object to be sealed is sealed by the adhesive layer of the sealing sheet.
In the case of the structure of the sealing sheet (β) of the present invention, the release film is removed and the adhesive layer is attached on the object to be sealed, so that the object to be sealed is sealed by the adhesive layer of the sealing sheet. Stop it.

The bonding conditions for adhering the adhesive layer of the sealing sheet and the object to be sealed are not particularly limited. The adhesion temperature is, for example, 23 to 100 ° C., preferably 23 to 80 ° C., more preferably 23 ° C. to 40 ° C. This bonding process may be performed while pressurizing.
Then, by curing this adhesive layer, the encapsulant of the present invention can be produced.
As the curing conditions for curing the adhesive layer, the conditions described above can be used.

In the sealed body of the present invention, the object to be sealed is sealed with the sealing sheet of the present invention.
Therefore, in the sealed body of the present invention, the performance of the object to be sealed is maintained for a long period of time.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
Unless otherwise specified, parts and% in each example are based on mass.

In the following Examples and Comparative Examples, a modified polyolefin resin [(A) component], a compound having a cyclic ether group [(B) component], and a tackifier having a softening point of 80 ° C. or higher [(C) component]. , The thermal cationic polymerization initiator [(D) component], and the following as the silane coupling agent were used.
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)]
Hydrogenated bisphenol A type epoxy resin [manufactured by Mitsubishi Chemical Corporation, trade name: YX8034, cyclic ether equivalent: 270 g / eq, liquid at 25 ° C]
Adhesive-imparting agent with a softening point of 80 ° C or higher [Component (C)]
4-Methyl-α-methylstyrene / indene copolymer resin (manufactured by Mitsui Chemicals, trade name: FMR0150, softening point 145 ° C)
Thermal cationic polymerization initiator [component (D)]
Sulfonium salt compound (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: San-Aid SI-B3A, anion: tetrakis (pentafluorophenyl) borate, cation: (4-acetoxyphenyl) benzyl (methyl) sulfonium)
Silane Coupling Agent Epoxy-based silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-4803, 8-glycidoxyoctyltrimethoxysilane)

[Example 1]
100 parts of acid-modified α-olefin polymer (A), 200 parts of compound (B) having a cyclic ether group, 25 parts of tackifier (C), 0.6 part of thermal cationic polymerization initiator (D), and silane cup. 0.1 part of the ring agent was dissolved in methyl ethyl ketone to prepare a resin composition (1) having a solid content concentration of 30%.
This resin composition (1) was applied onto the peeled surface of a release film (manufactured by Lintec Corporation, trade name: SP-PET382150), and the obtained coating film was dried at 100 ° C. for 1 minute to have a thickness of 10 μm. An adhesive layer was formed, and a peeling-treated surface of another release film (manufactured by Lintec Corporation, trade name: SP-PET38131) was bonded onto the adhesive layer to obtain a sealing sheet (1).

[Example 2]
The resin composition is the same as in Example 1 except that the content of the compound (B) having a cyclic ether group is changed to 300 parts and the content of the thermal cationic polymerization initiator (D) is changed to 0.9 parts. (2) was prepared, and a sealing sheet (2) was obtained using this resin composition.

[Example 3]
The resin composition is the same as in Example 1 except that the content of the compound (B) having a cyclic ether group is changed to 400 parts and the content of the thermal cationic polymerization initiator (D) is changed to 1.2 parts. (3) was prepared, and a sealing sheet (3) was obtained using this resin composition.

[Comparative Example 1]
Example 1 except that an imidazole-based curing catalyst [2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Corporation, trade name: Curesol 2E4MZ)] was used instead of using the thermal cationic polymerization initiator (D). A resin composition (4) was prepared in the same manner as in the above, and a sealing sheet (4) was obtained using this resin composition.

The sealing sheets (1) to (4) obtained in Examples 1 to 3 and Comparative Example 1 were measured and evaluated as follows. The results are shown in Table 1.
[Measurement of storage elastic modulus of sealing sheet before curing]
The adhesive layers of the sealing sheets obtained in Examples or Comparative Examples were laminated and laminated at 23 ° C. using a heat laminator to obtain a laminate having a thickness of 1 mm. Using this laminate as a sample, the storage elastic modulus of the adhesive layer before curing was measured at a frequency of 1 Hz and 23 ° C. using a storage elastic modulus measuring device (manufactured by Antonio Par, product name: Physica MCR301).
Table 1 shows the storage elastic modulus at 23 ° C.

[Measurement of storage elastic modulus of sealing sheet after curing]
The adhesive layers of the sealing sheets obtained in Examples or Comparative Examples were laminated and laminated at 23 ° C. using a heat laminator to obtain a laminate having a thickness of 200 μm. Then, the laminate was heated at 100 ° C. for 1 hour to cure the adhesive layer. Using this cured laminate as a sample, using a storage elastic modulus measuring device (manufactured by TA Instruments, product name: DMAQ800), the cured adhesive is used at a frequency of 11 Hz and a temperature range of 23 ° C to 150 ° C. The storage elastic modulus of the layer was measured.
Table 1 shows the storage elastic modulus at 23 ° C. (before curing) and the storage elastic modulus at 80 ° C. (after curing).

From Table 1, the following can be seen.
The resin compositions (1) to (3) containing the component (A), the component (B), the component (C), and the component (D) are excellent in film forming property and sheet processability in a normal temperature environment. When the organic EL element is sealed using the sealing sheets (1) to (3) formed by using these resin compositions, the storage elastic modulus after curing is high and the sealing property is excellent. , The generation of dark spots can be suppressed (Examples 1 to 3).
On the other hand, the sealing sheet (4) formed by using the resin composition (4) obtained by using the imidazole-based curing catalyst instead of the component (D) is stored at 80 ° C. after the thermosetting treatment. The elastic modulus is low. Therefore, when the organic EL element is sealed using the sealing sheet (4), the sealing property is inferior and the generation of dark spots cannot be suppressed (Comparative Example 1).

Claims (11)

A resin composition containing the following components (A), (B), (C), and (D).
Component (A): Modified polyolefin resin (B) Component: Compound having a cyclic ether group (C) Component: Adhesive-imparting agent having a softening point of 80 ° C. or higher (D) Component: Thermal cationic polymerization initiator The resin composition according to claim 1, wherein the component (A) is an acid-modified polyolefin resin. The resin composition according to claim 1 or 2, wherein the cyclic ether group of the component (B) is an oxylan group or an oxetane group. The resin composition according to any one of claims 1 to 3, wherein the content of the component (B) is 100 to 500 parts by mass with respect to 100 parts by mass of the component (A). The resin composition according to any one of claims 1 to 4, wherein the content of the component (C) is 1 to 200 parts by mass with respect to 100 parts by mass of the component (A). The resin composition according to any one of claims 1 to 5, wherein the content of the component (D) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (B). The resin composition according to any one of claims 1 to 6, further comprising a silane coupling agent. The resin composition according to claim 7, wherein the content of the silane coupling agent is 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (A). A sealing sheet composed of two release films and an adhesive layer sandwiched between the two release films.
A sealing sheet in which the adhesive layer is formed by using the resin composition according to any one of claims 1 to 8. A sealed body in which the material to be sealed is sealed using the sealing sheet according to claim 9. The sealed body according to claim 10, wherein the material to be sealed is an electronic device.