KR20190130565A - Gas barrier films, and encapsulation bodies - Google Patents

Abstract

The gas barrier film of this invention is a gas barrier film which has a laminated body formed by laminating | stacking a peeling sheet, a base layer, a gas barrier layer, and an adhesive bond layer in this order, The said adhesive bond layer is a polyolefin resin (A). And a layer formed of an adhesive composition containing a thermosetting component (B).

Description

Gas barrier films, and encapsulation bodies

The present invention relates to a gas barrier film and an encapsulation body in which an encapsulated object is sealed with the gas barrier film.

In recent years, the organic EL element has attracted attention as a light emitting element capable of high luminance light emission by low voltage direct current driving. However, the organic EL device has a problem that light emission characteristics such as light emission luminance, light emission efficiency, light emission uniformity, and the like tend to decrease with time.

The problem of deterioration in performance over time represented by an organic EL element is a problem generally applied to an electronic member or an optical member that has recently attracted attention. As the cause, it is considered that oxygen, moisture, or the like penetrates inside the electronic member or the optical member, causing performance deterioration.

And as a countermeasure against this cause, several methods of sealing the electronic member, optical member, etc. which become a to-be-enclosed object with the gas barrier sealing material which have a laminated constitution are proposed.

For example, Patent Literature 1 discloses a gas barrier adhesive sheet having a layer structure of a release sheet / protective layer / gas barrier layer / adhesive layer / peel sheet as a sealing material. The invention of the gas barrier adhesive sheet of such a structure is based on the idea of providing the transfer laminated body which has a gas barrier layer (paragraph 0004 of patent document 1). That is, in the case of the transfer laminate, the pressure-sensitive adhesive layer is bonded to the packaged object, and then the release sheet is removed. Thus, the release sheet functions as the support until the gas barrier member is applied to the packaged object and is protected. Since the layer does not need to have a function as a support, the choice of the material of the protective layer is widened. Although an adhesive layer or an adhesive bond layer is indispensable to such a transfer laminated body, Patent Document 1 describes an acrylic pressure sensitive adhesive, a rubber pressure sensitive adhesive, a polyurethane pressure sensitive adhesive, and a silicone pressure sensitive adhesive as an adhesive to form an adhesive layer.

In addition, Patent Literature 2 discloses a gas barrier film having a layer structure of a cured resin layer / gas barrier layer / adhesive layer as a sealing material. Also in the invention concerning patent document 2, the form in which the process sheet was laminated | stacked on the cured resin layer is disclosed (refer paragraph 0138 of patent document 2), and the gas barrier film in this case is a laminated body for transcription | transfer similarly to patent document 1 Can be used. The gas barrier film using the cured resin layer of the invention which concerns on patent document 2 is excellent in heat resistance, solvent resistance, interlayer adhesiveness, gas barrier property, low birefringence, and excellent optical isotropy (paragraph 0007 of patent document 2) . Patent Literature 2 describes an adhesive or pressure-sensitive adhesive such as acrylic, silicone or rubber as a material for forming an adhesive layer.

WO2013 / 018602 WO2013 / 065812

In the encapsulant disclosed in Patent Literatures 1 and 2, the advantages of adopting a form called a transfer laminate are recognized, but over a long period of time, excellent encapsulation performance with respect to the encapsulated product (on the encapsulated product due to the action from the outside world). There was room for improvement in maintaining the performance of preventing damage).

Then, this invention was made | formed in order to solve the said subject, The original performance which the to-be-encapsulated object retained over a long term with respect to the gas barrier film which is a form of the transfer laminated body is preferably maintained, and sealed to the to-be-enclosed object It is an object to provide a gas barrier film excellent in performance, and to provide a sealing body in which an encapsulated object is sealed with the gas barrier film.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in view of the said subject, the inventors formed the adhesive bond layer with the adhesive composition containing polyolefin resin (A) and a thermosetting component (B), and the original performance which the to-be-enclosed thing had over the long term It was preferably maintained, and found that the sealing performance with respect to the to-be-encapsulated object was excellent, and came to complete this invention.

That is, this invention is as follows.

[1] A gas barrier film having a laminate obtained by laminating a release sheet, a base layer, a gas barrier layer, and an adhesive layer in this order, wherein the adhesive layer includes a polyolefin resin (A) and a thermosetting component (B). A gas barrier film, which is a layer formed of an adhesive composition containing a.

[2] The gas barrier film according to the above [1], wherein the polyolefin resin (A) contains a modified polyolefin resin (A1).

[3] The gas barrier film according to the above [1] or [2], wherein the thermosetting component (B) contains a thermosetting epoxy resin (B1).

[4] The gas barrier film according to any one of the above [1] to [3], wherein the adhesive layer is directly laminated on the gas barrier layer.

[5] The gas barrier film according to any one of the above [1] to [4], wherein the adhesive layer is laminated on the gas barrier layer via an adhesion improving layer.

[6] The gas barrier film according to any one of the above [1] to [5], wherein the base layer is a layer formed of a composition for an underlayer containing an energy ray curable component.

[7] The gas barrier film according to any one of the above [1] to [6], wherein the base layer is a layer further formed of a composition for a base layer containing a thermoplastic resin.

[8] The gas barrier film according to the above [7], wherein the glass transition temperature (Tg) of the thermoplastic resin is 140 ° C or higher.

[9] The gas barrier film according to any one of [1] to [8], wherein the base layer has a thickness of 0.1 to 10 µm.

[10] The gas barrier film according to any one of [1] to [9], wherein the gas barrier layer is a layer containing a polysilazane compound and formed by modification treatment.

[11] The encapsulated material of at least one selected from the group consisting of an organic EL element, an organic EL display element, an inorganic EL element, an inorganic EL display element, an electronic paper element, a liquid crystal display element, and a solar cell element is the above-mentioned [1]. The sealing body formed by sealing with the gas barrier film in any one of-[10].

[12] A method for producing an encapsulation product comprising the step of adhering the adhesive layer included in the gas barrier film according to any one of claims 1 to 10 to the encapsulated object, and the step of peeling the release sheet from the gas barrier film. .

According to the present invention, the gas barrier film, which is a form of a transfer laminate, preferably retains the original performance of the encapsulated product over a long period of time, thereby providing a gas barrier film having excellent encapsulation performance on the encapsulated product. In addition, the encapsulated object can be provided with the sealing body by which the to-be-encapsulated object is sealed by the said gas barrier film.

[Gas Barrier Film]

The gas barrier film of this invention has a laminated body which laminates a peeling sheet, a base layer, a gas barrier layer, and an adhesive bond layer in this order, and the said adhesive bond layer is a polyolefin resin (A) and a thermosetting component (B) ) Is a layer formed of an adhesive composition containing.

In addition, "gas barrier property" says here the characteristic of preventing permeation | transmission of gas, such as oxygen and water vapor.

The gas barrier film of the present invention is not particularly limited as long as the gas barrier film is formed by laminating a release sheet, a base layer, a gas barrier layer, and an adhesive layer in this order, but the adhesive layer may be directly laminated on the gas barrier layer. You may laminate on the gas barrier layer through an adhesive improvement layer.

As a layer structure which the gas barrier film of this invention has, the aspect shown below which has a 2nd peeling sheet laminated | stacked arbitrarily on an adhesive bond layer is mentioned, for example.

1st peeling sheet / base layer / gas barrier layer / adhesive layer / 2nd peeling sheet

1st peeling sheet / base layer / gas barrier layer / adhesive improvement layer / adhesive layer / 2nd peeling sheet

In the aspect of the layer structure described above, the first release sheet and the second release sheet may be the same or different.

The aspect of said laminated constitution showed the state before using a gas barrier film as a sealing material, and when using, it peels and removes a 2nd peeling sheet normally and adheres the surface of the exposed adhesive bond layer, and a to-be-encapsulated object. To obtain an encapsulation material.

Moreover, after sticking the surface of the adhesive bond layer of a sealing material and the surface of a to-be-sealed | blocked object, a 1st peeling sheet is peeled off normally, and a resin layer can be exposed, and it can be set as the layer structure shown below.

Base layer / gas barrier layer / adhesive layer

Base layer / gas barrier layer / adhesive improvement layer / adhesive layer

Even if it does not have a base material, the gas barrier film of this invention functions as a support body and a protective member of a gas barrier film, until the 1st peeling sheet is peeled off.

[Laminated body]

The laminated body of this invention is comprised by laminating | stacking a peeling sheet, a base layer, a gas barrier layer, and an adhesive bond layer in this order, and comprises an adhesive bond layer, The adhesive composition containing polyolefin resin (A) and a thermosetting component (B) To form.

The water vapor transmission rate of the laminate constituting the gas barrier film of the present invention is preferably 5.0 g / m 2 / day or less, more preferably 0.5 g / m 2 / day or less, still more preferably 5 × 10 ⁻² ( g / m 2 / day) or less, and still more preferably 5 × 10 ⁻³ (g / m 2 / day) or less.

In this invention, since the water vapor transmission rate of the said laminated body exists in the said range, the gas barrier film which has the outstanding gas barrier property with high effect of preventing permeation | transmission of gas, such as oxygen and water vapor, is obtained.

Here, "water vapor transmission rate" refers to the value measured in 40 degreeC and the high-temperature, high-humidity environment of 90% of a relative humidity using a water vapor transmission rate measuring apparatus, but a more specific measuring method is based on the method of the Example mentioned later. Moreover, although it is preferable to peel off and remove a 1st peeling sheet after the gas barrier film of this invention is applied to a to-be-encapsulated object, since the water vapor transmission rate of a peeling sheet is generally very high compared with the water vapor transmission rate of a gas barrier layer, The water vapor transmission rate of the laminated body measured with 1 peeling sheet left is considered to reflect the gas barrier performance of the membranous body in which the 1st peeling sheet was removed from the laminated body and formed on a to-be-encapsulated object. Therefore, the water vapor transmission rate of the gas barrier film in this invention is made into the numerical value measured with leaving the 1st peeling sheet in order to maintain the self-supporting property of a gas barrier film, as shown in the Example mentioned later.

