TWI811382B - Sealing sheet and sealing body - Google Patents

Abstract

The present invention provides a sealant composition, which is a sealant composition containing a compound having a cyclic ether group and a binder resin having a functional group capable of performing a curing reaction with the compound having a cyclic ether group, and is characterized by: : The storage modulus before hardening at 23°C is 10 ⁴ Pa or more, and the storage modulus after hardening in the temperature range of -20°C or more and +90°C or less is 10 ⁸ Pa or more; a sealing sheet made of A sealing sheet composed of two release films and a sealant layer sandwiched by the release films, the sealant layer being formed using the sealant composition; and a sealing body using the sealing sheet to seal the object Sealed.

Description

Sealing sheet and sealing body

The present invention relates to a sealing sheet having a sealant composition and a sealant layer formed from the sealant composition, and a sealing body in which a sealant is sealed using the sealing sheet.

In recent years, organic EL 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 light-emitting characteristics, such as light-emitting brightness, light-emitting efficiency, and light-emitting uniformity, tend to decrease over time.

It is considered that the cause of the problem of lowered luminescence characteristics is that oxygen, moisture, etc. penetrate into the inside of the organic EL element, causing the electrodes, organic layers, etc. to deteriorate. Therefore, in order to solve this problem, there is a proposal to use an adhesive sheet having excellent moisture barrier properties as a sealing material (sealing sheet).

As a sealing sheet having such characteristics, Patent Document 1 proposes a thermosetting composition containing a cationic polymerizable compound having two or more epoxy groups in one molecule, a thermal cationic polymerization initiator, and a thermosetting composition selected from the group consisting of: A polyether compound with a weight average molecular weight of 250 to 10,000, which is a group composed of polyalkylene oxide and crown ether, and a leveling agent.

This document also describes that when the thermosetting composition described in this document is used, a cured material layer with less unevenness, cissing, etc. and high surface smoothness can be formed on a coated object such as an organic EL element.

Furthermore, Patent Document 2 also describes a resin composition for sealing organic EL elements, characterized in that it contains an epoxy resin, a hardener, and a hygroscopic metal oxide with an average particle diameter of 10 μm or less, and the hardener is ionic liquids.

This document also states that when the resin composition described in this document is used, it can be melted into a molten material with an appropriate viscosity required in the lamination step of full sealing, and it can be cured at a low temperature to form a high adhesion strength (adhesion strength). layer of hardened material. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent No. 5763280 [Patent Document 2] Japanese Patent No. 5601202

As described in Patent Documents 1 and 2, by using a curable composition containing an epoxy resin, a sealing sheet excellent in moisture barrier properties can be easily obtained. However, in recent years, as electronic equipment has become more highly functional, requirements for the components constituting the electronic equipment have become increasingly stringent, and sealing materials with better sealing properties in a wide temperature range have been required to be developed.

The present invention was made in view of the above-mentioned actual situation, and an object thereof is to provide a sealant composition that is easily processed into a sheet-like object, has excellent processability, and can form a sealant layer with excellent sealing properties in a wide temperature range; A sealing sheet having a sealant layer formed of a sealant composition; and a sealing body formed by sealing a sealing object using the aforementioned sealing sheet.

In order to solve the above-mentioned problems, the inventors of the present invention concentrated on studying sealant compositions. As a result, they discovered a sealant composition that contains a compound having a cyclic ether group and a binder resin having a functional group that can undergo a curing reaction with the compound having a cyclic ether group, and each has specific properties before and after curing. It has a storage modulus of more than 100%, can be easily formed into a sheet, and has excellent sealing properties against sealed objects such as organic EL elements in a wide temperature range from low temperature (-20°C) to high temperature (+90°C). Excellent, the present invention was completed.

In this manner, according to the present invention, the following sealant compositions (1) to (17), sealing sheets (18) and (19), and sealing body (20) can be provided.

(1) A sealant composition containing a compound having a cyclic ether group and a binder resin having a functional group capable of performing a curing reaction with the compound having a cyclic ether group, characterized in that : The storage modulus before hardening at 23°C is 10 ⁴ Pa or more, and the storage modulus after hardening in the temperature range from -20°C to +90°C is 10 ⁸ Pa or more.

(2) The sealant composition according to (1), wherein the storage modulus before hardening at 23°C is 1.5×10 ⁷ Pa or less.

(3) The sealant composition according to (1) or (2), wherein the content of the compound having a cyclic ether group is 45 to 90 mass % in terms of solid content relative to the entire sealant composition. .

(4) The sealant composition as described in (1) or (2), wherein the content of the binder resin having a functional group is 5 to 50% by mass based on the solid content of the entire sealant composition. .

(5) The sealant composition as described in (1) or (2), wherein the content of the compound having a cyclic ether group is 110 to 1800 parts by mass relative to 100 parts by mass of the binder resin having a functional group .

(6) The sealant composition as described in (1) or (2), wherein the compound having a cyclic ether group is liquid at 25°C, and the content of the compound having a cyclic ether group is relative to the sealant composition. The total content of the material is 53% by mass or more in terms of solid content.

(7) The sealant composition according to (1) or (2), wherein the compound having a cyclic ether group contains an epoxy resin having a glycidyl ether group.

(8) The sealant composition according to (1) or (2), wherein the molecular weight of the compound having a cyclic ether group is 100 to 5,000.

(9) The sealant composition according to (1) or (2), wherein the weight average molecular weight (Mw) of the binder resin having functional groups is 10,000 to 1,000,000.

(10) The sealant composition as described in (1) or (2), wherein the functional group of the binder resin having functional groups is selected from the group consisting of carboxyl groups, acid anhydride groups, epoxy groups and hydroxyl groups At least one of them.

(11) The sealant composition according to (1) or (2), wherein the glass transition temperature (Tg) of the binder resin is 90°C or higher.

(12) The sealant composition as described in (1) or (2), wherein the binder resin having functional groups is selected from the group consisting of olefin resins, phenoxy resins and acetal resins At least one.

(13) The sealant composition according to (1) or (2), wherein the content of the liquid compound having a cyclic ether group contained in the sealant composition is 65 mass % or less.

(14) The sealant composition according to (1) or (2), further containing a curing catalyst.

(15) The sealant composition according to (14), wherein the content of the hardening catalyst is 0.01 to 15 parts by mass relative to 100 parts by mass of the compound having a cyclic ether group.

(16) The sealant composition according to (1) or (2), further containing a silane coupling agent.

(17) The sealant composition according to (16), wherein the content of the silane coupling agent is 0.01 to 5 mass % based on the solid content of the entire sealant composition.

(18) A sealing sheet composed of two release films and a sealant layer sandwiched by the release films. The sealant layer is made of any one of items (1) to (17). The sealant composition is formed from the sealant composition.

(19) The sealing sheet as described in (18), wherein the thickness of the sealant layer is 1~25 μm. (20) A sealing body formed by sealing the object to be sealed using the sealing sheet as described in (18) or (19).

According to the present invention, it is possible to provide a product that can be easily processed into a sheet-like object and has excellent processability, and can form a sealed object for organic EL elements and the like in a wide temperature range from low temperature (-20°C) to high temperature (+90°C). A sealant composition having a sealant layer with excellent sealing properties; a sealant sheet having a sealant layer formed using the sealant composition; and a sealed body sealed by the sealant sheet.

Form used to implement the invention

Hereinafter, the present invention will be divided into 1) sealant composition, 2) sealing sheet, and 3) sealing body and will be described in detail.

1) Sealant composition The sealant composition of the present invention is a sealant composition containing a compound having a cyclic ether group and a binder resin having a functional group capable of performing a curing reaction with the compound having a cyclic ether group. , characterized in that the storage modulus before hardening at 23°C is 10 ⁴ Pa or more, and the storage modulus after hardening in the temperature range of -20°C or more and +90°C or less is 10 ⁸ Pa or more.

[Storage Modulus] The sealant composition of the present invention has a storage modulus before hardening at 23°C of 10 ⁴ Pa or more, preferably 10 ⁵ Pa or more, and preferably 6×10 ⁵ Pa or more. Moreover, the storage modulus of the sealant composition of the present invention before curing at 23°C is 10 ⁸ Pa or less, preferably 10 ⁷ Pa or less, and preferably 4×10 ⁶ Pa or less. A sealant composition having a storage modulus before hardening at 23° C. within this range is easily formed into a sheet and has excellent processability. In addition, the sealant composition of the present invention has a storage modulus after curing in a temperature range of -20°C or more and +90°C or less: 10 ⁸ Pa or more, preferably 10 ⁸ Pa to 10 ¹¹ Pa, and preferably 2 ×10 ⁸ Pa~10 ¹⁰ Pa. A sealant composition with a cured storage modulus within this range of -23°C to +90°C has excellent sealing properties in a wide temperature range (-20°C to +90°C).

