TWI820103B - Resin composition, sealing sheet and sealing body - Google Patents

Abstract

The present invention provides a resin composition, which contains (A) component: modified polyolefin resin, (B) component: a compound having a cyclic ether group, and (C) component: photocationic polymerization initiator. A resin composition in which the content of the component (B) is greater than 50 parts by mass and 200 parts by mass or less based on 100 parts by mass of the component (A). According to the present invention, it is possible to provide a resin composition that has excellent sheet processability (film-forming properties) in a normal temperature environment; and a resin composition formed using the resin composition has a high storage elastic modulus after photocuring treatment and has A sealing sheet with an adhesive layer that has excellent adhesion strength and sealing properties, and a sealing body in which an object to be sealed is sealed using the sealing sheet.

Description

Resin composition, sealing sheet and sealing body

The present invention relates to a resin composition having excellent sheet strength and sheet processability in a normal temperature environment; and a sealing sheet having an adhesive layer formed using the resin composition and having excellent bonding strength and sealing properties. , and a sealed body formed by using the aforementioned sealing sheet to seal the sealed object.

In recent years, organic EL elements (organic electroluminescent elements) have attracted attention as light-emitting elements capable of emitting light with high brightness by low-voltage DC driving.

However, organic EL elements have a problem that their luminescence characteristics, such as luminous brightness, luminous efficiency, and luminous uniformity, tend to decrease over time.

As for the cause of the problem of reduced light-emitting characteristics, it is thought that oxygen, moisture, etc. invade the inside of the organic EL element and deteriorate the electrodes and organic layers. Therefore, attempts have been made to seal the organic EL element using a sealing material to prevent oxygen and moisture. immersion.

When a sealing material is used to seal an organic EL element, it must be embedded into the tiny gap of the organic EL element. Therefore, sealing materials with lower viscosity and viscosity stability have been developed previously.

For example, Patent Document 1 describes a resin composition containing a specific epoxy resin, an epoxy resin hardener, microcapsules, and a specific amount of filler. It is measured at 25 using an E-type viscometer. The viscosity at ℃ and 2.5rpm is 0.5~50pa. s.

Furthermore, Patent Document 1 also describes that by using a liquid epoxy resin and a liquid epoxy resin hardener and adjusting the filler content, both low viscosity and high moisture resistance of the cured product can be achieved; and the use of The display device obtained from the resin composition can maintain high bonding strength under high temperature and high humidity.

[Prior technical literature]

[Patent Document]

[Patent Document 1] Japanese International Publication No. 2012/014499

Since the resin composition described in Patent Document 1 has viscosity stability (can maintain a low viscosity), it has excellent coating properties and high sealing properties. However, since the resin composition is fluid before the curing reaction, a special coating device such as a dispenser must be used to seal the organic EL element, and the manufacturing process of the light-emitting device such as the organic EL element is complicated.

Therefore, there has been a demand for a resin composition that has excellent sheet strength and sheet processability in a normal temperature environment, can simplify the manufacturing process of light-emitting devices such as organic EL elements, and can form a high storage elastic modulus after curing. And it has a sealing piece with sufficient sealing performance.

The present invention was made in view of the above-mentioned actual situation, and its purpose is to provide a resin composition with excellent sheet strength and sheet processability in a normal temperature environment; and to provide a storage method after photocuring formed using the resin composition. A sealing sheet with an adhesive layer having a high elastic modulus and excellent bonding strength and sealing properties, and a sealing body in which an object to be sealed is sealed using the sealing sheet.

In order to solve the above-mentioned problems, the inventors of this case conducted intensive research and found that: (i) A resin composition containing a modified polyolefin resin, a compound having a cyclic ether group, and a photocationic polymerization initiator, wherein the content of the compound having a cyclic ether group is based on 100 parts by mass of the modified polyolefin resin A resin composition of more than 50 parts by mass and less than 200 parts by mass, which has excellent sheet strength and sheet processability in a normal temperature environment; and (ii) a sealing sheet having an adhesive layer formed using the resin composition, The present invention is achieved because the storage elastic modulus after photohardening treatment is relatively high and the adhesive strength and sealing properties are excellent.

Thus, according to the present invention, it is possible to provide the following resin compositions [1] to [9], sealing sheets [10] to [13], and sealing bodies [14] and [15].

[1] A resin composition containing the following (A) component, (B) component, and (C) component, the content of the above-mentioned component (B) relative to 100 parts by mass of the above-mentioned component (A) It is more than 50 parts by mass and less than 200 parts by mass,

(A) Component: Modified polyolefin resin

(B) Component: Compounds with cyclic ether groups

(C) Ingredient: 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], wherein the cyclic ether group of the component (B) is an oxirane group or an oxybutanyl group.

[4] The resin composition according to [1], wherein the component (C) is an aromatic sulfonium salt-based compound.

[5] The resin composition according to [1], wherein the content of the component (C) is 0.1 to 10 parts by mass relative to 100 parts by mass of the component (B).

[6] The resin composition according to [1], further containing an adhesion-imparting agent with a softening point of 80°C or higher.

[7] The resin composition according to [6], wherein the content of the tackifier having a softening point of 80° C. or higher is 1 to 200 parts by mass relative to 100 parts by mass of the component (A).

[8] The resin composition according to [1], further containing a silane coupling agent.

[9] The resin composition according to [8], wherein the content of the silane coupling agent is 0.01 to 10 parts by mass relative to 100 parts by mass of the component (A).

[10] A sealing sheet composed of a base material or a release film, and an adhesive layer formed on the base material or release film, and the adhesive layer is made of any one of items [1] to [9] It is formed from the resin composition described in the item.

[11] A sealing sheet composed of two release films and an adhesive layer sandwiched between the two release films. The adhesive layer is made of any one of [1] to [9]. formed from the resin composition described above.

[12] 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. The adhesive layer is used as shown in [1] to [ It is formed from the resin composition described in any one of items 9].

[13] The sealing sheet according to [12], wherein the gas barrier film is a metal foil, a resin film, or a thin film glass.

[14] A sealing body formed by sealing an object to be sealed using the sealing sheet as described in [10].

[15] The sealed body according to [14], wherein the sealed object is an electronic device.

According to the present invention, it is possible to provide a resin composition that has excellent sheet strength and sheet processability (referring to the ability to easily form a sheet, also known as "film-forming properties") in a normal temperature environment; and has the ability to use the resin The composition forms a sealing sheet with an adhesive layer that has a high storage elastic modulus after photohardening and has excellent bonding strength and sealing properties, and a sealing body formed by using the sealing sheet to seal the object to be sealed.

Form used to implement the invention

Hereinafter, the present invention is divided into 1) resin composition, 2) sealing sheet, and 3) sealing body and is explained in detail.

1) Resin composition

The resin composition of the present invention contains the following (A) component, (B) component, and (C) component,

(A) Component: Modified polyolefin resin

(B) Component: Compounds with cyclic ether groups

(C) Ingredient: Photocationic polymerization initiator

[(A) Component: Modified polyolefin resin]

The resin composition of the present invention contains modified polyolefin-based resin as component (A).

By containing modified polyolefin-based resin, a resin composition with excellent sheet processability can be obtained. compounds, and cured products of resin compositions with relatively excellent bonding strength. Furthermore, by using a resin composition containing a modified polyolefin-based resin, an adhesive layer having a thickness described below can be formed efficiently.

In the modified polyolefin resin system, a polyolefin resin as a precursor can be modified using a modifier to obtain a polyolefin resin into which functional groups have been introduced.

Polyolefin resin refers to a polymer containing repeating units derived from olefin-based monomers. The polyolefin resin may be a polymer composed of only one or more repeating units derived from olefinic monomers, or may be composed of repeating units derived from olefinic monomers, and may be derived from repeating units derived from olefinic monomers. A polymer composed of repeating units of copolymerized monomers.

The olefin-based monomer is preferably an α-olefin having 2 to 8 carbon atoms, more preferably ethylene, propylene, 1-butene, isobutylene, or 1-hexene, and more preferably ethylene or propylene.

These olefin-based monomers can be used individually by 1 type or in combination of 2 or more types.

Examples of the monomer copolymerizable with the olefin-based monomer include vinyl acetate, (meth)acrylate, styrene, and the like. Here, "(meth)acrylic acid" means acrylic acid or methacrylic acid (the same applies below).

These monomers copolymerizable with olefin-based monomers can be used individually by 1 type or in combination of 2 or more types.

Examples of polyolefin resins include very low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), and linear low density polyethylene (LLDPE). ), polypropylene (PP), ethylene-propylene copolymer, olefin elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid Ester copolymers, etc.

The modifier used for the modification treatment of polyolefin resin is a compound with functional groups in the molecule.

Examples of the functional group include carboxyl group, carboxylic acid anhydride group, carboxylic acid ester group, hydroxyl group, epoxy group, amide group, Ammonium group, nitrile group, amine group, acyl imide group, isocyanate group, acetyl group, thiol group, ether group, thioether group, sulfone group, phosphine group, nitro group, urethane group Ester group, alkoxysilyl group, silanol group, halogen atom, etc. Among these, carboxyl group, carboxylic anhydride group, carboxylic acid ester group, hydroxyl group, ammonium group, amine group, acyl imide group, isocyanate group and alkoxysilane group are preferred, carboxylic anhydride group is preferred, and alkoxysilane group is preferred. The group is preferably a carboxylic acid anhydride group.

The compound having a functional group may also have two or more functional groups in the molecule.

Examples of modified polyolefin-based resins include acid-modified polyolefin-based resins and silane-modified polyolefin-based resins. From the viewpoint that the present invention can obtain relatively excellent effects, acid-modified polyolefin-based resin is preferred.

