JP2017101145A - Adhesive composition, encapsulation sheet and encapsulated body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition excellent in adhesive strength and water blockage property, an encapsulation sheet having the adhesive layer formed by using the adhesive composition and an encapsulated body by encapsulating an article to be encapsulated by the encapsulation sheet.SOLUTION: There are provided an adhesive composition containing following (A) component, (B) component and (C) component, an encapsulation sheet having the adhesive layer formed by using the adhesive composition and an encapsulated body by encapsulating an article to be encapsulated by the encapsulation sheet. (A) component: a modified polyolefin resin. (B) component: a tackifier. (C) component: a crosslinking agent.SELECTED DRAWING: None

Description

  The present invention provides an adhesive composition excellent in adhesive strength and moisture barrier property, a sealing sheet having an adhesive layer formed using this adhesive composition, and an object to be sealed is sealed with the sealing sheet The present invention relates to a sealed body.

In recent years, organic EL elements have attracted attention as light-emitting elements that can emit light with high luminance by low-voltage direct current drive.
However, the organic EL element has a problem that light emission characteristics such as light emission luminance, light emission efficiency, and light emission uniformity are likely to deteriorate with time.
As a cause of the problem of the deterioration of the light emission characteristics, it is conceivable that oxygen, moisture or the like enters the inside of the organic EL element and degrades the electrode or the organic layer.
As a countermeasure, several methods using a sealing material have been proposed. For example, Patent Document 1 discloses a sheet-like sealing comprising an olefin polymer having a heat of fusion and a weight average molecular weight within a specific range, and a hydrocarbon-based synthetic oil having a kinematic viscosity at 40 ° C. within a specific range. The materials are listed.

JP2015-137333A

The sheet-like sealing material described in Patent Document 1 has a feature that it can be peeled off as necessary. However, this sheet-shaped sealing material tended to be inferior in adhesive strength.
Objects to be sealed such as organic EL elements are often used under harsh conditions such as outdoors or in a vehicle. Accordingly, there has been a demand for a sealing sheet excellent in adhesive strength and moisture barrier properties and an adhesive composition used as a molding material for such a sealing sheet.

  The present invention has been made in view of the above circumstances, and is an adhesive composition excellent in adhesive strength and moisture barrier properties, a sealing sheet having an adhesive layer formed using the adhesive composition, and a cover. It aims at providing the sealing body by which a sealing material is sealed with the said sealing sheet.

  As a result of intensive studies to solve the above problems, the present inventors have found that an adhesive composition containing a modified polyolefin resin, a tackifier, and a crosslinking agent is excellent in adhesive strength and moisture barrier properties. The invention has been completed.

Thus, according to the present invention, the following adhesive compositions (1) to (6), the sealing sheets (7) to (9), and the sealing bodies (10) and (11) are provided. .
(1) An adhesive composition containing the following component (A), component (B) and component (C).
(A) Component: Modified polyolefin resin (B) Component: Tackifier (C) Component: Crosslinking agent (2) The adhesive composition according to (1), wherein the component (A) is an acid-modified polyolefin resin. object.
(3) The adhesive composition according to (1) or (2), wherein the content of the component (A) is 50 to 99% by mass with respect to the total solid content of the adhesive composition.
(4) Adhesive composition in any one of (1)-(3) whose content of the said (B) component is 1-100 mass parts with respect to 100 mass parts of said (A) component. .
(5) The adhesive according to any one of (1) to (4), wherein the content of the component (C) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A). Composition.
(6) The adhesive composition according to any one of (1) to (5), further comprising the following component (D).
(D) Component: Silane coupling agent (7) A sealing sheet comprising two release films and an adhesive layer sandwiched between these release films, wherein the adhesive layer is (1) to The sealing sheet which is formed using the adhesive composition in any one of (6), and has thermoplasticity.
(8) A sealing sheet comprising a release film, a gas barrier film, and the adhesive film sandwiched between the release film and the gas barrier film, wherein the adhesive layer is (1) to (6). The sealing sheet which is formed using the adhesive composition in any one of these, and has thermoplasticity.
(9) The sealing sheet according to (8), wherein the gas barrier film is a metal foil, a resin film, or thin film glass.
(10) A sealed body in which an object to be sealed is sealed with the sealing sheet according to any one of (7) to (9).
(11) The sealed body according to (10), wherein the object to be sealed is an organic EL element, an organic EL display element, a liquid crystal display element, or a solar cell element.

