TW201837144A - Adhesive composition, sealing sheet and sealed body - Google Patents

Abstract

The present invention relates to: an adhesive composition which contains a rubber-based resin (component (A)), a curable resin (component (C)) and an allophanate-based crosslinking agent (component (D)); a sealing sheet which comprises an adhesive layer that is formed using this adhesive composition; and a sealed body which is obtained by sealing an object to be sealed with use of this sealing sheet. The present invention provides: an adhesive composition which does not decrease in the adhesive force even under high humidity conditions; a sealing sheet which comprises an adhesive layer that is formed using this adhesive composition; and a sealed body which is obtained by sealing an object to be sealed with use of this sealing sheet.

Description

   Adhesive composition, sealing sheet and sealing body   

The present invention relates to an adhesive composition that does not decrease in adhesion even when placed under high humidity conditions, a sealing sheet having an adhesive layer formed using the adhesive composition, and an object to be sealed sealed by the sealing sheet. The sealed body.

In recent years, organic EL devices have attracted attention as light-emitting devices capable of emitting light with high luminance driven by a low-voltage DC.

However, the organic EL element has a problem that light emission characteristics such as light emission brightness, light emission efficiency, and light emission uniformity tend to decrease with time.

As a cause of the problem of the decrease in light emission characteristics, it is presumed that oxygen, moisture, or the like is immersed in the organic EL element to deteriorate the electrode or the organic layer. Therefore, in order to solve this problem, it is proposed to use an adhesive sheet having excellent moisture shielding properties as a sealing material.

In addition, when manufacturing a display device such as a liquid crystal display panel (LCD) or a touch panel, an adhesive sheet for bonding optical members can be used. However, in recent years, in order to suppress mechanical deterioration of optical members, moisture shielding properties have been required. Best adhesive sheet.

As an adhesive sheet having such characteristics, Patent Document 1 describes an adhesive sheet containing a rubber-based resin as a main component, which has specific adhesive properties and the like.

It is described in this document that this adhesive sheet is an adhesive sheet with low water vapor permeability. Even when it is exposed to moist heat (when placed in a high-humidity environment), it still has sufficient adhesion and inhibits yellowing when it encounters moist heat. Since these characteristics are easily exhibited, it is preferable that the adhesive sheet contains a silane coupling agent in addition to the rubber-based resin.

[Prior technical literature]

[Patent Literature]

Patent Document 1: Japanese Patent Application Laid-Open No. 2016-53157.

As described in Patent Document 1, an adhesive composition using a rubber-based resin as a main component tends to be able to obtain an adhesive sheet having excellent moisture shielding properties.

However, according to the research by the present inventors, it was found that even if an adhesive composition containing a rubber-based resin as a main component and containing a silane coupling agent still has a reduced adhesive force after being placed under high humidity conditions. Then, a sealing sheet having an adhesive layer formed using such an adhesive composition is prone to blistering or embossing when placed under high humidity conditions.

The present invention has been made with a view to solving these problems, and an object thereof is to provide an adhesive composition that does not decrease in adhesion even under high humidity conditions, and has an adhesive formed by using the adhesive composition. Layer sealing sheet, and a sealed body in which the object to be sealed is sealed with the sealing sheet.

In addition, in the present invention, "the adhesive force of the adhesive composition will not decrease" means that the adhesive force of the adhesive layer formed by using the adhesive composition will not decrease. In addition, similarly, the characteristics of the adhesive layer may be described in this specification as the characteristics of the adhesive composition.

As a result of careful research in order to solve the above-mentioned problems, the inventors have found that the adhesive composition containing a rubber-based resin and a specific additive does not decrease the adhesive force even under a high humidity condition, and completed the present invention.

Therefore, according to the present invention, the following adhesive compositions of [1] to [12], the sealing sheets of [13] to [16], and the sealing bodies of [17] and [18] are provided.

[1] An adhesive composition containing the following (A) component, (C) component, and (D) component: (A) component: rubber-based resin; (C) component: curable resin; (D) Ingredients: Uremate-based crosslinking agent.

[2] The adhesive composition according to [1], wherein the component (A) is butyl rubber.

[3] The adhesive composition according to [1], further comprising the following component (B), (B) component: a tackifier.

[4] The adhesive composition according to [3], wherein the component (B) is an aliphatic petroleum resin.

[5] The adhesive composition according to [3], wherein the content of the component (B) is 1 to 50 parts by mass based on 100 parts by mass of the component (A).

[6] The adhesive composition according to [1], wherein the component (C) is a polymer having hydroxyl groups at both ends.

[7] The adhesive composition according to [1], wherein the content of the component (C) is 1 to 50 parts by mass based on 100 parts by mass of the component (A).

[8] The adhesive composition according to [1], wherein the component (D) is a urethane-modified hexamethylene diisocyanate.

[9] The adhesive composition according to [1], wherein the content of the component (D) is 1 to 70 parts by mass based on 100 parts by mass of the component (A).

[10] The adhesive composition according to [1], further comprising the following component (E), (E) component: a silane coupling agent.

[11] The adhesive composition according to [10], wherein the component (E) is a compound represented by the following formula (1),

(R ¹ represents an alkylene group having 3 or more carbon atoms, R ² represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ³ represents an alkyl group having 1 to 4 carbon atoms, Z represents a group containing a reactive group, and n is 0 or 1).

[12] The adhesive composition according to [10], wherein the content of the component (E) is 0.01 to 7 parts by mass based on 100 parts by mass of the component (A).

[13] A sealing sheet, which is a sealing sheet composed of two release films and an adhesive layer held between the release films, wherein the adhesive layer is as described in any one of [1] to [12]. Formed by an adhesive composition.

[14] A sealing sheet is a sealing sheet made of a release film, a gas barrier film, and an adhesive layer held between the release film and the gas barrier film, and the adhesive layer is used [1] ~ [ 12] Formed by the adhesive composition according to any one of the above.

[15] The sealing sheet according to [14], wherein the gas barrier film is a metal foil, a resin film, or a thin-film glass.

[16] The sealing sheet according to [13] or [14], wherein the thickness of the adhesive layer is 1 to 50 μm.

[17] A sealed body which is sealed by using the sealing sheet according to any one of [13] or [14].

[18] The sealed body according to [17], wherein the object to be sealed is an organic EL element, an organic EL display panel element, a liquid crystal display panel element, or a solar cell element.

According to the present invention, there is provided an adhesive composition that does not decrease in adhesion even when placed under high humidity conditions, a sealing sheet having an adhesive layer formed using the adhesive composition, and the object to be sealed is sealed as described above. A sealed body formed by sheet sealing.