The storage modulus of the sealant composition is measured using a conventional dynamic viscoelasticity measuring device. The storage modulus before hardening can be obtained by processing the sealant composition of the present invention into a sheet-like sealing sheet (without peeling sheet) and laminating it to a sample thickness of 1 mm using a laminating machine at 23°C. This product was used as a measurement sample and measured using a conventional storage modulus measuring device. Specifically, it can be measured using the method described in the Examples. In addition, the storage modulus after hardening can be obtained by processing the sealant composition of the present invention into a sheet-like sealing sheet (without peeling sheet) and laminating it at 23° C. to a sample thickness of 200 μm using a laminating machine. Thereafter, the sealant layer of the sealing sheet was cured under curing conditions of 100° C. for 1 hour, and this was used as a measurement sample, and measured using a conventional storage modulus measuring device. Specifically, it can be measured using the method described in the Examples.

[Compounds with cyclic ether groups] The sealant composition of the present invention contains a compound having a cyclic ether group (hereinafter sometimes referred to as "cyclic ether compound (A)"). The cyclic ether compound (A) can provide a cured product having excellent compatibility with a binder resin having a functional group and excellent adhesiveness. Therefore, by using this substance, it is possible to obtain a sealant composition excellent in sheet processability (film-forming properties) and a cured product of the sealant composition excellent in colorless transparency and water vapor barrier properties.

The cyclic ether compound (A) refers to a compound having one, preferably two or more cyclic ether groups in the molecule. Furthermore, in the present invention, the phenoxy resin described below is not included in the cyclic ether compound (A).

The molecular weight of the cyclic ether compound (A) is usually 100 to 5,000, preferably 200 to 3,000.

The cyclic ether equivalent of the cyclic ether compound (A) is preferably from 50 g/eq to 1000 g/eq, and preferably from 100 g/eq to 800 g/eq.

By using a sealant composition in which the cyclic ether equivalent of the cyclic ether compound (A) is in the above range, a sealing material with high adhesive strength and excellent curability can be formed more efficiently.

In the present invention, the cyclic ether equivalent means a value obtained by dividing the molecular weight by the number of cyclic ether groups.

Examples of the cyclic ether group include an oxirane group (epoxy group), an oxetanyl group (oxetanyl group), a tetrahydrofuranyl group, and a tetrahydropyranyl group (tetrahydropyranyl group). ), glycidyl group, glycidyl ether group, etc. Among them, from the viewpoint of obtaining a cured product of a sealant composition with better sheet processability (film-forming properties) and a sealant composition with better adhesive strength, those having an oxycyclopropane group or an oxycyclic ring Compounds with butyl, glycidyl or glycidyl ether groups are preferred, those with more than 2 oxycyclopropyl, oxycyclobutanyl, glycidyl or glycidyl ether groups in the molecule Compounds having oxycyclopropyl groups, glycidyl ether groups or glycidyl ether groups are particularly preferred.

Examples of compounds having an oxycyclopropyl group in the molecule include aliphatic epoxy compounds (excluding alicyclic epoxy compounds), aromatic epoxy compounds, alicyclic epoxy compounds, and the like.

Examples of aliphatic epoxy compounds include monofunctional epoxy compounds such as glycidyl 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 of alkylene oxide adduct, polyglycidyl esters of aliphatic long-chain polybasic acids, and epoxy compounds with triazine skeletons.

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 polyols such as cyclopentadienyl dimethanol diglycidyl ether, or by adding one or more alkylene oxides to propylene glycol, trimethylolpropane, glycerin, etc. Polyglycidyl etherates of polyether polyols obtained from aliphatic polyols, and diepoxypropyl esters of aliphatic long-chain dibasic acids; Monoglycidyl ether of aliphatic higher alcohol, glycidyl ester of higher fatty acid, 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 DENACOL EX-121, DENACOL EX-171, DENACOL EX-192, DENACOL EX-211, DENACOL EX-212, DENACOL EX-313, DENACOL EX-314, DENACOL EX-321, and DENACOL EX. -411, DENACOL EX-421, DENACOL EX-512, DENACOL EX-521, DENACOL EX-611, DENACOL EX-612, DENACOL EX-614, DENACOL EX-622, DENACOL EX-810, DENACOL EX-811, DENACOL EX -850, DENACOL EX-851, DENACOL EX-821, DENACOL EX-830, DENACOL EX-832, DENACOL EX-841, DENACOL EX-861, DENACOL EX-911, DENACOL EX-941, DENACOL EX-920, DENACOL EX -931 (above, manufactured by NAGASE CHEMTEX); Epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 10 0 MF ( Above, manufactured by Kyoeisha Chemical Co., Ltd.); Adeka Glycilol ED-503, Adeka Glycilol ED-503G, Adeka Glycilol ED-506, Adeka Glycilol ED-523T, ADEKARESIN EP-4088S, ADEKARESIN EP-4088L, ADEKARESIN EP-4080E (above) , manufactured by ADEKA Co., Ltd.); TEPIC-FL, TEPIC-PAS, TEPIC-UC (the above, manufactured by Nissan Chemical Co., Ltd.), etc.

Examples of the aromatic epoxy compound include polyols having at least one aromatic ring such as phenol, cresol, butylphenol, or mono/polyepoxypropyl ethers of their alkylene oxide adducts. Chemicals etc. Representative compounds of these aromatic epoxy compounds include bisphenol A, bisphenol F, or glycidyl etherates and epoxy novolacs obtained by adding an alkylene oxide to these compounds. Resin; Mono/polyepoxypropyl etherates of aromatic compounds with two or more phenolic hydroxyl groups such as resorcinol, hydroquinone, catechol, etc.; phenyldi Glycidyl etherates of aromatic compounds with two or more alcoholic hydroxyl groups such as methanol, phenyldiethanol, phenyldibutanol, etc.; phthalic acid, terephthalic acid, trimellitic acid, etc. Glycidyl ester of a polybasic acid aromatic compound having two or more carboxylic acids, glycidyl ester of benzoic acid, epoxide of styrene oxide or divinylbenzene, etc.

In addition, as the aromatic epoxy compound, commercially available products can also be used. Examples of commercially available products include DENACOL EX-146, DENACOL EX-147, DENACOL EX-201, DENACOL EX-203, DENACOL EX-711, DENACOL EX-721, ONCOAT EX-1020, ONCOAT EX-1030, and ONCOAT EX. -1040, ONCOAT EX-1050, ONCOAT EX-1051, ONCOAT EX-1010, ONCOAT EX-1011, ONCOAT 1012 (above, manufactured by NAGASE CHEMTEX); OGSOL PG-100, OGSOL EG-200, OGSOL EG-210, OGSOL EG-250 (above, manufactured by Osaka GAS CHEMICAL Co., Ltd.); HP4032, HP4032D, HP4700 (above, manufactured by DIC Corporation); ESN-475V (above, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.); JER (former EPICOAT) YX8800 (above, manufactured by DIC Corporation) Mitsubishi Chemical Corporation); MERPROOF G-0105SA, MERPROOF G-0130SP (above, manufactured by NOF Corporation); Epiclon N-665, Epiclon HP-7200 (above, manufactured by DIC Corporation); EOCN-1020, EOCN- 102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (the above, manufactured by Nippon Chemical Co., Ltd.); ADEKARESIN EP-4000, ADEKARESIN EP -4005, ADEKARESIN EP-4100, ADEKARESIN EP-4901 (the above, made by ADEKA); TECHMORE VG-3101L (the above, made by Printec), etc.

Examples of the alicyclic epoxy compound include polyglycidyl etherates of polyhydric alcohols having at least one alicyclic structure, or compounds containing cyclohexene and cyclopentene rings prepared by using an oxidizing agent. Compounds containing cyclohexene oxide and cyclopetene oxide obtained by epoxidation. 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 Acid ester, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylene bis(3,4-epoxycyclohexane), propane-2,2-diyl-bis(3, 4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylidene bis(3,4-cyclohexane) Oxycyclohexane carboxylate), dioctyl epoxy hexahydrophthalate, di-2-ethylhexyl epoxy hexahydrophthalate, 1-epoxyethyl-3,4- Epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pinene oxide, limonene dioxide, etc.

In addition, as the alicyclic epoxy compound, a commercially available product can also be used. Examples of commercially available products include YX8000, YX8034 (above, manufactured by Mitsubishi Chemical Corporation), CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2000, CELLOXIDE3000 (above, manufactured by DAICEL Corporation), EP-4088L (manufactured by ADEKA Corporation), and the like.

Examples of compounds having an oxetanyl group in the molecule include 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,4-bis[(3-ethyl) methyl-3-oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1 , 3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether , triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1 ,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane Difunctional aliphatic oxycyclobutane compounds, 3-ethyl-3-[(phenoxy)methyl]oxycyclobutane, 3-ethyl-3-(hexyloxymethyl)oxycyclobutane alkane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxycyclobutane, 3-ethyl-3-(hydroxymethyl)oxycyclobutane, 3-ethyl-3-( Monofunctional oxycyclobutane compounds such as chloromethyl) oxycyclobutane, etc.

