WO2019189617A1 - Resin composition, sealing sheet, and sealed body - Google Patents

Abstract

The present invention is a resin composition containing a component (A), a component (B), and a component (C), the component (A) being a modified polyolefin-based resin, the component (B) being a compound having a cyclic ether group, and the component (C) being a photo-cationic polymerization initiator. The present invention provides: a resin composition having excellent sheet processability (film forming properties); a sealing sheet having an adhesive layer which is formed with use of the resin composition and which has excellent adhesion strength, colorless transparency, and water-vapor blocking properties; and a sealed body obtained by sealing an object to be sealed, with use of the sealing sheet.

Description

Resin composition, sealing sheet and sealing body

The present invention is a resin composition excellent in sheet processability (film forming property), a sealing sheet having an adhesive layer formed using this resin composition and excellent in adhesive strength, colorless transparency and water vapor barrier property, And the to-be-sealed thing is related with the sealing body formed by sealing using the said sealing sheet.

In recent years, organic EL elements have attracted attention as light-emitting elements that can emit light with high luminance by low-voltage direct current drive.
However, the organic EL element has a problem that light emission characteristics such as light emission luminance, light emission efficiency, and light emission uniformity are likely to deteriorate with time.
As a cause of the problem of the deterioration of the light emission characteristics, it was considered that oxygen, moisture or the like entered the inside of the organic EL element and deteriorated the electrode or the organic layer. Therefore, the organic EL element was sealed using a sealing material. In addition, oxygen and moisture have been prevented from entering.
In addition, when sealing an object to be sealed such as an organic EL element using a sealing material, if an outgas is generated from the sealing material, the organic EL element or the like is deteriorated. Has also been done.

For example, Patent Document 1 discloses an organic EL device sealing composition containing a specific cationic curable compound, a photocationic polymerization initiator, and a specific glycoluril compound.
Patent Document 1 also describes that the cured product of the sealing composition has moisture resistance and low outgassing properties, and therefore can prevent deterioration of the organic EL element due to moisture and outgassing.

International Publication No. 2017/094809

By the way, objects to be sealed such as organic EL elements are often used under harsh conditions such as outdoors or in a vehicle. Therefore, there is a demand for a sealing sheet that is excellent in adhesive strength in addition to excellent moisture resistance and low outgas properties, and a resin composition that is suitably used as a raw material for such a sealing sheet. Moreover, the cured | curing material of the composition for organic electroluminescent element sealing as described in patent document 1 is also requested | required that it is excellent in colorless transparency from the specific optical use.
However, Patent Document 1 does not describe the adhesive strength of the cured product of the composition for sealing an organic EL element or the evaluation result of colorless and transparent physical properties.

The present invention is a resin composition excellent in sheet processability (film forming property), a sealing sheet having an adhesive layer formed using this resin composition and excellent in adhesive strength, colorless transparency and water vapor barrier property, And it aims at providing the sealing body by which a to-be-sealed thing is sealed using the said sealing sheet.

As a result of intensive studies to solve the above problems, the present inventors,
The resin composition containing (i) a modified polyolefin resin, a compound having a cyclic ether group, and a cationic photopolymerization initiator is excellent in sheet processability (film forming property), and (ii) this resin composition The sealing sheet having an adhesive layer formed using is excellent in adhesive strength, colorless transparency and water vapor barrier property,
As a result, the present invention has been completed.

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

[1] A resin composition containing the following component (A), component (B), and component (C).
(A) Component: Modified polyolefin resin (B) Component: Compound having 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 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 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 with respect to 100 parts by mass of the component (B). object.

[7] The resin composition according to any one of [1] to [6], further comprising a tackifier.
[8] The resin composition according to [7], wherein the content of the tackifier is 1 to 200 parts by mass with respect to 100 parts by mass of the component (A).
[9] The resin composition according to any one of [1] to [8], further comprising 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 with respect to 100 parts by mass of the component (A).

[11] A sealing sheet comprising a base material or a release film and an adhesive layer formed on the base material or the release film,
A sealing sheet in which the adhesive layer is formed using the resin composition according to any one of [1] to [10].
[12] A sealing sheet comprising 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 resin composition according to any one of [1] to [10].
[13] A sealing film 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 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 thin film glass.

[15] A sealed body obtained by sealing an object to be 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 excellent in sheet processability (referring to being easily molded into a sheet-like material, also referred to as “film-forming property”), an adhesive strength formed using this resin composition, A sealing sheet having an adhesive layer that is colorless and transparent (having a high total light transmittance and having very little coloring) and an excellent water vapor barrier property, and an object to be sealed using the sealing sheet A sealed body that is sealed is 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 this invention contains the following (A) component, (B) component, and (C) component.
(A) Component: Modified polyolefin resin (B) Component: Compound having cyclic ether group (C) Component: Photocationic polymerization initiator

[(A) component: modified polyolefin resin]
The resin composition of the present invention contains a modified polyolefin resin as the component (A).
By containing the modified polyolefin-based resin, a resin composition excellent in sheet processability (film forming property) and a cured product of the resin composition excellent in adhesive strength can be obtained. Moreover, the adhesive layer of the thickness mentioned later can be efficiently formed by using the resin composition containing modified polyolefin resin.