Adhesive Layer

MEANS TO SOLVE THE PROBLEM The present inventors used the gas barrier film which has a normal adhesive bond layer as a sealing material, The sealing body formed by sealing the to-be-sealed | blocked object with the said sealing material was exposed for a long time in the environment of high temperature, high humidity as an accelerated test, The knowledge which degrades the original performance which the thing had was acquired.

The reason for this is that the adhesion between the adhesive layer of the encapsulant and the adhesive surface of the encapsulated material is lowered, so that partial peeling occurs between the adhesive layer of the encapsulant and the encapsulated material, and oxygen, water vapor, etc. Gas was invaded, and the encapsulated material was thought to be adversely affected.

Then, the inventors examined the formation material of the adhesive bond layer which was excellent in adhesive strength for the long term with little adhesive fall of the adhesive bond layer of the sealing material and the adhesive surface of the to-be-sealed material.

MEANS TO SOLVE THE PROBLEM As a result of repeated examination, this inventor formed the adhesive bond layer from the adhesive composition containing polyolefin resin (A) and a thermosetting component (B), and in the adhesive surface of the sealing material and the to-be-encapsulated material over a long term, It was found that good adhesion was maintained.

The thickness of an adhesive bond layer becomes like this. Preferably it is 0.5-300 micrometers, More preferably, it is 3-200 micrometers, More preferably, it is 5-150 micrometers, More preferably, it is 5-80 micrometers.

When the thickness of the said adhesive bond layer exists in the said range, when using a gas barrier film as a sealing material, it becomes easy to use preferably.

(Adhesive Composition)

The adhesive bond layer of this invention is formed from the adhesive composition containing polyolefin resin (A) and a thermosetting component (B).

Thereby, the water vapor barrier property of an adhesive bond layer becomes high, sealing performance can be improved, the adhesive strength excellent in the adhesive surface of the adhesive material of an sealing material and the to-be-encapsulated object is obtained, and the adhesive bond of an sealing material and the to-be-encapsulated material is acquired, Good adhesion on cotton is maintained for a long time. Therefore, the original performance which the to-be-encapsulated object retained preferably is obtained, and the gas barrier film excellent in the sealing performance with respect to the to-be-encapsulated object is obtained.

Hereinafter, each component contained in the adhesive composition preferable as a formation material of an adhesive bond layer is described.

<Polyolefin resin (A)>

The adhesive composition of this invention contains polyolefin resin (A).

Thereby, the water vapor transmission rate of an adhesive bond layer becomes low and a gas barrier film is excellent in water barrier property.

"Polyolefin resin" refers to the polymer which has a repeating unit derived from an olefin monomer here.

As an olefinic monomer, a C2-C8 alpha olefin is preferable, Especially, ethylene, propylene, 1-butene, isobutylene, 1-pentene, 4-methyl-1- pentene, and 1-hexene are preferable. Do.

In addition, the polyolefin resin may have a unit derived from two or more kinds of α-olefins. Moreover, the polymer which consists only of the repeating unit derived from an olefinic monomer may be sufficient as polyolefin resin, and the polymer which consists of the repeating unit derived from the olefinic monomer and the repeating unit derived from the monomer copolymerizable with an olefinic monomer may be sufficient as it. As a monomer copolymerizable with an olefinic monomer, vinyl acetate, (meth) acrylic acid ester, styrene, etc. are mentioned, for example.

As polyolefin resin (A), For example, ultra low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene, polypropylene (PP), Ethylene-propylene copolymer, olefin elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, polyisobutylene, polyisoprene, etc. Can be mentioned.

As said polyolefin resin (A), it is preferable to contain modified polyolefin resin (A1). Thereby, an adhesive bond layer becomes more excellent in adhesive strength.

Here, "modified polyolefin resin (A1)" means the polymer in which the polyolefin resin (A) used as a precursor reacts with a modifier, and the functional group which a modifier has in the polyolefin resin (A) used as a main chain is introduced as a side chain. Say it.

In addition, the modifier may have 2 or more types of functional groups in a molecule | numerator.

As a functional group which a modifier has, the functional group which can be introduce | transduced as a side chain into the polyolefin resin (A) which becomes a principal chain, For example, the group derived from a carboxyl group, carboxylic anhydride, a carboxylic ester group, a hydroxyl group , Epoxy group, amide group, ammonium group, nitrile group, amino group, imide group, isocyanate group, acetyl group, thiol group, ether group, thioether group, sulfone group, phosphone group, nitro group, urethane group, halogen atom, alkoxysilyl, etc. Can be mentioned.

Among these functional groups, carboxyl group, group derived from carboxylic anhydride, carboxylic acid ester group, hydroxyl group, ammonium group, amino group, imide group, isocyanate, alkoxysilyl group are preferable, and the group derived from carboxylic anhydride is especially preferable. Do.

(Acid Modified Polyolefin Resin)

Examples of the modified polyolefin resins include acid-modified polyolefin resins and silane-modified polyolefin resins.

Among these, acid-modified polyolefin resin is preferable from a viewpoint of high reactivity with a thermosetting component (B).

The term "acid-modified polyolefin resin" refers to a polymer in which an acid group is introduced as a side chain to a polyolefin resin (A) which becomes a main chain by reacting with a compound having an acid group by the polyolefin resin (A) serving as a precursor. .

Moreover, the method and conditions which introduce | transduce the acidic radical of the compound which has an acidic group as a side chain into the polyolefin resin (A) used as a principal chain can employ | adopt a well-known side chain introduction method.

The compound having an acid group is not particularly limited as long as it can be introduced into the polyolefin resin (A) serving as the main chain as the side chain, but preferably an unsaturated carboxylic acid and an anhydride thereof are mentioned.

As unsaturated carboxylic acid and its anhydride, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, glutamic acid, tetrahydrophthalic acid, aconic acid, maleic anhydride, itaconic anhydride, glutamic anhydride Citraconic anhydride, aconitic anhydride, norbornene dicarboxylic acid anhydride, tetrahydrophthalic anhydride, and the like. These unsaturated carboxylic acids and their anhydrides can be used individually by 1 type or in combination of 2 or more type.

Among these unsaturated carboxylic acids and anhydrides thereof, maleic anhydride is preferred because an adhesive composition having better adhesion strength can be easily obtained.

A commercial item can also be used as acid-modified polyolefin resin.

Examples of commercially available acid-modified polyolefin resins include admer (registered trademark) (manufactured by Mitsui Chemical Co., Ltd.), Unistol (registered trademark) (manufactured by Mitsui Chemical Co., Ltd.), BondyRam (manufactured by Polyram), orevac (registered trademark). (Made by ARKEMA Corporation), Modic (trademark) (made by Mitsubishi Chemical Corporation), etc. are mentioned.

The compounding quantity of the compound which has an acidic radical made to react with the polyolefin resin (A) used as a precursor becomes like this. Preferably it is 0.1-5 mass parts with respect to 100 mass parts of polyolefin resin (A) used as a precursor, More preferably, it is 0.2-. 3 mass parts, More preferably, it is 0.2-1.0 mass part.

When the compounding quantity of the compound which has the said acidic radical exists in the said range, an adhesive composition is more excellent in adhesive strength.

(Silane-modified polyolefin resin)

The term "silane-modified polyolefin resin" refers to a polymer in which a polyolefin resin (A) serving as a precursor reacts with a compound having a silane group, and a silane group is introduced as a side chain into the polyolefin resin (A) serving as a main chain. .

Moreover, the method and conditions which introduce | transduce the silane group of the compound which has a silane group as a side chain into the polyolefin resin (A) used as a principal chain can employ | adopt a well-known side chain introduction method.

The compound having a silane group is not particularly limited as long as it can be introduced into the polyolefin-based resin (A) serving as the main chain as the side chain, but an unsaturated silane compound is preferable.

As an unsaturated silane compound, a vinyl silane compound is preferable, For example, a vinyl trimethoxysilane, a vinyl triethoxysilane, a vinyl tripropoxy silane, a vinyl triisopropoxy silane, a vinyl tributoxy silane, a vinyl tri Pentyloxysilane, vinyltriphenoxysilane, vinyltribenzyloxysilane, vinyltrimethylenedioxysilane, vinyltriethylenedioxysilane, vinylpropionyloxysilane, vinyltriacetoxysilane, vinyltricarboxysilane and the like. have. These unsaturated silane compounds can be used individually by 1 type or in combination of 2 or more type.

Specific silane-modified polyolefin resins include, for example, silane-modified polyethylene resins and silane-modified ethylene-vinyl acetate copolymers. Among them, silane-modified low density polyethylene, silane-modified ultra low density polyethylene, and silane-modified linear type Silane modified polyethylene resins, such as low density polyethylene, are preferable.

A commercial item can also be used as a silane modified polyolefin resin.

Examples of commercially available silane-modified polyolefin resins include, for example, Linkron (registered trademark) (manufactured by Mitsubishi Chemical Co., Ltd.). Of course, ultra low density polyethylene linkons and ethylene-vinyl acetate copolymerization linkons are preferable.

The compounding quantity of the compound which has a silane group made to react with the polyolefin resin (A) used as a precursor becomes like this. Preferably it is 0.1-10 mass parts, More preferably, it is 0.3-10 with respect to 100 mass parts of polyolefin resin (A) used as a precursor. 7 mass parts, More preferably, it is 0.5-5 mass parts.

When the compounding quantity of the compound which has the said silane group exists in the said range, the adhesive composition containing the silane modified polyolefin resin obtained is more excellent in adhesive strength.

The weight average molecular weight (Mw) of the polyolefin resin (A) is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000, still more preferably 25,000 to 250,000, even more preferably 30,000 to 150,000.