  According to the present invention, an adhesive composition excellent in adhesive strength and moisture barrier property, a sealing sheet having an adhesive layer formed using this adhesive composition, and an object to be sealed are the sealing sheet. A sealed body that is sealed is provided.

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

1) Adhesive composition The adhesive composition of this invention contains the following (A) component, (B) component, and (C) component.
(A) Component: Modified polyolefin resin (B) Component: Tackifier (C) Component: Crosslinking agent

(A) component: Modified polyolefin-type resin The adhesive composition of this invention contains modified polyolefin-type resin as (A) component.
The adhesive composition of the present invention is excellent in adhesive strength by containing a modified polyolefin resin. Moreover, the adhesive layer of the thickness mentioned later can be efficiently formed by using the adhesive composition containing modified polyolefin resin.

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

  The polyolefin resin refers to a polymer containing repeating units derived from olefinic monomers. The polyolefin resin may be a polymer composed only of repeating units derived from olefinic monomers, or derived from monomers that are copolymerizable with olefinic monomers and repeating units derived from olefinic monomers. The polymer which consists of these repeating units may be sufficient.

The olefin monomer is preferably an α-olefin having 2 to 8 carbon atoms, more preferably ethylene, propylene, 1-butene, isobutylene, or 1-hexene, and further preferably ethylene or propylene.
Examples of the monomer copolymerizable with the olefin monomer include vinyl acetate, (meth) acrylic acid ester, and styrene.

  Examples of polyolefin resins include very low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene, polypropylene (PP), and ethylene-propylene. Examples thereof include a polymer, an olefin-based elastomer (TPO), an ethylene-vinyl acetate copolymer (EVA), an ethylene- (meth) acrylic acid copolymer, and an ethylene- (meth) acrylic acid ester copolymer.

  The weight average molecular weight (Mw) of the polyolefin resin is 10,000 to 2,000,000, preferably 20,000 to 500,000.

The modifier used for the modification treatment of the polyolefin resin is a compound having a functional group in the molecule, that is, a group that can contribute to a crosslinking reaction described later.
Functional groups include carboxyl groups, carboxylic anhydride groups, carboxylic ester groups, hydroxyl groups, epoxy groups, amide groups, ammonium groups, nitrile groups, amino groups, imide groups, isocyanate groups, acetyl groups, thiol groups, ether groups. Thioether group, sulfone group, phosphone group, nitro group, urethane group, halogen atom and the like. Among these, a carboxyl group, a carboxylic anhydride group, a carboxylic ester group, a hydroxyl group, an ammonium group, an amino group, an imide group, and an isocyanate group are preferable, a carboxylic anhydride group and an alkoxysilyl group are more preferable, and a carboxylic anhydride Physical groups are particularly preferred.
The compound having a functional group may have two or more kinds of functional groups in the molecule.

  Examples of the modified polyolefin resin include an acid-modified polyolefin resin and a silane-modified polyolefin resin, and an acid-modified polyolefin resin is preferable from the viewpoint of obtaining the better effect of the present invention.

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

Examples of the unsaturated carboxylic acid to be reacted with the polyolefin resin include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, Examples thereof include aconitic anhydride, norbornene dicarboxylic acid anhydride, and tetrahydrophthalic acid anhydride.
These can be used alone or in combination of two or more. Among these, maleic anhydride is preferable because an adhesive composition having better adhesive strength can be easily obtained.

  The amount of the unsaturated carboxylic acid to be reacted with the polyolefin resin is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, and still more preferably 0.2 to 100 parts by mass with respect to 100 parts by mass of the polyolefin resin. 1.0 part by mass. The adhesive composition containing the acid-modified polyolefin resin thus obtained is more excellent in adhesive strength.

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

  Examples of the polyolefin resin that is a precursor of the silane-modified polyolefin resin include the polyolefin resins exemplified as the polyolefin resin to be graft-modified with the aforementioned acid.