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

1) Adhesive composition

The adhesive composition system of this invention contains the following (A) component, (C) component, and (D) component: (A) component: rubber-type resin; (C) component: curable resin; (D) component : Uremate-based crosslinking agent.

[(A) Component: Rubber-based resin]

The adhesive composition of the present invention contains a rubber-based resin as the (A) component.

Since the adhesive composition of the present invention contains a rubber-based resin, it is excellent in moisture shielding properties.

Examples of the rubber-based resin include natural rubber, and one or two or more monomers selected from alkyl (meth) acrylate, styrene, and (meth) acrylonitrile are graft-polymerized in the natural rubber. Modified natural rubber, polyisobutylene resin, butadiene rubber, chloroprene rubber, isoprene rubber, styrene-butadiene copolymer (SBR), styrene-isoprene copolymer, Acrylonitrile-butadiene copolymer (nitrile rubber), methyl methacrylate-butadiene copolymer, urethane rubber, styrene-1,3-butadiene-styrene block copolymer (SBS) , Styrene-isoprene-styrene block copolymer (SIS), ethylene-propylene-non-conjugated diene terpolymer, and the like. These rubber-based resins can be used alone or in combination of two or more. Among these, a polyisobutylene-based resin is preferred as the rubber-based resin.

The polyisobutylene resin refers to a polymer (including the concept of a copolymer) containing isobutylene as a monomer component, and may be a homopolymer made of only isobutylene as a monomer component, or isobutene and other components as monomer components. A copolymer obtained by polymerizing monomers. The polyisobutylene-based resin may be a part of the brominated or chlorinated halogenated polyisobutylene-based resin, or may be partially substituted with a functional group such as a hydroxyl group or a carboxyl group.

Examples of the other monomer include isoprene, n-butene, butadiene, and styrene. Other monomers may be used alone or in combination of two or more. When the polyisobutylene-based resin is a copolymer, among the raw material monomers, the maximum amount of the isobutylene-based monomer is the main component.

Among the above, from the viewpoint of good moisture shielding property, the polyisobutylene resin is a homopolymer in which the monomer component is only isobutylene, and isobutylene-isoprene obtained by polymerizing isobutylene and isoprene as the monomer components. A pentadiene copolymer (butyl rubber) is preferred.

Among these, from the standpoint of improving the durability and weather resistance of the formed adhesive layer, the polymer has a dense molecular structure when it contains a large amount of polymer, and polymerizable double bonds do not remain in the main chain and side chains. Isobutylene is preferred.

The content of the constituent units made of isobutene having no polymerizable double bond remaining in the main chain and the side chain is preferably 80 to 99% by mass, and more preferably 90 to 99% by mass relative to all the constituent units of the polyisobutylene resin. %, More preferably 95 to 99% by mass.

The polyisobutylene-based resin can be obtained, for example, by a method of polymerizing a monomer component such as isobutylene in the presence of a Lewis acid catalyst such as aluminum chloride or boron trifluoride.

The mass average molecular weight (Mw) of the rubber-based resin is preferably 10,000 to 3,000,000, and more preferably 20,000 to 1,000,000.

In the present invention, the mass average molecular weight (Mw) is subjected to gel permeation chromatography (GPC), and can be obtained as a standard polystyrene conversion value.

[(C) component: curable resin]

The adhesive composition of this invention contains a curable resin as (C) component.

Since the adhesive composition of the present invention contains a curable resin, the adhesive composition does not easily decrease in adhesion even under high humidity conditions.

The curable resin refers to a polymer having two or more functional groups capable of reacting with the urethane-based crosslinking agent of the component (D). Examples of the related functional group include a hydroxyl group.

Examples of the curable resin include polycarbonate polyol, polyether polyol, polyester polyol, polylactone polyol, polydiene polyol, hydrogenated polydiene polyol, and polycrystalline silicon having hydroxyl groups at both ends. Equal to polymers with hydroxyl groups at both ends.

The curable resin may be used alone or in combination of two or more.

Among these, a polydienepolyol or a hydrogenated polydienepolyol is preferred because it is easy to obtain an adhesive composition that is not easily reduced in adhesion even under high humidity conditions.

Examples of the polydiene polyol include polybutadiene polyol and polyisoprene polyol.

Examples of the hydrogenated polydiene polyol include hydrogenated polybutadiene polyol and hydrogenated polyisoprene polyol.

As the polydiene polyol or hydrogenated polydiene polyol, a commercially available product can be used.

Examples of related commercial products include Nisso PB G-1000, G-2000, G-3000, manufactured by Japan Soda Co., Ltd., Poly bd R-15HT, R-45HT, and Cray manufactured by Idemitsu Kosan Co., Ltd. Krasol LBH2000, LBH-P2000, LBH3000, LBH-P3000 (Polybutadiene Polyol) manufactured by Valley Corporation, NISSO PB GI-1000, GI-2000, GI-3000, Mitsubishi Chemical Corporation POLYTAIL H, Ltd., Krasol HLBH-P2000, HLBH-P3000 (Hydrogenated Polybutadiene Polyol) manufactured by Cray Valley, Poly ip (Polyisoprene Polyol) manufactured by Idemitsu Kosan Co., Ltd. , EPOL (hydrogenated polyisoprene polyol) manufactured by Idemitsu Kosan Co., Ltd. and the like.

The mass average molecular weight (Mw) of the curable resin is preferably 1,000 to 5,000, and more preferably 1,000 to 4,000. Since the mass average molecular weight (Mw) of the curable resin is within the above range, an adhesive composition having better adhesive force can be obtained.

The content of the curable resin is not particularly limited, but it is usually 1 to 50 parts by mass and preferably 5 to 40 parts by mass based on 100 parts by mass of the component (A).

The content of the hardening resin is 1 part by mass or more with respect to 100 parts by mass of the component (A), which can effectively form an adhesive layer with better adhesion. Since the content is 50 parts by mass or less, aggregation of the adhesive layer can be avoided. Force is reduced.

[(D) component: Urea-based crosslinking agent]

The adhesive composition of this invention contains a urethane type crosslinking agent as (D) component.

The urethane-based crosslinking agent can form a crosslinked structure with the component (C), and the adhesive layer system obtained by using the adhesive composition of the present invention containing these components has high cohesive force, Those who do not easily reduce adhesion under high humidity conditions.

The urethane-based cross-linking agent is a modified form of a polyisocyanate and contains a urethane bond (hereinafter, referred to as a "ureate-modified polyisocyanate").

The urethane-modified polyisocyanate can be obtained, for example, by reacting a polyisocyanate compound with a monoalcohol compound and / or a polyhydric alcohol compound in the presence of a urethane-forming catalyst.