When the said weight average molecular weight (Mw) exists in the said range, even when there is much content of polyolefin resin (A) in an adhesive composition, it becomes easy to maintain the shape of the sheet | seat formed from an adhesive composition.

Here, "weight average molecular weight (Mw)" refers to the value calculated | required by conversion of standard polyethylene using tetrahydrofuran as a solvent and using gel permeation chromatography.

Polyolefin resin (A) may be comprised only by modified polyolefin resin (A1), and may be comprised by modified polyolefin resin (A1) and non-modified polyolefin resin.

The content of the modified polyolefin resin (A1) is preferably 50 to 100% by mass, more preferably 65 to 100% by mass, furthermore, based on the total amount (100% by mass) of the polyolefin resin (A) described above. Preferably it is 80-100 mass%, More preferably, it is 90-100 mass%.

When content of the said modified polyolefin resin (A1) exists in the said range, an adhesive composition is more excellent in adhesive strength.

The content of the polyolefin-based resin (A) is preferably 30 to 95 mass%, more preferably 45 to 90 mass%, even more preferably relative to the total amount (100 mass%) of the active ingredients of the adhesive composition described above. Is 50-85 mass%.

The "active component of an adhesive composition" refers to the component except the solvent contained in an adhesive composition here.

When content of the said polyolefin resin (A) exists in the said range, an adhesive composition is more excellent in adhesive strength.

<Thermosetting Component (B)>

The adhesive composition of this invention contains a thermosetting component (B).

Thereby, the adhesive strength excellent in the adhesive surface of the sealing material and the to-be-enclosed object is easy to be obtained.

"The thermosetting component (B)" refers to the component which becomes a network structure and hardens | cures in the insoluble insoluble state when it heats here.

As a thermosetting component (B), a thermosetting epoxy resin, a melamine resin, a urea resin, a maleimide resin, etc. are mentioned, for example.

It is preferable to contain a thermosetting epoxy resin (B1) as said thermosetting component (B).

"The thermosetting epoxy resin (B1)" refers to the epoxy compound which becomes a network structure and hardens | cures in the insoluble insoluble state when it heats here.

Moreover, it is preferable to contain a polyfunctional epoxy resin (B2) as said thermosetting epoxy resin (B1).

"Polyfunctional epoxy resin (B2)" refers to the compound which has 2 or more of epoxy groups at least in a molecule | numerator here.

As a polyfunctional epoxy resin (B2), since the outstanding adhesive strength becomes easier to be obtained in the adhesive surface of the adhesive bond layer of a sealing material and a to-be-encapsulated material, the bifunctional epoxy resin which has two epoxy groups in a molecule | numerator is preferable.

As a bifunctional epoxy resin, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, and brominated bisphenol F diglycid Aromatic epoxy, such as dil ether, brominated bisphenol S diglycidyl ether, and a novolak-type epoxy resin (for example, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, a brominated phenol novolak-type epoxy resin) Compound; Alicyclic epoxy compounds such as hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether and hydrogenated bisphenol S diglycidyl ether; Pentaerythritol polyglycidyl ether, 1,6-hexanediol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, neopentyl glycol diglycidyl ether, trimethylolpropanepolyglycidyl ether, 2, Aliphatic epoxy compounds such as 2-bis (3-glycidyl-4-glycidyloxyphenyl) propane and dimethyloltricyclodecane diglycidyl ether; Etc. can be mentioned. These bifunctional epoxy resins can be used individually by 1 type or in combination of 2 or more type.

The content of the thermosetting component (B) is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, still more preferably relative to the total amount (100% by mass) of the active ingredient of the adhesive composition described above. It is 10-30 mass%.

The "active component of an adhesive composition" refers to the component except the solvent contained in an adhesive composition here.

When content of the said thermosetting component (B) exists in the said range, the outstanding adhesiveness in the adhesive surface of the adhesive bond layer of a sealing material and to-be-enclosed object will become easy to be maintained.

Content of the thermosetting component (B) in the said adhesive composition becomes like this. Preferably it is 5-110 mass parts, More preferably, it is 10-100 mass parts with respect to 100 mass parts of polyolefin resin (A). The adhesive layer formed from the adhesive composition whose content of a thermosetting component (B) exists in this range is more excellent in water vapor barrier property.

<Curing Catalyst (C)>

It is preferable that the adhesive composition of this invention contains a curing catalyst (C) further from a viewpoint that the adhesive bond layer with a higher adhesive strength becomes easy to be obtained.

Here, "hardening catalyst (C)" refers to the catalyst which hardens a thermosetting component (B).

As a curing catalyst (C), an imidazole series curing catalyst is preferable from a viewpoint of advancing hardening of a thermosetting component (B) preferably.

Examples of the imidazole series curing catalysts include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and 2-ethyl-4-methyl. Midazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and the like. have. These imidazole series curing catalysts can be used individually by 1 type or in combination of 2 or more type.

Among these imidazole series curing catalysts, 2-ethyl-4-methylimidazole is preferable.

Content of the curing catalyst (C) contained in an adhesive composition becomes like this. Preferably it is 0.1-10 mass parts, More preferably, it is 0.5-5 mass parts with respect to 100 mass parts of thermosetting components (B).

When content of the said curing catalyst (C) exists in the said range, an adhesive bond layer has the outstanding adhesiveness also at the time of high temperature.

<Silane coupling agent (D)>

The adhesive composition of the present invention may further contain a silane coupling agent (D).

Thereby, adhesive strength in normal temperature and high temperature environment becomes more excellent.

Here, "silane coupling agent (D)" refers to the organosilicon compound which has 2 or more types of different reactors in a molecule | numerator.

As a silane coupling agent (D), the organosilicon compound which has at least 1 alkoxysilyl group in a molecule | numerator is preferable from a viewpoint of obtaining the outstanding adhesive strength.

As such a silane coupling agent, For example, polymerizable unsaturated group containing silicon compounds, such as vinyl trimethoxysilane, vinyl triethoxysilane, and methacryloxypropyl trimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, etc. Silicon compounds having an epoxy structure of; Amino group-containing silicon compounds such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane ; 3-chloropropyltrimethoxysilane; 3-isocyanate propyl triethoxysilane; Etc. can be mentioned. These silane coupling agents can be used individually by 1 type or in combination of 2 or more type.

Content of the silane coupling agent (D) contained in an adhesive composition becomes like this. Preferably it is 0.01-5.0 mass parts, More preferably, it is 0.05-1.0 mass part with respect to 100 mass parts of polyolefin resin (A).

When content of the said silane coupling agent (D) exists in the said range, even if it is exposed in a high temperature, high humidity environment for a long time, it becomes easy to maintain the outstanding adhesiveness in the contact surface of the adhesive bond layer of a sealing material, and a to-be-encapsulated object.

(menstruum)

The adhesive composition is preferably in the form of a solution by adding a solvent in view of making it easy to adjust the adhesive composition to a property suitable for application when the adhesive layer is formed by application.

As a solvent, For example, 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; aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-heptane; Alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, and methylcyclohexane; Etc. can be mentioned.

Among these, a ketone solvent is preferable, and dimethyl ethyl ketone is especially preferable.

The usage-amount of the solvent used for preparation of an adhesive composition may be used so that solid content concentration may be 8-48 mass%, More preferably, it is 8-38 mass%, More preferably, it is 8-28 mass%.

(Other ingredients)

Adhesive composition does not inhibit hardening of this invention other than said polyolefin resin (A), said thermosetting component (B), said curing catalyst (C), said silane coupling agent (D), and said solvent. In the range which does not carry out, you may contain another component further. As another component, a ultraviolet absorber, an antistatic agent, an optical stabilizer, antioxidant, a resin stabilizer, a filler, a pigment, an extender, a softener, a tackifier, etc. are mentioned, for example.

[Base layer]

By having a base layer, the gas barrier film of this invention suppresses damage and deterioration of a gas barrier layer, and can peel-release a peeling sheet efficiently.

It is preferable to laminate a base layer directly on a peeling sheet.

In addition, the underlayer is interposed between the release sheet and the gas barrier layer.

The thickness of the underlayer is preferably 0.1 to 10 µm, more preferably 0.5 to 5 µm.

When the thickness of the base layer is in the above range, the damage and deterioration of the gas barrier layer can be easily suppressed, and the peeling sheet can be easily peeled off efficiently. If the underlying layer is as thin as about 0.1 to 10 µm, it is easy to adjust the thickness of the entire gas barrier film to a small range, which is preferable for applications in which miniaturization of electronic devices such as organic EL elements is required. When a gas barrier film is comprised with a base material and a gas barrier layer, when a base material is made into such a thin thickness, handling of a gas barrier film may become difficult. In this invention, since a peeling sheet exists in the side opposite to the side laminated | stacked with the gas barrier layer of a base layer, the problem of handleability is eliminated. And since a peeling sheet is normally removed after apply | coating a gas barrier film to a to-be-sealed | blocked object, the member derived from the gas barrier film which remain | survives in a sealing body can be made thin.

In the case where the base layer is made thin, depending on the application, it may be desirable to set the thickness of the base layer to 1 to 20 μm, and in that case, the thickness of the base layer is more preferably 3 to 15 μm. to be.

The maximum cross-sectional height Rt of the roughness curve in each surface of the underlayer on the side of the base layer in contact with the release sheet or on the side of the underlayer opposite to the side in contact with the release sheet of the underlayer is preferably 1 to 1. 300 nm, More preferably, it is 1-200 nm, More preferably, it is 2-150 nm.

The maximum cross-sectional height Rt of a base layer can be measured by observing the surface of a base layer using an optical interference microscope. For example, in the manufacturing process of a gas barrier film, when a base layer is formed on a peeling sheet, the surface of the exposed base layer can be made into a measurement object.