Acid-modified polyolefin resin refers to a polyolefin resin graft-modified with an acid. For example, an unsaturated carboxylic acid is reacted with a polyolefin resin to introduce a carboxyl group (graft modification). In addition, in this specification, the term acid refers to the concept including acid anhydride, the term unsaturated carboxylic acid refers to the concept including unsaturated carboxylic acid anhydride, and the term carboxyl group refers to the concept including carboxylic acid anhydride group.

Examples of the unsaturated carboxylic acid used to react the polyolefin resin include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, and aconitum. Acid, maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, etc.

These can be used individually by 1 type or in combination of 2 or more types. Among these, maleic anhydride is preferred because it is easy to obtain a resin composition having relatively excellent sheet processability and a cured product of a resin composition having relatively excellent adhesive strength.

The amount of the unsaturated carboxylic acid used to react the polyolefin resin is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, and more preferably 0.2 to 1 part by mass relative to 100 parts by mass of the polyolefin resin. Progress like this The obtained resin composition containing an acid-modified polyolefin-based resin can easily obtain a cured product having relatively excellent bonding strength.

As the acid-modified polyolefin-based resin, commercially available products can also be used. Examples of commercially available products include ADMER (registered trademark) (manufactured by Mitsui Chemicals Co., Ltd.), UNISTOLE (registered trademark) (manufactured by Mitsui Chemicals Co., Ltd.), BondyRam (manufactured by Polyram Co., Ltd.), orevac (registered trademark) (ARKEMA Co., Ltd. (manufactured by Mitsubishi Chemical Corporation), Modic (registered trademark) (manufactured by Mitsubishi Chemical Corporation), etc.

Silane-modified polyolefin-based resin refers to a polyolefin resin graft-modified using an unsaturated silane compound. Silane-modified polyolefin resin is a structure formed by graft copolymerization of an unsaturated silane compound with side chains onto a main chain polyolefin resin. Examples include silane-modified polyethylene resin and silane-modified ethylene-vinyl acetate copolymer, silane-modified lower density polyethylene, silane-modified ultra-low-density polyethylene, and silane-modified linear low-density polyethylene. Silane-modified polyethylene resin such as ethylene is preferred.

As the unsaturated silane compound reacted with the above-mentioned polyolefin resin, a vinyl silane compound is preferred. Examples of vinylsilane compounds include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, and ethylene. Tripentyloxysilane, vinyltriphenoxysilane, vinyltribenzyloxysilane, vinyltriethylenedioxysilane, vinyltriethylenedioxysilane, vinylpropyloxysilane Silane, vinyl triacetyloxysilane, vinyl tricarboxysilane, etc.

These can be used individually by 1 type or in combination of 2 or more types.

In addition, the conditions for graft polymerizing the unsaturated silane compound onto the polyolefin resin of the main chain may be any conventional graft polymerization method commonly used.

The amount of unsaturated silane compound used to react the polyolefin resin is relative to the polyolefin resin. For 100 parts by mass of fat, 0.1 to 10 parts by mass is preferred, 0.3 to 7 parts by mass is more preferred, and 0.5 to 5 parts by mass is more preferred. The resin composition containing the silane-modified polyolefin resin obtained in this way can easily obtain a cured product having relatively excellent bonding strength.

As the silane-modified polyolefin-based resin, commercially available products can also be used. Examples of commercially available products include LINKLON (registered trademark) (manufactured by Mitsubishi Chemical Corporation) and the like. 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 suitably used.

The modified polyolefin-based resin can be used alone or in combination of two or more types.

The number average molecular weight (Mn) of the modified polyolefin-based resin is preferably 10,000 to 2,000,000, and more preferably 20,000 to 1,500,000.

The number average molecular weight (Mn) of the modified polyolefin-based resin can be determined as a standard polystyrene-converted value by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

[(B) Component: Compound with cyclic ether group]

The resin composition of the present invention contains a compound having a cyclic ether group as component (B).

Since the compound having a cyclic ether group has excellent compatibility with component (A), by using this compound, a resin composition having excellent sheet strength and sheet processability in a normal temperature environment can be obtained, as well as a resin composition having excellent sheet processability. A hardened product of a colorless, transparent and water vapor barrier resin composition.

In addition, in this manual, the normal temperature environment refers to an environment of 20℃±15℃ (5~35℃) (JIS Z 8703).

Examples of the cyclic ether group include an oxirane group (epoxy group), an oxetane group (oxetanyl group), a tetrahydrofuran group, and a tetrahydrofuran group. Hydropyranyl etc.

The so-called compounds with cyclic ether groups refer to compounds with at least one cyclic ether group in the molecule. compound. In particular, from the viewpoint of obtaining a cured product of a resin composition having relatively excellent adhesion strength, a compound having an oxirane group or an oxybutanyl group is preferred, and one having two or more ethylene oxide groups in the molecule is preferred. Compounds having an oxirane group or an oxetane group are particularly preferred, and compounds having three or more oxirane groups in the molecule are particularly preferred.

Examples of compounds having an oxirane group in the molecule include aliphatic epoxy compounds (excluding alicyclic epoxy compounds), aromatic epoxy compounds, alicyclic epoxy compounds, and heterocyclic epoxy compounds. Compounds etc.

Examples of aliphatic epoxy compounds include monofunctional epoxy compounds such as glycidyl etherates of aliphatic alcohols and glycidyl esters of alkyl carboxylic acids; aliphatic polyols, or alkylene oxide additions thereof; Polyfunctional epoxy compounds such as polyglycidyl etherates, polyglycidyl esters of aliphatic long-chain polybasic acids, and epoxy compounds with triazine skeletons. Among these, epoxy compounds having a triazine skeleton are preferred.

Representative compounds of these aliphatic epoxy compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and C12-13 mixed alkyl ether. Glycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether ether, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dineopenterythritol, diepoxypropyl ether of polyethylene glycol, diepoxypropyl ether of polypropylene glycol, Glycidyl ethers of polyhydric alcohols such as cyclopentadienyl dimethanol diglycidyl ether, or fats such as propylene glycol, trimethylolpropane, glycerin, etc. added by one or more alkylene oxides Polyglycidyl etherates of polyether polyols obtained from aliphatic polyols, and diepoxypropyl esters of aliphatic long-chain diprotic acids; Monoglycidyl ether of aliphatic higher alcohols and glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized polybutadiene; 2,4 , 6-tris(glycidoxy)-1,3,5-triazine, etc.

In addition, as the aliphatic epoxy compound, a commercially available product can also be used. Examples of commercially available products include DENACOLEX-121, DENACOLEX-171, DENACOLEX-192, DENACOLEX-211, DENACOLEX-212, DENACOLEX-313, DENACOLEX-314, DENACOLEX-321, DENACOLEX-411, DENACOLEX-421, DENACOLEX- 512, DENACOLEX-521, DENACOLEX-611, DENACOLEX-612, DENACOLEX-614, DENACOLEX-622, DENACOLEX-810, DENACOLEX-811, DENACOLEX-850, DENACOLEX-851, DENACOLEX-821, DENACOLEX-830, DENACOLEX-8 32. DENACOLEX-841, DENACOLEX-861, DENACOLEX-911, DENACOLEX-941, DENACOLEX-920, DENACOLEX-931 (above, made by NAGASECHEMTEX); EpoliteM-1230, Epolite40E, Epolite100E, Epolite200E, Epolite400E, Epolite70P, Epolite te200P, Epolite400P, Epolite1500NP , Epolite1600, Epolite80MF, Epolite100MF (above, manufactured by Gyoei Chemical Co., Ltd.); AdekaGlycilolED-503, AdekaGlycilolED-503G, AdekaGlycilolED-506, AdekaGlycilolED-523T, AdekaResinEP-4088S, AdekaResinEP-4088L, AdekaRes inEP-4080E (above, manufactured by ADEKA ); TEPIC-FL, TEPIC-PAS, TEPIC-UC (above, manufactured by Nissan Chemical Co., Ltd.), etc.

Examples of aromatic epoxy compounds include polyhydric phenols having at least one aromatic ring such as phenol, cresol, butylphenol, and mono/polyepoxypropyl ethers of their alkylene oxide adducts. Chemicals etc.

Representative examples of these aromatic epoxy compounds include bisphenol A, bisphenol F, or glycidyl etherates and epoxy novolacs of compounds obtained by adding an alkylene oxide to these bisphenols. (epoxy novolak) resin; resorcinol, hydroquinone, catechol, etc. have more than 2 Mono/polyglycidyl etherates of aromatic compounds with phenolic hydroxyl groups; epoxy of aromatic compounds with more than 2 alcoholic hydroxyl groups such as phenyl dimethanol, phenyl diethanol, phenyl dibutanol, etc. Propyl etherate; glycidyl ester of polybasic acid aromatic compounds with two or more carboxylic acids such as phthalic acid, terephthalic acid, trimellitic acid, glycidyl ester of benzoic acid, styrene oxide or Epoxides of diethylbenzene, etc.

In addition, as the aromatic epoxy compound, commercially available products can also be used. Examples of commercially available products include DENACOLEX-146, DENACOLEX-147, DENACOLEX-201, DENACOLEX-203, DENACOLEX-711, DENACOLEX-721, ONCOATEX-1020, ONCOATEX-1030, ONCOATEX-1040, ONCOATEX-1050, ONCOATEX- 1051, ONCOATEX-1010, ONCOATEX-1011, ONCOAT1012 (above, manufactured by NAGASECHEMTEX Co., Ltd.); OGSOLPG-100, OGSOLEG-200, OGSOLEG-210, OGSOLEG-250 (above, manufactured by Osaka GASCHEMICAL Co., Ltd.); HP4032, HP4032D, HP4700 (above) , DIC Corporation); ESN-475V (above, manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation); JER (same as EPICOAT) YX8800 (manufactured by Mitsubishi Chemical Corporation); MERPROOFG-0105SA, MERPROOFG-0130SP (above, manufactured by NOF Corporation); EpiclonN-665, EpiclonHP-7200 (above, made by DIC Corporation); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H , NC-7000L (above, manufactured by Nippon Kayaku Corporation); AdekaResinEP-4000, AdekaResinEP-4005, AdekaResinEP-4100, AdekaResinEP-4901 (above, manufactured by ADEKA Corporation); TECHMORE VG-3101L (above, manufactured by Printec Corporation), etc.