The urethanization catalyst can be appropriately selected from known catalysts such as a metal salt of a carboxylic acid.

Polyisocyanate compounds are compounds having at least two isocyanate groups in the molecule. Examples of the polyisocyanate compound include an aromatic polyisocyanate, an aromatic aliphatic polyisocyanate, an alicyclic polyisocyanate, and an aliphatic polyisocyanate.

Examples of the aromatic polyisocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-xylene diisocyanate (MDI), 2, 4- or 2 Aromatic diisocyanates such as 1,6-benzylidene diisocyanate (TDI) or mixtures thereof, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate; trimethylbenzene-4, Aromatic triisocyanates such as 4 ', 4 ”-triisocyanate, 1,3,5-triisocyanate benzene, 2,4,6-triisocyanate toluene; 4,4'-xylene-2,2', 5,5 Aromatic tetraisocyanate and the like such as' -tetraisocyanate.

Examples of the aromatic aliphatic polyisocyanate include 1,3- or 1,4-xylylene diisocyanate (XDI) or a mixture thereof, and ω, ω'-diisocyanate-1,4-diethylbenzene Aromatic aliphatic diisocyanates such as 1,3- or 1,4-bis (1-isocyanate-1-methylethyl) benzene (TMXDI) or mixtures thereof; 1,3,5-triisocyanate methylbenzene And other aromatic aliphatic triisocyanates.

Examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, and 3-isocyanate methyl-3,5 , 5-trimethylcyclohexyl isocyanate (IPDI), 4,4'-methylenebis (cyclohexyl isocyanate) (H ₁₂ MDI), methyl-2,4-cyclohexane diisocyanate, methyl-2 Cycloaliphatic diisocyanate, 1,6-cyclohexane diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane (H ₆ XDI) or mixtures of these: 1,3,5 -Triisocyanate cyclohexane, 1,3,5-trimethyl isocyanate cyclohexane, 2- (3-isocyanatepropyl) -2,5-bis (isocyanatemethyl) -bicyclic (2.2.1) Heptane, 2- (3-isocyanatopropyl) -2,6-bis (isocyanatemethyl) -bicyclo (2.2.1) heptane, 3- (3-isocyanatepropyl) -2,5- Bis (isocyanatomethyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2. 1) heptane, 6- (2-isocyanateethyl) -2-isocyanatemethyl-3- (3-isocyanatepropyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanate group Ethyl) -2-isocyanate Ester methyl-2- (3-isocyanatepropyl) -bicyclo (2.2.1) -heptane, 6- (2-isocyanateethyl) -2-isocyanatemethyl-2- (3- Alicyclic triisocyanates such as isocyanatopropyl) -bicyclo (2.2.1) heptane and the like.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, and 1,2 -Butene diisocyanate, 2,3-butene diisocyanate, 1,3-butene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6 -Aliphatic diisocyanates such as diisocyanate methylhexanoic acid; lysine triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate- Aliphatic triisocyanates such as 4-isocyanate methyloctane, 1,3,6-triisocyanate hexane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyloctane Wait.

Among these, as the polyisocyanate compound, an aliphatic polyisocyanate is preferred, and hexamethylene diisocyanate is preferred.

The polyisocyanate compound may be used singly or in combination of two or more kinds.

Examples of the unit alcohol compound include aliphatic unit alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, and octanol; and alicyclic unit alcohols such as cyclopentanol and dimethylcyclohexanol. ; Aromatic aliphatic unit alcohols such as benzyl alcohol; phenols such as phenol and cresol.

Examples of the polyol compound include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,6-hexanediol, and neopentyl glycol. , Diethylene glycol, triethylene glycol, dipropylene glycol, cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1 Diol compounds such as octene-3,8-diol, dihydroxyethoxytoluene, xylene glycol, dihydroxyethylene glycol terephthalate; glycerol, 2-methyl-2 -Hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, 1,1,1-ginsyl (hydroxymethyl) propane, Triol compounds such as 2,2-bis (hydroxymethyl) -3-butanol; neopentyl tetraol, D-sorbitol, xylitol, D-mannitol and other polyhydric alcohols having 4 or more hydroxyl groups, etc. .

The content of the urethane-based crosslinking agent is not particularly limited, but it is usually 1 to 70 parts by mass and preferably 5 to 60 parts by mass based on 100 parts by mass of the component (A).

The content of the urethane-based cross-linking agent is 1 part by mass or more relative to 100 parts by mass of the component (A), and the crosslinked structure can be sufficiently formed. Since it is 70 parts by mass or less, the cohesive force of the adhesive layer can be avoided. The reduction.

The adhesive composition of the present invention preferably contains a thickener as the component (B) in addition to the components (A), (C), and (D).

Since the adhesive composition of the present invention contains a tackifier, it has a good moisture shielding property and a high adhesive force.

The tackifier is not particularly limited as long as the tackiness of the tackifier layer can be improved, and a known one can be used. Examples of the tackifier include alicyclic petroleum resins, aliphatic petroleum resins, terpene resins, ester resins, coumarone-indene resins, rosin resins, epoxy resins, phenol resins, acrylic resins, Butyral resin, olefin resin, chlorinated olefin resin, vinyl acetate resin, and these modified resins or hydrogen-added resins.

Among these, an aliphatic petroleum resin is preferred because it has better moisture shielding properties and is easy to obtain an adhesive composition with high adhesion.

Tackifiers can be used alone or in combination of two or more.

As the thickener, a commercially available product can be used as it is. Examples of commercially available products include aliphatic petroleum resins such as ESCOREZ 1000 series (manufactured by Exxon Chemical), Quintone A, B, R, CX series (manufactured by ZEON, Japan); ARKONP, M series (manufactured by Arakawa Chemical Co., Ltd.) ), ESCOREZ series (manufactured by Exxon Chemical), EASTOTAC series (manufactured by Eastman Chemical), IMARV series (manufactured by Idemitsu Kosan Co., Ltd.) and other alicyclic petroleum resins; YS RESIN P, A series (manufactured by Anhara Oil & Fats Co., Ltd.), Teronene resins such as Clearon P series (manufactured by YASUHARA CHEMICAL), Piccolyte A, C series (manufactured by Hercules); Foral series (manufactured by Hercules), PENSEL A series, ESTER GUM, SUPER ESTER, and PINECHRYSTAL Manufactured) and other ester resins.

The mass average molecular weight (Mw) of the thickener is preferably 100 to 10,000, and more preferably 500 to 5,000.

The softening point of the thickener is preferably 50 to 160 ° C, more preferably 60 to 140 ° C, and even more preferably 70 to 130 ° C.