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

These cyclic ether compounds (A) can be used individually by 1 type or in combination of 2 or more types. Among them, the one that is liquid at 25° C. (liquid ) is better. Here, the so-called liquid refers to one of the aggregated states of matter, a state that has a roughly certain volume but does not have an inherent shape.

The content of the cyclic ether compound (A) in the sealant composition is preferably 45 to 90 mass %, more preferably 50 to 85 mass %, and more preferably 50 to 85 mass % in terms of solid content relative to the entire sealant composition. Preferably, it is 60~80% by mass. By setting the content of the cyclic ether compound (A) in the above range, it is easy to obtain a cured product of the sealant composition having more excellent adhesive strength.

[Binder resin with functional groups] The sealant composition of the present invention, in addition to the cyclic ether compound (A), also contains a binder resin (hereinafter referred to as "binder") having a functional group that can undergo a curing reaction with the cyclic ether compound (A). Resin (B)" case).

The weight average molecular weight (Mw) of the binder resin (B) is not particularly limited, but is preferably 10,000 or more from the viewpoint of better compatibility with the cyclic ether compound (A) and easier production of flakes. , 10,000~1,000,000 is better, 10,000~800,000 is better. The weight average molecular weight (Mw) of the binder resin (B) can be determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent and as a standard polystyrene conversion value.

The content of the binder resin (B) in the sealant composition is preferably 5 to 50 mass %, and more preferably 10 to 45 mass % in terms of solid content relative to the entire sealant composition. By setting the content of the binder resin (B) to 5 to 45% by mass in terms of solid content relative to the entire sealant composition, a sealant composition with better sheet formability and processability can be easily obtained.

Examples of the functional group that the binder resin (B) has include a carboxyl group, a carboxylic anhydride group, a carboxylic acid ester group, a hydroxyl group, an epoxy group, an amide group, an ammonium group, a nitrile group, an amine group, and an amide group. , isocyanate group, acetyl group, thiol group, ether group, thioether group, styrene group, phosphine group, nitro group, urethane group, alkoxysilyl group, silanol group, halogen atom, etc. Among these, a carboxyl group, a carboxylic anhydride group, a carboxylate group, a hydroxyl group, and an epoxy group are preferred, and a carboxyl group, a carboxylic anhydride group, an epoxy group, and a hydroxyl group are preferred. The binder resin (B) may have two or more functional groups in the molecule.

As long as the binder resin (B) is compatible with the cyclic ether compound (A) and has a functional group capable of performing a curing reaction with the cyclic ether group of the cyclic ether compound (A), There are no special restrictions. Among them, at least one selected from the group consisting of modified olefin-based resins, phenoxy-based resins, and acetal-based resins is preferred. These resins can be used individually by 1 type or in combination of 2 or more types.

(Modified olefin resin) Modified olefin-based resin is an olefin-based resin into which functional groups have been introduced, and can be obtained by subjecting an olefin-based resin as a precursor to a modification process using a modifier.

Olefin-based resin refers to a polymer containing repeating units derived from olefin-based monomers. The olefin-based resin may be a polymer composed only of repeating units derived from an olefin-based monomer, or may be a polymer composed of repeating units derived from an olefin-based monomer and a monomer copolymerizable with an olefin-based monomer. A polymer composed of repeating units.

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 olefin resins include ultra-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.

A compound that has a functional group in the molecule as a modifier used in the modification treatment of olefin resins. Examples of the functional group include the same ones listed as the functional groups possessed by the binder resin (B). The compound having a functional group may also have two or more functional groups in the molecule.

In the present invention, from the viewpoint of obtaining more excellent effects of the present invention, acid-modified olefin-based resin is preferred as the modified olefin-based resin. Acid-modified olefin-based resin refers to an olefin-based resin graft-modified using an acid. For example, an olefin resin is reacted with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride (hereinafter referred to as "unsaturated carboxylic acid, etc.") to introduce (graft-modify) a carboxyl group or a carboxylic acid anhydride group. accomplished thing.

Examples of the unsaturated carboxylic acid that reacts the olefin-based resin include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, and aconitum. unsaturated carboxylic acids such as maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic acid anhydride, tetrahydrophthalic anhydride, etc. Saturated carboxylic anhydride. 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 sealant composition with better sheet processability (film-forming properties) and a cured product of the sealant composition with better adhesive strength.

The amount of the unsaturated carboxylic acid used to react the olefin 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 olefin resin. . The resin composition containing the acid-modified olefin-based resin obtained in this way can easily obtain a cured product having more excellent adhesive strength.

The method of introducing unsaturated carboxylic acid units or unsaturated carboxylic acid anhydride units into the olefin-based resin is not particularly limited. For example, an olefin resin and an unsaturated carboxylic acid are heated and melted above the melting point of the olefin resin in the presence of a radical generating agent such as an organic peroxide or azonitrile. A method of reacting; or a method of dissolving an olefin resin and an unsaturated carboxylic acid in an organic solvent and then heating, stirring and reacting in the presence of a radical generating agent to make the unsaturated carboxylic acid Methods such as graft copolymerization of olefin resins.

As the acid-modified olefin-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) (manufactured by ARKEMA Co., Ltd.) , Modic (registered trademark) (manufactured by Mitsubishi Chemical Corporation), etc.

The weight average molecular weight (Mw) of the modified olefin-based resin is preferably 10,000 to 1,000,000, more preferably 30,000 to 500,000. The weight average molecular weight (Mw) of the modified olefin-based resin can be determined in terms of standard polystyrene conversion by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

(Phenoxy resin) Phenoxy resins generally correspond to high molecular weight epoxy resins and have a polymerization degree of about 100 or more. The phenoxy resin used in the present invention is a binder resin having an epoxy group as a functional group.

The phenoxy resin used in the present invention has a weight average molecular weight (Mw) of 10,000 to 1,000,000. The weight average molecular weight (Mw) of the phenoxy resin can be determined in terms of standard polystyrene conversion using gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. This kind of phenoxy resin, which is equivalent to a high molecular weight epoxy resin, usually has a glass transition temperature of 130°C or less. Furthermore, the 5 wt% reduction temperature is higher than 350°C and has excellent heat deformation resistance. In addition, the phenoxy resin used in the present invention preferably has an epoxy equivalent of 5,000 or more, more preferably 7,000 or more.

The phenoxy resin used in the present invention is not particularly limited as long as it is an epoxy resin with a weight average molecular weight of 10,000 to 1,000,000. Examples include bisphenol A type, bisphenol F type, bisphenol S type phenoxy resin, copolymer type phenoxy resin of bisphenol A type and bisphenol F type, distillates thereof, naphthalene type benzene Oxygen resin, novolac type phenoxy resin, biphenyl type phenoxy resin, cyclopentadiene type phenoxy resin, etc. These phenoxy resins can be used individually by 1 type or in combination of 2 or more types.

Phenoxy resins can be obtained by reacting bifunctional phenols and epihalohydrins to a high molecular weight, or by performing an addition polymerization reaction between bifunctional epoxy resins and bifunctional phenols. For example, it can be obtained by reacting bifunctional phenols and epihalohydrin in the presence of an alkali metal hydroxide in an inert solvent at a temperature of 40 to 120°C. In addition, in the presence of a catalyst such as an alkali metal compound, an organic phosphorus compound, a cyclic amine compound, etc., and in an amide solvent, an ether solvent, a ketone solvent, or a lactone with a boiling point of 120° C. or higher, ) type solvent, alcohol type solvent, and other organic solvents, it can also be obtained by performing an addition polymerization reaction between a difunctional epoxy resin and difunctional phenols with a solid content concentration of 50% by weight or less and heating to 50 to 200°C.

Bifunctional phenols are not particularly limited as long as they are compounds having two phenolic hydroxyl groups. Examples include monocyclic difunctional phenols such as hydroquinone, 2-bromohydroquinone, resorcin, and catechol, bisphenol A, bisphenol F, and bisphenol F. Bisphenols such as phenol AD and bisphenol S, dihydroxybiphenyls such as 4,4'-dihydroxybiphenyl, dihydroxyphenyl ethers such as bis(4-hydroxyphenyl)ether, and straight-chain Alkyl, branched alkyl, aryl, hydroxymethyl, allyl, cyclic aliphatic group, halogen (tetrabromobisphenol A, etc.), nitro, etc. are introduced into the aromatic ring of the phenol skeleton. By introducing straight-chain alkyl groups, branched-chain alkyl groups, allyl groups, substituted allyl groups, cyclic aliphatic groups, alkoxycarbonyl groups, etc. into the carbon atoms located in the center of the bisphenol skeleton, Polycyclic difunctional phenols, etc.

Examples of epihalohydrins include epichlorohydrin, epibromhydrin, epiiodohydrin, and the like.