Examples of the alicyclic epoxy compound include polyglycidyl etherates of polyhydric alcohols having at least one alicyclic structure, or compounds containing cyclohexene or cyclopentene rings that have been treated by using an oxidizing agent. Epoxidation to obtain compounds containing cyclohexeneoxide or cyclopentane oxide things.

Representative compounds of these alicyclic epoxy compounds include hydrogenated bisphenol A diglycidyl ether and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylic acid. Ester, 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)hexanedi Ester, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylbis(3,4-epoxycyclohexane), propane-2,2-diyl-bis(3,4 -Epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylidene bis(3,4-epoxycyclohexanecarboxylic acid ester), dioctyl epoxy hexahydrophthalate, di-2-ethylhexyl epoxy hexahydrophthalate, 1-epoxyethyl-3,4-epoxy ring Hexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pinene oxide, limonenedioxide, etc.

In addition, as the alicyclic epoxy compound, a commercially available product can also be used. Examples of commercially available products include CELLOXIDE2021P, CELLOXIDE2081, CELLOXIDE2000, CELLOXIDE3000 (manufactured by Daicel Corporation), and the like.

Examples of heterocyclic epoxy compounds include isocyanurate ring-containing epoxy compounds such as tripoxypropylisocyanurate.

Examples of compounds having an oxybutanyl group in the molecule include 3,7-bis(3-oxetanyl)-5-oxy-nonane, 1,4-bis[(3-ethyl) -3-Oxobutanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxobutanylmethoxy)methyl]ethane, 1,3- Bis[(3-ethyl-3-oxobutanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxobutanylmethyl)ether, triethylene glycol Bis(3-ethyl-3-oxobutanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxobutanylmethyl) ether, 1,4-bis(3- Difunctional aliphatic oxybutanes such as ethyl-3-oxobutanylmethoxy)butane and 1,6-bis(3-ethyl-3-oxobutanylmethoxy)hexane Alkane compound, 3-ethyl-3-[(phenoxy)methyl]oxycyclobutane, 3-ethyl-3-(hexyloxymethyl)oxycyclobutane, 3-ethyl-3- (2-ethylhexyloxymethyl)oxycyclobutane, 3-ethyl-3-(hydroxymethyl)oxycyclobutane, 3-ethyl-3-(chloromethyl)oxycyclobutane, etc. Monofunctional oxycyclobutane compounds, etc.

As a compound having an oxybutanyl group in the molecule, commercially available products can also be used. As commercially available products, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (the above, manufactured by Maruzen Petrochemical Co., Ltd.); ARONOXETANEOXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (above, manufactured by Toa Gosei Co., Ltd.); ETERNACOLLOXBP, OXTP (above, manufactured by Ube Kosan Co., Ltd.), etc.

Among these compounds having a cyclic ether group, from the viewpoint of imparting flexibility to the resin composition and obtaining a cured product of the resin composition having relatively excellent adhesion strength, those that are liquid at 25° C. Things are better. In addition, the cyclic ether group is preferably an oxirane group. From the viewpoint of improving the curability of the resin composition, it is preferably a polyfunctional epoxy compound or a difunctional aliphatic oxycyclobutane compound. The compound having two or more cyclic ether groups in the molecule is preferred.

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 from 100 g/eq to 500 g/eq, and more preferably from 150 g/eq to 300 g/eq.

By using a resin composition of a compound having a cyclic ether group having a cyclic ether equivalent in the above range, a sealing material having strong adhesion strength and excellent curability can be produced efficiently.

These compounds having a cyclic ether group can be used alone or in combination of two or more types.

In addition, in the present invention, the cyclic ether equivalent 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 50 parts by mass and not more than 200 parts by mass, preferably not less than 60 parts by mass and not more than 180 parts by mass, and more preferably 70 parts by mass relative to 100 parts by mass of the component (A). More than 150 parts by mass.

By setting the content of the compound having a cyclic ether group within the above range, a cured product of the resin composition having relatively excellent adhesive strength can be easily obtained.

[(C) Component: Photocationic polymerization initiator]

The resin composition of the present invention contains a photocationic polymerization initiator as component (C).

The photocationic polymerization initiator is a compound that generates cationic species by irradiating light and starts a curing reaction of the cationic curable compound, and is composed of a cationic part that absorbs light and an anionic part that becomes a source of acid generation.

(oxonium)鹽系化合物、溴鹽系化合物等。該等之中，從與(B)成分具有優異的相溶性，且所得到的樹脂組合物具有優異的保存安定性的觀點而言，係以鋶鹽系化合物為佳，以具有芳香族基之芳香族鋶鹽系化合物為較佳。 Examples of the photocationic polymerization initiator include sulfonium salt-based compounds, iodonium salt-based compounds, phosphonium salt-based compounds, ammonium salt-based compounds, antimonate-based compounds, diazonium salt-based compounds, and selenium salt-based compounds.

(oxonium) salt compounds, bromide salt compounds, etc. Among these, sulfonium salt-based compounds are preferred, and those having an aromatic group are preferred from the viewpoint of excellent compatibility with component (B) and excellent storage stability of the resulting resin composition. Aromatic sulfonium salt-based compounds are preferred.

六氟磷酸鹽、7-[二(對甲苯甲醯基)鋶基]-2-異丙基-9-氧硫

六氟銻酸鹽、7-[二(對甲苯甲醯基)鋶基]-2-異丙基肆(五氟苯基)硼酸鹽、苯基羰基-4’-二苯基鋶基-二苯基硫醚-六氟磷酸鹽、苯基羰基-4’-二苯基鋶基-二苯基硫醚-六氟銻酸鹽、4-三級丁基苯基羰基-4’-二苯基鋶基 -二苯基硫醚-六氟磷酸鹽、4-三級丁基苯基羰基-4’-二苯基鋶基-二苯基硫醚-六氟銻酸鹽、4-三級丁基苯基羰基-4’-二苯基鋶基-二苯基硫醚-肆(五氟苯基)硼酸鹽、苯硫基二苯基鋶基六氟銻酸鹽、苯硫基二苯基鋶基六氟磷酸鹽、4-{4-(2-氯苯甲醯基)苯硫基}苯基雙(4-氟苯基)鋶基六氟銻酸鹽、苯硫基二苯基鋶基六氟銻酸鹽的鹵化物、4,4’,4”-三(β-羥乙氧基苯基)鋶基六氟銻酸鹽、4,4’-雙[二苯基鋶基]二苯基硫醚-雙六氟銻酸鹽、二苯基[4-(苯硫基)苯基]鋶基三氯參五氟乙基磷酸鹽、參[4-(4-乙醯基苯基磺胺基)苯基]鋶基參[(三氟甲基)磺醯基]碳化物等。 Examples of the sulfonium salt-based compound include triphenylsonium hexafluorophosphate, triphenylsonium hexafluoroantimonate, triphenylsonium tetra(pentafluorophenyl)borate, and 4,4'- Bis[diphenylsulfonyl]diphenylsulfide-bishexafluorophosphate, 4,4'-bis[bis(β-hydroxyethoxy)phenylsulfonyl]diphenylsulfide-bishexafluorophosphate Antimonate, 7-[bis(p-toluyl)sulfonyl]-2-isopropyl-9-oxysulfide

Hexafluorophosphate, 7-[bis(p-toluyl)sulfonyl]-2-isopropyl-9-oxosulfide

Hexafluoroantimonate, 7-[bis(p-toluyl)sulfonyl]-2-isopropyls(pentafluorophenyl)borate, phenylcarbonyl-4'-diphenylsulfonyl-di Phenyl sulfide-hexafluorophosphate, phenylcarbonyl-4'-diphenylsulfonyl-diphenyl sulfide-hexafluoroantimonate, 4-tertiary butylphenylcarbonyl-4'-diphenyl sulfonyl-diphenyl sulfide-hexafluorophosphate, 4-tertiary butylphenylcarbonyl-4'-diphenyl sulfide-diphenyl sulfide-hexafluoroantimonate, 4-tertiary Butylphenylcarbonyl-4'-diphenylsulfonyl-diphenylsulfide-4(pentafluorophenyl)borate, phenylthiodiphenylsulfonylhexafluoroantimonate, phenylthiodiphenyl sulfonyl hexafluorophosphate, 4-{4-(2-chlorobenzoyl)phenylthio}phenylbis(4-fluorophenyl)sulfonyl hexafluoroantimonate, phenylthiodiphenyl Halide of sulfonyl hexafluoroantimonate, 4,4',4"-tris(β-hydroxyethoxyphenyl)sulfonyl hexafluoroantimonate, 4,4'-bis[diphenyl sulfonate ]Diphenyl sulfide-bis hexafluoroantimonate, diphenyl[4-(phenylthio)phenyl]sonium trichloropentafluoroethyl phosphate, diphenyl[4-(4-acetyl) Phenyl sulfonamide) phenyl] sulfonyl ginseng [(trifluoromethyl) sulfonyl] carbide, etc.