The content of the thickener is not particularly limited, but it is usually 1 to 50 parts by mass and preferably 5 to 45 parts by mass with respect to 100 parts by mass of the component (A).

Since the content of the tackifier is 1 part by mass or more relative to 100 parts by mass of the component (A), an adhesive layer with better adhesion can be efficiently formed, and since the content is 50 parts by mass or less, aggregation of the adhesive layer can be avoided Reduced force.

[Other ingredients]

In addition to the components (A) and (C), the component (D), and the component (B) added as necessary, the adhesive composition of the present invention preferably contains a silane coupling agent as the component (E).

Since the adhesive composition of the present invention contains a silane coupling agent, the adhesive force tends to be further improved under normal temperature, high temperature and high humidity environments.

As the silane coupling agent, a conventional silane coupling agent can be used and is not particularly limited. Among them, a silane compound represented by the following formula (1) is preferred.

[Chemical 2]

In formula (1), R ¹ represents an alkylene group having 3 or more carbon atoms, R ² represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ³ represents an alkyl group having 1 to 4 carbon atoms. Z represents a group containing a reactive group, and n is 0 or 1.

The carbon number of the alkylene group represented by R ¹ is 3 or more, preferably 3 to 20, and more preferably 4 to 15.

Since the number of carbons of the alkylene group is 3 or more, it becomes easy to initiate a crosslinking reaction.

Examples of the alkylene group represented by R ¹ include trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and the like. Decamethylene and so on.

The carbon number of the monovalent hydrocarbon group represented by R ² is 1 to 10, preferably 1 to 6, and more preferably 1 to 4.

Examples of the monovalent hydrocarbon group represented by R ² include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, isobutyl, third butyl, n-pentyl, and n-hexyl. , N-heptyl, n-octyl, n-nonyl, n-decyl and other alkyl groups; vinyl, 1-propenyl, 2-propenyl, isopropenyl, 3-butenyl, 4-pentenyl, 5 -Alkenyl such as hexenyl; alkynyl such as ethynyl, propynyl, butynyl; aromatic groups such as phenyl, 1-naphthyl, 2-naphthyl, and the like.

The carbon number of the alkyl group represented by R ³ is 1 to 4, preferably 1 to 3, and more preferably 1 or 2.

Examples of the alkyl group represented by R ³ include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, isobutyl, and third butyl.

The reactive group contained in Z is not particularly limited as long as it is a group capable of imparting a crosslinking reaction.

The reactive group is preferably an epoxy group or an amine group.

Examples of the epoxy group-containing Z include an epoxy group, an epoxy group, and an epoxy cyclohexyl group.

Examples of the amine group-containing Z include an amine group, a 2-aminoethylamino group, and a phenylamino group.

Examples of the silane coupling agent represented by formula (1) include 3-glycidylpropylmethyldimethoxysilane, 3-glycidylpropyltrimethoxysilane, and 3-glycidyl Propylmethyldiethoxysilane, 3-glycidylpropyltriethoxysilane, 8-glycidyloctyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethylamino) propylmethyldimethoxysilane, 3 -(2-aminoethylamino) propyltrimethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 8- (aminoethylamino) octyltrimethoxysilane, and the like.

Silane coupling agents can be used alone or in combination of two or more.

When the adhesive composition of the present invention contains a silane coupling agent, the content of the silane coupling agent is preferably 0.01 to 7 parts by mass, and more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the component (A).

Adhesive compositions having a silane coupling agent content within this range tend to have excellent adhesion even at high temperatures.

Examples of the components (A) to (D) and components other than the silane coupling agent included in the adhesive composition of the present invention include solvents and various additives.

Examples of the solvent include aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isopropyl ketone; n-pentane and n-hexane , N-heptane and other aliphatic hydrocarbon solvents; cyclopentane, cyclohexane, methyl cyclohexane and other alicyclic hydrocarbon solvents.

These solvents can be used alone or in combination of two or more.

The amount of the solvent to be used may be appropriately determined in consideration of coating properties and the like.

Examples of the additives include additives such as ultraviolet absorbers, antistatic agents, light stabilizers, antioxidants, resin stabilizers, fillers, pigments, extenders, and softeners.

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

When the adhesive composition of the present invention contains such additives, its content can be appropriately determined depending on the purpose.

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

The adhesive composition of the present invention is one having good adhesion. In particular, even after being placed under high humidity conditions, there is a feature that it is difficult to reduce the adhesion force.

For example, when a 180 ° peel test is performed on a test piece obtained using the adhesive composition of the present invention, the x value calculated by the following formula is preferably 1.0 or more.

[Formula 1] x = B / A

In the formula, A represents the adhesive force obtained by carrying out a 180 ° peel test at a temperature of 23 ° C and a relative humidity of 50%, and B represents a test piece that is left to stand at a temperature of 60 ° C and a relative humidity of 90% for 168 hours, and then at After standing at 23 ° C and 50% relative humidity for 24 hours, the adhesive force obtained by performing a 180 ° peel test at 23 ° C and 50% relative humidity.

The A value is not particularly limited, but is usually 2 to 25 N / 25 mm, and preferably 2 to 20 N / 25 mm.

The B value is not particularly limited, but is usually 5 to 35 N / 25 mm, and preferably 5 to 30 N / 25 mm.

These test pieces for the 180 ° peel test can be prepared according to the method described in the examples.

Since the adhesive composition of the present invention has good water-shielding properties and adhesion, the adhesive composition of the present invention is suitable for forming a sealing material.

2) sealing sheet

The sealing sheet of the present invention is the following sealing sheet (α) or sealing sheet (β).

Sealing sheet (α): a sealing sheet made of two release films and an adhesive layer held between the release films, the adhesive layer being formed using the adhesive composition of the present invention.

Sealing sheet (β): a sealing sheet made of a release film, a gas barrier film, and an adhesive layer held between the release film and the gas barrier film, wherein the adhesive layer is the adhesive composition of the present invention Formed by.

In addition, when these sealing sheets show the state before use, when using the sealing sheet of this invention, a peeling film is peeled and removed normally.

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

As a release film, a conventionally known person can be used, for example, the thing which has the release layer which performed the peeling process with the release agent on the base material for release films is mentioned.

Examples of the substrate for the release film include paper substrates such as cellophane, coated paper, and high-quality paper; laminates of these paper substrates with thermoplastic resins such as polyethylene; polyethylene terephthalate resins , Polybutylene terephthalate resin, polyethylene naphthalate resin, polypropylene resin, polyethylene resin and other plastic films.