  A silane-modified polyolefin resin refers to a resin obtained by graft modification with an unsaturated silane compound to a polyolefin resin. The silane-modified polyolefin resin has a structure in which an unsaturated silane compound as a side chain is graft copolymerized with a polyolefin resin as a main chain. Examples include silane-modified polyethylene resins and silane-modified ethylene-vinyl acetate copolymers, and silane-modified polyethylene resins such as silane-modified low-density polyethylene, silane-modified ultra-low-density polyethylene, and silane-modified linear low-density polyethylene are preferable.

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

  The amount of the unsaturated silane compound to be reacted with the polyolefin resin is preferably 0.1 to 10 parts by mass, particularly preferably 0.3 to 7 parts by mass with respect to 100 parts by mass of the polyolefin resin. Furthermore, it is preferable that it is 0.5-5 mass parts. When the amount of the unsaturated silane compound to be reacted is in the above range, the adhesive composition containing the resulting silane-modified polyolefin resin is more excellent in adhesive strength.

  A commercial item can also be used for a silane modified polyolefin resin. Commercially available products include, for example, Linklon (registered trademark) (manufactured by Mitsubishi Chemical Corporation), among others, low density polyethylene-based linklon, linear low-density polyethylene-based linkron, and ultra-low-density polyethylene-based. Of these, Rincron of ethylene-vinyl acetate copolymer system can be preferably used.

(B) Component: Tackifier The adhesive composition of the present invention contains a tackifier as the component (B).
The adhesive composition of the present invention is excellent in water vapor barrier properties by containing a tackifier. Moreover, the adhesive composition of this invention becomes the thing excellent in the adhesive strength in normal temperature and a high temperature environment by using together a tackifier and the crosslinking agent mentioned later.

The tackifier is not particularly limited, and conventionally known tackifiers can be used.
Examples of tackifiers include rosin resins such as polymerized rosin, polymerized rosin ester, and rosin derivatives; terpene resins such as polyterpene resins, aromatic modified terpene resins and hydrides thereof, and terpene phenol resins; coumarone and indene resins; aliphatic Petroleum resins such as petroleum resins, aromatic petroleum resins and their hydrides, aliphatic / aromatic copolymer petroleum resins; and low molecular weight polymers of styrene or substituted styrenes.
These tackifiers can be used alone or in combination of two or more.

The weight average molecular weight of the tackifier is preferably 100 to 10,000, more preferably 500 to 5,000.
The softening point of the tackifier is preferably 50 to 160 ° C, more preferably 60 to 140 ° C, and still more preferably 70 to 130 ° C.

  A commercial item can also be used for a tackifier. Commercially available products include aliphatic petroleum resins such as Quinton (registered trademark) A, B, R, CX series (manufactured by Nippon Zeon Co., Ltd.); Alcon P, M series (manufactured by Arakawa Chemical Co., Ltd.), ESCOREZ (registered trademark) series (ExxonMobil Chemical Co., Ltd.), EASTOTAC (registered trademark) series (Eastman Chemical Co., Ltd.), ILARV (registered trademark) series (Idemitsu Kosan Co., Ltd.) and other alicyclic petroleum resins; YS Resin P, A Terpene resins such as series, Clearon (registered trademark) P series (manufactured by Yasuhara Chemical), picolite A, C series (manufactured by PINOVA);・ Ester resins such as ester and Pine Crystal (registered trademark) (Arakawa Chemical Industries) Etc. The.

  The content of the tackifier is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the component (A). An adhesive composition having a tackifier content within this range is more excellent in water vapor barrier properties and adhesive strength.

(C) Component: Crosslinking Agent The adhesive composition of the present invention contains a crosslinking agent as the (C) component.
The adhesive composition of the present invention is excellent in adhesive strength in a normal temperature and high temperature environment by using a crosslinking agent and a tackifier in combination.

The crosslinking agent is a compound having a group capable of reacting with a functional group of the modified polyolefin resin or a partial structure capable of reacting with a functional group of the modified polyolefin resin (hereinafter sometimes referred to as “crosslinkable group”). And it is a compound which forms a crosslinked structure by reacting with a modified polyolefin resin.
Examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent.

