WO2018221510A1 - Sheet-shaped adhesive, gas-barrier laminate, and sealant - Google Patents

Abstract

The sheet-shaped adhesive according to the present invention is formed from an adhesive composition containing (A) a modified polyolefin resin and (B) a thermosetting component, and satisfies the following conditions (I) and (II). Condition (I): when the sheet-shaped adhesive is allowed to stand for 20 minutes in a 120°C environment, the amount of outgas generation per 1 cm³ is not more than 20 mg/cm³. Condition (II): when a laminate of the sheet-shaped adhesive applied on a 50 μm-thick polyethylene terephthalate film is pressed onto a glass plate using a roller and conditions of a temperature of 60°C, a pressure of 0.2 MPa, and a speed of 0.2 m/min, in order to bond the sheet-shaped adhesive side face of the laminate to the glass plate, and the sheet-shaped adhesive is then cured for 2 hours at 100°C followed by holding for 24 hours in a 23°C/50% relative humidity environment, the adhesive strength of the laminate for the glass plate, as measured in accordance with JIS Z 0237 : 2000 using conditions of a peel rate of 300 mm/min and a peel angle of 180°, is at least 10 N/25 mm.

Description

Sheet adhesive, gas barrier laminate, and sealing body

The present invention relates to a sheet-like adhesive, a gas barrier laminate having the sheet-like adhesive as an adhesive layer, and a sealing body in which an object to be sealed such as an electronic device is sealed with the gas barrier laminate. .

In recent years, organic EL elements have attracted attention as light-emitting elements that can emit light with high luminance by low-voltage direct current drive.
However, the organic EL device has a problem that light emission characteristics such as light emission luminance, light emission efficiency, and light emission uniformity are likely to deteriorate with time.
As a cause of the problem of the deterioration of the light emission characteristics, it was considered that oxygen, moisture or the like entered the inside of the organic EL element and deteriorated the electrode or the organic layer. Therefore, the organic EL element was sealed using a sealing material. In addition, oxygen and moisture have been prevented from entering.
Specifically, the organic EL element formed on the substrate is covered with a sealing material around the organic EL element and the peripheral surface of the organic EL element, and the sealing material is cured, whereby organic EL elements have been sealed.
Moreover, when sealing an organic EL element using a sealing material, when an outgas generate | occur | produces from a sealing material, since an organic EL element will be deteriorated, the development of the low outgassing sealing material has been performed.

For example, Patent Document 1 describes an organic EL device sealing composition containing a specific cationic curable compound, a photocationic polymerization initiator, and an azole compound.
Patent Document 1 describes that a cured product having low outgassing properties and moisture resistance can be formed by using a sealing composition using an azole compound used as a curing retarder.

WO2015 / 111525

However, according to studies by the present inventors, it has been found that the amount of outgas in the encapsulant varies depending not only on the curing retarder but also on the type and content of each component contained in the composition.
Therefore, there is a demand for a sealing material that has low outgassing properties and has a high effect of suppressing deterioration of an object to be sealed. Moreover, even if the low outgassing property of the sealing material is achieved, it may be required to further suppress the deterioration of the characteristics of the electronic device that becomes the sealed object, such as the light emission characteristics of the organic EL element.

Furthermore, in general, when a resin layer containing a resin is directly laminated on the gas barrier layer of the gas barrier film, the gas barrier layer and the resin layer have a low affinity with the resin. Problems may occur in the interlayer adhesion. In particular, when a gas barrier layer containing a polymer compound and subjected to a modification treatment is used, the interlayer adhesion between the gas barrier layer and the resin layer is often inferior.
Therefore, the sealing material is also required to have excellent interlayer adhesion with the gas barrier layer.

The present invention has been made in view of the above circumstances, and can be a sealing material having a high effect of suppressing deterioration of an object to be sealed, and is excellent in interlayer adhesion with a gas barrier layer. It is an object of the present invention to provide a gas barrier laminate having an adhesive as an adhesive layer, and a sealing body in which an object to be sealed such as an electronic device is sealed with the gas barrier laminate.