By the said maximum cross-sectional height Rt being in the said range, peeling removal of a peeling sheet can be made easy efficiently, protecting a gas barrier layer preferably.

In addition, the said largest cross-sectional height Rt can be made into the said range by adjusting the average particle diameter and content of the inorganic filler mentioned later.

(Composition for Base Layer)

It is preferable that the base layer of this invention is formed from the composition for base layers containing an energy ray curable component. Moreover, it is also preferable that the composition for underlayers contains a thermoplastic resin.

Thereby, while making it easy to suppress a damage and deterioration of a gas barrier layer, it can make it easy to peel off and remove a peeling sheet efficiently.

Hereinafter, each component contained in the composition for base layers preferable as a formation material of a base layer is described.

<Thermoplastic>

When the composition for base layers contains a thermoplastic resin, the base layer which has moderate flexibility becomes easy to be obtained.

The term "thermoplastic resin" refers to a resin having a property of being melted or softened by heating and solidified when cooled.

As a thermoplastic resin, resin which has ring structures, such as resin which has aromatic ring structure, alicyclic structure, is mentioned, for example, Resin which has aromatic ring structure is preferable.

As resin which has an aromatic ring structure, polysulfone resin, polyarylate resin, polycarbonate resin, alicyclic hydrocarbon resin is preferable, and polysulfone resin is especially preferable. The polysulfone resin may be a modified polysulfone resin.

Where "polysulfone-based resin" refers to the main chain in the sulfone group (-SO ₂ -) it refers to point to a resin made of a polymer having.

As polysulfone resin, resin which consists of a high molecular compound which has a repeating unit represented by following (a)-(h) is mentioned.

Among these, as polysulfone resin, polyether sulfone resin and polysulfone resin are preferable, and polysulfone resin is more preferable especially.

[Formula 1]

[Formula 2]

Glass transition temperature (Tg) of a thermoplastic resin becomes like this. Preferably it is 140 degreeC or more, More preferably, it is 160 degreeC or more, More preferably, it is 180 degreeC or more.

"Glass transition temperature (Tg)" is here of tan-delta (loss elastic modulus / storage elastic modulus) obtained by viscoelasticity measurement (measurement by tension mode in the range of 0-250 degreeC with a frequency of 11 Hz and a heating rate of 3 degree-C / min). Refer to the temperature of the maximum point.

By the said glass transition temperature (Tg) being in the said range, it becomes easy to form the base layer excellent in heat resistance.

The weight average molecular weight (Mw) of the thermoplastic resin is usually 100,000 to 3,000,000, preferably 200,000 to 2,000,000, and more preferably 500,000 to 2,000,000.

Moreover, molecular weight distribution (Mw / Mn) of a thermoplastic resin becomes like this. Preferably it is 1.0-5.0, More preferably, it is 2.0-4.5.

"Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)" refer to the value of polystyrene conversion measured by the gel permeation chromatography (GPC) method here.

The content of the thermoplastic resin is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and even more preferably 50 to 90% by mass based on the total amount (100% by mass) of the active ingredient of the composition for the underlayer. 70 mass%.

In addition, a "active component of the composition for underlayer" refers to the component except the solvent contained in the composition for underlayer here.

When content of the said thermoplastic resin exists in the said range, the gas barrier film with moderate flexibility and strength will be easy to be obtained.

(Energy ray curable component)

By forming the base layer from the composition for the base layer containing the energy ray curable component, there is an advantage that a gas barrier film having a high transparency, a low birefringence, and a high optical isotropy is obtained. When obtaining a gas barrier film, when using a general polyester base material etc., optical anisotropy is high and light extraction property at the time of applying to a display etc. is inferior. On the other hand, although substrates with high optical isotropy, such as cycloolefin polymer, exist, handling is difficult and it may be difficult to improve manufacturing aptitude. By forming a base layer with the composition for base layers containing an energy ray curable component, it is possible to obtain a gas barrier film with high optical isotropy simply. In addition, the composition for base layers contains the advantage that the base layer which is excellent in solvent resistance becomes easy to be obtained by containing an energy ray curable component.

An energy ray curable component means resin which hardening reaction starts and changes to hardened | cured material by irradiating or heating energy rays, such as an electron beam and an ultraviolet-ray. The said energy ray curable component is a mixture which has a polymeric compound as a main component normally.

In addition, the said polymeric compound is a compound which has an energy-beam polymerizable functional group. As said energy-beam polymerizable functional group, ethylenically unsaturated groups, such as a (meth) acryloyl group, a vinyl group, an allyl group, and a styryl group, are illustrated.

As a polymeric compound, a (meth) acrylate derivative is mentioned, for example, As a specific example of a (meth) acrylate derivative, it is tricyclodecane dimethanol di (meth) acrylate, polyethylene, for example. Glycoldi (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, 1,10-decanedioldi (meth) acrylate, 1,6 -Hexane diol di (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, etc. are mentioned.

The molecular weight of the (meth) acrylate derivative is usually 3000 or less, preferably 200 to 2000, and more preferably 200 to 1000.

The energy ray curable component may contain an oligomer as a polymeric compound. Examples of the oligomers include polyester acrylate oligomers, epoxy acrylate oligomers, urethane acrylate oligomers, and polyol acrylate oligomers. Moreover, the energy ray curable component may contain polymerization initiators, such as a photoinitiator and a thermal polymerization initiator.

As an energy-beam curable component, the component (ultraviolet curable component) hardened | cured by ultraviolet irradiation is preferable. By using an ultraviolet curable component, the layer which consists of hardened | cured material of an energy ray curable component can be formed efficiently.

As a polymerization initiator, a photoinitiator is preferable, Specifically, an alkylphenone type photoinitiator, a phosphorus type photoinitiator, an oxime ester type photoinitiator, a benzophenone type photoinitiator, and a thioxanthone type photoinitiator are Especially, a phosphorus photoinitiator is more preferable especially.

As a phosphorus photoinitiator, it is 2,4,6- trimethyl benzoyl- diphenyl phosphine oxide, bis (2, 4, 6- trimethyl benzoyl)-phenyl phosphine oxide, ethyl (2, 4, 6, for example). -Trimethylbenzoyl) -phenylphosphinate, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, and the like.

Content of the polymerization initiator contained in an energy-beam curable component becomes like this. Preferably it is 0.5-6.5 mass parts, More preferably, it is 0.5-5.5 mass parts, More preferably, 0.5-4.5 with respect to 100 mass parts of said polymeric compounds. It is a mass part.

Content of an energy-beam curable component becomes like this. Preferably it is 30-90 mass% with respect to the total amount (100 mass%) of the active component of the composition for base layers mentioned above, More preferably, it is 50-70 mass%.

In addition, a "active component of the composition for underlayer" refers to the component except the solvent contained in the composition for underlayer here.

When content of the said energy-beam curable component exists in the said range, the base layer excellent in solvent resistance will become easy to be obtained.

<Weapon filler>

The composition for base layers may contain the inorganic filler. Examples of the inorganic material constituting the inorganic filler include metal oxides such as silica, aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide; Metal fluorides such as magnesium fluoride and sodium fluoride; Etc. can be mentioned. The surface of the inorganic filler may be modified with an organic compound.

Although the average particle diameter of an inorganic filler is not specifically limited, Preferably it is 5-100 nm. When the average particle diameter of an inorganic filler is too small, it may become difficult to fully raise the peelability of a peeling film. On the other hand, if the average particle diameter of an inorganic filler is in such a small range, it is easy to maintain the gas barrier property of the gas barrier layer formed on a base layer high.

The average particle diameter of an inorganic filler can be measured by the dynamic light scattering method using a particle size distribution measuring apparatus.

Content of an inorganic filler becomes like this. Preferably it is 10-70 mass%, More preferably, it is 50-70 mass% with respect to the total amount (100 mass%) of the active ingredient of the composition for base layers mentioned above.

In addition, a "active component of the composition for underlayer" refers to the component except the solvent contained in the composition for underlayer here.

When content of the said inorganic filler exists in the said range, it can make it easy to peel off and remove a peeling sheet efficiently, protecting a gas barrier layer preferably.

When the composition for the underlayer used in one aspect of the present invention contains a thermoplastic resin, the energy ray curable component contains a polymerizable compound and a polymerization initiator, and the composition for the underlayer does not contain an inorganic filler, The total content of the polymerizable compound and the polymerization initiator is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, furthermore, based on the total amount (mass%) of the active ingredients of the composition for the underlayer. Preferably it is 90-100 mass%.

In addition, a "active component of the composition for underlayer" refers to the component except the solvent contained in the composition for underlayer here.

(menstruum)

It is preferable that the composition for a base layer adds a solvent and forms it as a solution from a viewpoint of making it easy to adjust the composition for a base layer to the property suitable for application | coating in the process of forming a base layer by application | coating.

As a solvent, For example, Aliphatic hydrocarbon solvents, such as n-hexane and n-heptane; Aromatic hydrocarbon solvents such as toluene and xylene; Halogenated hydrocarbon solvents such as dichloromethane, ethylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane and monochlorobenzene; Alcohol solvents such as methanol, ethanol, propanol, butanol, and propylene glycol monomethyl ether; Ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone; Ester solvents such as ethyl acetate and butyl acetate; Cellosolve solvents such as ethyl cellosolve; Ether solvents such as 1,3-dioxolane; Etc. can be mentioned.

Among these, a halogenated hydrocarbon solvent is preferable, and dichloromethane is especially preferable.

As for the usage-amount of the solvent used for preparation of the composition for underlayers, solid content concentration of a thermoplastic resin becomes like this. Preferably it is 5-45 mass%, More preferably, it is 5-35 mass%, More preferably, it is 5-25 mass%. You can use

(Other ingredients)

In addition to a thermoplastic resin, an energy-beam curable component, an inorganic filler, and a solvent, the composition for underlayers may contain another component in the range which does not impair the effect of this invention. As another component, a plasticizer, antioxidant, a ultraviolet absorber, etc. are mentioned, for example.