The modified polyolefin resin is a polyolefin resin having a functional group introduced, which is obtained by subjecting a polyolefin resin as a precursor to a modification treatment using a modifier.

The polyolefin resin refers to a polymer containing repeating units derived from olefinic monomers. The polyolefin resin may be a polymer composed of only one or two or more repeating units derived from an olefin monomer, or may be a copolymer of a repeating unit derived from an olefin monomer and an olefin monomer. The polymer which consists of a repeating unit derived from the other monomer which can superpose | polymerize may be sufficient.

The olefin 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.
Examples of other monomers copolymerizable with the olefin monomer include vinyl acetate, (meth) acrylic acid ester, and styrene. Here, “(meth) acrylic acid” represents acrylic acid or methacrylic acid (the same applies hereinafter).

Examples of 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 copolymer, olefin elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, etc. .

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 groups, carboxylic anhydride groups, carboxylic ester groups, hydroxyl groups, epoxy groups, amide groups, ammonium groups, nitrile groups, amino groups, imide groups, isocyanate groups, acetyl groups, thiol groups, ether groups. 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. Carboxylic anhydride groups are 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 resin include acid-modified polyolefin resins and silane-modified polyolefin resins, and acid-modified polyolefin resins are preferable from the viewpoint of obtaining the better effect of the present invention.

The acid-modified polyolefin resin is a resin obtained by graft-modifying a polyolefin resin with an acid. For example, a polyolefin resin may be reacted with an unsaturated carboxylic acid to introduce a carboxyl group (graft modification). In this 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. Is included.

Examples of the unsaturated carboxylic acid 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 thereof include aconitic anhydride, norbornene dicarboxylic acid anhydride, and tetrahydrophthalic acid anhydride.
These can be used alone or in combination of two or more. Among these, maleic anhydride is preferable because a resin composition excellent in sheet processability (film forming property) and a cured product of the resin composition excellent in adhesive strength are easily obtained.

The amount of the unsaturated carboxylic acid 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 3 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 easy to obtain a cured product having better adhesive strength.

A commercially available product can also be used as the acid-modified polyolefin resin. 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), Modic (registered trademark) (manufactured by Mitsubishi Chemical Corporation) and the like.

“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 with 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 preferable.

As the unsaturated silane compound to be reacted with the polyolefin resin, a vinyl silane compound is preferable. Vinyl silane compounds include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tripropoxy silane, vinyl triisopropoxy silane, vinyl tributoxy silane, vinyl tripentyloxy silane, vinyl triphenoxy silane, vinyl tribenzyloxy silane, vinyl tri Examples include methylenedioxysilane, vinyltriethylenedioxysilane, vinylpropionyloxysilane, vinyltriacetoxysilane, and vinyltricarboxysilane.
These can be used alone or in combination of two or more.
In addition, what is necessary is just to employ | adopt the usual method of a well-known graft polymerization for the conditions in case graft-polymerizing an unsaturated silane compound to the polyolefin resin which is a principal chain.

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 still more preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the polyolefin resin. 5 parts by mass. In the resin composition containing the silane-modified polyolefin resin thus obtained, it becomes easy to obtain a cured product having better adhesive strength.

Commercially available products can also be used as the silane-modified polyolefin resin. Examples of commercially available products include Lincron (registered trademark) (manufactured by Mitsubishi Chemical Corporation). Among these, low-density polyethylene-based linklon, 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 resin 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 obtained 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 is excellent in compatibility with the component (A), by using this compound, a resin composition excellent in sheet processability (film forming property), colorless transparency and water vapor blocking. A cured product of the resin composition having excellent properties can be obtained.

Examples of the cyclic ether group include an oxirane group (epoxy group), an oxetane group (oxetanyl group), a tetrahydrofuryl group, and a tetrahydropyranyl group.
The compound having a cyclic ether group refers to a compound having at least one cyclic ether group in the molecule. Especially, it is a compound which has an oxirane group or an oxetane group from a viewpoint that the hardened | cured material of the resin composition excellent in sheet workability (film forming property) and adhesive strength can be obtained. And compounds having two or more oxirane groups or oxetane groups in the molecule are particularly preferred.

As a compound which has an oxirane group in a molecule | numerator, an aliphatic epoxy compound (except an alicyclic epoxy compound), an aromatic epoxy compound, an alicyclic epoxy compound etc. are mentioned, for example.
Examples of aliphatic epoxy compounds include monofunctional epoxy compounds such as glycidyl ethers of aliphatic alcohols and glycidyl esters of alkylcarboxylic acids;
Examples thereof include polyfunctional epoxy compounds such as polyglycidyl etherified products of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, and 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, neopentyl glycol diester. Glycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, dicyclopentadiene dimethanol Polyglycol glycidyl ether such as diglycidyl ether, propylene glycol, triglyceride Ji trimethylolpropane, one to aliphatic polyhydric alcohols such as glycerin, or two or more polyglycidyl ethers of polyether polyols obtained by adding an alkylene oxide, diglycidyl esters of aliphatic long chain dibasic acid;
Monoglycidyl ethers of higher aliphatic 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 commercial item can also be used as an 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, Call EX-920, Denacol EX-931 (manufactured by Nagase ChemteX Corporation);
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 GLYCIROL ED-503, ADEKA GLYCIROL ED-503G, ADEKA GLYCIROL ED-506, ADEKA GLYCIROL ED-523T, ADEKA RESIN EP-4088S, ADEKA RESIN EP-4088L, ADEKA RESIN EP-4080E (above, manufactured by ADEKA)
Examples include TEPIC-FL, TEPIC-PAS, and TEPIC-UC (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.
Representative 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 products of aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone, catechol;
Glycidyl etherified products of aromatic compounds having two or more alcoholic hydroxyl groups such as phenyldimethanol, phenyldiethanol and 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, epoxides of styrene oxide or divinylbenzene.