Examples of the iodide salt-based compound include diphenyliodonium tetra(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and bis(4-nonanoate). Phylphenyl) iodonium hexafluorophosphate, (triisopropylphenyl) iodonium 4 (pentafluorophenyl) borate, etc.

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

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

Examples of the antimonate-based compounds include triphenylsulfonyl hexafluoroantimonate, p-(phenylthio)phenyldiphenylsulfonyl hexafluoroantimonate, and 4-chlorophenyldiphenylsulfonate. Hexafluoroantimonate, bis[4-(diphenylsulfonyl)phenyl]sulfide bis-hexafluoroantimonate and diallyliodonium hexafluoroantimonate, etc.

These photocationic polymerization initiators can be used individually by 1 type or in combination of 2 or more types.

In addition, as the photocationic polymerization initiator, commercially available products can also be used. Examples of commercially available products include CyracureUVI-6970, CyracureUVI-6974, CyracureUVI-6990, CyracureUVI-950 (above, manufactured by Union Carbide), IRGACURE250, IRGACURE261, IRGACURE264 (above, manufactured by CibaSpecialtyChemicals), SP-150, SP- 151, SP-170, OPTOMERSP-171 (the above, made by ADEKA), CG-24-61 (made by Ciba Specialty Chemicals), DAICATII (made by Daicel), UVAC1590, UVAC1591 (the above, made by Daicel CYTEC), CI-2064, CI-2639, CI-2624, CI-2481, CI-2734, CI-2855, CI-2823, CI-2758, CIT-1682 (above, made by Soda Corporation of Japan), PI-2074 (made by Rhodia Corporation), FFC509 (made by 3M Corporation) ), BBI-102, BBI-101, BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103, NDS-103 (above, manufactured by MIDORI Chemical Co., Ltd.), CD-1010, CD-1011, CD-1012 (made by Sartomer Co., Ltd.), CPI-100P, CPI-101A, CPI-200K, CPI-310B (above, made by SAN-APRO Co., Ltd.), etc.

Relative to 100 parts by mass of the aforementioned component (B), the content of the photocationic polymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 9 parts by mass, and more preferably 0.5 to 8 parts by mass.

By setting the content of the photocationic polymerization initiator within the above range, a cured product of the resin composition having relatively excellent adhesive strength can be easily obtained.

The resin composition of the present invention may contain other components other than the aforementioned component (A), component (B), and component (C).

Examples of the other components include a tackifier having a softening point of 80° C. or higher, a silane coupling agent, a solvent, and the like.

[Tackiness-imparting agent with a softening point of 80°C or above]

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 resins obtained by hydrogenating these rosin-based resins; and terpenes. Terpene resins such as terpene resins, aromatic modified terpene resins, terpene phenol resins, etc.; hydrogenated terpene resins obtained by hydrogenating these terpene resins; α-methylstyrene monopolymer resin, α-methylstyrene/styrene copolymer resin, styrene monomer/aliphatic monomer copolymer resin, styrene monomer/α-methyl Styrene-based resins such as styrene-based/aliphatic monomer copolymerized resins, styrene-based monomer single-polymerized resins, styrene-based monomer/aromatic monomer copolymerized resins; Hydrogenated styrenic resin produced by hydrogenating vinyl resin; pentene, isoprene, piperine, 1,3-pentadiene, etc. produced by thermal decomposition of naphtha C5-based petroleum resin obtained by copolymerizing the C5-based petroleum resin and hydrogenated petroleum resin of the C5-based petroleum resin; C9 obtained by copolymerizing C9-based fractions such as indene and vinyltoluene generated by thermal decomposition of naphtha Petroleum resin and hydrogenated petroleum resin of C9 petroleum resin.

Among these, styrene-based resin is preferred, and styrene-based monomer/aliphatic monomer copolymer-based resin is preferred.

These adhesive imparting agents can be used individually by 1 type or in combination of 2 or more types.

As a tackifier with a softening point of 80° C. or higher, commercially available products can also be used. Examples of commercially available products include terpene-based resins such as YSRESINP, PX, PXN, ASeries, Clearon (registered trademark) PSeries (manufactured by YASUHARACHEMICAL), PicolightA, CSeries (manufactured by Pinova Co., Ltd.); Quintone (registered trademark) A and B , R, CX Series (manufactured by Japan ZEON Co., Ltd.) and other aliphatic petroleum resins; Quintone (registered trademark) 1000 Series (manufactured by Japan ZEON Co., Ltd.) and other aliphatic petroleum resins; FTR (registered trademark) Series (manufactured by Mitsui Chemicals Co., Ltd. ) and other styrenic resins; ArkonP, MSeries (manufactured by Arakawa Chemical Co., Ltd.), ESCOREZ (registered Alicyclic petroleum resins such as Standard) Series (manufactured by ExxonMobil Chemical Co., Ltd.), EASTOTAC (registered trademark) Series (manufactured by EASTMAN CHEMICALS Co., Ltd.), IMARV (registered trademark) Series (manufactured by Idemitsu Kosan Co., Ltd.); Foral Series (manufactured by Pinova Co., Ltd.), Pensel (registered trademark) ASeries, ESTERGUM, SUPER. Rosin or rosin ester-based resins such as ESTER and PainCrystal (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 softening point of the tackifier having a softening point of 80°C or higher is preferably 80°C to 150°C, more preferably 100°C to 150°C, and more preferably 120°C to 150°C, from the viewpoint of imparting excellent adhesiveness.

In addition, in this manual, the so-called high-temperature environment refers to an environment of 40 to 80°C.

When the resin composition of the present invention contains an adhesion-imparting agent with a softening point of 80° C. or higher, the content is preferably 1 to 200 parts by mass, and more preferably 10 to 150 parts by mass relative to 100 parts by mass of the component (A). .

By containing a tackifier with a softening point of 80° C. or higher, flexibility can be easily imparted to the resin composition.

[Silane coupling agent]

Examples of the silane coupling agent include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyl Silane coupling agents with (meth)acrylyl groups such as methyl diethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, etc. ; Vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinylparaben (2-methoxysilane (ethoxy)silane, etc. Silane coupling agent with vinyl group; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Methyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other silane coupling agents with epoxy groups; p-styryltrimethoxysilane, p-styryltriethoxysilane Silane coupling agents with styrene groups; N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-amino Propyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl Silane coupling agents with amine groups such as hydrochloride of 2-aminoethyl-3-aminopropyltrimethoxysilane; 3-ureidopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane Silane coupling agents with ureido groups such as ethoxysilane; silane coupling agents with halogen atoms such as 3-chloropropyltrimethoxysilane and 3-chloropropyltriethoxysilane; 3-mercaptopropylmethyldi Methoxysilane, 3-mercaptopropyltrimethoxysilane and other silane coupling agents with mercapto groups; bis(trimethoxysilylpropyl)tetrasulfide, bis(triethoxysilylpropyl)tetrasulfide Silane coupling agents with thioether groups; 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and other silane coupling agents with isocyanate groups; allyltrichlorosilane, allyl Silane coupling agents with allyl groups such as triethoxysilane and allyltrimethoxysilane; Silane coupling agents with hydroxyl groups such as 3-hydroxypropyltrimethoxysilane and 3-hydroxypropyltriethoxysilane.

These silane coupling agents can be used individually by 1 type or in combination of 2 or more types.

When the resin composition of the present invention contains a silane coupling agent, its content is preferably 0.01 to 10 parts by mass, and more preferably 0.02 to 5 parts by mass relative to 100 parts by mass of the component (A).

By containing a silane coupling agent, it is easy to obtain a cured product of the resin composition having relatively excellent bonding strength under normal temperature and high temperature environments.

Furthermore, by setting the content of the silane coupling agent within the above range, it is easy to obtain a cured product of the resin composition having more excellent bonding strength under normal temperature and high temperature environments.

Examples of the solvent include aliphatic hydrocarbon solvents such as n-hexane and n-heptane; aromatic hydrocarbon solvents such as toluene and xylene; methylene chloride, ethane chloride, chloroform, carbon tetrachloride, 1, Halogenated hydrocarbon solvents such as 2-dichloroethane and monochlorobenzene; alcohol solvents such as methanol, ethanol, propanol, butanol, and propylene glycol monomethyl ether; acetone, methyl ethyl ketone, and 2-pentanone Ketone solvents such as , isophorone, cyclohexanone, etc.; ester solvents such as ethyl acetate, butyl acetate, etc.; thiolsu solvents such as ethyl thiolsu; 1,3-dioxolane ( Ether-based solvents such as 1,3-dioxolane), etc.

These solvents can be used individually by 1 type or in combination of 2 or more types. The content of the solvent can be appropriately determined taking into consideration the coating properties, film thickness, etc.

In addition, the resin composition of the present invention may contain components other than the aforementioned tackifier having a softening point of 80° C. or higher, a silane coupling agent, and a solvent within a range that does not impair the effects of the present invention.

Examples of components other than the tackifier, silane coupling agent, and solvent having a softening point of 80° C. or higher include antistatic agents, stabilizers, antioxidants, plasticizers, lubricants, color pigments, and the like. The contents of these components may be appropriately determined according to the purpose.

The resin composition of the present invention can appropriately mix predetermined components according to commonly used methods. Stir and prepare.

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 composed of a base material or a release film, and an adhesive layer formed on the base material or release film, and the adhesive layer uses the resin of the present invention. A thing formed from a composition.

Sealing sheet (β): A sealing sheet composed of two release films and an adhesive layer sandwiched between the two release films. The adhesive layer is formed using the resin composition of the present invention. formed thing.

Sealing sheet (γ): 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. The adhesive layer is A product formed using the resin composition of the present invention.

In addition, these sealing sheets represent the state before use. When using the sealing sheet of the present invention, the release film is usually peeled off and removed.