The present inventors have found that a sheet-like adhesive formed from an adhesive composition containing a modified polyolefin resin (A) and a thermosetting component (B) can solve the above problems, and the present invention. It came to complete.

That is, the present invention relates to the following [1] to [18].
[1] A sheet-like adhesive formed from an adhesive composition containing a modified polyolefin resin (A) and a thermosetting component (B), which satisfies the following requirements (I) and (II) Adhesive.
Requirement (I): The amount of outgas generated per cm ³ when the sheet-like adhesive is allowed to stand for 20 minutes in an environment of 120 ° C. is 20 mg / cm ³ or less. Requirement (II): Thickness The laminate in which the sheet-like pressure-sensitive adhesive is stuck on a 50 μm polyethylene terephthalate film is pressed against a glass plate with a roller at a temperature of 60 ° C., a pressure of 0.2 MPa, and a speed of 0.2 m / min. The surface of the sheet-like pressure-sensitive adhesive side of the body and the glass plate are bonded together, the sheet-like adhesive is cured at 100 ° C. for 2 hours, and then 24 ° C. at 23 ° C. and 50% relative humidity. After storage for a period of time, the adhesive strength of the laminate from the glass plate measured according to JIS Z0237: 2000 under conditions of a peeling speed of 300 mm / min and a peeling angle of 180 ° is 10 N / 2. [2] The sheet-like adhesive according to [1], wherein the thermosetting component (B) which is 5 mm or more contains a polyfunctional epoxy compound.
[3] The sheet-like adhesive according to [2], wherein the polyfunctional epoxy compound has an epoxy equivalent of 100 to 300 g / eq.
[4] The sheet-like adhesive according to any one of [1] to [3], wherein the modified polyolefin resin (A) is an acid-modified polyolefin resin.
[5] In any one of [1] to [4], the content of the modified polyolefin resin (A) is 15 to 95% by mass with respect to the total amount of active ingredients of the adhesive composition. The sheet-like adhesive according to the description.
[6] Any one of [1] to [5], wherein the content of the thermosetting component (B) is 5 to 150 parts by mass with respect to 100 parts by mass of the modified polyolefin resin (A). The sheet-like adhesive described in 1.
[7] The sheet-like adhesive according to any one of [1] to [6], further comprising a silane coupling agent (C).
[8] The sheet adhesive according to [7], wherein the content of the silane coupling agent (C) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the modified polyolefin resin (A).
[9] An adhesive layer comprising a sheet-like adhesive formed from an adhesive composition containing a gas barrier film having a base material layer, a modified polyolefin resin (A) and a thermosetting component (B); A gas barrier laminate having the following requirements (I) and (IIa):
Requirement (I): The amount of outgas generated per cm ³ when the sheet-like adhesive is allowed to stand for 20 minutes in an environment of 120 ° C. is 20 mg / cm ³ or less Requirement (IIa): the gas barrier The sheet laminate adhesive of the gas barrier laminate and the glass plate are pressed against the glass plate with a roller under the conditions of a temperature of 60 ° C., a pressure of 0.2 MPa, and a speed of 0.2 m / min. After the sheet adhesive was cured at 100 ° C. for 2 hours and stored at 23 ° C. in an environment with a relative humidity of 50% for 24 hours, the peeling speed was 300 mm / min and the peeling angle was 180 °. [10] The thermosetting component (B), which has a pressure-sensitive adhesive strength of the laminate from the glass plate of 10 N / 25 mm or more, measured according to JIS Z0237: 2000 under the conditions of Including carboxymethyl compound, the gas barrier laminate according to [9].
[11] The gas barrier laminate according to [10], wherein the polyfunctional epoxy compound has an epoxy equivalent of 100 to 300 g / eq.
[12] The gas barrier laminate according to any one of [9] to [11], wherein the modified polyolefin resin (A) is an acid-modified polyolefin resin.
[13] In any one of [9] to [12], the content of the modified polyolefin resin (A) is 15 to 95% by mass with respect to the total amount of active ingredients of the adhesive composition. The gas barrier laminate as described.
[14] Any one of [9] to [13], wherein the content of the thermosetting component (B) is 5 to 150 parts by mass with respect to 100 parts by mass of the modified polyolefin resin (A). 2. Gas barrier laminate as described in 1.
[15] The gas barrier laminate according to any one of [9] to [14], further comprising a silane coupling agent (C).
[16] The gas barrier laminate according to [15], wherein the content of the silane coupling agent (C) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the modified polyolefin resin (A).
[17] The gas barrier film has a base layer and a gas barrier layer, and the gas barrier layer is a polymer layer containing a polymer compound and subjected to a modification treatment. [9] to [16] The gas barrier laminate according to any one of the above.
[18] The gas barrier laminate according to [17], wherein the gas barrier layer and the adhesive layer are directly laminated.
[19] The sheet-like adhesive according to any one of [1] to [8], or the gas barrier laminate according to any one of [9] to [18], The sealing body formed by sealing using the adhesive layer which has as a sealing material.
[20] The sealed body according to [19], wherein the object to be sealed is an organic EL element, an organic EL display element, a liquid crystal display element, or a solar cell element.