Moreover, a commercial item can also be used as an 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, Oncoat EX -1040, on-coat EX-1050, on-coat EX-1051, on-coat EX-1010, on-coat EX-1011, on-coat 1012 (above, manufactured by Nagase ChemteX);
Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (above, manufactured by Osaka Gas Chemical Company);
HP4032, HP4032D, HP4700 (above, manufactured by DIC);
ESN-475V (Nippon Steel & Sumikin Chemical Co., Ltd.);
JER (former Epicoat) YX8800 (Mitsubishi Chemical Corporation);
Marproof G-0105SA, Marproof G-0130SP (above, manufactured by NOF Corporation);
Epicron N-665, Epicron HP-7200 (above, manufactured by DIC);
EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (above, Nippon Kayaku Co., Ltd.);
Adeka Resin EP-4000, Adeka Resin EP-4005, Adeka Resin EP-4100, Adeka Resin EP-4901 (above, manufactured by ADEKA);
TECHMORE VG-3101L (manufactured by Printec Co., Ltd.).

As the alicyclic epoxy compound, 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. An oxide containing compound is mentioned.
Typical examples 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) adip 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, ethylenebis (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 commercial item can also be used as an alicyclic epoxy compound. Examples of commercially available products include Celoxide 2021P, Celoxide 2081, Celoxide 2000, and Celoxide 3000 (manufactured by Daicel).

Examples of the compound 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 fats such as butane and 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane Group oxetane compounds, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl And monofunctional oxetane compounds such as -3- (hydroxymethyl) oxetane and 3-ethyl-3- (chloromethyl) oxetane.

A commercial item can also be used as a compound which has an oxetane group in a molecule | numerator. Commercially available products include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.);
Aron Oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (above, manufactured by Toagosei Co., Ltd.);
Etanacol OXBP, OXTP (manufactured by Ube Industries, Ltd.) and the like can be mentioned.

Among these compounds having a cyclic ether group, from the viewpoint that a cured product of a resin composition excellent in sheet processability (film forming property) and a resin composition excellent in adhesive strength can be obtained at 25 ° C. What is liquid is preferable. Moreover, what a cyclic ether group is an oxirane group is preferable.

The molecular weight of the compound having a cyclic ether group is usually 700 to 5000, preferably 1200 to 4000.
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 the 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 high adhesive strength and excellent curability can be efficiently produced.
These compounds having a cyclic ether group can be used singly 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 5 to 50 parts by mass, more preferably 5 to 40 parts by mass, and further preferably 5 to 25 parts by mass with respect to 100 parts by mass of the component (A). It is.
By making content of the compound which has a cyclic ether group into the said range, it becomes easy to obtain the hardened | cured material of the resin composition which is excellent by adhesive strength.

[(C) component: photocationic polymerization initiator]
The resin composition of the present invention contains a cationic photopolymerization initiator as the component (C).
The cationic photopolymerization initiator is a compound that generates a cationic species upon irradiation with light and initiates a curing reaction of the cationically curable compound, and includes a cationic part that absorbs light and an anion part that is a source of acid generation.

Examples of the cationic photopolymerization initiator 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. And bromine salt compounds. Among these, from the viewpoint of excellent compatibility with the component (B) and excellent storage stability of the resulting resin composition, sulfonium salt compounds are preferable, and aromatic sulfonium salt compounds having an aromatic group are more preferable. preferable.

Examples of the sulfonium salt compounds include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4′-bis [diphenylsulfonio] diphenyl sulfide-bishexafluoro. Phosphate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide-bishexafluoroantimonate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluorophosphate, 7 -[Di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate, 7- [di (p-toluyl) sulfonio] -2-isopro Rutetrakis (pentafluorophenyl) borate, phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide-hexafluorophosphate, phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide-hexafluoroantimonate, 4-tert-butylphenylcarbonyl -4'-diphenylsulfonio-diphenyl sulfide-hexafluorophosphate, 4-tert-butylphenylcarbonyl-4'-diphenylsulfonio-diphenyl sulfide-hexafluoroantimonate, 4-tert-butylphenylcarbonyl-4'-diphenyl Sulfonio-diphenylsulfide-tetrakis (pentafluorophenyl) borate, thiophenyldiphenylsulfonium hexafluo Loantimonate, thiophenyldiphenylsulfonium hexafluorophosphate, 4- {4- (2-chlorobenzoyl) phenylthio} phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, thiophenyldiphenylsulfonium hexafluoroantimonate halide, 4 , 4 ′, 4 ″ -tri (β-hydroxyethoxyphenyl) sulfonium hexafluoroantimonate, 4,4′-bis [diphenylsulfonio] diphenyl sulfide-bishexafluoroantimonate, diphenyl [4- (phenylthio) phenyl ] Sulfonium trifluorotrispentafluoroethyl phosphate, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tris [(tri Ruoromechiru) sulfonyl] methanide and the like.