As a base material constituting the sealing sheet (α), a resin film can generally be utilized.

Examples of the resin component of the resin film include polyamide, polyamide, polyamideimide, polyphenylene ether, polyetherketone, polyetheretherketone, polyolefin, polyester, polycarbonate, polyamide Polyether, polyphenylenesulfide, polyarylate, acrylic resin, cycloolefin polymer, aromatic polymer, polyurethane polymer, etc. The thickness of the base material is not particularly limited. From the viewpoint of heat shrinkage and versatility in the drying step of the agent layer, 10 to 500 μm is preferred, 10 to 300 μm is more preferred, and 15 to 200 μm is more preferred.

The release film constituting the sealing sheet (α) not only functions as a support during the manufacturing step of the sealing sheet (α), but also functions as a protective sheet for the adhesive layer until the sealing sheet (α) is used.

As the release film, a conventionally known one can be used. For example, a release film base material having a release layer that has been released by a release agent can be used.

Examples of base materials for release films include paper base materials such as glassine paper, coated paper, and fine paper; laminated papers obtained by bonding thermoplastic resins such as polyethylene to these paper base materials; Plastic films such as polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polypropylene resin, polyethylene resin, etc.

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. Resin etc.

The thickness of the release film is not particularly limited, but is usually about 20 to 250 μm.

The manufacturing method of the sealing sheet (α) is not particularly limited. For example, the sealing sheet (α) can be produced using a casting method.

When the sealing sheet (α) is manufactured using a casting method, the resin combination of the present invention can be applied to the base material or the release layer that has been subjected to release film release treatment by using a conventional method, and the obtained The coating film was dried to obtain a sealing sheet (α).

Examples of methods for applying the resin composition include spin coating, spray coating, rod coating, blade coating, roll coating, blade coating, and die coating. ), gravure coating method, etc.

Examples of methods for drying the coating film include hot air drying, hot roll drying, and infrared ray drying. Previously known drying methods such as irradiation.

Conditions for drying the coating film are, for example, 80 to 150° C. for 30 seconds to 5 minutes.

Since the adhesive layer of the sealing sheet (α) is formed using the resin composition of the present invention, it has photocurability.

The conditions for photohardening the adhesive layer are not particularly limited. The adhesive layer can be photohardened by irradiating active energy rays such as ultraviolet rays, visible rays, X-rays, and electron rays.

In the present invention, from the viewpoint of obtaining a sealing sheet having excellent colorless transparency (which means a high total light transmittance and very little coloring), photocuring by ultraviolet irradiation is preferred.

Specific examples of ultraviolet sources that irradiate ultraviolet rays include light sources such as ultrahigh-pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, blacklight fluorescent lamps, and metal halide lamps. Moreover, as the wavelength of the ultraviolet ray to be irradiated, a wavelength range of 190 to 380 nm can be used.

The ideal amount of ultraviolet irradiation is about 50 to 1,000 mW/cm ² in illumination and 50 to 1,000 mJ/cm ² in light intensity.

The irradiation time of ultraviolet rays is usually 0.1 to 1,000 seconds, preferably about 1 to 500 seconds.

The thickness of the adhesive layer of the sealing sheet (α) after photohardening treatment is usually 1 to 50 μm, preferably 5 to 30 μm. An adhesive layer having a thickness within the above range can be suitably used as a sealing material.

The thickness of the adhesive layer can be measured in accordance with JIS K 7130 (1999) using a conventional thickness meter.

The adhesive layer after photohardening treatment has excellent bonding strength.

For example, the bonding strength of the adhesive layer obtained by laminating the sealing sheet before photohardening treatment to other materials (gas barrier film, alkali-free glass, etc.) and then photohardening treatment at a temperature of 23°C. When conducting a 180° peel test under a relative humidity of 50%, the test is usually 1~30N/25mm, preferably 5~20N/25mm.

Furthermore, the bonding strength of the adhesive layer obtained by laminating the sealing sheet before photocuring treatment to other materials (gas barrier film, alkali-free glass, etc.) and subsequently photocuring treatment at temperature is Let it stand for 168 hours at a temperature of 60°C and a relative humidity of 90%. Next, let it stand for 24 hours at a temperature of 23°C and a relative humidity of 50%. Then, let it stand for 24 hours at a temperature of 23°C and a relative humidity of 50%. In the 180° peel test, 1~30N/25mm is preferred, and 5~20N/25mm is preferred.

These 180° peel tests can be measured using the method described in the Examples.

The adhesive layer after photohardening treatment has excellent colorless transparency.

The total light transmittance of the adhesive layer with a thickness of 20 μm after photohardening treatment is preferably more than 85%, and more preferably more than 90%. There is no special upper limit for total light transmittance, but it is usually below 95%.

As described above, in the resin composition of the present invention, a modified polyolefin-based resin is used as the component (A), and a compound with a cyclic ether group that is highly compatible with the component (A) is used as the component (B). )Element. As a result, the adhesive layer after the photohardening treatment of the present invention has a high total light transmittance.

The total light transmittance can be measured in accordance with JISK7361-1:1997 using a total light transmittance measuring device, for example.

In addition, when the adhesive layer with a thickness of 20 μm after photohardening treatment is measured for color, the L* value is based on the CIE1976L*a*b* color system specified in JIS Z 8781-4 (2013). , preferably 90~98. In addition, the a* value is preferably -2~2, and the b* value is preferably -2~2.

In the L*a*b* color system, L* represents brightness, a* and b* represent hue and chroma respectively. When a* is a positive value, it represents the red direction; when a* is a negative value, it represents the green direction; when b* is a positive value, it represents the yellow direction; when b* is a negative value, it represents the hue and chroma of the blue direction. The absolute values of a* and b* become smaller and gradually become colorless.

The adhesive layer after photohardening treatment should have smaller deviations in the red direction (+a*), green direction (-a*), yellow direction (+b*), and blue direction (-b*). .

A resin composition capable of forming an adhesive layer in which L* is in the above range and the color gamut of a* and b* is in the above range can be suitably used because the total light transmittance is high and the coloring is very little. It is a sealing material for light-emitting devices such as organic EL elements.

Therefore, the sealing sheet of the present invention can be suitably used for optical applications such as sealing materials for light-emitting devices such as organic EL elements.

The L*a*b* value in the CIE1976L*a*b* color system can be measured using a spectrophotometer in accordance with JIS Z 8781-4:2013.

The yellowness (YI value) of the sealing sheet is usually 0.01~2, preferably 0.01~1. The yellowness can be measured using a spectrophotometer in accordance with JIS K 7373:2006.

In addition, the adhesive layer after photohardening treatment has excellent water vapor barrier properties.

The water vapor transmittance of an adhesive layer with a thickness of 20 μm after photohardening treatment is usually 0.1~200g/ ^m2 /day, preferably 0.1~150g/ ^m2 /day.

This water vapor transmission rate can be measured using a conventional gas transmission rate measuring device, for example.

The storage elastic modulus of the light-hardened sealing sheet at 60°C is usually 0.1~100MPa, preferably 1~800MPa.

Generally, organic EL elements can be used in a temperature environment of -20-80°C. Therefore, a sealing sheet whose storage elastic modulus at 60° C. is in the above range after photohardening treatment has excellent sealing performance for light-emitting devices such as organic EL elements in the above temperature environment. The storage elastic modulus of the light-cured sealing sheet at 60° C. can be measured using the method described in the Examples.

Examples of the release film and adhesive layer constituting the sealing sheet (β) are the same as those already shown as the release film and adhesive layer constituting the sealing sheet (α). Since the sealing sheet (β) protects both sides of the adhesive layer with a release film, it has better operability than the sealing sheet (α).

The two release films of the sealing sheet (β) may be the same or different, but the two release films preferably have different release powers. Since the peeling force of the two peeling films is different, it is not easy to use the sealing sheet. create problems. That is, by making the peeling force of two peeling films different, the step of peeling off a peeling film can be performed more efficiently at the beginning.

The manufacturing method of the sealing sheet (β) is not particularly limited.

For example, when the sealing sheet (β) is manufactured using a casting method, the resin composition of the present invention can be applied to the peeled portion of the release film that has been peeled off using the same method as that shown in the manufacturing method of the sealing sheet (α). layer, and by drying the obtained coating film to produce an adhesive layer with a release film, and then by superimposing another release film on the adhesive layer, a sealing sheet (β) can be obtained.

The release film and the adhesive layer constituting the sealing sheet (γ) are the same as those already shown as the release film and the adhesive layer constituting the sealing sheet (α) or the sealing sheet (β).

The gas barrier film constituting the sealing sheet (γ) is not particularly limited as long as it has water vapor barrier properties.

The water vapor transmission rate of the gas barrier film in an environment with a temperature of 40°C and a relative humidity of 90% (hereinafter abbreviated as "90%RH") is preferably 0.1g/m ² /day or less, and 0.05g/m ² is preferred. /day or less is preferred, and 0.005g/m ² /day or less is even more preferred.

By using the gas barrier film at a temperature of 40°C. The water vapor transmission rate in an environment of 90% RH is less than 0.1g/m ² /day, which can effectively prevent oxygen and moisture from intruding into the interior of organic EL elements formed on the substrate and causing deterioration of electrodes and organic layers. .

The transmittance of water vapor and the like of the gas barrier film can be measured using a conventional gas transmittance measuring device.

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

Examples of the resin component constituting the base material include the same resin components that can be used as the resin film constituting the sealing sheet (α).

The thickness of the base material is not particularly limited, but from the viewpoint of ease of operation, 0.5 to 500 μm is preferred, 1 to 200 μm is more preferred, and 5 to 100 μm is more preferred.