The isocyanate-based crosslinking agent is a compound having an isocyanate group as a crosslinkable group.
Isocyanate-based crosslinking agents include: trimethylolpropane-modified tolylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, etc .; aliphatic polyisocyanates such as pentamethylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate Isocyanates; cycloaliphatic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate; biurets and isocyanurates of these compounds, and low molecules such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane and castor oil An adduct that is a reaction product with an active hydrogen-containing compound; and the like.

The epoxy-based crosslinking agent is a compound having an epoxy group as a crosslinkable group.
Examples of the epoxy crosslinking agent include 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, ethylene glycol diglycidyl ether, Examples include 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl aniline, diglycidyl amine and the like.

An aziridine-based crosslinking agent is a compound having an aziridine group as a crosslinkable group.
Examples of the aziridine-based crosslinking agent include diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane tri-β-aziridinylpropionate, tetramethylolmethanetri-β-aziridinylpro Pionate, toluene-2,4-bis (1-aziridinecarboxamide), triethylenemelamine, bisisophthaloyl-1- (2-methylaziridine), tris-1- (2-methylaziridine) phosphine, tri And methylolpropane tri-β- (2-methylaziridine) propionate.

Examples of the metal chelate-based crosslinking agent include chelate compounds in which the metal atom is aluminum, zirconium, titanium, zinc, iron, tin, etc. Among them, aluminum chelate compounds are preferable.
Aluminum chelate compounds include diisopropoxy aluminum monooleyl acetoacetate, monoisopropoxy aluminum bis oleyl acetoacetate, monoisopropoxy aluminum monooleate monoethyl acetoacetate, diisopropoxy aluminum monolauryl acetoacetate, diisopropoxy aluminum mono Examples include stearyl acetoacetate and diisopropoxyaluminum monoisostearyl acetoacetate.
These crosslinking agents can be used alone or in combination of two or more.

The content of the crosslinking agent in the adhesive composition of the present invention is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the component (A). . An adhesive composition having a crosslinking agent content within this range is more excellent in adhesive strength.
In particular, the content of the cross-linking agent is such that the cross-linkable group of the cross-linking agent (in the case of the metal chelate cross-linking agent) is 0.1 to 5 equivalents relative to the functional group of the component (A). An amount that becomes 0.2 to 3 equivalents is more preferable.

The adhesive composition of the present invention may contain a silane coupling agent as the component (D).
By containing the silane coupling agent, the adhesive composition of the present invention is superior in adhesive strength under normal temperature and high temperature environment.

As the silane coupling agent, an organosilicon compound having at least one alkoxysilyl group in the molecule is preferable.
Examples of the silane coupling agent include polymerizable unsaturated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 2- (3,4 -Epoxycyclohexyl) silicon compound having an epoxy structure such as ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) An amino group-containing silicon compound such as -3-aminopropylmethyldimethoxysilane; 3-chloropropyltrimethoxysilane; 3-isocyanatopropyltriethoxysilane;
These silane coupling agents can be used alone or in combination of two or more.

  When the adhesive composition of this invention contains a silane coupling agent, Preferably content of a silane coupling agent is 0.01-1.0 mass part with respect to 100 mass parts of said (A) component, More preferably, it is 0.05-0.5 mass part.

The adhesive composition of the present invention may contain a solvent.
Solvents 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 isobutyl ketone; n-pentane, n-hexane, and n- And aliphatic hydrocarbon solvents such as heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, and methylcyclohexane;
These solvents can be used alone or in combination of two or more.
The content of the solvent can be appropriately determined in consideration of coating properties and the like.

The adhesive composition of the present invention may contain other components as long as the effects of the present invention are not hindered.
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 alone or in combination of two or more.
When the adhesive composition of this invention contains these additives, the content can be suitably determined according to the objective.

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

  The adhesive composition of the present invention is excellent in adhesive strength and moisture barrier properties. For this reason, the adhesive composition of this invention is used suitably when forming a sealing material.