Examples of the iodonium salt compounds include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, (triccumyl) iodonium tetrakis (pentafluoro). Phenyl) borate and the like.

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

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

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 singly or in combination of two or more.

Moreover, a commercial item can also be used as a photocationic polymerization initiator. Commercially available products include Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, Cyracure UVI-950 (above, manufactured by Union Carbide), Irgacure 250, Irgacure 261, Irgacure 264 (above, Ciba Specialty Chemicals) ), SP-150, SP-151, SP-170, Optomer SP-171 (manufactured by ADEKA), CG-24-61 (manufactured by Ciba Specialty Chemicals), DACAT 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-16 2 (above, manufactured by Nippon Soda Co., Ltd.), 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 (above, manufactured by Midori Chemical), CD-1010, CD-1011, CD-1012 (manufactured by Sartomer), CPI-100P, CPI-101A, CPI-200K, CPI -310B (manufactured by Sun Apro).

The content of the cationic photopolymerization initiator is usually 0.02 to 2 parts by weight, preferably 0.03 to 1 part by weight, more preferably 0.04 to 0 parts per 100 parts by weight of the component (B). .5 parts by mass.
By making content of a photocationic polymerization initiator into the said range, it becomes easy to obtain the hardened | cured material of the resin composition excellent in adhesive strength.
When there is too much content of a photocationic polymerization initiator, the elasticity modulus after hardening will become high too much, and there exists a possibility that the adhesive strength of the hardened | cured material of a resin composition may fall.

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

Examples of the tackifier 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, 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, styrene monomer / α-methylstyrene / aliphatic monomer copolymer system Styrene resins such as resins, styrene monomer monopolymer resins, styrene monomer / aromatic monomer copolymer resins; hydrogenated styrene resins obtained by hydrogenating these styrene resins;
A C5 petroleum resin obtained by copolymerizing C5 fractions such as pentene, isoprene, piperine, 1.3-pentadiene produced by thermal decomposition of petroleum naphtha, and a hydrogenated petroleum resin of this C5 petroleum resin;
And C9 petroleum resins obtained by copolymerizing C9 fractions such as indene and vinyltoluene produced by thermal decomposition of petroleum naphtha, and hydrogenated petroleum resins of these C9 petroleum resins. Among these, a styrene resin is preferable, and a styrene monomer / aliphatic monomer copolymer resin is more preferable.
These tackifiers can be used alone or in combination of two or more.

A commercial item can also be used for a tackifier. Commercially available products include terpene resins such as YS resin P, A series, Clearon (registered trademark) P series (manufactured by Yashara Chemical), picolite A, C series (manufactured by PINOVA);
Aliphatic petroleum resins such as Quinton (registered trademark) A, B, R, CX series (manufactured by Nippon Zeon);
Styrenic resins such as FTR (registered trademark) series (Mitsui Chemicals);
Alcon P, M series (manufactured by Arakawa Chemical Co., Ltd.), ESCOREZ (registered trademark) series (manufactured by ExxonMobil Chemical Co., Ltd.), EASTOTAC (registered trademark) series (manufactured by Eastman Chemical Co., Ltd.), ILARV (registered trademark) series (Idemitsu) Alicyclic petroleum resins such as Kosan)
Examples include ester series 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).

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 still more preferably 70 to 130 ° C. from the viewpoint of imparting excellent tackiness.

When the resin composition of the present invention contains a tackifier, the content thereof 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 making content of a tackifier into the said range, it becomes easy to obtain the hardened | cured material of the resin composition which is excellent by adhesive strength.

Silane coupling agents include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltri A silane coupling agent having a (meth) acryloyl group such as methoxysilane;
Silane coupling agents 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;
Silane coupling agents 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 A silane coupling agent having an amino group such as hydrochloride of (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane;
Silane coupling agents having a ureido group such as 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane;
Silane coupling agents having a halogen atom such as 3-chloropropyltrimethoxysilane and 3-chloropropyltriethoxysilane;
Silane coupling agents having a mercapto group such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane;
Silane coupling agents having sulfide groups such as bis (trimethoxysilylpropyl) tetrasulfide and bis (triethoxysilylpropyl) tetrasulfide;
Silane coupling agents having an isocyanate group such as 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane;
Silane coupling agents having an allyl group such as allyltrichlorosilane, allyltriethoxysilane, and allyltrimethoxysilane;
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 100 parts by mass with respect to 100 parts by mass of the component (A). 5 parts by mass.
By making content of a silane coupling agent into the said range, it becomes easy to obtain the hardened | cured material of the resin composition which is excellent by adhesive strength.