The material of the gas barrier layer is not particularly limited as long as it can provide required gas barrier properties. Examples of the gas barrier layer include a gas barrier layer composed of an inorganic vapor-deposited film; a gas barrier layer containing a gas barrier resin; and a layer containing a polymer compound (hereinafter referred to as a "polymer layer"). " case) the gas barrier layer obtained by performing the modification process [At this time, the so-called gas barrier layer does not refer to only the area modified by the ion implantation process, but "includes the modified area The polymer layer of the area"], etc.

Among them, a gas barrier layer composed of an inorganic evaporated film or a polymer layer is modified because it is thin and can efficiently form a layer with excellent gas barrier properties. Barrier layer is better. The gas barrier film may also have two or more types of such gas barrier layers.

Examples of inorganic vapor-deposited films include vapor-deposited films of inorganic compounds and metals.

Examples of raw materials for vapor-deposited films of inorganic compounds include inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, tin oxide, and zinc tin oxide; silicon nitride, aluminum nitride, and titanium nitride. Inorganic nitrides such as; inorganic carbides; inorganic sulfides; inorganic nitrogen oxides such as silicon oxynitride; inorganic carbon oxides; inorganic carbon nitrides; inorganic nitrogen carbon oxides, etc.

Examples of raw materials for metal vapor deposition films include aluminum, magnesium, zinc, tin, and the like.

These can be used individually by 1 type or in combination of 2 or more types.

Among them, inorganic vapor-deposited films using inorganic oxides, inorganic nitrides, or metals as raw materials are preferred from the viewpoint of gas barrier properties, and inorganic vapor-deposited films using colorless transparency are preferred. Inorganic evaporated films using materials or inorganic nitrides as raw materials are preferred. In addition, the inorganic evaporated film can be Single layer or multiple layers.

From the viewpoint of gas barrier properties and workability, the thickness of the inorganic evaporated film is usually 1 nm or more and 2,000 nm or less, preferably 3 nm or more and 1,000 nm or less, preferably 5 nm or more and 500 nm or less, and more preferably 40 nm. Above and below 200nm.

The method of forming the inorganic vapor deposition film is not particularly limited, and conventional methods can be used. Examples of methods for forming an inorganic vapor deposition film include PVD (physical vapor deposition) methods such as vacuum vapor deposition, sputtering, and ion plating, thermal CVD (chemical vapor deposition), and plasma CVD. CVD method such as optical CVD method, 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 partially saponified products thereof, ethylene-vinyl alcohol copolymers, polyacrylonitrile, and polychloride. Ethylene, polyvinylidenechloride, polychlorotrifluoroethylene, etc., resins that are not easily permeable to oxygen, water vapor, etc.

From the viewpoint of gas barrier properties, the thickness of the gas barrier layer containing the gas barrier resin is usually from 1 nm to 2,000 nm, preferably from 3 nm to 1,000 nm, and preferably from 5 nm to 500 nm. , more preferably 40nm or more and 200nm or less.

An example of a method for forming a gas barrier layer containing a gas barrier resin is to apply a gas barrier layer-forming solution containing a gas barrier resin to a base material or other layer, and then apply the resulting solution Method to properly dry the coating film.

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

The drying method of the coating film is not particularly limited, and the methods listed as methods for drying the coating film of the above-mentioned resin composition can be used.

Examples of the polymer compound used in the gas barrier layer formed by modifying the surface of the polymer layer include silicon-containing polymer compounds, polyimide, polyamide, and polyamide. Amine, polyphenylene ether, polyetherketone, polyetheretherketone, polyolefin, polyester, polycarbonate, polystyrene, polyethersulfide, polyphenylene sulfide, polyarylate (polyarylate), acrylic resin, alicyclic Formula hydrocarbon resin, aromatic polymer, etc.

These polymer compounds can be used individually by 1 type or in combination of 2 or more types.

Among these polymer compounds, silicon-containing polymer compounds are preferred from the viewpoint of being able to form a gas barrier layer having relatively excellent gas barrier properties. Examples of silicon-containing polymer compounds include polysilazane compounds, polycarbosilazane compounds, polysilane compounds, polyorganosiloxane compounds, and poly(disilylphenylene) compounds. , and poly(disilylethynyl) compounds, etc. In particular, polysilazane-based compounds are preferred from the viewpoint that a gas barrier layer having excellent gas barrier properties can be formed even if it is thin. By performing a modification process on the layer containing the polysilazane compound, a layer (silicon oxynitride layer) containing oxygen, nitrogen, and silicon as main constituent atoms can be formed.

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

The compounds represented by the repeating units are preferred. In addition, the number average molecular weight of the polysilazane-based compound used is not particularly limited, but is preferably 100 to 50,000.

In the aforementioned formula (1), n represents an arbitrary natural number.

Rx, Ry, and Rz each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkyl group, Non-hydrolyzable groups such as aryl group or alkylsilyl group.

Examples of the unsubstituted or substituted alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, and tertiary butyl. , n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and other alkyl groups with 1 to 10 carbon atoms.

Examples of the cycloalkyl group of the unsubstituted or substituted cycloalkyl group include cycloalkyl groups having 3 to 10 carbon atoms such as cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.

Examples of the unsubstituted or substituted alkenyl group include carbon atoms such as vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, and 3-butenyl. Alkenyl groups with numbers 2 to 10.

Examples of substituents for the alkyl group, cycloalkyl group and alkenyl group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; thiol group; epoxy group; glycidoxy group; (Meth)acryloxy group; unsubstituted or substituted aryl groups such as phenyl, 4-methylphenyl, 4-chlorophenyl, etc.

Examples of the aryl group that is an unsubstituted or substituted aryl group include aryl groups having 6 to 15 carbon atoms such as phenyl, 1-naphthyl, and 2-naphthyl.

Substituents for the aryl group include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkyl groups having 1 to 6 carbon atoms such as methyl and ethyl groups; and 1 carbon atoms such as methoxy and ethoxy groups. ~6 alkoxy; nitro; cyano; hydroxyl; thiol; epoxy; glycidoxy; (meth)acryloxy; phenyl, 4-methylphenyl, 4- Unsubstituted or substituted aryl groups such as chlorophenyl groups, etc.

Examples of the alkylsilyl group include trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, tritertiary butylsilyl group, methyldiethylsilyl group, and dimethylsilyl group. diethyl silicon Alkyl, methylsilyl, ethylsilyl, etc.

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

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

Furthermore, in the present invention, a modified polysilazane compound can also be used as the polysilazane compound. Examples of modified polysilazane include those disclosed in Japanese Patent Application Laid-Open Nos. 62-195024, 2-84437, 63-81122, 1-138108, and 2 -175726, Japanese Patent Application Publication No. 5-238827, Japanese Patent Application Publication No. 6-122852, Japanese Patent Application Publication No. 6-306329, Japanese Patent Application Publication No. 6-299118, Japanese Patent Application Publication No. 9-31333, Japanese Patent Application Publication No. 5-345826 Official Gazette No. 4-63833, etc.

Among these, the polysilazane-based compound is one in which Rx, Ry, and Rz are all hydrogen atoms, from the viewpoint of ease of acquisition and the ability to form an ion implantation layer having excellent gas barrier properties. Perhydropolysilazane is preferred.

In addition, as the polysilazane-based compound, a commercially available product as a glass coating agent or the like can be used as it is.

The polysilazane compound can be used individually by 1 type or in combination of 2 or more types.

In addition to the above-mentioned polymer compounds, the polymer layer may contain other components within a range that does not hinder the object of the present invention. As other components, the additives 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 can form a better gas barrier The gas barrier layer is preferably at least 50% by mass, and preferably at least 70% by mass.

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

The polymer layer can be formed, for example, by applying a liquid of a polymer compound dissolved or dispersed in an organic solvent on a substrate or other layer using a conventional coating method, and drying the resulting coating film.

As the organic solvent, the solvents listed as components other than the above-mentioned (A) component, (B) component, and (C) component can be used.

These organic solvents can be used individually by 1 type or in combination of 2 or more types.

The coating method is not particularly limited, and methods listed as methods for coating the above-mentioned resin composition can be used.

The drying method of the coating film is not particularly limited, and the methods listed as methods for drying the coating film of the above-mentioned resin composition can be used.

The heating temperature is usually 80~150℃, and the heating time usually ranges from tens of seconds to tens of minutes.

Examples of methods for modifying the surface of the polymer layer include ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, heat treatment, and the like.

The ion implantation process is a method of implanting accelerated ions into the polymer layer to modify the polymer layer as described below.

Plasma treatment is a method of exposing the polymer layer to plasma to modify the polymer layer. For example, plasma treatment can be performed according to the method described in Japanese Patent Application Laid-Open No. 2012-106421.

Ultraviolet irradiation treatment is a method of irradiating ultraviolet rays to the polymer layer 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, from the viewpoint of being able to efficiently modify the polymer layer to its interior without roughening the surface of the polymer layer, and forming a gas barrier layer with relatively excellent gas barrier properties, it is What is obtained by subjecting a layer containing a silicon-containing polymer compound to an ion implantation process is preferred.

Examples of ions implanted into the polymer layer include ions of rare gases such as argon, helium, neon, krypton, and xenon; ions of fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, sulfur, etc.; methane, ethane, etc. Ions of alkane-based gases such as alkane; ions of alkylene-based gases such as ethylene and propylene; ions of diene-based gases such as pentadiene and butadiene; ions of acetylene-based gases such as acetylene; ions of benzene, toluene, etc. Ions of aromatic hydrocarbon-based gases; ions of cycloalkane-based gases such as cyclopropane; ions of cycloolefin-based gases such as cyclopentene; ions of metals and organic silicon compounds, etc.