2) Sealing sheet The sealing sheet of this invention is the following sealing sheet ((alpha)) or sealing sheet ((beta)).
Sealing sheet (α): a sealing sheet comprising two release films and an adhesive layer sandwiched between these release films, wherein the adhesive layer uses the adhesive composition of the present invention. A sealing sheet (β) formed by the method having a thermoplastic property: a release film, a gas barrier film, an adhesive layer sandwiched between the release film and the gas barrier film, It is a sealing sheet made of the above, wherein the adhesive layer is formed using the adhesive composition of the present invention and has thermoplasticity. The state before use is shown, and when the sealing sheet of the present invention is used, the release film is usually peeled off.

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

A conventionally well-known thing can be utilized as a peeling film. For example, what has the peeling layer by which the peeling process was carried out with the release agent on the base material for peeling films is mentioned.
As the substrate for the release film, paper substrates such as glassine paper, coated paper, and high-quality paper; laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper substrates; polyethylene terephthalate resin, polybutylene terephthalate resin, Examples thereof include plastic films such as polyethylene naphthalate resin, polypropylene resin, and polyethylene resin.
Examples of the release agent include rubber elastomers such as silicone resins, olefin resins, isoprene resins, and butadiene resins, long chain alkyl resins, alkyd resins, and fluorine resins.

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

The adhesive layer constituting the sealing sheet (α) is formed using the adhesive composition of the present invention. For this reason, this adhesive bond layer is excellent in adhesive strength and moisture barrier property.
The peeling adhesive strength at 23 ° C. of the adhesive layer of the sealing sheet (α) of the present invention is usually from 17 N / 25 mm to 50 N / 25 mm, preferably from 18.5 N / 25 mm to 50 N / 25 mm. The peel adhesion strength at 70 ° C. is usually more than 12 N / 25 mm and 50 N / 25 mm or less, preferably 12.5 N / 25 mm or more and 50 N / 25 mm.
The water vapor permeability of the adhesive layer of the sealing sheet (α) of the present invention is usually ¹ to 250 g · m ⁻² · day ⁻¹ , preferably ^{2 to} 250 g · m ⁻² · day ⁻¹ .
The peel adhesion strength and water vapor transmission rate are measured according to the methods described in the examples.

  Further, the adhesive layer of the sealing sheet (α) has a crosslinked structure formed therein, and has thermoplasticity. Therefore, the adhesive layer of the sealing sheet (α) is suitably used as a heat seal adhesive.

The thickness of the adhesive layer of the sealing sheet (α) is usually 1 to 50 μm, preferably 5 to 25 μm.
An adhesive layer having a thickness within the above range is suitably used as a sealing material.

The manufacturing method of a sealing sheet ((alpha)) is not specifically limited. For example, the sealing sheet (α) can be manufactured using a casting method.
When manufacturing the sealing sheet (α) by a casting method, the adhesive composition of the present invention is applied to the release-treated surface of the release film using a known method, and the obtained coating film is dried. A sealing sheet (α) can be obtained by producing an adhesive layer with a release film and then stacking another release film on the adhesive layer.

Examples of the method for applying the adhesive composition include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
As drying conditions when drying a coating film, 30 seconds-5 minutes are mentioned at 80-150 degreeC, for example.
After the drying treatment, the adhesive layer may be cured by leaving it still for about one week. By curing the adhesive layer, the crosslinked 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).
The gas barrier film which comprises a sealing sheet ((beta)) will not be specifically limited if it is a film which has a moisture barrier property.

The gas barrier film preferably has a water vapor transmission rate of 0.1 g / m ² / day or less in an environment of a temperature of 40 ° C. and a relative humidity of 90% (hereinafter abbreviated as “90% RH”). It is more preferable that it is 0.05 g / m ² / day or less, and it is more preferable that it is 0.005 g / m ² / day or less.
The gas barrier film has a water vapor permeability of 0.1 g / m ² / day or less in an environment of 40 ° C. and 90% RH, so that oxygen or oxygen can be contained inside the organic EL element or the like formed on the transparent substrate. It is possible to effectively suppress the penetration of moisture and the like and the deterioration of the electrode and the organic layer.
The transmittance of water vapor and the like of the gas barrier film can be measured using a known gas permeability measuring device.