[Peel sheet]

A conventionally well-known thing can be used for the peeling sheet (1st peeling sheet) laminated | stacked on a base layer.

As a release film, a conventionally well-known thing can be used. For example, what has a peeling layer peeled by the peeling agent on the base material for peeling sheets is mentioned. As a base material for peeling sheets, Paper base materials, such as glassine paper, a coated paper, a quality paper; Laminated paper which laminated thermoplastic resins, such as polyethylene, on these paper base materials; Plastic films such as polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polypropylene resin and polyethylene resin; Etc. can be mentioned. Examples of the release agent include rubber-based elastomers such as silicone resins, olefin resins, isoprene resins, butadiene resins, long chain alkyl resins, alkyd resins, and fluorine resins. Moreover, you may use the paper base material and plastic film which were illustrated as a base material for peeling sheets as it is, without forming a peeling layer.

When using a 2nd peeling sheet, two peeling films of a 1st peeling sheet and a 2nd peeling sheet may respectively use the same thing, and may use a different thing. When using two peeling films different from each other, it is preferable to use what has a peeling force different from each other. When the peeling force of two peeling films differs, a problem will not arise easily at the time of use of a gas barrier film. That is, by making peeling force of two peeling films different, the process of peeling peeling film for the first time from a gas barrier film can be performed more efficiently.

It is preferable that a 2nd peeling sheet has a peeling layer from a viewpoint of making peelability with an adhesive bond layer favorable.

The thickness of a release sheet becomes like this. Preferably it is 10-300 micrometers, More preferably, it is 20-125 micrometers, More preferably, it is 30-100 micrometers.

[Gas Barrier Layer]

By having a gas barrier layer, the gas barrier film of this invention can exhibit the outstanding gas barrier property with the high effect of preventing permeation | transmission of gas, such as oxygen and water vapor.

The gas barrier layer is interposed between the base layer and the adhesive layer.

Although the gas barrier layer can obtain the gas barrier property which satisfy | fills a fixed level even if it is one layer, the effect of gas barrier property can be heightened by laminating | stacking two or more gas barrier layers.

The two or more gas barrier layers may have the same thickness or different thicknesses.

The thickness of one gas barrier layer is usually in the range of 20 nm to 50 m, preferably 30 nm to 1 m, and more preferably 40 nm to 500 nm.

When the thickness of one layer of the gas barrier layer is in the above range, a gas barrier film having gas barrier properties that satisfies a constant level having a high effect of preventing the permeation of gases such as oxygen and water vapor is easily obtained.

When using two or more gas barrier layers, it is preferable that each gas barrier layer is a layer formed with the same composition all.

Thereby, interlayer adhesiveness between two or more gas barrier layers can be improved.

As a preferable aspect of a gas barrier layer, (i) the gas barrier layer which consists of an inorganic vapor deposition film, (ii) the gas barrier layer containing a gas barrier resin, and (iii) the layer containing a high molecular compound (henceforth a "polymer layer" Gas barrier layer formed by modifying the surface of the substrate (in this case, the gas barrier layer does not mean only the modified region, but means "a polymer layer including the modified region"). It is at least one species.

Among these, as a more preferable aspect of a gas barrier layer, it is at least 1 sort (s) chosen from the group which consists of (i) the gas barrier layer which consists of an inorganic vapor deposition film, and (iii) the gas barrier layer which modifies the surface of a polymer layer.

(i) a gas barrier layer formed of an inorganic vapor deposition film

As an inorganic vapor deposition film, an inorganic compound and a metal vapor deposition film are mentioned.

As a raw material of the vapor deposition film of an inorganic compound, Inorganic oxides, such as a silicon oxide, aluminum oxide, magnesium oxide, zinc oxide, an indium oxide, tin oxide, zinc oxide; Inorganic nitrides such as silicon nitride, aluminum nitride and titanium nitride; Inorganic carbide; Inorganic sulfides; Inorganic oxynitrides such as silicon oxynitride; Inorganic oxide carbides; Inorganic nitride carbides; Inorganic oxynitride carbides; and the like.

As a raw material of the metal vapor deposition film, aluminum, magnesium, zinc, tin, etc. are mentioned.

The raw materials of the vapor deposition film of these inorganic compounds and metals can be used individually by 1 type or in combination of 2 or more type.

As an inorganic vapor deposition film, the inorganic vapor deposition film which uses at least 1 sort (s) selected from the group which consists of an inorganic oxide, an inorganic nitride, and a metal from a gas barrier property is preferable.

Among these inorganic vapor deposition films, from the viewpoint of transparency, an inorganic vapor deposition film having at least one selected from the group consisting of inorganic oxides and inorganic nitrides as a raw material is more preferable.

In addition, a single layer may be sufficient as an inorganic vapor deposition film, and a multilayer may be sufficient as it.

The thickness of the inorganic vapor deposition film is preferably from 1 to 2,000 nm, more preferably from 3 to 1,000 nm, even more preferably from 5 to 500 nm, even more preferably from 40 to 200 nm from the viewpoint of gas barrier properties and handleability. .

The method of forming an inorganic vapor deposition film is not specifically limited, A well-known method can be employ | adopted.

As a method of forming an inorganic vapor deposition film, For example, PVD methods, such as a vacuum vapor deposition method, a sputtering method, an ion plating method; CVD methods such as thermal CVD method, plasma CVD method, and optical CVD method; Atomic layer deposition method (ALD method); Etc. can be mentioned.

(ii) a gas barrier layer comprising a gas barrier resin

As the gas barrier resin, for example, polyvinyl alcohol, partially saponified polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, and polychlorotrifluoro Resin which is hard to permeate | transmit gas, such as oxygen and water vapor, such as ethylene, is mentioned.

The thickness of the gas barrier layer containing the gas barrier resin is preferably from 1 to 2,000 nm, more preferably from 3 to 1,000 nm, even more preferably from 5 to 500 nm, even more preferably from the viewpoint of gas barrier properties. Is 40-200 nm.

As a method of forming a gas barrier layer containing a gas barrier resin, the method of apply | coating the solution containing gas barrier resin on a peeling film or a base material, and drying the obtained coating film suitably is mentioned, for example. have.

The coating method of the solution containing a gas barrier resin is not specifically limited, The spin coating method, the spray coating method, the bar coating method, the knife coating method, the roll coating method, the blade coating method, the die coating method, the gravure coating method, etc. Known coating methods are mentioned.

As a drying method of a coating film, well-known drying methods, such as hot air drying, hot roll drying, and infrared irradiation, are mentioned.

(iii) a gas barrier layer formed by modifying the surface of the polymer layer

In the gas barrier layer in which the surface of the polymer layer is modified, the polymer compound to be used includes a silicon-containing polymer compound, polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, Polyolefin, polyester, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, acrylic resin, alicyclic hydrocarbon resin, aromatic polymer and the like. These high molecular compounds can be used individually by 1 type or in combination of 2 or more type.

In addition to the polymer compound described above, the polymer layer may further contain other components within a range that does not impair the effects of the present invention. As another component, a hardening | curing agent, an antioxidant, a light stabilizer, a flame retardant, etc. are mentioned, for example.

Content of a high molecular compound becomes like this. Preferably it is 50 mass% or more, More preferably, it is 70 mass% or more with respect to the total amount (100 mass%) of the active ingredient of the composition for polymeric layers mentioned above.

In addition, a "active component of a composition for polymer layers" refers to the component except the solvent contained in a composition for polymer layers here.

When content of the said high molecular compound exists in the said range, it is easy to form the gas barrier layer excellent in gas barrier property.

Although the thickness in particular of a polymer layer is not restrict | limited, Preferably it is 20 nm-50 micrometers, More preferably, it is 30 nm-1 micrometer, More preferably, it is 40 nm-500 nm.

A polymer layer can be formed by apply | coating the liquid which melt | dissolved or disperse | distributed the high molecular compound to the organic solvent, for example by a well-known coating method on a peeling film or a base material layer, and drying the obtained coating film.

As an organic solvent, Aromatic hydrocarbon solvent, 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; aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-heptane; Alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane; Etc. can be mentioned. These organic solvents can be used individually by 1 type or in combination of 2 or more type.

The coating method of the solution which melt | dissolved or disperse | distributed the high molecular compound in the organic solvent is not specifically limited, The bar coating method, the spin coating method, the dipping method, the roll coating method, the gravure coating method, the knife coating method, the air knife coating method, the roll knife The coating method, the die coating method, the screen printing method, the spray coating method, the gravure offset method, etc. are mentioned.

As a drying method of the coating film for forming a polymer layer, well-known drying methods, such as hot air drying, hot roll drying, and infrared irradiation, are mentioned. Heating temperature becomes like this. Preferably it is 80-150 degreeC, and heating time is several ten second-several ten minutes normally.

In the gas barrier layer formed by modifying the surface of the polymer layer, examples of the method of modifying the surface of the polymer layer include ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, heat treatment, and the like.

As described later, the ion implantation treatment is a method of injecting accelerated ions into the polymer layer to modify the polymer layer.

Plasma treatment is a method of exposing a polymer layer in plasma and reforming a polymer layer. For example, the plasma treatment can be performed according to the method described in JP 2012-106421 A.

Ultraviolet irradiation treatment is a method of modifying a polymer layer by irradiating an ultraviolet-ray to a polymer layer. For example, according to the method of Unexamined-Japanese-Patent No. 2013-226757, an ultraviolet-ray modification process can be performed.

As a gas barrier layer in which the surface of a polymer layer is modified, it is preferable that it is obtained by performing an ion implantation process to the layer containing a silicon-containing high molecular compound from the point which is more excellent in gas barrier property.