In addition, in the present invention, commercially available products can also be used as the phenoxy resin. Examples include, for example, YX7200, YL7553, YL6794, YL7213, YL7290, YL7482 manufactured by Mitsubishi Chemical Corporation; YX8100 (bisphenol S skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical Corporation; Toto Kasei Trade names made by the company: FX280, FX293, FX 293S (phenoxy resin containing fluorine skeleton); Trade names made by Mitsubishi Chemical Corporation: jER1256, jER4250; Trade names made by Nippon Steel Chemical Corporation: YP-50, YP -50S (Both are phenoxy resins containing bisphenol A skeleton); Trade name: YX6954 (phenoxy resin containing bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical Corporation; Manufactured by Nippon Steel Chemical Corporation Trade name: ZX-1356-2, etc.

(Acetal-based resin having functional groups) Acetal-based resin is a polymer compound containing an oxymethylene group (-CH ₂ O-) as a main structural unit. Acetal-based resins include polyacetal homopolymers and polyacetal copolymers. In addition to oxymethylene, the latter polyacetal copolymer also contains oxyalkylene groups with 2 to 10 carbon atoms (oxyethylene, oxypropyl, oxytrimethylene, oxytetramethylene, etc.) as structural unit. The ratio of the oxyalkylene group having 2 to 10 carbon atoms in the polyacetal copolymer is about 0.01 to 30 mol% relative to the entire structural unit.

Acetal-based resins can be produced by adding aldehydes such as formaldehyde and acetaldehyde; trioxane, ethylene oxide, propylene oxide, and 1,3-dioxolane. It is obtained by polymerizing cyclic ethers such as (1,3-dioxolane).

The polyacetal copolymer can be a copolymer composed of two components, a terpolymer composed of three components, etc. The polyacetal copolymer can also be a random copolymer, a block copolymer, a graft copolymer, etc. In addition, the polyacetal resin may not only be linear, but may also have a branched structure or a cross-linked structure. Furthermore, the terminals of the polyacetal resin may be stabilized by, for example, esterification with carboxylic acids such as acetic acid or anhydrides thereof.

In the present invention, the acetal resin used as the binder resin (B) is a resin having a functional group.

The acetal-based resin having a functional group can be obtained, for example, by modifying the acetal-based resin using a polymerizable compound having a functional group. Examples of the polymerizable compound having a functional group include an ethylenically unsaturated bond-containing compound having a functional group and an acetylene bond-containing compound having a functional group. Examples of the functional groups that the polymerizable compound has include the same ones listed as the functional groups that the binder resin (B) has.

Examples of the polymerizable compound having a functional group include glycidyl ethers such as allyl glycidyl ether and chalcone glycidyl ether; glycidyl (methyl) Acrylates, glycidyl vinyl benzoate, allyl glycidyl benzoate, glycidyl cinnamate, glycidyl cinnamyl acetate, glycidyl dimer acid, epoxy stearate Glycidyl propyl esters or epoxy esters of alcohols and acrylic acid or methacrylic acid esters; compounds with epoxy groups as functional groups such as epoxyhexene and limonene oxide; acrylic acid, methacrylic acid, propylene oxide, etc. Compounds with carboxyl groups as functional groups such as propiolic acid, crotonic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid; maleic anhydride, itaconic acid Compounds with carboxylic anhydride groups as functional groups such as acid anhydride, citraconic anhydride, norbornenedioic anhydride (himic anhydride); allyl alcohol, 2-hydroxyethyl (meth)acrylate, 2-hydroxy(meth)acrylate Propyl ester, butylene glycol mono(meth)acrylate, hexylene glycol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, glycerol mono(meth)acrylate, vinyl phenol, etc. Compounds with hydroxyl groups as functional groups, etc.

In addition, in the present invention, polyvinyl acetal resin can also be used as the acetal-based resin. Polyvinyl acetal resin is a binder resin with hydroxyl groups as functional groups.

Polyvinyl acetal resin is a resin obtained by reacting aldehyde with polyvinyl alcohol to acetalize it. Examples of aldehydes used include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, hexanal, heptaldehyde, n-octylaldehyde, 2-ethylhexanal, and cyclohexanal. , furfural, glyoxal, glutaraldehyde, benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenyl Acetaldehyde, β-phenylpropionaldehyde, etc. In addition, for example, derivatives of aldehydes such as acetals (dialkyl acetals, etc.), vinyl esters, vinyl ethers, and vinyl halides that supply the corresponding aldehydes by hydrolysis can also be used in the acetalization reaction.

The content rate of the vinyl alcohol unit (-CH ₂ -CH(OH)-) occupied by the total structural units constituting the polyvinyl acetal resin is 5 mol% or more and 50 from the viewpoint of adhesive force, etc. Mol% or less is preferred. The content rate of acetalized vinyl alcohol units in the total structural units constituting the polyvinyl acetal resin can be, for example, 10 mol% or more, from the viewpoint of adhesive force, solubility, etc. , 40 mol% or more is preferred, and 50 mol% or more is preferred. In addition, the polyvinyl acetal resin may have a vinyl ester unit [-CH ₂ -CH(OC(=O)-R)-: R represents a hydrocarbon group] as a structural unit. The content of the vinyl ester unit in the total structural units is preferably 0.1 mol% or more and 30 mol% or less from the viewpoint of adhesion, etc., and 0.3 mol% or more and 20 mol% or less is more preferred. .

In the sealant composition of the present invention, in addition to or instead of the polyvinyl acetal resin, a polyvinyl acetal resin obtained by subjecting a polyvinyl acetal resin to carboxylic acid modification by a common method can be used. carboxylic acid modified acetal resin.

Acetal-based resins and carboxylic acid-modified polyvinyl acetal resins can be synthesized by common methods and are also commercially available. Examples of commercially available products include, for example, trade names: S-LEC BX-1, BX-2, BX-5, BX-55, BX-7, BH-3, and BH-S manufactured by Sekisui Chemical Industry Co., Ltd. , KS-3Z, KS-5, KS-5Z, KS-8, KS-23Z; Trade names made by Denki Chemical Industry Co., Ltd.: Denka BUTYLAL 4000-2, 5000A, 6000C, 6000EP, etc. The acetal-based resin having a functional group can be used alone or in combination of two or more types.

[hardening catalyst] The curing catalyst used in the sealant composition of the present invention is not particularly limited as long as it can cure the compound having a cyclic ether group. It is preferable to contain a compound that hardens a compound having a cyclic ether group by heat, a thermal cationic polymerization initiator, etc., and a thermal cationic polymerization initiator is more preferred.

Examples of compounds that harden a compound having a cyclic ether group by heat include tertiary amines such as benzylmethylamine and 2,4,6-benzodimethylaminomethylphenol; 2-methylimidazole, Imidazole compounds such as 3-ethyl-4-methylimidazole and 2-heptadecanylimidazole; Lewis acids such as boron trifluoride‧monethylamine complex and boron trifluoride‧piperazine complex, etc.

The thermal cationic polymerization initiator is a compound that can generate cationic species that initiate polymerization by heating. The thermal cationic polymerization initiator is not particularly limited and can be appropriately selected according to the hardening conditions and the type of the cationically polymerizable compound.

Examples of the thermal cationic polymerization initiator include sulfonium salts, imidazole-based curing catalysts, quaternary ammonium salts, phosphonium salts, diazonium salts, and iodonium salts. Salt etc. Among these, it is preferable to use a sulfonium salt or an imidazole-based curing catalyst from the viewpoint of ease of acquisition and the ability to obtain a cured product having superior adhesiveness and transparency.

Examples of sulfonium salts include triphenylsonium tetrafluoroborate, triphenylsonium hexafluoroantimonate, triphenylsonium hexafluoroarsenate, and gins(4-methoxyphenyl)sonium hexafluoroarsenate. acid salt, diphenyl (4-phenylthiophenyl) sulfonium hexafluoroarsenate, etc.

In addition, as the strontium salt, a commercially available product can also be used. Specific examples of commercially available products include ADEKAOPTON SP-150, ADEKAOPTON SP-170, ADEKAOPTON CP-66, and ADEKAOPTON CP-77 (the above, manufactured by Asahi Denka Co., Ltd.); SANEIDO SI-60L, SANEIDO SI-80L, and SANEIDO SI-100L, SANEIDO SI-B2A, SANEIDO SI-B3 (above, manufactured by Sanshin Chemical Co., Ltd.); CYRACURE UVI-6974, CYRACURE UVI-6990 (above, manufactured by Union Carbide Co., Ltd.), UVI-508, UVI-509 (above) , manufactured by General Electric Co., Ltd.), FC-508, FC-509 (above, manufactured by Minnesota Mining and Manufacturing Co., Ltd.), CD-1010, CD-1011 (above, manufactured by Sastomma Co., Ltd.), CI SERIES (manufactured by Nippon Soda Co., Ltd.) wait.