Examples of the solvent include aliphatic hydrocarbon solvents 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;
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;
And ether solvents such as 1,3-dioxolane.
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 coating properties, film thickness, and the like.

Moreover, the resin composition of this invention may contain components other than the said tackifier, a silane coupling agent, and a solvent in the range which does not inhibit the effect of this invention.
Examples of components other than the tackifier, the silane coupling agent, and the solvent include an antistatic agent, a stabilizer, an antioxidant, a plasticizer, a lubricant, and a coloring pigment. What is necessary is just to determine these content suitably according to the objective.

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 comprising a base material or a release film and an adhesive layer formed on the base material or the release film, wherein the adhesive layer is the resin composition of the present invention. The sealing sheet which is formed using.
Sealing sheet (β): A sealing sheet comprising 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. The sealing sheet which is formed using.
Sealing sheet (γ): 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, wherein the adhesive layer is the resin composition of the present invention. The sealing sheet which is formed using a thing.
In addition, these sealing sheets represent the state before use, and when using the sealing sheet of this invention, a peeling film is peeled and removed normally.

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

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.

A conventionally well-known thing can be utilized as a peeling film. For example, what has the peeling layer by which the peeling process was carried out with the release agent on the base material for peeling films is mentioned.
As the substrate for the release film, paper substrates such as glassine paper, coated paper, and high-quality paper; laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper substrates; polyethylene terephthalate resin, polybutylene terephthalate resin, Examples thereof 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 manufacturing method of a sealing sheet ((alpha)) is not specifically limited. For example, the sealing sheet (α) can be manufactured using a casting method.
When the sealing sheet (α) is produced by a casting method, the resin composition of the present invention is applied to the release layer surface of the substrate or the release film subjected to the release treatment using a known method, and the obtained coating is obtained. The sealing sheet (α) can be obtained by drying the film.

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

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 condition for drying the coating film is, 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.

The conditions for photocuring are not particularly limited. The adhesive layer can be photocured by irradiating active energy rays such as ultraviolet rays, visible rays, X-rays and electron beams.
In the present invention, photocuring by ultraviolet irradiation is preferable from the viewpoint of obtaining a sealing sheet having excellent transparency.

Specific examples of the ultraviolet light source for irradiating ultraviolet light include light sources such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, and a metal halide lamp. Further, the wavelength range of 190 to 380 nm can be used as the wavelength of the ultraviolet rays to be irradiated.
The irradiation amount of ultraviolet rays is preferably about 50 to 1000 mW / cm ² in illuminance and about 50 to 1000 mJ / cm ^{2 in} light quantity.
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 is excellent in 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 under the conditions of a temperature of 23 ° C. and a relative humidity of 50%. This 180 ° peel test can be measured by the method described in the examples.

The adhesive layer of the sealing sheet of the present invention is excellent in 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 on the total light transmittance, but it is usually 95% or less.
As described 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.

Further, an adhesive layer having a thickness of 20 μm obtained by photo-curing treatment, when measured, is L * in the CIE 1976 L * a * b * color system defined in JIS Z 8781-4 (2013). The value is 90 to 98. The a * value is −2 to 2. The b * value is −2 to 2.

In the L * a * b * color system, L * indicates lightness, and a * and b * indicate hue and saturation, respectively. When a * is a positive value, the red direction, when a * is a negative value, the green direction, when b * is a positive value, the yellow direction, and when b * is a negative value, the blue direction. Indicates saturation. It becomes colorless as the absolute value of a * and b * decreases.

The L * value of the adhesive layer obtained by the photocuring treatment is preferably 92 to 98, more preferably 94 to 98.
The a * value is usually −2 to 2, preferably −1 to 1, and more preferably −0.5 to 0.5.
Further, the b * value is usually from −2 to 2, preferably from −1 to 1, and more preferably from −0.5 to 0.5.
The adhesive layer obtained by the photocuring treatment is less biased in the red direction (+ a *), the green direction (−a *), the yellow direction (+ b *), and the blue direction (−b *).
The resin composition capable of forming an adhesive layer in which L * is in the above range and the color gamuts of a * and b * are in the above range has high total light transmittance and very little coloring. Therefore, it is suitably used as a sealing material for light emitting devices such as organic EL elements.
For this reason, the sealing sheet of this invention is used suitably in optical uses, such as a sealing material of light emitting devices, such as an organic EL element.
The L * a * b * value in the CIE1976 L * a * b * color system can be measured by the method described in the examples.

The yellowness (YI value) of the sealing sheet is usually from 0.01 to 2, preferably from 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 is excellent in 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.

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).

The two release films in the sealing sheet (β) may be the same or different, but the two release films preferably have different release forces. When the peel strengths of the two release films are different, problems are less likely to occur when the sealing sheet is used. That is, the process of peeling a peeling film first can be performed more efficiently by making the peeling force of two peeling films differ.

The manufacturing method of a sealing sheet ((beta)) is not specifically limited.
For example, when the sealing sheet (β) is manufactured by a casting method, the method similar to the method shown in the manufacturing method of the sealing sheet (α) is used, and the resin composition of the present invention is peeled off from the release film. The release layer is coated, dried, and the resulting coating is dried and photocured to produce an adhesive layer with a release film, and then another release film is placed on the adhesive layer. The sealing sheet (β) can be obtained by overlapping the layers.