Examples of the release agent include rubber-based elastomers such as siloxane-based resins, olefin-based resins, isoprene-based resins, and butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, and fluorine-based resins. Wait.

The two peeling films in the sealing sheet (α) may be the same or different, but it is preferable that the two peeling films have different peeling forces. Since the peeling forces of the two peeling films are different, problems are unlikely to occur during the use of the sealing sheet. In other words, since the peeling forces of the two peeling films are different, the step of peeling the peeling film first can be performed more efficiently.

The thickness of the adhesive layer of the sealing sheet (α) is not particularly limited, but is usually 1 to 50 μm, and preferably 5 to 30 μm.

The adhesive layer having a thickness within the above range is suitable for use as a sealing material.

The method for producing the sealing sheet (α) is not particularly limited. The sealing sheet (α) can be produced, for example, by a casting method.

When a sealing sheet (α) is produced by a casting method, the adhesive composition of the present invention is coated on the release-treated surface of a release film using a conventional method, and the resulting coating film is dried to produce an adhesive layer with a release film. Next, another sheet of release film is laminated on the adhesive layer to obtain a sealing sheet (α).

Examples of the method of the coating adhesive composition include a spin coating method, a spray coating method, a bar coating method, a knife coating method, a roll coating method, a doctor blade coating method, a die coating method, and a gravure coating method. Buffa and so on.

Examples of the drying conditions when the coating film is dried include 80 to 150 ° C. for 30 seconds to 5 minutes.

After the drying process, it can be left as it is for about 1 week to mature the adhesive layer. By maturing the adhesive layer, the cross-linked structure can be sufficiently formed.

Examples of the release film and the adhesive layer constituting the sealing sheet (β) are the same as those shown as the release film and the adhesive layer constituting the sealing sheet (α), respectively.

The gas barrier film constituting the sealing sheet (β) is not particularly limited as long as it has a moisture-shielding film.

Examples of the gas barrier film include those having a gas barrier layer directly or through another layer such as an undercoat layer on the base material layer.

[Substrate layer]

The base material layer constituting the gas barrier laminate of the present invention is not particularly limited as long as it is excellent in transparency and can support the gas barrier layer and the like.

As the base material layer, a resin film can be generally used.

Examples of the resin component of the resin film include polyimide, polyimide, polyimide, polyphenylene ether, polyetherketone, polyetheretherketone, polyolefin, polyester, polycarbonate, and polyimide. Rhenium, polyethersulfonium, polyphenylene sulfide, acrylic resin, cycloolefin polymer, aromatic polymer, etc.

The said resin film may contain various additives in the range which does not inhibit the effect of this invention. Examples of the additive include an ultraviolet absorber, an antistatic agent, a stabilizer, an antioxidant, a plasticizer, a lubricant, and a coloring pigment. The content of these additives may be appropriately determined depending on the purpose.

The resin film can be obtained by preparing a resin composition containing a resin component and various additives as needed, and molding these into a film shape. The molding method is not particularly limited, and a known method such as a casting method or a melt extrusion method can be used.

The thickness of the substrate layer is not particularly limited, and it may be determined in accordance with the purpose of the gas barrier laminate. The thickness of the substrate layer is usually 0.5 to 500 μm, and preferably 1 to 100 μm.

The gas barrier layer constituting the gas barrier film is a layer having a characteristic (gas barrier property) of suppressing the penetration of gas such as oxygen or water vapor. The gas barrier layer is formed on one side (A) of the above-mentioned base material layer, and is laminated directly or through other layers.

The thickness of the gas barrier layer is usually 1 to 2000 nm, preferably 3 to 1000 nm, and more preferably 5 to 500 nm.

Examples of the gas barrier layer include a gas barrier layer made of metal foil, a gas barrier layer made of thin film glass, a gas barrier layer made of a gas barrier resin, a gas barrier layer made of an inorganic film, and a polymer layer. A modified gas barrier layer on the surface [At this time, the gas barrier layer means not only the modified region but also the "layer containing the modified region"] and the like.

Among these, from the viewpoints of gas barrier properties, transparency, productivity, etc., a gas barrier layer made of an inorganic film and a modified gas barrier layer on the surface thereof is preferred.

The metal foil is a thin metal stretcher. Examples of the metal foil include metal foils such as aluminum, nickel, stainless steel, iron, copper, and titanium.

The metal foil may be a single layer, or a layered body in which layers made of the same material or layers made of dissimilar materials are laminated.

Examples of the material of the thin-film glass include multi-component oxide glasses such as alkali-free glass, borosilicate glass, and aluminosilicate glass.

Examples of the gas barrier resin include oxygen or water vapor such as polyvinyl alcohol or a part of saponified product thereof, an ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, and polyvinyl chloride trifluoroethylene. Wait for resin that is not easy to penetrate.

Examples of the inorganic film include a vapor-deposited film of an inorganic compound or a metal.

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

Examples of the raw material of the metal vapor-deposited film include aluminum, magnesium, zinc, and tin.

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

Among these, an inorganic vapor-deposited film using an inorganic oxide, an inorganic nitride, or a metal as a raw material is preferable from the viewpoint of gas barrier properties, and an inorganic oxide or an inorganic nitrogen is preferable from the viewpoint of transparency. An inorganic vapor-deposited film as a raw material is preferred.

Examples of the method for forming the inorganic film include a PVD (physical vapor deposition) method such as a vacuum deposition method, a sputtering method, and an ion coating method; a thermal CVD (chemical vapor deposition) method; a plasma CVD method; and a photoCVD CVD method.

The thickness of the inorganic film varies depending on the inorganic compound or metal used, but from the viewpoint of gas barrier properties and operability, it is preferably from 1 to 2000 nm, more preferably from 3 to 1000 nm, and more preferably from 5 to 500 nm.

The modified gas barrier layer on the surface of the polymer layer. Examples of the polymer used in the formation of the polymer layer include a polymer compound containing silicon.

Examples of the silicon-containing polymer compound include a polysilazane-based compound, a polycarbosilane-based compound, a polysilane-based compound, a polyorganosiloxane compound, a poly (disilylidene) -based compound, and the like. And poly (disiladeneethynyl) -based compounds, etc., polysilazane-based compounds are preferred.

The polysilazane-based compound is a compound having a repeating unit of -Si-N-bond (silazane bond) in the molecule. Specifically, a compound having a repeating unit represented by the formula (1) is preferred.

The number average molecular weight of the polysilazane-based compound used is not particularly limited, but it is preferably 100 to 50,000.

In the formula (1), n represents an arbitrary natural number. Rx, Ry, and Rz each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted group Non-hydrolyzable groups such as aromatic groups and alkylsilyl groups.