This plasma can be used individually by 1 type or in combination of 2 or more types.

Among them, ions of rare gases such as argon, helium, neon, krypton, and xenon are preferred because they can more easily implant ions and form a gas barrier layer with excellent gas barrier properties.

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

Examples of methods of implanting ions include irradiation of ions accelerated by an electric field (ion beam); methods of implanting ions in plasma (plasma ions); and so on. Particularly, the target gas barrier can be easily formed. From the perspective of the barrier layer, the latter method of implanting plasma ions (plasma ion implantation method) is preferred.

The plasma ion implantation method can generate a gas in a plasma containing a rare gas or the like, for example. It is performed by generating plasma in a body environment and applying a negative high voltage pulse to the polymer layer, and implanting ions (cations) in the plasma into the surface of the polymer layer. More specifically, the plasma ion implantation method can be performed using the method described in pamphlet No. WO2010/107018 or the like.

The thickness of the region where ions are implanted by ion implantation can be controlled by controlling 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. Just wait and decide, usually it is 10nm or more and 400nm or less.

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

The manufacturing method of the sealing sheet (γ) is not particularly limited. For example, in the method of manufacturing the sealing sheet (β) described above, the sealing sheet (γ) can be manufactured by replacing one piece of the release film with a gas barrier film.

Moreover, after manufacturing the sealing sheet (β), one peeling film is peeled off, and the exposed adhesive layer and the gas barrier film are attached, and the sealing sheet (γ) can also be manufactured. At this time, when the sealing sheet (β) has two release films with different peeling forces, from the viewpoint of workability, it is preferable to peel the release film with the smaller peeling force.

As described above, the cured product of the adhesive layer of the sealing sheet of the present invention has excellent bonding strength and sealing properties. Therefore, the sealing sheet of the present invention can be suitably used for optical applications such as sealing materials of light-emitting devices such as organic EL elements.

3)Sealing body

The sealing body of the present invention is a product that seals an object to be sealed using the sealing sheet of the present invention.

The term "sealed using the sealing sheet of the present invention" means that the peeling film constituting the sealing sheet of the present invention is removed to expose the adhesive layer, and the adhesive layer is closely adhered to the object to be sealed, and the object to be sealed is sealed. Things covered.

Examples of the sealing body of the present invention include a substrate, a component (to-be-sealed object) formed on the substrate, and a sealing material for sealing the component, and the sealing material is derived from the sealing sheet of the present invention. The substance of the adhesive layer (the hardened substance of the adhesive layer).

The substrate system is not particularly limited, and various substrate materials can be used. In particular, it is preferable to use a substrate material with a high transmittance of visible light. In addition, materials with high barrier properties to prevent moisture and gas from entering from the outside of the element, and excellent solvent resistance and weather resistance are preferred. Specific examples include transparent inorganic materials such as quartz and glass; polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, and polyphenylene sulfide. Ether, polyvinylidene fluoride, cellulose acetate, brominated phenoxy, polyarylamine (aramid), polyimide, polystyrene, polyarylate (polyarylate), polystyrene, Transparent plastics such as polyolefins, and the aforementioned gas barrier film.

The thickness of the substrate is not particularly limited and can be appropriately selected considering the transmittance of light and the performance of isolating the inside and outside of the element.

Examples of the object to be sealed include organic EL elements such as organic EL displays and organic EL lighting; liquid crystal elements such as liquid crystal displays; electronic paper; solar cell elements such as organic thin film solar cells; and electronic devices such as light emitting diodes. .

The manufacturing method of the sealing body of the present invention is not particularly limited.

For example, in the case of the sealing sheet (α) of the present invention, the adhesive layer is attached to the object to be sealed, and the object to be sealed is sealed with the adhesive layer of the sealing sheet. When using a release film for the sealing sheet (α), remove the release film after sealing.

In the case of the structure of the sealing sheet (β) of the present invention, the release film of one side of the sealing sheet (β) is removed and the gas barrier film is bonded to the exposed adhesive layer. Next, the peeling film of the other side is removed. The film is removed, an adhesive layer is attached to the object to be sealed, and the object to be sealed is sealed with the adhesive layer of the sealing sheet.

In the configuration of the sealing sheet (γ) of the present invention, the release film is removed and the adhesive layer is attached to the object to be sealed, so that the object to be sealed is sealed with the adhesive layer of the sealing sheet.

The bonding conditions for bonding the adhesive layer of the sealing sheet to the object to be sealed are not particularly limited. The subsequent temperature is, for example, 23 to 100°C, preferably 23 to 80°C, and more preferably 23 to 40°C. This subsequent treatment can also be performed while applying pressure.

After the adhesive layer of the sealing sheet is bonded to the object to be sealed, the sealed body can be obtained by photocuring the adhesive layer.

As hardening conditions when hardening the adhesive layer, the conditions described above can be used.

Furthermore, in the present invention, before the adhesive layer of the sealing sheet is adhered to the object to be sealed, the adhesive layer can be irradiated with active energy rays to start photohardening of the adhesive layer. Even after the thus formed adhesive layer is irradiated with active energy rays, the resin composition of the present invention is firmly adhered to the adherend because the adhesive layer has sufficient adhesiveness while the curing reaction is not fully progressing. In addition, peeling during or after attachment can be prevented; in addition, the adhesive layer hardens over time, and finally a sealed body with excellent durability can be obtained. The advantage of irradiating the adhesive layer with active energy rays before attaching it to the object to be sealed is that it can avoid damage to the object to be sealed (electronic devices, etc.) caused by the active energy rays; or even The gas barrier film constituting the sealing sheet (γ) does not transmit active energy rays and can efficiently irradiate the adhesive layer with active energy rays.

As curing conditions when photocuring the adhesive layer of the sealing sheet, the conditions described above can be used. Moreover, when using the sealing sheet (β) and the sealing sheet (γ), in terms of operability, if the release film is active energy ray transmissive, the release film on the adhesive layer may not be peeled off, but the release film may be peeled off. It is better to irradiate the film side with ultraviolet rays.

Here, "having active energy ray transmittance" means that 65% of the irradiated active energy rays The above transmission properties are preferably above 70%.

The sealing system of the present invention uses the sealing sheet of the present invention to seal an object to be sealed.

Therefore, the sealing body of the present invention can continue to maintain the performance of the sealed object for a long period of time.

[Example]

Hereinafter, an Example is given and this invention is demonstrated in more detail. However, the present invention is not limited to the following examples at all.

The parts and % in each example are based on quality unless notified in advance.

In the following Examples and Comparative Examples, the following were used as the modified polyolefin-based resin [(A) component], the compound having a cyclic ether group [(B) component], and the photocationic polymerization initiator [(C) ) ingredient], an adhesion-imparting agent with a softening point of 80°C or above, and a silane coupling agent system.

Modified polyolefin resin [(A) component]

Acid-modified α-olefin polymer [manufactured by Mitsui Chemicals Co., Ltd., trade name: UNISTOLEH-200, number average molecular weight: 47,000]

Compounds having cyclic ether groups [(B) component]

(1) Compound (B-1) having a cyclic ether group

Triepoxypropylisocyanurate [manufactured by Nissan Chemical Co., Ltd., trade name: TEPIC-FL, cyclic ether equivalent: 165-185g/eq, liquid at 25°C]

(2) Compound (B-2) having a cyclic ether group

Hydrogenated bisphenol A type epoxy resin [manufactured by Mitsubishi Chemical Corporation, trade name: YX8000, cyclic ether equivalent: 205g/eq, liquid at 25°C]

(3) Compound (B-3) having a cyclic ether group

Hydrogenated bisphenol A type epoxy resin [manufactured by Mitsubishi Chemical Corporation, trade name: YX8034, cyclic ether equivalent: 270g/eq, liquid at 25°C]

Photocationic polymerization initiator [(C) component]

Triarylsulfonium salt [manufactured by SAN-APRO, trade name: CPI-200K, anion: anion having a hexafluorophosphate skeleton]

Adhesion-imparting agent with a softening point of 80°C or higher [styrenic monomer/aliphatic monomer copolymer resin (manufactured by Mitsui Chemicals, brand name: FTR6100, softening point 95°C)]

Epoxy silane coupling agent (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: KBM-4803, 8-glycidoxyoctyltrimethoxysilane)

[Example 1]

100 parts by mass of the acid-modified α-olefin polymer (A), 100 parts by mass of the compound having a cyclic ether group (B-1), 1.0 parts by mass of the photocationic polymerization initiator (C), and 50 parts by mass of the adhesion-imparting agent part, and 0.1 part by mass of silane coupling agent were dissolved in methyl ethyl ketone to prepare a resin composition (1) with a solid content concentration of 30%.

The resin composition (1) was applied to the release-treated surface of a release film (manufactured by LINTEC, trade name: SP-PET382150), and the resulting coating film was dried at 100° C. for 2 minutes to form a film with a thickness of 10 μm. The adhesive layer is formed, and the release-treated surface of another release film (manufactured by LINTEC, trade name: SP-PET381031) is bonded thereto to obtain a sealing sheet (1).

[Example 2]

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

[Example 3]

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

[Comparative example 1]

In Example 2, an imidazole-based curing catalyst [2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd., trade name: CUREZOLE2E4MZ)] was used instead of the photocationic polymerization initiator (C). A resin composition (4) was prepared in the same manner as in Example 2, and a sealing sheet (4) was obtained using this resin composition.

The following measurements and evaluations were performed on the sealing sheets (1) to (4) obtained in Examples 1 to 3 and Comparative Example 1. The results are shown in Table 1.