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 which comprises a sealing sheet ((gamma)) will not be specifically limited if it is a film which has water vapor | steam barrier property.

The gas barrier film preferably has a water vapor transmission rate 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”). It is more preferable that it is 0.05 g / m ² / day or less, and it is more preferable that it is 0.005 g / m ² / day or less.
Since the water vapor permeability of the gas barrier film under an environment of 40 ° C. and 90% RH is 0.1 g / m ² / day or less, oxygen or moisture is contained inside the element such as an organic EL element formed on the substrate. Etc. can effectively prevent the electrode and the organic layer from deteriorating.
The transmittance 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 film glass, and resin film. Among these, a resin film is preferable, and a gas barrier film having a base material and a gas barrier layer is more preferable.

As a resin component which comprises a base material, the thing similar to the resin component of the resin film which can be utilized as a base material which comprises the said sealing sheet ((alpha)) is mentioned.
The thickness of the substrate 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.

A material etc. will not be specifically limited if a gas barrier layer can provide desired gas barrier property. The gas barrier layer is obtained by subjecting a gas barrier layer made of an inorganic vapor deposition film, a gas barrier layer containing a gas barrier resin, or a layer containing a polymer compound (hereinafter sometimes referred to as “polymer layer”) to a modification treatment. Gas barrier layer [in this case, the gas barrier layer does not mean only a region modified by ion implantation or the like, but a “polymer layer including a modified region”]. ] Etc. are mentioned.
Among these, since a thin layer having excellent gas barrier properties can be efficiently formed, a gas barrier layer made of an inorganic vapor deposition film or a gas barrier layer obtained by subjecting a polymer layer to a modification treatment is preferable. The gas barrier film may have two or more of these gas barrier layers.

Examples of the inorganic vapor deposition film include vapor deposition films of inorganic compounds and metals.
As a raw material for the vapor deposition film of the inorganic compound, inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, tin oxide, and zinc tin oxide;
Inorganic nitrides such as silicon nitride, aluminum nitride, titanium nitride;
Inorganic carbides; inorganic sulfides; inorganic oxynitrides such as silicon oxynitride;
Inorganic oxide carbides; inorganic nitride carbides; inorganic oxynitride carbides and the like.
Examples of the raw material for the metal vapor deposition film include aluminum, magnesium, zinc, and tin.
These can be used singly or in combination of two or more.

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

The thickness of the inorganic vapor-deposited film is usually from 1 nm to 2000 nm, preferably from 3 nm to 1000 nm, more preferably from 5 nm to 500 nm, and further preferably from 40 nm to 200 nm, from the viewpoints of gas barrier properties and handling properties.

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 a photo CVD method. And CVD method such as, atomic layer deposition method (ALD method).

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 polychlorotrifluoromethane. Examples thereof include resins that are difficult to transmit oxygen, water vapor, and the like, such as ethylene.

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

Examples of a method for forming a gas barrier layer containing a gas barrier resin include a method in which a gas barrier layer forming solution containing a gas barrier resin is applied on a substrate or other layer, and the obtained coating film is appropriately dried. .

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

In the gas barrier layer in which the surface of the polymer layer is modified, the polymer compound used is a silicon-containing polymer compound, polyimide, polyamide, polyamideimide, polyphenylene ether, polyetherketone, polyetheretherketone, polyolefin, polyester. , Polycarbonate, 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 that a gas barrier layer having better gas barrier properties can be formed. Examples of silicon-containing polymer compounds include polysilazane compounds, polycarbosilane compounds, polysilane compounds, polyorganosiloxane compounds, poly (disilanylene phenylene) compounds, and poly (disilanylene ethynylene) compounds. Is mentioned. Among these, a polysilazane compound is preferable from the viewpoint that a gas barrier layer having excellent gas barrier properties can be formed even if it is thin. By subjecting the layer containing the polysilazane compound to a modification treatment, a layer (silicon oxynitride layer) having oxygen, nitrogen, and silicon as main constituent atoms can be formed.

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

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

In said formula (1), n represents arbitrary natural numbers.
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, unsubstituted or substituted Represents a non-hydrolyzable 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.

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

In the present invention, a modified polysilazane compound can also be used as the polysilazane compound. Examples of the modified polysilazane include, for example, 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-5-345826 Examples described in JP-A No. 4-63833 are listed.
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.
Moreover, as a polysilazane compound, a commercially available product as a glass coating material or the like can be used as it is.
The polysilazane compounds can be used alone or in combination of two or more.

The polymer layer may contain other components in addition to the polymer compound described above as long as the object of the present invention is not impaired. As other components, the additive mentioned as components other than the said (A) component, (B) component, and (C) component can be contained.
The content of the polymer compound in the polymer layer is preferably 50% by mass or more, and more preferably 70% by mass or more because a gas barrier layer having better gas barrier properties can be formed.

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

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

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

The application method is not particularly limited, and the methods mentioned as the method for applying the resin composition can be used.
The method for drying the coating film is not particularly limited, and the methods mentioned 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, and heat treatment.
As will be described later, the ion implantation treatment is a method of injecting accelerated ions into the polymer layer to modify the polymer layer.
The plasma treatment is a method for modifying the 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 for modifying the polymer layer by irradiating the polymer layer with ultraviolet rays. For example, the ultraviolet modification treatment can be performed according to the method described in JP2013-226757A.