Examples of the unsubstituted or substituted alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, and the like. Alkyl groups having 1 to 10 carbon atoms such as n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, and n-octyl.

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

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

Examples of the substituent of the above-mentioned alkyl group, cycloalkyl group and alkenyl group include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; hydroxyl group; mercapto group; epoxy group; epoxy propyl group; (methyl) Propylene fluorenyloxy; unsubstituted or substituted aromatic groups such as phenyl, 4-methylphenyl, and 4-chlorophenyl.

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

Examples of the substituent of the aromatic group include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkyl groups having 1 to 6 carbon atoms such as a methyl group and an ethyl group; and carbons such as a methoxy group and an ethoxy group. 1 to 6 alkoxy groups; nitro; cyano; hydroxyl; mercapto; epoxy; epoxypropyl; (meth) acryloxy; phenyl, 4-methylphenyl, 4-chloro Unsubstituted or substituted aromatic groups such as phenyl.

Examples of the alkylsilyl group include trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, tritertiary butylsilyl group, methyldiethylsilyl group, dimethylsilyl group, and diethylsilyl group. Ethylsilyl, methylsilyl, ethylsilyl, etc.

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

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

In the present invention, as the polysilazane-based compound, a polysilazane modified product can be used. Examples of the modified polysilazane include Japanese Patent Laid-Open No. 62-195024, Japanese Patent Laid-Open No. 2-84437, Japanese Patent Laid-Open No. 63-81122, Japanese Patent Laid-Open No. 1-138108, and the like, Japanese Patent Laid-Open No. 2-175726, Japanese Patent Laid-Open No. 5-238827, Japanese Patent Laid-Open No. 5-238827, Japanese Patent Laid-Open No. 6-122852, Japanese Patent Laid-Open No. 6-306329, Japanese Patent Laid-Open No. 6-306329 Those described in Japanese Patent Publication No. 299118, Japanese Patent Application Laid-Open No. 9-31333, Japanese Patent Application Laid-Open No. 5-345826, Japanese Patent Application Laid-Open No. 4-63833, and the like.

Among these, as the polysilazane-based compound, from the viewpoint of easy availability and formation of an ion-implanted layer having excellent gas barrier properties, perhydropolysilicon nitrogen in which all of Rx, Ry, and Rz are hydrogen atoms Alkanes are preferred.

As the polysilazane-based compound, a glassy coating material or the like can be directly used as a commercially available product.

The polysilazane-based compound may be used singly or in combination of two or more kinds.

In addition to the polymer compound containing silicon, the polymer layer may contain other components within a range not hindering the object of the present invention. Examples of the other components include a hardener, an antioxidant, a light stabilizer, and a flame retardant.

The content of the silicon-containing polymer compound in the polymer layer is more preferably 50% by mass or more, and more preferably 70% by mass or more, in terms of forming a gas barrier layer having better gas barrier properties.

The thickness of the polymer layer is not particularly limited, but it is usually 1 to 2000 nm, preferably 3 to 1000 nm, and more preferably 5 to 500 nm.

The polymer layer can be applied, for example, by dissolving or dispersing a polymer compound containing silicon in an organic solvent, by a conventional coating method, or directly or through another layer onto the substrate layer to make the resulting coating film. Formed on drying.

Examples of the organic solvent include aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isopropyl ketone; n-pentane and n-hexane Aliphatic hydrocarbon solvents such as alkane and n-heptane; alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane.

These solvents can be used alone or in combination of two or more.

Examples of the coating method include a bar coating method, a spin coating method, a dipping method, a roll coating method, a gravure coating method, a knife coating method, an air knife coating method, a roll knife coating method, and a die coating method. Cloth method, screen printing method, spray coating method, gravure transfer method, and the like.

Examples of the drying method of the coating film include conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation. The heating temperature is usually 80 ~ 150 ° C, and the heating time is usually from tens of seconds to tens of minutes.

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

As described later, the ion implantation process is a method in which accelerated ions are implanted into the polymer layer to modify the polymer layer.

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

The ultraviolet irradiation treatment is a method of irradiating ultraviolet rays to a polymer layer to modify the polymer layer. For example, UV-modification treatment can be performed according to the method described in Japanese Patent Application Laid-Open No. 2013-226757.

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, and sulfur; methane and ethane Ions such as alkane-based gases; Ions based on olefins such as ethylene and propylene; Ions based on diene-based gases such as pentadiene and butadiene; Ions based on acetylene-based gases such as acetylene; Aromatics such as benzene and toluene Ions of family hydrocarbon-based gases; Ions of cycloalkane-based gases such as cyclopropane; Ions of cycloolefin-based gases such as cyclopentene; Ions of metals; Ions of organosilicon compounds, etc.

These plasmas can be used alone or in combination of two or more.

Among these, since the ions can be more easily implanted, a gas barrier layer having better gas barrier properties can be formed, and ions of rare gases such as argon, helium, neon, krypton, and xenon are preferred.

The amount of ion implantation can be appropriately determined in accordance with the purpose of use of the gas-barrier laminated body (necessary gas-barrier properties, transparency, etc.) and the like.

Examples of the method of implanting ions include a method of irradiating ions (ion beams) accelerated by an electric field, and a method of implanting ions in a plasma. Among them, since the target gas barrier layer can be formed more easily, the latter plasma implantation method (plasma ion implantation method) is preferred.

Plasma ion implantation method, for example, generates a 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 to ions (cations) in the plasma to the polymer layer. Part of the surface is implanted. More specifically, the plasma ion implantation method can be implemented by a method described in WO2010 / 107018 and the like.

By ion implantation, the thickness of the region where the ions are implanted can be controlled by the type of ions, the implantation conditions such as applied voltage, and processing time. The thickness can be determined according to the thickness of the polymer layer or the purpose of the laminate. It is 10 ~ 400nm.

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

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

Since the gas barrier film has a water vapor transmission rate of 0.1 g / m ² / day or less under the environment of a temperature of 40 ° C and 90% RH, it can effectively prevent oxygen or moisture from entering the organic EL element formed on the transparent substrate. Wait for the inside of the device to deteriorate the electrode or organic layer.

The transmission rate of water vapor or the like of the gas barrier film can be measured using a conventional gas transmission rate measuring device.

The primer layer is not particularly limited, and a known one can be used. For example, the undercoat layer described in WO2012 / 039387, WO2013 / 147090, etc. is mentioned.

The manufacturing method of a sealing sheet ((beta)) is not specifically limited. For example, in the manufacturing method of the sealing sheet ((alpha)) demonstrated previously, one sheet of a peeling film can be replaced with a gas barrier film, and a sealing sheet ((beta)) can be manufactured.