[Adhesion force measurement]

Peel off one piece of the release film of the sealing sheet to expose the adhesive layer. The exposed adhesive layer was superimposed on the gas barrier film [(substrate: PET (thickness: 50 μm)); gas barrier layer: polysilazane layer implanted with argon ions; water vapor transmission rate: 0.02g/ m ² /day)], and use a laminating machine to laminate them at 23°C. Next, the other release film of the sealing sheet was peeled off, and the exposed adhesive layer was overlapped on alkali-free glass (made by Corning Co., Ltd., trade name: EAGLEXG), and these were bonded using a laminating machine at 23°C. Next, an ultraviolet irradiation device (manufactured by EYEGRAPHICS, trade name: US2-0801<2>) is used to irradiate ultraviolet rays from the base material surface side with an illumination intensity of 400 mW/cm ² and a light amount of 800 mJ/cm ² to harden the adhesive layer to produce the product. Test piece. In addition, the sealing sheet (4) obtained in Comparative Example (1) was placed on a hot plate heated to 80° C., with the alkali-free glass facing down, and left to stand for 2 hours. Instead of irradiating ultraviolet rays, the adhesive layer was hardening.

As the peeling test (a), a 180° peeling test was performed after the test piece was allowed to stand for 24 hours at a temperature of 23° C. and a relative humidity of 50%.

As the peel test (b), the test piece was left to stand for 168 hours at a temperature of 60°C and a relative humidity of 90%. Next, it was left to stand for 24 hours at a temperature of 23°C and a relative humidity of 50%. Conduct a 180° peel test at 23°C and 50% relative humidity.

In these peeling tests (a) and (b), in addition to the above test conditions, they were conducted in accordance with the adhesive force measurement method described in JIS Z 0237:2009.

[Measurement of storage elastic modulus of hardened sealing sheet]

The adhesive layers of the sealing sheets were stacked and laminated at 23° C. using a laminating machine to obtain a laminated body with a thickness of 1 mm. Subsequently, this laminated body was irradiated with ultraviolet rays using an ultraviolet irradiation device (manufactured by EYEGRAPHICS, trade name: US2-0801<2>) at an illumination intensity of 200 mW/cm ² and a light intensity of 200 mJ/cm ² to harden the adhesive layer. In addition, the sealing sheet (4) obtained in Comparative Example (1) was left to stand on a hot plate that heated the sealing sheet to 80° C. for 2 hours to harden the adhesive layer instead of irradiating ultraviolet rays. The hardened laminated body was used as a sample, and a storage elastic modulus measuring device (manufactured by Anton Paar, product name: Physica MCR301) was used to obtain a temperature of 23°C to 150°C under the conditions of frequency 1 Hz and temperature rise rate 3°C/min. The value of the stored elastic modulus over the temperature range.

The values of storage elastic modulus at 60°C are shown in Table 1.

[Evaluation test of organic EL elements]

The following method was used to manufacture an organic EL element having a glass substrate formed with an indium tin oxide (ITO) film (thickness: 100 nm, sheet resistance: 50Ω/□ (ohms per square)) as an anode.

First, 50 nm of N,N'-bis(naphthyl-1-yl)-N,N'-bis(phenyl)-benzidine) (manufactured by Luminescence Technology) and 50 nm of ginseng (8-hydroxy-quinoline) were used. Aluminum phylinate (manufactured by Luminescence Technology Co., Ltd.) was sequentially evaporated on the ITO film of the glass substrate at a speed of 0.1 to 0.2 nm/min to form a light-emitting layer.

On the obtained light-emitting layer, lithium fluoride (LiF) (manufactured by High Purity Chemical Research Institute Co., Ltd.) as an electron implantation material was implanted at a speed of 0.1 nm/minute and 4 nm, and then aluminum (Al) (High Purity Chemical Research Institute Co., Ltd.) was Laboratory Co., Ltd.) was evaporated at a speed of 0.1 nm/minute and 150 nm to form a cathode, and an organic EL element was obtained.

In addition, the degree of vacuum during vapor deposition was all 1×10 ^-4 Pa or less.

Peel off one piece of the release film of the sealing sheet, and overlap the exposed adhesive layer on the surface of the gas barrier layer of the gas barrier film (water vapor transmission rate: 0.0004g/ ^m2 /day), and use nitrogen gas Use a laminating machine to laminate them at 23°C. Next, peel off and remove the other release film of the sealing sheet, and overlap the exposed adhesive layer to cover the organic EL element formed on the glass substrate, and use a laminating machine at 23°C in a nitrogen atmosphere. Attached.

Next, the products obtained using the sealing sheets (1) to (3) obtained in Examples (1) to (3) were irradiated using an ultraviolet irradiation device (manufactured by EYEGRAPHICS Co., Ltd., trade name: US2-0801<2>). The surface side of the glass substrate is irradiated with ultraviolet rays at an illumination intensity of 400 mW/cm ² and a light intensity of 800 mJ/cm ² to harden the adhesive layer, thereby obtaining a bottom-emitting electronic device in which an organic EL element is sealed.

Moreover, the sealing sheet (4) obtained using the comparative example (1) was obtained by placing it on a hot plate heated to 80° C. with the glass substrate facing down and leaving it for 2 hours to harden the adhesive layer. A bottom-emitting electronic device formed by sealing an organic EL element.

After the electronic device was allowed to stand for 500 hours in an environment with a temperature of 60° C. and a relative humidity of 90%, the organic EL element was started, and the presence or absence of dark spots (non-luminous spots) was observed and evaluated based on the following criteria.

◎: The dark spot is more than 95% of the luminous area

○: Dark spots are more than 90% of the luminous area

△: The dark spot is more than 85% of the luminous area

[Table 1]

From Table 1, we know the following situation.

It is formed using resin compositions (1) to (3) containing (A) component, (B) component, and (C) component, and containing 100 mass parts of (B) component with respect to 100 mass parts of (A) component. The sealing sheets (1)~(3) have little reduction in adhesion even after being left standing under high humidity conditions. Therefore, when the organic EL element is sealed using these sealing sheets (1) to (3), the gas barrier film can be suppressed from floating and peeling off the object to be sealed.

In addition, these resin compositions (1) to (3) have excellent film-forming properties and sheet processability under normal temperature environments. Therefore, when organic EL elements are sealed using the sealing sheets (I) to (3) formed using these resin compositions, they have excellent sealing properties due to their high storage elastic modulus and can suppress the occurrence of darkening. points (Examples 1 to 3).

On the other hand, the sealing sheet (4) formed using the resin composition (4) has a low storage elastic modulus at 60°C after the photocuring process. Therefore, when the organic EL element is sealed using the sealing sheet (4), the sealing performance is poor and the occurrence of dark spots cannot be suppressed (Comparative Example 1).

Claims (14)

A sealing sheet composed of a base material or a release film, and an adhesive layer formed on the base material or release film, the adhesive layer being formed using the following resin composition 1, (resin Composition 1) A resin composition containing the following components (A), (B), and (C). The content of the component (B) relative to 100 parts by mass of the component (A) It is more than 50 parts by mass and less than 200 parts by mass, (A) component: modified polyolefin resin (B) component: a compound with a cyclic ether group that is liquid at 25°C (C) component: photocation Polymerization initiator. A sealing sheet composed of two release films and an adhesive layer sandwiched between the two release films. The adhesive layer is formed using the following resin composition 1: (Resin Composition 1) Resin The composition is a resin composition containing the following components (A), (B) and (C), and the content of the component (B) is greater than 50 parts by mass relative to 100 parts by mass of the component (A), And it is 200 parts by mass or less, (A) component: modified polyolefin-based resin (B) component: a compound having a cyclic ether group that is liquid at 25° C. (C) component: photocationic polymerization initiator. A sealing sheet composed of a peeling film, a gas barrier film, and a combination of the aforementioned peeling film and It consists of an adhesive layer sandwiched between gas barrier films. The adhesive layer is formed using the following resin composition 1. (Resin composition 1) The resin composition contains the following components (A) and (B). ) component and a resin composition of component (C), the content of the component (B) is greater than 50 parts by mass and less than 200 parts by mass relative to 100 parts by mass of the component (A), component (A): Change Polyolefin-based resin (B) component: a compound having a cyclic ether group that is liquid at 25°C. (C) component: photocationic polymerization initiator. The sealing sheet according to claim 3, wherein the gas barrier film is a metal foil, a resin film, or a thin film glass. The sealing sheet according to any one of claims 1 to 3, wherein the component (A) is an acid-modified polyolefin resin. The sealing sheet according to any one of claims 1 to 3, wherein the cyclic ether group of the component (B) is an oxirane group or an oxybutanyl group. The sealing sheet according to any one of claims 1 to 3, wherein the component (C) is an aromatic sulfonium salt compound. The sealing sheet according to any one of claims 1 to 3, wherein the content of the component (C) is 0.1 to 10 parts by mass relative to 100 parts by mass of the component (B). For the sealing sheet described in any one of claims 1 to 3 of the patent application, the resin composition 1 further contains an adhesion-imparting agent with a softening point of 80°C to 150°C. The sealing sheet as described in item 9 of the patent application, wherein relative to the aforementioned component (A) 100 parts by mass, the content of the aforementioned adhesive imparting agent with a softening point of 80°C to 150°C is 1 to 200 parts by mass. For the sealing sheet described in any one of claims 1 to 3 of the patent application, the resin composition 1 further contains a silane coupling agent. For the sealing sheet described in item 11 of the patent application, the content of the silane coupling agent is 0.01 to 10 parts by mass relative to 100 parts by mass of the component (A). A sealing body is formed by using a sealing sheet as described in any one of claims 1 to 3 of the patent application to seal an object to be sealed. The sealed body described in Item 13 of the patent application, wherein the sealed object is an electronic device.