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

The resin component constituting the base material is polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, acrylic Examples include resins, cycloolefin polymers, aromatic polymers, polyurethane polymers, and the like.
Although there is no restriction | limiting in particular in the thickness of a base material, From a viewpoint of the ease of handling, Preferably it is 0.5-500 micrometers, More preferably, it is 1-200 micrometers, More preferably, it is 5-100 micrometers.

  A material etc. will not be specifically limited if a gas barrier layer can provide desired gas barrier property. Examples of the gas barrier layer include an inorganic film and a layer obtained by subjecting a layer containing a polymer compound to a modification treatment. Among these, the gas barrier layer is preferably a gas barrier layer made of an inorganic film and a gas barrier layer obtained by implanting ions into a layer containing a polymer compound because a layer having a small thickness and excellent gas barrier properties can be efficiently formed. .

The inorganic film is not particularly limited, and examples thereof include an inorganic vapor deposition film.
Examples of the inorganic vapor deposition film include vapor deposition films of inorganic compounds and metals.
As the raw material for the vapor-deposited film of the inorganic compound, 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 oxynitrides such as silicon oxynitride; inorganic oxide carbides; inorganic nitride carbides; inorganic oxynitride carbides and the like.
Examples of the raw material for the metal vapor deposition film include aluminum, magnesium, zinc, and tin.
In a gas barrier layer obtained by ion implantation into a layer containing a polymer compound (hereinafter sometimes referred to as “polymer layer”), the polymer compound used is a silicon-containing polymer such as polyorganosiloxane or polysilazane compound. Compound, polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin polymer, aromatic System polymers and the like. These polymer compounds can be used alone or in combination of two or more.
Among these, from the viewpoint of forming a gas barrier layer having excellent gas barrier properties, silicon-containing polymer compounds are preferable, and polysilazane compounds are more preferable.

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

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

In said formula (1), n represents arbitrary natural numbers.
Rx, Ry, and Rz each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, unsubstituted or substituted Represents a non-hydrolyzable group such as an aryl group having a group or an alkylsilyl group; Among these, as Rx, Ry, and Rz, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group is preferable, and a hydrogen atom is particularly preferable. Examples of the polysilazane compound having a repeating unit represented by the formula (1) include inorganic polysilazanes in which Rx, Ry, and Rz are all hydrogen atoms, and organic polysilazanes in which at least one of Rx, Ry, and Rz is not a hydrogen atom. It may be.

  The polysilazane compounds can be used alone or in combination of two or more. In the present invention, a modified polysilazane compound can also be used as the polysilazane compound. In the present invention, as the polysilazane compound, a commercially available product as a glass coating material or the like can be used as it is.

The polymer layer may contain other components in addition to the above-described polymer compound as long as the object of the present invention is not impaired. Examples of other components include curing agents, other polymers, anti-aging agents, light stabilizers, and flame retardants.
The content of the polymer compound in the polymer layer is preferably 50% by mass or more and more preferably 70% by mass or more because a gas barrier layer having better gas barrier properties can be obtained.

The thickness of the polymer layer is not particularly limited, but is preferably in the range of 50 to 300 nm, more preferably 50 to 200 nm.
In the present invention, even if the thickness of the polymer layer is nano-order, a gas barrier laminate having a sufficient gas barrier property can be obtained.

  As a method for forming a polymer layer, for example, a known device such as a spin coater, a knife coater, a gravure coater, or the like is used to form a layer forming solution containing at least one kind of a polymer compound, and optionally other components and a solvent The method of using and apply | coating and forming the coating film obtained by drying moderately is mentioned.

Examples of the polymer layer modification treatment include ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, and heat treatment.
The ion implantation process is a method of modifying the polymer layer by implanting ions into the polymer layer, as will be described later.
The plasma treatment is a method for modifying the polymer layer by exposing the polymer layer to plasma. For example, plasma treatment can be performed according to a method described in Japanese Patent Application Laid-Open No. 2012-106421.
The ultraviolet irradiation treatment is a method for modifying the polymer layer by irradiating the polymer layer with ultraviolet rays. For example, the ultraviolet modification treatment can be performed according to the method described in JP2013-226757A.
Among these, the ion implantation treatment is preferable because the gas barrier layer can be efficiently modified to the inside without roughening the surface of the polymer layer and more excellent in gas barrier properties.