In addition, after the sealing sheet (α) is manufactured, one of the peeling films is peeled off, and the exposed adhesive layer and the gas barrier film can be attached to produce a sealing sheet (β). In this case, when the sealing sheet (α) has two peeling films having different peeling forces, it is preferable to peel the peeling film having a small peeling force from the viewpoint of operability.

The adhesive layer of the sealing sheet of the present invention has good adhesion and moisture shielding property. Therefore, the sealing of the organic EL element using the sealing sheet of the present invention can effectively suppress the deterioration.

3) Sealing body

The sealing system of the present invention is obtained by sealing a sealed object using the sealing sheet of the present invention.

The phrase "the object to be sealed is sealed using the sealing sheet of the present invention" means that the release film constituting the sealing sheet of the present invention is removed, the adhesive layer is exposed, and the adhesive layer is adhered to the object to be sealed to cover the object to be sealed.

The sealing body of the present invention includes, for example, a transparent substrate, an element (an object to be sealed) formed on the transparent substrate, and a sealing material for sealing the element. Examples of the sealing material include adhesion of the sealing sheet of the present invention.剂 层。 The agent layer.

The transparent substrate is not particularly limited, and various substrate materials can be used. In particular, it is preferable to use a substrate material having a high visible light transmittance. In addition, a material having a high shielding performance against moisture or gas from the outside of the device and a solvent-resistant or weather-resistant material is preferred. Specific examples include transparent inorganic materials such as quartz or glass; polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, and polyphenylene sulfide Transparent plastics such as ether, polyvinylidene fluoride, cellulose acetate, brominated phenoxy, polyaramide, polyimide, polystyrene, polyaromatic ester, polyfluorene, and polyolefin And the above gas barrier film.

The thickness of the transparent substrate is not particularly limited, but may be appropriately selected in consideration of the light transmittance or the performance inside and outside the shielding element.

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

The manufacturing method of the sealing body of this invention is not specifically limited. For example, the adhesive layer of the sealing sheet of the present invention is superimposed on the object to be sealed and adhered, so that the adhesive layer of the sealing sheet is adhered to the object to be sealed.

The sealing system of the present invention is obtained by sealing the object to be sealed with the sealing sheet of the present invention.

Therefore, in the sealed body of the present invention, the performance of the object to be sealed is maintained over a long period of time.

[Example]

Hereinafter, the present invention will be described in more detail with examples. However, the present invention is not limited to the following examples.

Unless otherwise stated, the parts and% in each case are quality standards.

[Manufacturing example 1]

As a (meth) acrylate-based ionizing radiation-hardening compound, 20 parts of dipentaerythritol hexaacrylate (produced by Shin Nakamura Chemical Co., Ltd .: A-DPH) was dissolved in 100 parts of methyl isobutyl ketone. A photopolymerization initiator (manufactured by BASF, trade name: Irgacure127) was added to 100 parts of the solid content of the undercoat layer forming solution, and the amount was 3 parts to prepare an undercoat layer forming solution.

Subsequently, 50 μ m in thickness of polyethylene terephthalate film (hereinafter referred to as "PET film") (manufactured by Toyobo Co., COSMOSHINE A-4300) was coated with the primer layer-forming solution, The obtained coating film was dried to form an undercoat layer having a thickness of 1 μm .

Next, a coating agent ("AZNN110-20", manufactured by Merck Performance Materials, Inc.) containing perhydropolysilazane as a main component was coated on this undercoat layer, and the obtained coating film was heated at 120 ° C for 2 minutes to form A polysilazane layer with a thickness of 200 nm.

Next, plasma ion implantation was performed on the polysilazane layer using a plasma ion implantation device in accordance with the following conditions to modify the surface of the polysilazane layer to obtain a gas barrier film.

The water vapor transmission rate of this gas barrier film was 0.02 g / m ² / day.

[Processing conditions for plasma ion implantation]

Plasma generated gas: Argon

Gas flow: 100sccm

Duty ratio: 0.5%

Repetition frequency: 1000Hz

Applied voltage: -10kV

RF output: 1000W

RF power: (frequency) 13.56MHz, (applied power) 1000W

Cabin pressure: 0.2Pa

Pulse width: 5μsec

Processing time (ion implantation time): 5 minutes

Transport speed: 0.2m / min

[Compounds used in Examples or Comparative Examples]

In the examples or comparative examples, the following compounds were used.

Rubber-based resin (1): butyl rubber, mass average molecular weight (Mw): 34,000, manufactured by JSR Corporation, trade name: JSR BUTYL268

Rubber-based resin (2): butyl rubber, mass average molecular weight (Mw): 28,000, manufactured by JSR Corporation, trade name: JSR BUTYL365

Tackifier (1): aliphatic petroleum resin, made by Japan Zeon Co., Ltd., trade name: Quintone A-100

Curable resin (1): hydrogenated polybutadiene polyol, manufactured by Cray Valley, trade name: Krasol HLBH-P2000

Curable resin (2): polybutadiene polyol, manufactured by Cray Valley, trade name: Krasol LBH-P2000

Crosslinking agent (1): Uremate modified hexamethylene diisocyanate, manufactured by Mitsui Chemicals Co., Ltd., trade name: TAKENATE D-178NL

Crosslinking agent (2): Pentamethylene diisocyanate polyisocyanate, manufactured by Mitsui Chemicals Co., Ltd., trade name: STABiO D-370N

Silane coupling agent (1): 8- (aminoethylamino) octyltrimethoxysilane, manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: KBM6803

Silane coupling agent (2): 3-glycidylpropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: KBM403

Silane coupling agent (3): 8-epoxypropyloctyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM4803

[Example 1]

80 parts of rubber-based resin (1), 20 parts of rubber-based resin (2), 20 parts of tackifier (1), 15 parts of curable resin (1), 5 parts of cross-linking agent (1), and silane coupling agent ( 1) 0.1 part of the adhesive composition (1) dissolved in toluene to prepare a solid content concentration of 17%.

This adhesive composition (1) was applied to a release-treated surface of a release film (manufactured by LINTEC, trade name: SP-PET382150), and the obtained coating film was dried at 100 ° C. for 1 minute to form an adhesive having a thickness of 20 μm. Layer, and the peeling process surface of another peeling film (made by LINTEC company, brand name: SP-PET381031) was bonded together, and the sealing sheet (1) was obtained.

[Examples 2 to 8, Comparative Example 1]

The composition described in Table 1 was changed, and adhesive compositions (2) to (9) were prepared. Except that these adhesive compositions were used, the rest were the same as in Example 1, and sealing sheets (2) to (9) were obtained.