Examples of the imidazole-based curing catalyst include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecanylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole. methyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, etc.

Specific examples of quaternary ammonium salts include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, and tetraethylammonium tetrafluorophosphate. Borate, tetraethylammonium p-toluenesulfonate, N,N-dimethyl-N-benzylanilinium hexafluoroantimonate , N,N-dimethyl-N-benzylpyridinium tetrafluoroborate, N,N-dimethyl-N-benzylpyridinium hexafluoroantimonate ), N,N-diethyl-N-benzyltrifluoromethanesulfonate, N,N-dimethyl-N-(4-methoxybenzyl)pyridinium hexafluoroantimonate (N, N-dimethyl-N-(4-methoxybenzyl) pyridinium hexafluoroantimonate), N,N-diethyl-N-(4-methoxybenzyl)toluidinium hexafluoroantimonate (N,N-diethyl-N -(4-methoxybenzyl) toluidinium hexafluoroantimonate) etc. Specific examples of the phosphonium salt include ethyltriphenylphosphonium hexafluorantimonate, tetrabutylphosphonium hexafluorantimonate, and the like.

Examples of the diazonium salt include AMERICURE (manufactured by American Can Co., Ltd.), ULTRASET (manufactured by Asahi Denka Co., Ltd.), and the like.

Examples of iodonium salts include diphenyliodonium hexafluoroarsenate, bis(4-chlorophenyl)iodonium hexafluoroarsenate, and bis(4-bromophenyl)iodonium hexafluoroarsenate. , phenyl (4-methoxyphenyl) iodonium hexafluoroarsenate, etc. In addition, as commercially available products, UV-9310C (manufactured by Toshiba Silicone Co., Ltd.), Photoinitiator 2074 (manufactured by Rhone-Poulenc Co., Ltd.), UVE SERIES (manufactured by General Electric Co., Ltd.), and FC SERIES (Minnesota Mining and Manufacturing Co., Ltd.) can also be used. company system), etc. These hardening catalysts can be used individually by 1 type or in combination of 2 or more types.

The content of the hardening catalyst is not particularly limited. It is preferably 0.1 to 15 parts by mass, preferably 1 to 10 parts by mass, and most preferably 1 to 5 parts by mass relative to 100 parts by mass of the cyclic ether compound (A). . When the content of the curing catalyst is at least a certain level, the cyclic ether compound (A) is likely to be sufficiently cured. On the other hand, when the content of the curing catalyst is below a certain level, not only is the stability of the sealant composition less likely to be damaged during storage, but the amount of unreacted curing catalyst remaining in the cured product can be reduced, and the cured product is less likely to be damaged. heat resistance, etc. The hardening catalyst may be composed of only one compound or a combination of two or more compounds.

[Silane coupling agent] The sealant composition of the present invention may further contain a silane coupling agent. By containing a silane coupling agent, a sealant layer with better wet-heat durability can be easily obtained.

As the silane coupling agent, a conventional silane coupling agent can be used. In particular, an organosilicon compound having at least one alkoxysilyl group in the molecule is preferred. Examples of the silane coupling agent include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyl Silane couplings having (meth)acrylyl groups such as methyl diethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, etc. Mixture; Vinyltrimethoxysilane, Vinyltriethoxysilane, Dimethoxymethylvinylsilane, Diethoxymethylvinylsilane, Trichlorovinylsilane, Vinyltrimethoxysilane (2-methyl Silane coupling agents with vinyl groups such as oxyethoxy)silane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 8-glycidoxyoctyltrimethoxysilane, etc. Silane coupling agent based on styryl group; silane coupling agent with styryl group such as p-styryltrimethoxysilane, p-styryltriethoxysilane, etc.; N-(2-aminoethyl)-3-aminopropyl group Methyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3 -Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl‧butylene)propylamine (3-triethoxysilyl-N - (1,3-dimethylbutylidene) propylamine), N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane Silane coupling agents with amine groups such as hydrochloride; 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, etc. with ureido )-based silane coupling agents; silane coupling agents with halogen atoms such as 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, etc.; 3-mercaptopropylmethyldimethoxysilane, Silane coupling agents with mercapto groups such as 3-mercaptopropyltrimethoxysilane; bis (trimethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) Silane coupling agents with sulfide groups such as bis (triethoxysilylpropyl) tetrasulfide; 3-isocyanatopropyltrimethoxysilane (3-isocyanatopropyltrimethoxysilane), 3-isocyanatopropyltriethoxy Silane coupling agents with isocyanato group (isocyanato group) such as 3-isocyanatopropyltriethoxysilane; silane coupling agents with olefins such as allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, etc. Propyl silane coupling agents; 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 sealant composition of the present invention contains a silane coupling agent, the content of the silane coupling agent in the entire sealant composition is preferably 0.01 to 5 mass %, and preferably 0.05 to 1 mass %. Moreover, the content of the silane coupling agent 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). When the content of the silane coupling agent is within the above range, a sealant layer excellent in wet heat durability can be more easily obtained.

The sealant composition of the present invention may also contain solvents. Examples of solvents include aromatic hydrocarbon-based solvents such as benzene and toluene; ester-based solvents such as ethyl acetate and butyl acetate; ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; Aliphatic hydrocarbon-based solvents such as n-pentane, n-hexane, and n-heptane; alicyclic hydrocarbon-based solvents such as cyclopentane, cyclohexane, and methylcyclohexane, 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 account coatability and the like.

The sealant composition of the present invention may contain other components as long as the effects of the present invention are not inhibited. Examples of other components include additives such as ultraviolet absorbers, antistatic agents, light stabilizers, antioxidants, resin stabilizers, fillers, pigments, extenders, and softeners. These can be used individually by 1 type or in combination of 2 or more types. When the adhesive composition of the present invention contains these additives, their content can be appropriately determined according to the purpose.

The sealant composition of the present invention can be prepared by appropriately mixing and stirring predetermined ingredients according to a common method.

[Sealing sheet] The sealing sheet of the present invention is composed of two release films and a sealant layer sandwiched between the two release films. The sealant layer is a sheet-like object having a sealant layer formed from the sealant composition of the present invention. .

The shape, size, etc. of the sealing sheet of the present invention are not particularly limited. Moreover, it can be a thin rectangular thing or a long strip shape. In the specification of this application, "long strip" refers to a shape having a length that is 5 times or more relative to the width, and preferably has a length that is 10 times or more. Specifically, it refers to a shape that can be rolled up. It takes the shape of a film that is long enough to be stored or transported in the form of a roll. The upper limit of the ratio of the length to the width of the film is not particularly limited, but may be, for example, 100,000 times or less.

The thickness of the sealant layer of the sealing sheet of the present invention is usually 1 to 50 μm, preferably 1 to 25 μm, and preferably 5 to 25 μm. A sealing sheet having a sealant layer with a thickness within the above range can be suitably used as a sealing material. The thickness of the sealant layer can be measured in accordance with JIS K 7130 (1999) using a conventional thickness meter.

The release film constituting the sealing sheet functions as a support in the sealing sheet manufacturing step and also functions as a protective sheet for the sealant layer until the sealing sheet is used. In addition, the aforementioned sealing sheet refers to a state before use. When using the sealing sheet of the present invention, the release film is usually peeled off and removed.

As the release film, a conventionally known one can be used. For example, a release film base material having a release layer subjected to release treatment with a release agent can be cited.

Examples of the base material for the release film include paper base materials such as glassine paper, coated paper, and fine paper; and laminated paper in which a thermoplastic resin such as polyethylene is bonded to these paper base materials. ; Plastic films of 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, and alkyds. resin, fluorine resin, etc. The thickness of the release film is not particularly limited, but is usually about 20 to 250 μm.

The sealing sheet of the present invention has one release film on both sides of the sealant layer, and a total of two release films. At this time, the two peeling films may be the same or different. It is preferred that the two peeling films have different peeling forces. Due to the different peeling forces of the two pieces of release film, problems are less likely to occur when using the sealing sheet. That is, by making the peeling force of two peeling films different, the step of peeling off a peeling film initially can be performed more efficiently.

The manufacturing method of the sealing sheet is not particularly limited. For example, the sealing sheet can be manufactured using a casting method. When the sealing sheet is manufactured using the casting method, a conventional method can be used, by applying the sealant composition of the present invention to the base material or the peeling surface of the release film that has been peeled off, and drying the resulting coating film. , and the sealing sheet can be obtained.

Examples of methods for producing the sealant composition include spin coating, spray coating, rod coating, blade coating, roll coating, blade coating, die coating, and gravure coating. Coating method, etc.

Examples of methods for drying the coating film include conventionally known drying methods such as hot air drying, hot roller drying, and infrared irradiation. Conditions for drying the coating film include, for example, 80 to 150° C. for 30 seconds to 5 minutes.