As ions implanted into the polymer layer, ions of rare gases such as argon, helium, neon, krypton, and xenon; ions such as fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur;
Ions of alkane gases such as methane and ethane; Ions of alkene gases such as ethylene and propylene; Ions of alkadiene gases such as pentadiene and butadiene; Ions of alkyne gases such as acetylene; Benzene, toluene, etc. Ions of aromatic hydrocarbon gases such as: ions of cycloalkane gases such as cyclopropane; ions of cycloalkene gases such as cyclopentene; ions of metals; ions of organosilicon compounds;
These ions can be used alone or in combination of two or more.
Among these, ions of rare gases such as argon, helium, neon, krypton, and xenon are preferable because ions can be more easily implanted and a gas barrier layer having particularly excellent gas barrier properties can be obtained.

  The method for implanting ions is not particularly limited. For example, there are a method of irradiating ions accelerated by an electric field (ion beam), a method of injecting ions in plasma (ion of plasma generation gas), etc., and a gas barrier layer can be easily obtained. A method of implanting ions is preferred. In the plasma ion implantation method, for example, plasma is generated in an atmosphere containing a plasma generation gas, and a negative high voltage pulse is applied to a layer into which ions are implanted, whereby ions (positive ions) in the plasma are ionized. Can be performed by injecting into the surface portion of the layer to be injected.

The manufacturing method of a sealing sheet ((beta)) is not specifically limited. For example, in the manufacturing method of the sealing sheet (α) described above, the sealing sheet (β) can be manufactured by replacing one of the release films with a gas barrier film.
Moreover, after manufacturing a sealing sheet ((alpha)), the sealing sheet ((beta)) is manufactured by peeling the one peeling film and sticking the exposed adhesive bond layer and a gas-barrier film. You can also. In this case, when the sealing sheet (α) has two release films having different release forces, it is preferable to release the release film having the smaller release force from the viewpoint of handleability.

3) Sealing body The sealing body of the present invention is formed by sealing an object to be sealed with the sealing sheet of the present invention.
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. The sealing material is an adhesive layer of the sealing sheet of the present invention.

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 blocking performance for blocking moisture and gas to enter from the outside of the element and having excellent solvent resistance and weather resistance is preferable. Specifically, transparent inorganic materials such as quartz and glass; polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, polyphenylene sulfide, polyvinylidene fluoride, acetyl cellulose, brominated phenoxy, aramids, polyimides, And transparent plastics such as polystyrenes, polyarylates, polysulfones, and polyolefins.
The thickness of the transparent substrate is not particularly limited, and can be appropriately selected in consideration of light transmittance and performance for blocking the inside and outside of the element.

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

The manufacturing method of the sealing body of this invention is not specifically limited. For example, after the peeling film is peeled from the sealing sheet of the present invention and the exposed adhesive layer is stacked on the object to be sealed, the sealed body of the present invention can be manufactured by heating.
The heating conditions are not particularly limited, and conventional heat sealing conditions can be used as appropriate.
For example, the heating temperature is usually 23 to 120 ° C, preferably 40 to 100 ° C.
Moreover, heating time is 0.1 to 60 minutes normally, Preferably it is 0.2 to 60 minutes.

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

[Example 1]
100 parts of modified polyolefin resin (α-olefin polymer, manufactured by Mitsui Chemicals, trade name: Unistor H-200, weight average molecular weight: 52,000), tackifier (mainly using 1,3-pentadiene) Petroleum resin, manufactured by Nippon Zeon Co., Ltd., trade name: Quinton A100), 30 parts of a crosslinking agent (isocyanate-based crosslinking agent, manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate HX) are dissolved in methyl ethyl ketone, and the solid content concentration An 18% coating solution was prepared.
This coating solution was applied onto the release-treated surface of a release film (product name: SP-PET382150, manufactured by Lintec Corporation), and the resulting coating film was dried at 100 ° C. for 2 minutes, and an adhesive layer having a thickness of 20 μm. Was formed, and the release treatment surface of another release film (trade name: SP-PET381031 manufactured by Lintec Co., Ltd.) was bonded thereto to obtain a sealing sheet 1.