Examples of the silicon-containing polymer compound include polysilazane compounds, polycarbosilane compounds, polysilane compounds, polyorganosiloxane compounds, poly (disilanylenephenylene) compounds, and poly (disilanyleneethynylenes). ) Compounds and the like, and polysilazane compounds are preferred among these.

A polysilazane type compound is a compound which has a repeating unit containing a -Si-N- bond (silazane bond) in a molecule | numerator. Specifically, the compound which has a repeating unit represented by following General formula (1) is preferable.

[Formula 3]

In general formula (1), n represents a repeating unit and represents one or more integers (i). 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 aryl group Or non-hydrolyzable groups such as alkylsilyl groups.

As the alkyl group of the unsubstituted or substituted alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n- C1-C10 alkyl groups, such as a pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, are mentioned.

As a cycloalkyl group of the unsubstituted or cycloalkyl group which has a substituent, C3-C10 cycloalkyl groups, such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group, are mentioned, for example.

As an alkenyl group of the alkenyl group which has an unsubstituted or substituted group, For example, carbon number, such as a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, and 3-butenyl group, etc. Alkenyl group of -10 is mentioned.

As a substituent in the said alkyl group, said cycloalkyl group, and said alkenyl group having a substituent, Halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; Hydroxyl group; Thiol group; Epoxy group; Glycidoxy group; (Meth) acryloyloxy group; Unsubstituted or substituted aryl groups, such as a phenyl group, 4-methylphenyl group, and 4-chlorophenyl group; Etc. can be mentioned.

In addition, in this specification, description of "(meth) acryloyl" means "acryloyl" and / or "methacryloyl". Similarly, description of "(meth) acryl" also means "acryl" and / or "methacryl".

As an aryl group of the aryl group which has no unsubstitution or a substituent, C6-C15 aryl groups, such as a phenyl group, 1-naphthyl group, and 2-naphthyl group, are mentioned, for example.

As a substituent in the case where said aryl group has a substituent, Halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; C1-C6 alkyl groups, such as a methyl group and an ethyl group; C1-C6 alkoxy groups, such as a methoxy group and an ethoxy group; Nitro group; Cyano group; Hydroxyl group; Thiol group; Epoxy group; Glycidoxy group; (Meth) acryloyloxy group; Unsubstituted or substituted aryl groups, such as a phenyl group, 4-methylphenyl group, and 4-chlorophenyl group; Etc. can be mentioned.

Examples of the alkylsilyl group include trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, tri-tert-butylsilyl group, methyldiethylsilyl group, dimethylsilyl group, diethylsilyl group, methylsilyl group and ethylsilyl group Etc. can be mentioned.

Among these, as Rx, Ry, and Rz, a hydrogen atom, a C1-C6 alkyl group, or a phenyl group is preferable, and a hydrogen atom is more preferable especially.

As a polysilazane type compound which has a repeating unit represented by General formula (1), organic polysilazane in which at least 1 of inorganic polysilazane, Rx, Ry, Rz which are all hydrogen atoms, Rx, Ry, Rz is not a hydrogen atom Any of these may be sufficient.

Moreover, in this invention, polysilazane modified substance can also be used as said polysilazane type compound. As said polysilazane modified substance, Unexamined-Japanese-Patent No. 62-195024, Unexamined-Japanese-Patent No. 2-84437, Unexamined-Japanese-Patent No. 63-81122, Unexamined-Japanese-Patent No. 1-, for example. 138108 et al., 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 And those described in JP-A-306329, JP-A-6-299118, JP-A 9-31333, JP-A 5-345826, JP-A 4-63833, and the like. have.

Among these, as the polysilazane-based compound, in view of being able to form an ion implantation layer having easy availability and excellent gas barrier properties, in the general formula (1), Rx, Ry, and Rz are all hydrogen atoms. Hydropolysilazane is preferred.

Moreover, as said polysilazane type compound, the commercial item marketed as a glass coating material etc. can also be used as it is.

The said polysilazane type compound may be used independently, or may use 2 or more types together.

Moreover, the number average molecular weight (Mn) of the said polysilazane type compound is not specifically limited, The compound which is 100-50,000 can be used preferably.

The number average molecular weight (Mn) is subjected to gel permeation chromatography, and can be obtained as a standard polystyrene conversion value.

As an ion implanted in the said polymer layer, Ion of rare gas, such as argon, helium, neon, krypton, xenon; Ions such as fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine and sulfur; Ions of alkanes such as methane and ethane; Ions of alkene-based gases such as ethylene and propylene; Ions of alkadiene-based gases such as pentadiene and butadiene; Ions of alkyne-based gases such as acetylene; Ions of aromatic hydrocarbon gas such as benzene and toluene; Ions of cycloalkane-based gases such as cyclopropane; Ions of cycloalkene-based gases such as cyclopentene; Ion of metal; Ions of organosilicon compounds; Etc. can be mentioned.

These ions may be used independently or may use 2 or more types together.

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

As a method of implanting ions, a method of irradiating ions (ion beams) accelerated by an electric field, a method of implanting ions in a plasma, and the like can be given.

Among these methods, since the target gas barrier layer can be formed easily, the latter method of plasma ion implantation (plasma ion implantation method) is preferable.

In the plasma ion implantation method, for example, a plasma is generated in an atmosphere containing a plasma generating gas such as a rare gas, and a negative high voltage pulse is applied to the polymer layer, whereby ions (cations) in the plasma are generated. It can be carried out by injecting to the surface portion of the. More specifically, the plasma ion implantation method can be performed by the method described in WO2010 / 107018 pamphlet or the like.

The implantation amount of ions can be appropriately determined in accordance with the purpose of use of the gas barrier film (necessary gas barrier property, transparency, etc.).

By ion implantation, the thickness of the region into which ions are implanted can be controlled according to the implantation conditions such as the type of ions, the applied voltage, the treatment time, and the like, and the thickness of the polymer layer or the purpose of use of the gas barrier film can be adjusted. However, it is preferably 10 to 400 nm.

The implantation of ions can be confirmed by performing elemental analysis measurements of around 10 nm from the surface of the polysilazane layer using X-ray photoelectron spectroscopy (XPS).

The gas barrier layer may be a single layer or a multilayer. For example, you may use together the gas barrier layer which consists of (i) the gas barrier layer which consists of inorganic vapor deposition films, and (iii) the surface of a polymer layer.

When the above-mentioned adhesive bond layer is laminated | stacked on a gas barrier layer through an adhesive improvement layer, it is preferable that the layer adjacent to an adhesive improvement layer is a gas barrier layer which consists of an inorganic vapor deposition film.

Adhesion Enhancement Layer

The gas barrier film of the present invention is not particularly limited as long as the gas barrier film is formed by laminating the base layer, the gas barrier layer, and the adhesive layer in this order. However, the adhesive layer is laminated on the gas barrier layer via the adhesion improving layer. It may be configured.

 The gas barrier film of this invention can improve the adhesiveness of a gas barrier layer and an adhesive bond layer by having an adhesive improvement layer.

Preferably the thickness of an adhesive improvement layer is 700 nm or less, More preferably, it is 50-700 nm, More preferably, it is 100-500 nm, More preferably, it is 150-400 nm.

By the thickness of the said adhesion improvement layer being in the said range, the effect which improves the adhesiveness of a gas barrier layer and an adhesive bond layer can be exhibited preferably.

It is preferable that an adhesive improvement layer is a layer containing an organic substance. Specifically, the layer containing a polyester resin; A layer containing an acrylic resin; A layer which consists of hardened | cured material of the curable composition containing energy-beam curable compounds, such as a polyfunctional acrylate compound and a polyfunctional urethane acrylate compound; Layer which consists of hardened | cured material of curable composition containing thermosetting resins, such as a thermosetting epoxy resin and a melamine resin; Etc. can be mentioned.

An adhesive improvement layer is a layer which consists of hardened | cured material of the curable composition containing a thermosetting epoxy resin preferably. By using the curable composition containing a thermosetting epoxy resin, the adhesiveness improvement layer which is more excellent in the adhesiveness of a gas barrier layer and an adhesive bond layer, especially the said adhesiveness after storing under high temperature, high humidity conditions can be formed.

A thermosetting epoxy resin is a compound (henceforth a "polyfunctional epoxy compound") which has at least 2 epoxy groups in a molecule | numerator.

As a thermosetting epoxy resin which can be used for an adhesive improvement layer, the epoxy resin which has glycidylamino group derived from metaxylylenediamine, and the epoxy which has glycidylamino group derived from 1, 3-bis (aminomethyl) cyclohexane Resins, epoxy resins having glycidylamino groups derived from diaminodiphenylmethane, epoxy resins having glycidylamino groups or glycidyloxy groups derived from paraaminophenols, having glycidyloxy groups derived from bisphenol A Epoxy resins, epoxy resins having glycidyloxy groups derived from bisphenol F, epoxy resins having glycidyloxy groups derived from phenol novolac, epoxy resins having glycidyloxy groups derived from resorcinol, and the like. have.

Among these thermosetting epoxy resins, an epoxy resin containing an aromatic ring in a molecule is preferable.

These thermosetting epoxy resins may be used independently, or may use 2 or more types together.

Content of the thermosetting epoxy resin in curable composition becomes like this. Preferably it is 10-60 mass% with respect to solid content whole quantity of a curable composition, More preferably, it is 20-50 mass%.

In addition, "solid content of a curable composition" refers to the component except the solvent contained in a curable composition here.

It is preferable that a curable composition contains a polyfunctional amine compound. Since the hardening reaction advances more efficiently, the curable composition containing a polyfunctional amine compound can form an adhesive improvement layer efficiently.

Examples of the polyfunctional amine compound include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane and diaminodi Phenyl methane, metaphenylenediamine, etc. are mentioned.

These polyfunctional amine compounds may be used independently or may use 2 or more types together.