The sealant layer of the sealing sheet of the present invention has thermosetting property. That is, by heating the sealant layer, at least the epoxy group of the compound having a cyclic ether group reacts with the functional group of the binder resin, thereby hardening the sealant layer.

The conditions for thermally hardening the sealant layer are not particularly limited. The heating temperature is usually 80~200℃, preferably 90~150℃. The heating time usually ranges from 30 minutes to 12 hours, preferably 1 to 6 hours.

The hardened sealant layer has excellent adhesive strength. The adhesive strength of the hardened sealant layer is usually 1~20N/25mm, preferably 2.5~15N/25mm, when performing a 180∘ peel test at a temperature of 23°C and a relative humidity of 50%. This 180∘ peel test can be performed, for example, under the conditions of a temperature of 23° C. and a relative humidity of 50%, and based on the adhesive force measurement method described in JIS Z0237:2009.

The sealant layer after hardening treatment has excellent colorless transparency. The total light transmittance of the sealant layer with a thickness of 20 μm after hardening treatment is preferably more than 85%, and preferably more than 90%. There is no special upper limit for total light transmittance, but it is usually below 95%. As described above, the sealant composition of the present invention is used in combination with the binder resin (B) and the cyclic ether compound (A) that is highly compatible with the binder resin (B). As a result, the total light transmittance of the hardened sealant layer becomes higher. The total light transmittance can be measured in accordance with JIS K7361-1:1997.

In addition, the water vapor transmission rate of the hardened sealant layer is usually 0.1~200 g. m ^-2 ． day ^-1 , preferably 0.1~150 g. m ^-2 ． day ^-1 . The water vapor transmission rate can be measured using a conventional gas transmission rate measuring device.

As described above, the cured product of the sealant layer of the sealing sheet of the present invention is excellent in adhesive strength, colorless transparency, and water vapor barrier properties. 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.

3)Sealing body The sealing body of the present invention is a product in which an object to be sealed is sealed using the sealing sheet of the present invention. The sealing body of the present invention has a sealant layer formed of the sealant composition of the present invention that has excellent sealing properties in a wide temperature range of -20°C to +90°C. Excellent sealing performance.

The term "the object to be sealed is 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 sealant layer, and the sealant layer is closely adhered to the object to be sealed and It hardens and will be covered by the seal. Examples of the sealing body of the present invention include, for example, a substrate, a component (sealed object) formed on the substrate, and a sealing material for sealing the component. The sealing material is derived from the present invention. The sealant layer of the sealing sheet (hardened product of the sealant layer).

The substrate is not particularly limited, and various substrate materials can be used. In particular, it is preferable to use a substrate material with high visible light transmittance. In addition, a material with high isolation performance to prevent moisture, gas, etc. from intruding from outside the element, and excellent solvent resistance, weather resistance, etc. is preferred. Specific examples include transparent inorganic materials such as quartz and glass; polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, and polyphenylene sulfide. , polyvinylidene fluoride, cellulose acetate, brominated phenoxy, polyarylimine (aramid), polyimide, polystyrene, polyarylate (polyarylate), polystyrene, poly Transparent plastics such as olefins and the aforementioned gas barrier films. The thickness of the substrate is not particularly limited and can be appropriately selected taking into consideration the light transmittance and the performance of isolating the inside and outside of the element.

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

The method of manufacturing the sealing body of the present invention is not particularly limited. For example, a method of removing a release film of the sealing sheet of the present invention, attaching the exposed sealant layer to the object to be sealed, and curing the sealant layer by heating the obtained sealant. In the present invention, the release sheet on the hardened sealant layer can also be peeled off, and then the gas barrier film can be attached to the exposed sealant layer.

In addition, (α) can also be used to remove one release film of the sealing sheet of the present invention, affix the gas barrier film to the exposed sealant layer, and then remove the other release film and affix the adhesive layer to the exposed sealant layer. On the object to be sealed, the sealant layer of the sealing sheet is hardened by heating the obtained sealing object, and the object to be sealed is sealed using the sealant layer of the sealing sheet; (β) A method of applying one part of the sealing sheet of the present invention to the object to be sealed. The release film is removed, and the exposed sealant layer is attached to the object to be sealed. After that, the other release film is removed, and the gas barrier film is attached to the exposed sealant layer, and the obtained sealant is A method in which the sealant layer of the sealing sheet is hardened by heating, and the sealant layer of the sealing sheet is used to seal the object to be sealed.

The adhesion conditions for adhering the sealant layer of the sealing sheet to the object to be sealed are not particularly limited. The adhesion temperature, for example, can be 23~100°C, preferably 23~80°C, more preferably 23°C~40°C. This adhesion treatment can also be performed while applying pressure. As the hardening conditions when hardening the sealant layer, the conditions described above can be used.

The water vapor transmittance 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/day is preferred. m ² /day or less is preferred, and 0.005 g/m ² /day or less is even more preferred. The gas barrier film has a water vapor transmission rate of 0.1g/m ² /day or less under an environment of 40°C and 90% RH, which can effectively inhibit the intrusion of oxygen, moisture, etc. into the organic EL formed on the substrate. It can effectively suppress the deterioration of electrodes, organic layers, etc. inside components. 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 base material include resin films. Examples of the resin component of the resin film include polyamide, polyamide, polyamide imide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, poly Carbonate, polystyrene, polyether sulfide, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin polymer, aromatic polymer, polyurethane polymer, etc. The thickness of the base material is not particularly limited, but from the viewpoint of thermal shrinkage in the drying step of the sealant layer and versatility, it is preferably 10 to 500 μm, more preferably 10 to 300 μm, and more preferably 15 to 200 μm. The thickness of the base material is not particularly limited, but from the viewpoint of ease of handling, it is preferably 0.5 to 500 μm, more preferably 1 to 200 μm, and more preferably 5 to 100 μm.

The gas barrier layer is not particularly limited in terms of material, etc., 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 "polymer"). layer"). [In this case, the so-called gas barrier layer does not only mean the area that has been modified by ion implantation, etc., but means "including the area that has been modified. The polymer layer of the area"], etc. Among them, a gas barrier layer composed of an inorganic vapor-deposited film or a gas barrier obtained by modifying a polymer layer can be used to efficiently form a thin layer with excellent gas barrier properties. 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 deposition 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, titanium nitride, etc. Inorganic nitrides; inorganic carbides; inorganic sulfides; inorganic nitrogen oxides such as silicon oxynitride; inorganic carbon oxides; inorganic carbon nitrides; inorganic oxygen nitrogen carbides, 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 from the viewpoint of colorless transparency, inorganic vapor-deposited films using inorganic oxides as raw materials are preferred. Or an inorganic evaporated film using inorganic nitride as a raw material is preferred. In addition, the inorganic vapor deposition film may be a single layer or multiple layers.

The thickness of the inorganic vapor-deposited film is usually 1 nm or more and 2000 nm or less, preferably 3 nm or more and 1000 nm or less, preferably 5 nm or more and 500 nm or less, and more preferably 40 nm or more and 500 nm or less, from the viewpoint of gas barrier properties and operability. 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 spraying, thermal CVD (chemical vapor deposition), and plasma CVD. , CVD method such as photo CVD method, atomic layer deposition method (ALD method).

Examples of polymer compounds used in the gas barrier layer formed on the surface of the modified polymer layer include silicon-containing polymer compounds, polyimide, polyamide, and polyamideimide. , polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polystyrene, polyether sulfide, polyphenylene sulfide, polyarylate (polyarylate), acrylic resin, alicyclic hydrocarbon Resins, aromatic polymers, 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 more excellent gas barrier properties. Examples of silicon-containing polymer compounds include polysilazane compounds, polycarbosilane compounds, polysilane compounds, polyorganosiloxane compounds, and poly(disilane) compounds. Poly(disilanylene phenylene)-based compounds and poly(disilanylene ethynylene)-based compounds. Among them, 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 subjecting the layer containing the polysilazane compound to a modification treatment, a layer (silicon oxynitride layer) having oxygen, nitrogen, and silicon as its main constituent atoms can be formed.

Polysilazane-based compounds are polymer compounds having repeating units containing -Si-N- bonds (silazane bonds) in the molecule. Specifically, with 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 are each independent and 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 A non-hydrolyzable group such as an aryl group or an alkylsilyl group.

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 formula (1) may be an inorganic polysilazane in which all Rx, Ry, and Rz are hydrogen atoms, and at least one of Rx, Ry, and Rz is not a hydrogen atom. Any of organopolysilazane.

Furthermore, in the present invention, a modified polysilazane 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, Japanese Patent Application Publication No. 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, Japanese Patent Application Publication No. 4-63833, etc.

Among these, as a polysilazane-based compound, Rx, Ry, and Rz are all fully hydrogenated hydrogen atoms from the viewpoint of ease of acquisition and ability to form an ion implantation layer with excellent gas barrier properties. Polysilazane is preferred.

In addition, as the polysilazane compound, commercially available products as glass coating materials can also be used as they are.