Among these gas barrier layers, ion implantation into a layer containing a silicon-containing polymer compound is possible from the viewpoint that it can be efficiently modified to the inside without roughening the surface of the polymer layer and a gas barrier layer having better gas barrier properties can be formed. Those obtained by treatment are preferred.

As ions implanted into the polymer layer, 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 gases such as methane and ethane;
Ions of alkenes 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;
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 preferable because ions can be more easily implanted and a gas barrier layer having better gas barrier properties can be formed.

The ion implantation amount can be appropriately determined according to the purpose of use of the gas barrier film (necessary gas barrier properties, colorless transparency, etc.).

Examples of the method of 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 them, the latter method of plasma ion implantation (plasma ion implantation method) is preferable from the viewpoint of easily forming the target gas barrier layer.

In the plasma ion implantation method, for example, plasma is generated in an atmosphere containing a plasma generation gas such as a rare gas, and a negative high voltage pulse is applied to the polymer layer to thereby remove ions (positive ions) in the plasma. It 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 a method described in WO2010 / 107018 pamphlet or the like.

By ion implantation, the thickness of the region into which ions are implanted can be controlled by 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, etc. Although it may be determined, it is usually 10 nm or more and 400 nm or less.

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

The manufacturing method of sealing sheet ((gamma)) is not specifically limited. For example, in the manufacturing method of 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.
Moreover, after manufacturing the sealing sheet (β), the single release film is peeled off, and the exposed adhesive layer and the gas barrier film are adhered to manufacture the sealing sheet (γ). You can also. In this case, when the sealing sheet (β) 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 adhesive layer of the sealing sheet of the present invention is excellent in adhesive strength, colorless transparency, and water vapor barrier properties. For this reason, the sealing sheet of this invention is used suitably in optical uses, such as a sealing material of light emitting devices, such as an organic EL element.

3) Sealing body The sealing body of the present invention is such that an object to be sealed is sealed using the sealing 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 sealed. This means that the object to be sealed is covered with the material.
The sealing body of the present invention includes, for example, a substrate, an element (an object to be sealed) formed on the substrate, and a sealing material for sealing the element, What the sealing material is the adhesive bond layer of the sealing sheet of this invention is mentioned.

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. In addition, a material having a high blocking performance for blocking moisture and gas to enter 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, 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 selected as appropriate in consideration of light transmittance and performance for blocking the inside and outside of the element.

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

The manufacturing method of the sealing body of this invention is not specifically limited.
For example, in the case of the configuration 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 sticking the adhesive layer on the object to be sealed. When 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 bonded to the exposed adhesive layer, and then the other release film is attached. By removing and adhering the adhesive layer on 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 configuration of the sealing sheet (γ) of the present invention, the release film is removed, and the adhesive layer is attached onto the object to be sealed, so that the object to be sealed is sealed with the adhesive layer of the sealing sheet. Stop.

There are no particular restrictions on the bonding conditions for bonding the adhesive layer of the sealing sheet and the object to be sealed. The bonding temperature is, for example, 23 to 100 ° C, preferably 23 to 80 ° C, more preferably 23 ° C to 40 ° C. This adhesion treatment may be performed while applying pressure.
In the present invention, a sealing sheet having an uncured adhesive layer (dried coating film of the resin composition of the present invention) is used, and the uncured adhesive layer of the sealing sheet is sealed. After bonding the object, the uncured adhesive layer may be photocured.
The conditions described above can be used as the curing conditions at this time.

The sealing body of the present invention is formed by sealing an object to be 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 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 indicated, the part and% in each example are based on mass.

In the following examples and comparative examples, the modified polyolefin resin [(A) component], the compound having a cyclic ether group [(B) component], and the photocationic polymerization initiator [(C) component] The thing of was used.
Modified polyolefin resin (component (A))
Acid-modified α-olefin polymer [Mitsui Chemicals, trade name: Unistor H-200, number average molecular weight: 47,000]

Compound having cyclic ether group [component (B)]
(1) Compound having cyclic ether group (B-1)
Dicyclopentadiene dimethanol diglycidyl ether [manufactured by ADEKA, trade name: Adeka Resin 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., trade 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, 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 type epoxy resin [Mitsubishi Chemical Corporation, trade 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, trade 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 (B-1) having a cyclic ether group, 0.1 part of photocationic polymerization initiator (C-1), tackifier [styrene monomer / 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)] 0.1 part was dissolved in toluene to prepare a resin composition (1) having a solid concentration of 27%.
This resin composition (1) was coated on the release-treated surface of a release film (product name: SP-PET382150, manufactured by Lintec Corporation), and the obtained coating film was dried at 100 ° C. for 2 minutes to have a thickness of 20 μm. An adhesive layer was formed, and the release-treated surface of another release film (manufactured by Lintec Corporation, trade name: SP-PET 381031) was bonded to the adhesive layer. Then, using an ultraviolet irradiation device (product name: US2-0801 <2>, manufactured by Eye Graphics Co., Ltd.), the coating film is cured by irradiating ultraviolet rays with an illuminance of 200 mW / cm ² and a light amount of 200 mJ / cm ² , and then sealed. 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, and these resin compositions were prepared. The sealing sheets (2) to (4) were obtained using

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

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

[Examples 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, and these resin compositions were prepared. Used to obtain sealing sheets (7) and (8).