Content of the polyfunctional amine compound in curable composition becomes like this. Preferably it is 25-80 mass% with respect to solid content whole quantity of a curable composition, More preferably, it is 35-75 mass%.

The curable composition may contain a silane coupling agent. When a curable composition contains a silane coupling agent, the adhesive improvement layer which is more excellent in adhesiveness with a gas barrier layer can be formed.

As a silane coupling agent, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltri Aminosilane coupling agents such as ethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane and 3- (2-aminoethyl) aminopropylmethyldiethoxysilane; Epoxysilane coupling agents such as 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane; 3-mercaptopropyl trimethoxysilane; 3-methacryloxypropyl trimethoxysilane; Polymer silane coupling agents described in JP-A-2000-239447 and JP-A-2001-40037; Etc. can be mentioned. These silane coupling agents may be used independently, or may use 2 or more types together.

When curable composition contains a silane coupling agent, content of a silane coupling agent becomes like this. Preferably it is 0.01-5 mass parts, More preferably, it is 0.01-3 mass parts with respect to 100 mass parts of thermosetting epoxy resins.

The curable composition may contain a solvent.

As a solvent, Aliphatic hydrocarbon solvents, such as n-hexane and n-heptane; Aromatic hydrocarbon solvents such as toluene and xylene; Halogenated hydrocarbon solvents such as dichloromethane, ethylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane and monochlorobenzene; Alcohol solvents such as methanol, ethanol, propanol, butanol, and propylene glycol monomethyl ether; Ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone; Ester solvents such as ethyl acetate and butyl acetate; Cellosolve solvents such as ethyl cellosolve; Ether solvents such as 1,3-dioxolane; Etc. can be mentioned.

These solvents may be used independently or may use 2 or more types together.

Although content of the solvent in a curable composition is not specifically limited, Preferably it is 85-99 mass%, More preferably, it is 90-97 mass% with respect to curable composition whole quantity.

The curable composition may contain various additives in the range which does not prevent the effect of this invention. As said additive, a ultraviolet absorber, an antistatic agent, a stabilizer, antioxidant, a plasticizer, a lubricating agent, a coloring pigment, etc. are mentioned. What is necessary is just to adjust content of these additives suitably according to the objective.

A curable composition can be prepared by mixing and stirring the said thermosetting epoxy resin and other components suitably according to a conventional method as needed.

An adhesive improvement layer can be formed by apply | coating the resin composition for forming adhesive improvement layers, such as a curable composition, on a gas barrier layer in accordance with a conventional method, and hardening or drying the obtained coating film.

As the coating method, a conventional wet coating method can be used. For example, bar coating, dipping, roll coating, gravure coating, knife coating, air knife coating, roll knife coating, die coating, screen printing, spray coating, gravure offset, spin A coating method, a blade coating method, etc. are mentioned.

When hardening or drying a coating film, you may heat a coating film according to a conventional method.

Heating temperature becomes like this. Preferably it is 70-180 degreeC, More preferably, it is 80-150 degreeC.

The heating time is preferably 30 seconds to 10 minutes, more preferably 1 to 7 minutes.

In the case where the polyolefin resin (A) included in the adhesive layer is a modified polyolefin resin (A1), and the gas barrier layer contains a polysilazane-based compound and is a layer formed by reforming treatment, the adhesive layer is directly in the gas barrier layer. It is preferable to laminate | stack. In the gas barrier layer as described above, the adhesive layer containing the polyolefin-based resin (A) tends to be difficult to adhere to, but when the polyolefin-based resin (A) contains the modified polyolefin-based resin (A1), Since good adhesiveness is also exhibited with respect to such a gas barrier layer, it can be one means of omitting an adhesive improvement layer.

[Encapsulation body]

The encapsulation body of the present invention is encapsulated using the gas barrier film of the present invention as an encapsulant, and a problem caused by defects due to interlayer peeling and / or intrusion of water vapor is not easily generated. It becomes. Therefore, a sealing body can be used suitably for the use which requires the maintenance of the performance of a to-be-sealed object over a long term. That is, excellent adhesiveness is maintained on the adhesive layer of the encapsulant and the encapsulated object, so that the original performance of the encapsulated material can be preferably maintained.

At least 1 sort (s) chosen from the group which consists of an organic electroluminescent element, an organic electroluminescent display element, an inorganic electroluminescent element, an inorganic electroluminescent display element, an electronic paper element, a liquid crystal display element, and a solar cell element is mentioned as a to-be-enclosed object.

(Manufacturing method of the sealing body)

Although the manufacturing method of the sealing body of this invention is not specifically limited, What has a process of adhering the adhesive bond layer which a gas barrier film has to a to-be-encapsulated object, and the process of peeling a peeling sheet from the gas barrier film of this invention. desirable.

For example, when the gas barrier film of this invention used as a sealing material is an aspect shown below, the 2nd peeling sheet is peeled off first.

Next, the exposed surface of the adhesive layer and the surface of the encapsulated material are superimposed, pressurized as necessary, heated under desired heating conditions, the adhesive layer is cured, and the encapsulated material is encapsulated with a gas barrier film that becomes an encapsulant. To get the encapsulation.

1st peeling sheet / base layer / gas barrier layer / adhesive layer / 2nd peeling sheet

In addition, after a 1st peeling sheet forms the surface of an adhesive bond layer and a to-be-enclosed object, it peels and removes normally. Peeling removal of a 1st peeling sheet may be before or after the process of heating a gas barrier film.

According to the manufacturing method of such an encapsulation body, even if a gas barrier film does not have a base material, since a 1st peeling sheet functions as a support body of a gas barrier film, until the 1st peeling sheet is peeled off, Breaking or deformation of the gas barrier film is prevented and the handleability is excellent.

Example

Hereinafter, an Example is given and this invention is demonstrated in detail. However, this invention is not limited to a following example at all. In addition, "part" and "%" described below are the "mass reference" unless there is particular notice.

(Example 1)

[Production of Gas Barrier Film]

(1) Formation process of base layer

As the thermoplastic resin, 60 parts of pellets (manufactured by BASF, "ULTRASON S3010", Tg = 180 ° C) of polysulfone resin (PSF) were dissolved in dichloromethane to prepare a 15% solution of PSF.

In this solution, 40 parts of tricyclodecane dimethanol diacrylate (made by Shin-Nakamura Chemical Co., Ltd., ADCP) as an energy-beam curable component, and bis (2,4,6-trimethylbenzoyl) -phenylphosphine as a polymerization initiator 1 part of oxides ("Irgacure 819" by BASF Corporation) were added and mixed, and the composition for base layers was prepared.

As a 1st peeling sheet, the composition for base layers prepared above on the non-processing surface of the easily-adhesive-processed polyethylene terephthalate (PET) film (Toyobo Co., Ltd. make, "PET50A-4100", thickness of 50 micrometers) to the die-coat method The coating film was applied to form a coating film. The coating film was dried by heating the coating film at 50 ° C. for 2 minutes and then at 140 ° C. for 2 minutes.

Next, on this dry coating film, the unprocessed surface of the easily-processed polyethylene terephthalate (PET) film (Toyobo Co., Ltd. make, "PET50A-4100", thickness 50micrometer) was bonded and laminated as a process sheet.

Next, using a belt conveyor type ultraviolet irradiation device (manufactured by Igraphics, product name: ECS-401GX), under a condition shown below, a high-pressure mercury lamp (manufactured by Igraphics, "H04-L41") and an ultraviolet light quantity Curing reaction was performed by irradiating an ultraviolet-ray through a process sheet | seat by the system (Ok Manufacturing Co., Ltd. make, "UV-351"), and the base layer of thickness 10micrometer was formed on said 1st peeling sheet.

<Condition by high pressure mercury lamp>

UV lamp height: 100 mm

UV lamp output: 3 ㎾

<Condition by ultraviolet photometer>

Illuminance of light wavelength 365 nm: 400 mW / cm 2

Light quantity: 800 mJ / ㎠

(2) Formation Step of Gas Barrier Layer

<1st floor>

Then, the polyethylene terephthalate (PET) film used as a process sheet was peeled off.

And the inorganic polysilazane system coating agent was apply | coated as the composition for gas barrier layers by the spin coat method which is a solution method on the base layer formed above, and the coating film was formed.

Here, said "inorganic polysilazane system coating agent" is density | concentration adjustment of "Aquamica NL110-20 (main component: perhydro polysilazane)" by Merck Performance Materials Co., Ltd. in 20% solution with xylene.

And the coating film was dried by heating the obtained coating film at 120 degreeC for 1 minute, and the polysilazane type compound layer of thickness 100nm was formed on said base layer.

Further, on the surface of the polysilazane-based compound layer formed above, a plasma ion implantation device (RF power supply: "RF56000" manufactured by Nippon Electronics Co., Ltd., high voltage pulse power supply: "PV-3-HSHV-0835" manufactured by Kurita Corporation) Using the conditions shown below, the reforming process by plasma ion implantation was performed and the 1st gas barrier layer was formed.

<Plasma ion implantation conditions>

Chamber internal pressure: 0.2 kPa

Plasma generating gas: argon

Gas flow rate: 100 sccm

RF output: 1000 W

RF frequency: 1000 GHz

RF pulse width: 50 μs

RF delay: 25 n seconds

DC voltage: -10 kV

DC frequency: 1000 Hz

DC pulse width: 5 μs

DC delay: 50 μs

Duty ratio: 0.5%

Processing time (ion implantation time): 200 seconds

<The second floor>

Next, the polysilazane-based compound layer having a thickness of 100 nm was formed on the first gas barrier layer subjected to the reforming treatment in the same manner as the formation of the first gas barrier layer.

In addition, on the surface of the polysilazane-based compound layer formed above, a modification treatment by plasma ion implantation was performed in the same manner as the modification treatment of the gas barrier layer of the first layer, thereby forming a gas barrier layer of the second layer. .