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. Examples of other components include hardeners, other polymers, antioxidants, light stabilizers, flame retardants, and the like.

The content of the polymer compound in the polymer layer is preferably 50 mass% or more, and more preferably 70 mass% or more, from the viewpoint of forming a gas barrier layer with better gas barrier properties.

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 more preferably from 40 nm to 500 nm.

The polymer layer can be coated on the substrate or other layers using a conventional coating method using, for example, a liquid in which a polymer compound is dissolved or dispersed in an organic solvent, and the resulting coating film is dried. And formed.

Specific examples of the organic solvent used depend on the type of base material and polymer compound used, and include aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate; methylethyl solvents; Ketone-based solvents such as ketones; ether-based solvents such as dibutyl ether, ethylene glycol, monobutyl ether, and 1,3-dioxolane; halogenated hydrocarbons such as chlorinated methane, dichloroethane, and dichloromethane. Solvents; aliphatic hydrocarbon solvents such as hexane, etc. These solvents can be used individually by 1 type or in mixture of 2 or more types.

The polymer compound solution can be prepared by dissolving the polymer compound in an organic solvent. The solid content concentration of the polymer compound in the polymer compound solution is preferably 1 to 60 mass %, more preferably 3 to 45 mass %, and more preferably 3 to 30 mass %. When the solid content concentration is within this range, the base material can be appropriately dissolved, and a solution having excellent coating workability can be obtained with an appropriate viscosity. The polymer compound solution may also contain other components such as components that assist dissolution within a range that does not hinder the effects of the present invention.

The method for applying the polymer compound solution to the base material is not particularly limited, and spin coating, spray coating, rod coating, blade coating, roll coating, and blade coating can be used. , die coating method, gravure coating method and other common coating methods.

The drying method of the coating film is not particularly limited, and methods listed as methods for drying conventionally known coating films can be used. The heating temperature is usually 80~150℃, and the heating time is usually 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, as described later, is a method of implanting accelerated ions into a polymer layer to modify the polymer layer. 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, 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 efficiently modifying the polymer layer to its interior without roughening the surface of the polymer layer, and forming a gas barrier layer with more excellent gas barrier properties, a gas barrier layer containing Preferably, the layer of the silicon-containing polymer compound is subjected to ion implantation treatment.

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, Ions of alkane-based gases such as ethane; ions of olefin-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 aromatic hydrocarbon-based gases such as benzene and toluene; ions of cycloalkane-based gases such as cyclopropane; ions of cycloolefin-based gases such as cyclopentene; metal ions; ions of organic silicon compounds, etc. This plasma can be used alone or in combination of two or more types. Among them, ions of rare gases such as argon, helium, neon, krypton, and xenon are preferred because ions can be implanted more easily and a gas barrier layer with better gas barrier properties can be formed.

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 a method of irradiating ions accelerated by an electric field (ion beam), a method of implanting ions in plasma (plasma ions), and the like. Among them, the latter method of implanting plasma ions (plasma ion implantation method) is preferable from the viewpoint of being able to easily form the target gas barrier layer.

The plasma ion implantation method, for example, generates plasma in an environment containing a plasma-generating gas such as a rare gas, and applies a negative high-voltage pulse to the polymer layer, whereby the plasma can be neutralized. ions (cations) are implanted into the surface of the polymer layer. More specifically, the plasma ion implantation method can be implemented using the method described in pamphlet WO2010/107018 or the like.

Through ion implantation, the thickness of the region where ions are implanted can be controlled by implantation conditions such as ion species, applied voltage, and processing time, and depends on the thickness of the polymer layer and the purpose of use of the gas barrier film. Just decide, usually 10nm or more and 400nm or less.

Implantation of ions can be confirmed by performing elemental analysis and measurement from the surface of the polymer layer to around 10 nm using X-ray photoelectron spectroscopy (XPS).

The sealing body of the present invention is a sealed object sealed using the sealing sheet of the present invention. Therefore, the sealing body of the present invention can continuously 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. The parts and % in each example are based on quality unless notified in advance.

[Storage modulus measurement method] (1) Storage modulus before hardening The storage modulus before hardening is obtained by processing the sealant compositions obtained in the Examples and Comparative Examples into a sheet shape and laminating the sealing sheet to a sample thickness of 1 mm using a laminating machine at 23°C. This substance was used as a measurement sample and measured. That is, a storage modulus measuring device (manufactured by Anton Paar, product name: Physica MCR301) was used to obtain an elastic modulus value of 23°C under the conditions of frequency 1Hz, deformation 1%, and temperature rise rate 3°C/min. . (2) Storage modulus after hardening [Determination of storage modulus of hardened sealing sheet] The storage modulus after hardening is a sealing sheet obtained by processing the sealant composition obtained in the Examples and Comparative Examples into a sheet shape, laminating it to a sample thickness of 200 μm using a laminating machine at 23°C, and then laminating it at 100 The sealant layer of the sealing sheet was cured under curing conditions of 1 hour at 10° C., and this was used as a measurement sample for measurement. That is, using a storage modulus measuring device (manufactured by TA Instruments, product name: DMAQ800), under the conditions of a frequency of 11 Hz, an amplitude of 5 μm, and a temperature rise rate of 3°C/min, a temperature range of -20°C to +90°C was obtained. The value of the elastic modulus.

[Evaluation test of organic EL elements] Glass having a film-formed indium tin oxide (ITO) film (thickness: 100 nm; sheet resistance: 50Ω/□ (ohms per square, ohms per square)) was produced using the following method. The substrate serves as the anode for the organic EL element. First, N,N'-bis(1-naphthyl)-N,N'-bis(phenyl)-benzidine) is evaporated sequentially on the ITO film of the aforementioned glass substrate at a speed of 0.1~0.2nm/min. (N,N'-bis(1-naphthyl)-N,N'-bis(phenyl)-benzidine); manufactured by Luminescence Technology Co., Ltd.) evaporated 50 nm, and ginseng (8-hydroxy-quinolinic acid) aluminum (tris ( 8-hydroxy-quinolinate) aluminum; Lumine scence Technology Co., Ltd.) 50nm to form a light-emitting layer. On the obtained light-emitting layer, lithium fluoride (LiF) (manufactured by High Purity Chemical Research Institute Co., Ltd.) was used as an electron implant material, and was formed into a thickness of 4 nm at a speed of 0.1 nm/min. After that, aluminum (Al) (high (manufactured by Purity Chemical Laboratory Co., Ltd.) was evaporated to a thickness of 100 nm at a rate of 0.1 nm/min to form a cathode, thereby obtaining an organic EL element. In addition, the degree of vacuum during vapor deposition was all 1×10 ^-4 Pa or less.

One piece of the release film of the sealing sheet obtained in the Example or Comparative Example was peeled off, the exposed sealant layer was overlapped on the metal foil film, and these were adhered using a laminating machine at 23°C. After that, the other release film was peeled off, and the exposed sealant layer was overlapped so as to cover the organic EL element formed on the glass substrate, and these were adhered using a laminating machine at 23°C. Afterwards, the sealant layer is heated at 100° C. for 2 hours to harden the sealant layer, thereby obtaining a bottom emission electronic device with a sealed organic EL element. After the electronic device was allowed to stand for 250 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-luminescent areas) was observed, and evaluation was performed based on the following criteria. ○: The dark spot is less than 40% of the luminous area. △: Dark spots are more than 40% and less than 50% of the luminous area ╳: The dark spot is more than 50% of the luminous area

[Example 1] 100 parts of modified olefin-based resin (acid-modified α-olefin polymer, manufactured by Mitsui Chemicals Co., Ltd., trade name: UNISTOLE H-200, weight average molecular weight: 52,000, functional group: carboxyl group) as a binder component, with ring 100 parts of an ether-like compound (manufactured by Nissan Chemical Co., Ltd., trade name: TEPIC-FL, weight average molecular weight: 525, functional group: epoxypropyl group), cationic polymerization initiator as a hardening catalyst (Sanshin Chemical Industry 1 part of silane coupling agent (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: KBM4803) was dissolved in methyl ethyl ketone to prepare a coating with a solid content concentration of 30%. liquid. This coating liquid 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 sealant layer with a thickness of 10 μm. , the release-treated surface of another release film (manufactured by LINTEC, product name: SP-PET381031) was bonded thereto to obtain the sealing sheet 1.

[Example 2] In Example 1, the sealing sheet 2 was obtained in the same manner as in Example 1, except that the amount of the compound having a cyclic ether group was changed to 150 parts.

[Example 3] In Example 1, the sealing sheet 3 was obtained in the same manner as in Example 1 except that the amount of the curing catalyst was changed to 1.5 parts.