[Example 9]
In Example 1, the resin composition (9) was used in the same manner as in Example 1, except that the photocationic polymerization initiator (C-2) was used instead of the photocationic polymerization initiator (C-1). 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 in Example 1.
Using this resin composition, an attempt was made to produce a sealing sheet in the same manner as in Example 1. However, the sheet processability (film forming property) was low, and the sealing sheet could not be obtained.

[Comparative Example 2]
A resin composition (12) was prepared in the same manner as in Example 1 except that the compound (B-1) having a cyclic ether group was not used in Example 1, and a sealing sheet was prepared using this resin composition. (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. Except not using it, it carried out similarly to Example 1, and prepared the resin composition (13), and obtained the sealing sheet (13) using this resin composition.

The sealing sheets (1) to (10), (12) and (13) obtained in Examples 1 to 10 and Comparative Examples 2 and 3 were subjected to the following measurements and evaluations. The results are shown in Table 1.
(Adhesion measurement)
One release film of the sealing sheet having a width of 25 mm was peeled off and the adhesive layer was exposed. The exposed adhesive layer was bonded to a polyethylene terephthalate film (manufactured by Lintec Corporation, thickness 50 μm, single layer product). Subsequently, the other peeling film of the sealing sheet was peeled and removed, and the exposed adhesive layer was pressure-bonded to a non-alkali glass (manufactured by Corning, trade name: Eagle XG) with a pressure-bonding roll to prepare a test piece.
The prepared test piece was subjected to a 180 ° peel test under the conditions of a temperature of 23 ° C. and a relative humidity of 50%.
In this peeling test, the adhesive strength measurement method described in JIS Z0237: 2009 was performed except for the test conditions described above.

[Total light transmittance measurement]
One release film of the sealing sheet was peeled off and the adhesive layer was exposed. Place this sealing sheet on soda lime glass (thickness 1 mm) so that the exposed adhesive layer faces soda lime glass, and then paste them at 23 ° C. using a laminator. A piece was made.
About the produced test piece, the total light transmittance was measured using the total light transmittance measuring apparatus (The product name: NDH-5000 by Nippon Denshoku Industries Co., Ltd.).

[Color measurement]
A test piece similar to that used for the total light transmittance was prepared.
For the prepared test piece, a spectrophotometer (manufactured by Shimadzu Corporation, product name: UV-3600) is used in accordance with JIS Z 8781-4 (2013) for the color value defined by the CIE 1976 L * a * b * color system. ).

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

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

From Table 1, the following can be understood.
The sealing sheets (1) to (10) formed using the resin compositions (1) to (10) containing the component (A), the component (B), and the component (C) have a temperature of 23 ° C. Excellent adhesion strength under conditions of 50% relative humidity (Examples 1 to 10).
In addition, the sealing sheets (1) to (10) have a high total light transmittance, a small absolute value of a * value and b * value, and a small yellowness YI, and are excellent in colorless transparency.
Further, the sealing sheets (1) to (10) are excellent in water vapor barrier properties.
On the other hand, the resin composition (11) containing no component (A) has a low sheet processability (film forming property), and a sealing sheet could not be obtained (Comparative Example 1).
Moreover, the sealing sheet (12) and (13) formed using the resin composition (12) which does not contain (B) component, and the resin composition (13) which does not contain (C) component have temperature 23 It is inferior in adhesive strength under the conditions of ° C. and 50% relative humidity (Comparative Examples 2 and 3).

Claims (16)

The resin composition containing the following (A) component, (B) component, and (C) component.
(A) Component: Modified polyolefin resin (B) Component: Compound having cyclic ether group (C) Component: Photocationic 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 oxirane group or an oxetane group. 4. The resin composition according to claim 1, wherein the content of the component (B) is 5 to 50 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 component (C) is an aromatic sulfonium salt compound. 6. The resin composition according to claim 1, wherein the content of the component (C) is 0.04 to 2 parts by mass with respect to 100 parts by mass of the component (B). The resin composition according to claim 1, further comprising a tackifier. The resin composition according to claim 7, wherein the content of the tackifier 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 8, further comprising a silane coupling agent. The resin composition according to claim 9, 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 comprising a substrate or a release film and an adhesive layer formed on the substrate or the release film,
A sealing sheet, wherein the adhesive layer is formed using the resin composition according to any one of claims 1 to 10. A sealing sheet comprising 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 claims 1 to 10. A release film, a gas barrier film, and a sealing sheet comprising 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 claims 1 to 10. The sealing sheet according to claim 13, wherein the gas barrier film is a metal foil, a resin film, or a thin film glass. A sealed body formed by sealing an object to be sealed using the sealing sheet according to any one of claims 11 to 14. The sealing body according to claim 15, wherein the object to be sealed is an electronic device.