The following tests were performed on the sealing sheets (1) to (9) obtained in Examples 1 to 8 and Comparative Example 1. In addition, the test was performed after 7 days of maturation at 23 ° C and 50% relative humidity after the completion of the sealing sheet.

[Adhesion measurement]

A peeling film of a sealing sheet having a width of 25 mm was peeled off, and the exposed adhesive layer was superposed on the gas barrier film obtained in Production Example 1. Next, one more peeling film was peeled off so that the exposed adhesive layer was superimposed on the alkali-free glass, and pressed with a pressure roller to obtain a test piece.

As a peel test (a), the test piece was subjected to a 180 ° peel test at a temperature of 23 ° C and a relative humidity of 50%.

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

In this peel test, other than the above test conditions, it was performed in accordance with the method for measuring the adhesive force described in JIS Z0237: 2000.

[Foaming evaluation]

The peeling film of one 125 mm square sealing sheet was peeled off, and the exposed adhesive layer was superimposed on the gas barrier film obtained in Production Example 1. Next, one more peeling film was peeled off, and the exposed adhesive layer was superimposed on the alkali-free glass, and it was attached using a roll bonding machine. Thereafter, a test piece was obtained by processing in a heating and pressure furnace (manufactured by LINTEC, model: RAD-9100) at a temperature of 50 ° C and a pressure of 0.5 MPa for 20 minutes. This test piece was placed in a constant temperature and humidity device (manufactured by ESPEC, model: PL-2KT), and allowed to stand for 72 hours at a temperature of 85 ° C and a relative humidity of 85%, and then visually observed to evaluate foaming according to the following criteria. Sex.

○: The number of blisters has not reached 5

×: Number of blisters occurred 5 or more.

[Evaluation test of organic EL element]

An organic EL element having a glass substrate formed with an indium tin oxide (ITO) film (thickness: 100 nm, sheet resistance: 50 Ω / □) as an anode was produced by the following method.

First, N, N'-bis (naphthalene-1-yl) -N, N'-bis (phenyl) -benzidine) (manufactured by Luminescence Technology) 50 nm on the ITO film of the glass substrate, 8-Hydroxyquinoline) aluminum (manufactured by Luminescence Technology) at 50 nm was sequentially vapor-deposited at a rate of 0.1 to 0.2 nm / min to form a light emitting layer.

On the obtained light-emitting layer, lithium fluoride (LiF) (produced by the High Purity Chemical Research Institute) as an electron injection material was vapor-deposited at a rate of 0.1 nm / minute at 4 nm, and then aluminum (Al) (high purity chemical research Co., Ltd.) was deposited at a rate of 0.1 nm / min to 100 nm to form a cathode, thereby obtaining an organic EL element.

The degree of vacuum at the time of vapor deposition was all 1 × 10 ^-4 Pa or less.

One peeling film of the sealing sheet obtained in the example or the comparative example was peeled off, and the exposed adhesive layer was superimposed on the gas barrier film obtained in the manufacturing example 1, and these were attached using a roll bonding machine. Next, one more peeling film was peeled off, and the exposed adhesive layer was overlapped so as to cover the organic EL element formed on the glass substrate, and this was attached using a roll bonding machine to obtain a bottom-emitting type in which the organic EL element was sealed. Electronic device.

This electronic device was left to stand for 250 hours under the environment of a temperature of 60 ° C. and a relative humidity of 90%. Then, the organic EL device was started, and the presence or absence of dull spots (non-light-emitting areas) was observed, and the area ratio of the dull spots to the whole was calculated.

As can be seen from Table 1, it is as follows.

The sealing sheets (1) to (8) of Examples 1 to 8 showed better adhesion after being left to stand in a high-humidity condition, and also had good sealing properties.

On the other hand, the sealing sheet (9) of Comparative Example 1 has a small adhesive force, and when placed under high humidity conditions, the adhesive force is greatly reduced, and then the sealing property of the sealing sheet (9) is deteriorated.

Claims (18)

    An adhesive composition comprising the following (A) component, (C) component, and (D) component: (A) component: rubber-based resin; (C) component: curable resin; (D) component: urea Formate-based crosslinking agent.         The adhesive composition according to item 1 of the patent application range, wherein the component (A) is butyl rubber.         The adhesive composition according to item 1 of the scope of patent application, which further contains the following (B) component, (B) component: a tackifier.         The adhesive composition according to claim 3, wherein the component (B) is an aliphatic petroleum resin.         According to the adhesive composition of claim 3, the content of the component (B) is 1 to 50 parts by mass relative to 100 parts by mass of the component (A).         The adhesive composition according to item 1 of the patent application scope, wherein the component (C) is a polymer having hydroxyl groups at both ends.         According to the adhesive composition of claim 1, the content of the component (C) is 1 to 50 parts by mass based on 100 parts by mass of the component (A).         The adhesive composition according to item 1 of the scope of patent application, wherein the component (D) is a urethane modified hexamethylene diisocyanate.         According to the adhesive composition of claim 1, the content of the component (D) is 1 to 70 parts by mass based on 100 parts by mass of the component (A).         The adhesive composition according to item 1 of the scope of patent application, which further contains the following (E) component and (E) component: a silane coupling agent.     The adhesive composition according to claim 10, wherein the component (E) is a compound represented by the following formula (1): R ¹ represents an alkylene group having 3 or more carbon atoms, R ² represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ³ represents an alkyl group having 1 to 4 carbon atoms, Z represents a group containing a reactive group, and n is 0 Or 1.     According to the adhesive composition of claim 10, the content of the component (E) is 0.01 to 7 parts by mass relative to 100 parts by mass of the component (A).         A sealing sheet is a sealing sheet composed of two release films and an adhesive layer held between the release films, and the adhesive layer is an adhesive using any one of claims 1 to 12 of the scope of patent application. Agent composition formed.         A sealing sheet is a sealing sheet made of a release film, a gas barrier film, and an adhesive layer held between the release film and the gas barrier film, and the adhesive layer uses the first to the twelfth aspects of the application patent scope. Formed by the adhesive composition according to any one of the items.         The sealing sheet according to item 14 of the application, wherein the gas barrier film is a metal foil, a resin film, or a thin-film glass.         The sealing sheet according to item 13 or 14 of the scope of patent application, wherein the thickness of the adhesive layer is 1 to 50 μm.         The utility model relates to a sealing body, which is obtained by sealing the object to be sealed by using the sealing sheet of the patent application scope item 13 or item 14.         The sealed body according to item 17 of the scope of patent application, wherein the sealed object is an organic EL element, an organic EL display panel element, a liquid crystal display panel element, or a solar cell element.