The sheet-like adhesive of the present invention can be a sealing material having a high effect of suppressing deterioration of an object to be sealed, and is excellent in interlayer adhesion with a gas barrier layer.

In the present specification, the lower limit value and the upper limit value described in a stepwise manner can be independently combined for a preferable numerical range (for example, a range of content and the like). For example, from the description “preferably 10 to 90, more preferably 30 to 60”, “preferable lower limit (10)” and “more preferable upper limit (60)” are combined to obtain “10 to 60”. You can also.

[Sheet adhesive]
The sheet-like adhesive according to the first embodiment of the present invention is a sheet-like adhesive formed from an adhesive composition containing a modified polyolefin resin (A) and a thermosetting component (B). It satisfies the requirements (I) and (II).
Requirement (I): The amount of outgas generated per 1 cm ³ when the sheet-like adhesive is allowed to stand for 20 minutes in an environment of 120 ° C. is 20 mg / cm ³ or less.
Requirement (II): A laminate in which the sheet adhesive is pasted on a polyethylene terephthalate film having a thickness of 50 μm is applied to a glass plate under conditions of a temperature of 60 ° C., a pressure of 0.2 MPa, and a speed of 0.2 m / min. The sheet-like adhesive side surface of the laminate and the glass plate are bonded together by pressing with a roller, and the sheet-like adhesive is cured at 100 ° C. for 2 hours, and then the relative humidity at 23 ° C. After storing for 24 hours in a 50% environment, the adhesive strength of the laminate from the glass plate, measured according to JIS Z0237: 2000 under conditions of a peeling speed of 300 mm / min and a peeling angle of 180 °, 10 N / 25 mm or more.

Outgas generation amount defined by the requirement (I) is, because it is 20 mg / cm ³ or less, the sheet-like adhesive of the present invention can be said to be a sealing material having excellent low outgassing.
Moreover, since the adhesive force prescribed | regulated by requirement (II) is 10 N / 25mm or more, the sheet-like adhesive of this invention is a sealing material which does not peel easily from a to-be-sealed surface after hardening. I can say that.
That is, since the sheet-like adhesive of the present invention is adjusted so as to satisfy the above requirements (I) and (II), it is excellent in low outgassing properties and can be easily peeled off from the sealed surface after curing. Therefore, it can be a sealing material having a high effect of suppressing deterioration of the object to be sealed.

In the sheet-like adhesive of the present invention, the outgas generation amount specified in the requirement (I) is more excellent in low outgassing properties, and from the viewpoint of increasing the effect of suppressing deterioration of the object to be sealed, preferably 18 mg / cm ³ or less, more preferably 15 mg / cm ³ or less, more preferably 10 mg / cm ³ or less, even more preferably 8 mg / cm ³ or less, even more preferably from 7 mg / cm ³ or less, more preferably 4mg / Cm ³ or less, more preferably 1 mg / cm ³ or less, and usually 0.1 mg / cm ³ or more.
In addition, in this specification, the outgas amount of the said sheet-like material prescribed | regulated by the requirement (I) means the value measured by the method as described in an Example.