[Example 4] 100 parts of phenoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name: YX7200B35, weight average molecular weight: 30000, functional group: glycidyl) as a binder component and a compound having a cyclic ether group (hydrogenated bisphenol A 250 parts of type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name: YX8034, molecular weight: 540, functional epoxy group), imidazole-based curing catalyst as a curing catalyst (manufactured by Shikoku Kasei Co., Ltd., trade name: CUREZOLE 2E4MZ ) 2 parts and 0.2 parts of silane coupling agent (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: KBM4803) were dissolved in methyl ethyl ketone to prepare a coating liquid with a solid content concentration of 35%. This coating liquid 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 sealant layer with a thickness of 10 μm. , the release-treated surface of another release film (manufactured by LINTEC, product name: SP-PET381031) was bonded thereto to obtain the sealing sheet 4.

[Example 5] In Example 4, a sealing sheet was obtained in the same manner as in Example 4, except that 2 parts of a cationic polymerization initiator (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SAN-AID SI-B3) was used as the curing catalyst. 5.

[Example 6] In Example 4, 100 parts of hydrogenated bisphenol A-type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name: YX8034) and dicyclopentadiene-type epoxy resin (manufactured by ADEKA Co., Ltd., trade name: EP-4088L, molecular weight : 330, functional group: epoxy group) 100 parts as a compound having a cyclic ether group, use a cationic polymerization initiator (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SAN-AID SI-B2A) 1 part as a hardening contact The sealing sheet 6 was obtained in the same manner as in Example 4 except that the medium was used.

[Example 7] In Example 4, 100 parts of phenoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name: YX7200B35, weight average molecular weight: 30000, functional group: glycidyl) and acetal resin (manufactured by Sekisui Chemical Co., Ltd., trade name: Sealing sheet 7 was obtained in the same manner as in Example 4 except that 30 parts of KS-5Z (functional group: hydroxyl group) was used as the adhesive component.

[Example 8] In Example 1, the binder component was changed to 100 parts of phenoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: YX6954BH30, weight average molecular weight: 39,000, functional group: glycidyl), and The compound was changed to 200 parts of hydrogenated bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name: YX8000, molecular weight: 357, functional group: epoxy group), and the curing catalyst was changed to a cationic polymerization initiator (three Manufactured by Shin Chemical Industry Co., Ltd., trade name: SAN-AID SI-B3) 2.5 parts, except having carried out similarly to Example 1, and obtained the sealing sheet 8.

[Example 9] In Example 8, the binder components were changed to 100 parts of phenoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: YX7200B35), the amount of the cyclic ether compound was changed to 130 parts, and the amount of curing catalyst was changed to 3.8 Except for this, the sealing sheet 9 was obtained in the same manner as in Example 8.

[Example 10] In Example 8, the same procedure as Example 8 was performed except that the binder component was changed to 100 parts of phenoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: YX7200B35) and the amount of curing catalyst was changed to 5 parts. The sealing sheet 10 is obtained by proceeding as follows.

[Example 11] In Example 10, the binder component was changed to 100 parts of phenoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., trade name: ZX-1356-2, weight average molecular weight: 65,000, functional group: epoxypropyl), Except for this, the sealing sheet 11 was obtained in the same manner as in Example 4.

[Comparative example 1] In Example 1, the sealing sheet 1r was obtained in the same manner as in Example 1 except that a curing catalyst was not used.

[Comparative example 2] In Example 1, the sealing sheet 2r was obtained in the same manner as in Example 1 except that the amount of the compound having a cyclic ether group was changed to 25 parts and the amount of the curing catalyst was changed to 0.01 part.

[Comparative example 3] In Example 4, the sealing sheet 3r was obtained in the same manner as in Example 4 except that a curing catalyst was not used.

[Comparative example 4] In Example 8, the amount of the compound having a cyclic ether group was set to 90 parts, and 0.01 part of the cationic polymerization initiator (manufactured by Sanshin Chemical Industry Co., Ltd., trade name: SAN-AID SI-B2A) was used as the curing catalyst. , Except for this, the same procedure as in Example 8 was performed to obtain the sealing sheet 4r.

The storage modulus of the sealant layer of the sealing sheets of Examples 1 to 11 and Comparative Examples 1r to 4r at 23°C before curing and the storage modulus at -20°C and +90°C after curing, and the organic EL The device (OLED) evaluation test results are shown in Table 1 and Table 2 below.

[Table 1]

[Table 2]

From Table 1, it is known that the storage modulus of the sealant layer of the sealing sheets of Examples 1 to 11 before hardening at 23°C is in the range of 6×10 ⁵ Pa to 8×10 ⁷ Pa, and the sheet formability is excellent. In addition, the storage modulus after hardening at -20°C is in the range of 8×10 ⁸ Pa ~ 9×10 ⁹ Pa, and the storage modulus after hardening at +90°C is in the range of 2×10 ⁸ Pa ~ 5×10 ⁹ The range of Pa. Generally, since the storage modulus tends to increase as the temperature decreases, the storage modulus after curing near room temperature (23°C) becomes the storage modulus after hardening at -20°C and +90°C. The middle value of the number. Therefore, it was found that the sealing sheets of Examples 1 to 11 have excellent sealing properties in a wide temperature range from -20°C to +90°C (especially the sealing sheets of Examples 1 to 7 before hardening at 23°C). The storage modulus is in the range of 6×10 ⁵ Pa to 4×10 ⁶ Pa, and the sheet formability and sealing properties are better). This situation can also be seen from the fact that the dark spots in the OELD test are less than 40% of the luminous area, and all evaluations are "○". On the other hand, for the sealing sheets of Comparative Examples 1r to 4r, the storage modulus at +90°C after hardening was a relatively low value of 5×10 ⁴ Pa to 5×10 ⁵ Pa, and the sealing properties were poor. In the OELD test, the dark spots were more than 40% and less than 50% of the light-emitting area, and were evaluated as "△" (Comparative Examples 2 and 4). The dark spots were more than 50% of the light-emitting area, and were evaluated as "╳" (Comparative Examples 2 and 4). Examples 1 and 3).

without.

without.

Claims (17)

A sealing sheet composed of two release films and a sealant layer sandwiched between the release films. The sealant layer is formed using the following sealant composition 1. The sealant combination Substance 1: A sealant composition containing a compound having a cyclic ether group and a binder resin having a functional group that can undergo a curing reaction with the compound having a cyclic ether group. The average weight of the binder resin having the functional group The molecular weight (Mw) is 10,000~1,000,000. The aforementioned binder resin with functional groups is at least one selected from the group consisting of olefin resin, phenoxy resin and acetal resin. Storage at 23°C before hardening The modulus is 10 ⁴ Pa or more, and the storage modulus after hardening in the temperature range from -20°C to +90°C is 10 ⁸ Pa or more. For the sealing sheet described in item 1 of the patent application, the thickness of the sealant layer is 1~25 μm. As for the sealing sheet described in item 1 of the patent application, the storage modulus of the aforementioned sealant composition 1 before hardening at 23°C is 1×10 ⁷ Pa or less. The sealing sheet described in claim 1, wherein the content of the compound having a cyclic ether group is 45 to 90 mass % in terms of solid content relative to the entire sealant composition 1. In the sealing sheet described in Item 1 of the patent application, the content of the aforementioned binder resin having a functional group is 5 to 50 mass % in terms of solid content relative to the entire sealant composition 1. For the sealing sheet described in Item 1 of the patent application, the content of the compound having a cyclic ether group is 110 to 1800 parts by mass relative to 100 parts by mass of the binder resin having a functional group. The sealing sheet as described in item 1 of the patent application, wherein the compound with a cyclic ether group is liquid at 25°C, and the content of the compound with a cyclic ether group is relative to the sealant combination. The solid content of the entire substance 1 is 53% by mass or more. The sealing sheet according to claim 1, wherein the compound having a cyclic ether group includes an epoxy resin having a glycidyl ether group. For the sealing sheet described in item 1 of the patent application, the molecular weight of the compound having a cyclic ether group is 100 to 5,000. The sealing sheet described in claim 1, wherein the functional group of the binder resin having functional groups is at least one selected from the group consisting of carboxyl groups, acid anhydride groups, epoxy groups and hydroxyl groups. For example, in the sealing sheet described in Item 1 of the patent application, the glass transition temperature (Tg) of the aforementioned binder resin is above 90°C. The sealing sheet according to claim 1, wherein the content of the liquid compound having a cyclic ether group contained in the sealant composition 1 is 65% by mass or less. The sealing sheet according to claim 1, wherein the sealant composition 1 further contains a hardening catalyst. For the sealing sheet described in Item 13 of the patent application, the content of the hardening catalyst is 0.01 to 15 parts by mass relative to 100 parts by mass of the compound having a cyclic ether group. The sealing sheet according to claim 1, wherein the sealant composition 1 further contains a silane coupling agent. The sealing sheet described in Item 15 of the patent application, wherein the content of the silane coupling agent is 0.01 to 5 mass % based on the solid content of the entire sealant composition 1. A sealing body is formed by sealing a sealed object using a sealing sheet as described in any one of items 1 to 16 of the patent application.