[Example 2]
A sealing sheet 2 was obtained in the same manner as in Example 1 except that the crosslinking agent was changed to an aluminum chelate crosslinking agent (trade name: M-5A, manufactured by Soken Chemical Co., Ltd.) in Example 1.

Example 3
In Example 1, the sealing sheet 3 was obtained in the same manner as in Example 1 except that the crosslinking agent was changed to 0.1 part of an epoxy-based crosslinking agent (trade name: TC-5, manufactured by Mitsubishi Chemical Corporation). .

[Comparative Example 1]
In Example 1, the sealing sheet 4 was obtained like Example 1 except the point which does not use a tackifier and a crosslinking agent.

[Comparative Example 2]
In Example 2, the sealing sheet 5 was obtained like Example 2 except the point which does not use a tackifier.

The following tests were conducted on the sealing sheets 1 to 5 obtained in Examples 1 to 3 and Comparative Examples 1 and 2.
(Water vapor transmission rate measurement)
Using a water vapor transmission rate measuring device (trade name: L80-5000, manufactured by LYSSY), the water vapor transmission rate of the sealing sheets 1 to 5 in an environment of a temperature of 40 ° C. and a relative humidity of 90% was measured.

(Measurement of peel adhesive strength)
One release film of the sealing sheet cut to a size of 25 mm × 300 mm was peeled off, and the exposed adhesive layer was layered on a polyethylene terephthalate sheet (trade name: Cosmo Shine PET50A4300, thickness 50 μm), heat laminator These were adhered at 110 ° C. using Next, another release film was peeled off, and the exposed adhesive layer was stacked on a glass plate, and these were pressure-bonded at 110 ° C. using a heat laminator.
Using this as a test piece, in accordance with JIS Z0237: 2009, in an environment of a temperature of 23 ° C., a relative humidity of 50% and an environment of a temperature of 70 ° C. (humidity is not controlled), the peeling angle is 180 °, respectively. A peel test was performed under the conditions, and the peel adhesive strength (N / 25 mm) was measured.
The measurement results are shown in Table 1.

Table 1 shows the following.
The adhesive layers of the sealing sheets 1 to 3 of Examples 1 to 3 are excellent in moisture barrier properties and adhesive strength at normal temperature and high temperature.
On the other hand, the adhesive layers of the sealing sheets 4 and 5 of Comparative Examples 1 and 2 are inferior in all of moisture barrier properties and adhesive strength at normal temperature and high temperature.

Claims (11)

The adhesive composition containing the following (A) component, (B) component, and (C) component.
(A) Component: Modified polyolefin resin (B) Component: Tackifier (C) Component: Crosslinking agent   The adhesive composition according to claim 1, wherein the component (A) is an acid-modified polyolefin resin.   The adhesive composition according to claim 1 or 2, wherein the content of the component (A) is 50 to 99 mass% with respect to the total solid content of the adhesive composition.   The adhesive composition according to any one of claims 1 to 3, wherein the content of the component (B) is 1 to 100 parts by mass with respect to 100 parts by mass of the component (A).   The adhesive composition according to any one of claims 1 to 4, wherein a content of the component (C) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A). Furthermore, the adhesive composition in any one of Claims 1-5 containing the following (D) component.
(D) component: Silane coupling agent A sealing sheet comprising two release films and an adhesive layer sandwiched between these release films,
The sealing sheet which is what the said adhesive bond layer is formed using the adhesive composition in any one of Claims 1-6, and has thermoplasticity. A sealing sheet comprising a release film, a gas barrier film, and an adhesive layer sandwiched between the release film and the gas barrier film,
The sealing sheet which is what the said adhesive bond layer is formed using the adhesive composition in any one of Claims 1-6, and has thermoplasticity.   The sealing sheet according to claim 8, wherein the gas barrier film is a metal foil, a resin film, or a thin film glass.   The sealing body by which a to-be-sealed thing is sealed with the sealing sheet in any one of Claims 7-9.   The sealing body according to claim 10, wherein the object to be sealed is an organic EL element, an organic EL display element, a liquid crystal display element, or a solar cell element.