(3) Formation process of adhesive layer

As polyolefin resin (A), as acid-modified polyolefin resin (The Mitsui Chemicals company make, "UNISTOL H-200", (alpha) -olefin polymer, weight average molecular weight (Mw): 52,000) 100 parts, and a thermosetting component (B), As a polyfunctional epoxy resin (manufactured by Mitsubishi Chemical Corporation, "YX8034", hydrogenated bisphenol A diglycidyl ether) 25 parts, and a curing catalyst (C), an imidazole series curing catalyst (manufactured by Shikoku Chemical Co., Ltd., "Quazole 2E4MZ"), 0.25 part of 2-ethyl-4-methylimidazole) was dissolved in methyl ethyl ketone, and the adhesive composition was prepared so that solid content concentration might be 18% solution.

As a 2nd peeling sheet, on the peeling process surface of a polyethylene terephthalate (PET) film (The product made by Lintec, "SP-PET382150"), the knife composition was applied so that the thickness after drying might be 25 micrometers for the adhesive composition prepared above. It applied and the coating film was formed. The coating film was dried by heating this coating film at 100 degreeC for 2 minutes, and the adhesive bond layer of 25 micrometers in thickness was formed on said 2nd peeling sheet.

Next, on this adhesive bond layer, the peeling process surface of the polyethylene terephthalate (PET) film (the Lintec company make, "SP-PET381031") was bonded together and laminated | stacked as a 3rd peeling sheet.

Thereafter, the polyethylene terephthalate (PET) film used as the third release sheet was peeled off.

And in the state which left the 2nd peeling sheet in the adhesive bond layer by overlapping the exposed adhesive bond layer surface and the surface of the 2nd layer gas barrier layer formed above, and heating at 60 degreeC using a heat laminator, 2 An adhesive layer having a thickness of 25 μm was formed on the gas barrier layer of the layer, and the gas barrier layer (with modification) of the first release sheet / base layer / 1 layer / 2 gas barrier layer (with modification) / adhesive layer / of the layer The gas barrier film of Example 1 which has the laminated constitution of a 2nd peeling sheet was manufactured.

[Production of Organic EL Device]

On the surface of the glass substrate, an indium tin oxide (ITO) film (thickness: 150 nm, sheet resistance: 30 Ω / □) was formed by sputtering, followed by solvent cleaning and UV / ozone treatment to form an anode. It was.

N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl) benzidene) (manufactured by Luminescence Technology) as a material for forming a light emitting layer on the anode (ITO film) formed above ) 60 nm, Tris (8-hydroxyquinolinate) aluminum (manufactured by Luminescence Technology) 40nm, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (manufactured by Luminescence Technology, Inc.) 10 nm and (8-hydroxyquinolinolate) lithium (manufactured by Luminescence Technology) were sequentially deposited at a rate of 0.1 to 0.2 nm / s to form a light emitting layer.

On the light emitting layer formed above, aluminum (Al) (manufactured by High Purity Chemical Research Institute) was deposited at 100 nm at a rate of 0.1 nm / s to form a cathode to have a layer structure of a glass substrate / anode / light emitting layer / cathode. An organic EL device was manufactured.

In addition, in the manufacturing process of an organic EL element, the vacuum degree at the time of sequentially depositing the formation material of the said light emitting layer on an anode (ITO film) was made into 1 * 10 <^-4> Pa or less.

[Manufacture of sealing body]

Next, the 2nd peeling sheet was peeled off from the gas barrier film manufactured in Example 1 mentioned above, and the surface of the adhesive bond layer of the gas barrier film used as a sealing material was exposed.

Next, the exposed surface of the adhesive layer and the surface of the organic EL device to be the packaged product prepared above are overlapped, and heated to 60 ° C. using a heat laminator under a nitrogen atmosphere, and the surface of the adhesive layer and the packaged object. The surface of the organic electroluminescent element used as this was adhere | attached while pressurizing, and the sealing body formed by sealing the organic electroluminescent element used as the to-be-encapsulated with the gas barrier film used as an sealing material was manufactured.

Moreover, the adhesive bond layer was hardened by heating the sealing body manufactured above at 100 degreeC for 2 hours, and the sealing body of Example 1 was manufactured.

(Comparative Example 1)

Rubber adhesive in the formation process of the adhesive bond layer of Example 1 (Nippon butyl company make, "Exxon Butyl 268", number average molecular weight: 260,000, copolymer of isobutylene and isoprene, content rate of isoprene: 1.7 mol%) 100 In the same manner as in Example 1, except that 20 parts of the part and the tackifier (Nippon Xeon Co., Ltd., `` Queenton A100 '') were dissolved in toluene to prepare an adhesive composition such that the solid content concentration was 20%. A gas barrier film was prepared.

In addition, in the manufacture of the sealing body of Example 1, the sealing body of Comparative Example 1 was manufactured like Example 1 except not having hardened the adhesive bond layer.

[Assessment Methods]

(1) Evaluation of Gas Barrier Properties

About each gas barrier film manufactured by said Example 1 and Comparative Example 1, what peeled and removed the 2nd peeling sheet and left the 1st peeling sheet was used as the sample for a measurement.

Water vapor transmission rate (g / m 2 / day of the laminate in a high temperature and high humidity environment at 40 ° C. and 90% relative humidity) using a water vapor transmission rate measuring apparatus (manufactured by MOCON, "AQUATRAN") for the measurement sample. ) Was measured. In addition, the detection lower limit of the water vapor transmission rate measuring apparatus is 0.0005 (g / m <2> / day).

From the result of the water vapor transmission rate (g / m <2> / day) measured in this way, the gas barrier property of the gas barrier film was evaluated on the basis of the two steps shown below.

A: water vapor transmission rate is 5 × 10 ⁻³ (g / m 2 / day) or less

B: Water vapor transmission rate exceeds 5x10 <^-3> (g / m <2> / day)

(2) Evaluation of bag performance on the bag

The 1st peeling sheet was peeled off from each sealing body manufactured by said Example 1 and Comparative Example 1, and what exposed the surface of the underlayer of a gas barrier film was made into the sample for a measurement.

After leaving the sample for measurement for 100 hours in a high-temperature, high-humidity environment at 40 ° C and a relative humidity of 90%, the organic EL device was started to measure the area of the non-light-emitting point (dark spot), and the initial stage before standing. The ratio (%) of the area of the non-light emission point with respect to the light emission area (100%) was calculated.

And the sealing performance with respect to the to-be-sealed | blocked material of the gas barrier film as a sealing material which sealed the organic electroluminescent element used as a to-be-sealed | blocked object on the basis of the four steps shown below was evaluated.

A: The ratio of the area of the non-emitting point is less than 5%

B: The ratio of the area of the non-emitting point is 5% or more and less than 10%

C: The ratio of the area of the non-emitting point is 10% or more and less than 90%

D: The ratio of the area of the non-emitting point is 90% or more

(Summary of the result)

From the evaluation results shown in Table 1, the following can be seen.

In the production of the gas barrier film of Comparative Example 1, the adhesive layer is formed of an adhesive composition containing a rubber-based adhesive and a tackifier, so that the encapsulated product of Comparative Example 1 is exposed to a high temperature, high humidity environment for a long time. In the case, adhesiveness was not maintained in the adhesive surface of the sealing material and the to-be-encapsulated object, and it turned out that the gas barrier film of the comparative example 1 is inferior to the sealing performance with respect to the to-be-encapsulated object.

On the other hand, in manufacture of the gas barrier film of Example 1, the sealing body of Example 1 originates from what formed the adhesive bond layer with the adhesive composition containing a polyolefin resin (A) and a thermosetting component (B). Even when exposed to a long time in an environment of high temperature and high humidity, excellent adhesion is maintained on the adhesive layer of the encapsulant and the encapsulated product, and the gas barrier film of Example 1 has excellent encapsulation performance on the encapsulated product. Could know.

Claims (12)

As a gas barrier film which has a laminated body formed by laminating a release sheet, a base layer, a gas barrier layer, and an adhesive bond layer in this order,
The gas-barrier film whose said adhesive bond layer is a layer formed from the adhesive composition containing polyolefin resin (A) and a thermosetting component (B). The method of claim 1,
The gas barrier film in which the said polyolefin resin (A) contains modified polyolefin resin (A1). The method according to claim 1 or 2,
The gas barrier film which said thermosetting component (B) contains a thermosetting epoxy resin (B1). The method according to any one of claims 1 to 3,
A gas barrier film, wherein the adhesive layer is laminated directly on the gas barrier layer. The method according to any one of claims 1 to 4,
The gas barrier film in which the said adhesive bond layer is laminated | stacked on the said gas barrier layer through an adhesion improving layer. The method according to any one of claims 1 to 5,
The gas barrier film which is a layer formed from the composition for base layers containing an energy-beam curable component. The method according to any one of claims 1 to 6,
The gas barrier film which is the layer formed from the composition for underlayers containing a thermoplastic resin further. The method of claim 7, wherein
The gas barrier film whose glass transition temperature (Tg) of the said thermoplastic resin is 140 degreeC or more. The method according to any one of claims 1 to 8,
The gas barrier film whose thickness of the said base layer is 0.1-10 micrometers. The method according to any one of claims 1 to 9,
A gas barrier film, wherein the gas barrier layer is a layer containing a polysilazane compound and formed by modification treatment. The at least 1 type of encapsulated object chosen from the group which consists of an organic electroluminescent element, an organic electroluminescent display element, an inorganic electroluminescent element, an inorganic electroluminescent display element, an electronic paper element, a liquid crystal display element, and a solar cell element is Claims 1-10. The sealing body sealed with the gas barrier film in any one of Claims. The manufacturing method of the sealing body provided with the process of adhering the adhesive bond layer which the gas barrier film as described in any one of Claims 1-10 to a to-be-encapsulated object, and the process of peeling the said peeling sheet from the said gas barrier film. Way.