Moreover, in the sheet-like adhesive of the present invention, the adhesive force defined by the requirement (II) is preferably 12 N / 25 mm or more, more preferably from the viewpoint of more reliably suppressing peeling from the sealed surface after curing. Is 14 N / 25 mm or more, more preferably 16 N / 25 mm or more, still more preferably 18 N / 25 mm or more, still more preferably 20 N / 25 mm or more, particularly preferably 22 N / 25 mm or more, and usually 30 N / 25 mm or less. is there.

Further, in the sheet-like adhesive of the present invention, the polyethylene terephthalate film used in the requirement (II) is a film substantially made of polyethylene terephthalate, and has polyethylene terephthalate as a main component. The polyethylene terephthalate film can be blended with commonly used additives. The polyethylene terephthalate film is usually stretched, and biaxial stretching is common as the stretching method.

In addition, from the viewpoint of improving the adhesion when a sheet-like adhesive is laminated on the polyethylene terephthalate film, the surface of the resin film may be subjected to an easy adhesion treatment by an oxidation method, an unevenness method, or the like. .
Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), hot air treatment, ozone, and ultraviolet irradiation treatment. Examples of the unevenness method include sand blast method and solvent treatment method. Etc.

The thickness of the sheet-like adhesive of the present invention is appropriately set according to the use, but is preferably 2 to 50 μm, more preferably 5 to 25 μm, and still more preferably 10 to 20 μm.
In addition, the shape of the sheet adhesive of this invention is also set suitably according to a use, for example, tetragons, such as a square and a rectangle, a polygon, a circle, and an ellipse etc. are mentioned.

The sheet-like adhesive of the present invention is formed from an adhesive composition containing a modified polyolefin resin (A) and a thermosetting component (B). Then, the adhesive composition contains the modified polyolefin resin (A) and the thermosetting component (B) in combination so that the sheet adhesive satisfies the above requirements (I) and (II). The adhesive composition is prepared.
Hereinafter, the adhesive composition used in the present invention will be described in detail with reference to a specific method for preparing an adhesive composition for forming a sheet-like adhesive satisfying the above requirements (I) and (II). To do.

<Adhesive composition>
The adhesive composition used in the present invention contains a modified polyolefin resin (A) and a thermosetting component (B).
In the following description, “modified polyolefin resin (A)” and “thermosetting component (B)” are also referred to as “component (A)” and “component (B)”, respectively.

The adhesive composition used in the present invention is a component other than the components (A) and (B) as long as the sheet adhesive of the present invention satisfies the above requirements (I) and (II) and does not impair the effects of the present invention. Other components may be contained.
As said other component, 1 or more types chosen from a silane coupling agent (C), an imidazole series curing catalyst (D), and a tackifier (E) are mentioned.
In the following description, “silane coupling agent (C)”, “imidazole-based curing catalyst (D)”, and “tackifier (E)” are referred to as “component (C)” and “component (D), respectively. ) "And" component (E) ".

In the adhesive composition used in the present invention, the total content of components (A) and (B) is preferably 70% by mass or more with respect to the total amount (100% by mass) of the active ingredients of the adhesive composition. More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more, More preferably, it is 99 mass% or more, and is 100 mass% or less normally.

In the adhesive composition used in the present invention, the total content of the components (A), (B), (C), (D), and (E) is the total amount of active ingredients of the adhesive composition (100 % By weight) is preferably 80 to 100% by weight, more preferably 85 to 100% by weight, still more preferably 90 to 100% by weight, and still more preferably 95 to 100% by weight.
In addition, in this invention, the active ingredient of an adhesive composition refers to the component except the dilution solvent which does not relate to the physical property contained in an adhesive composition.

(Component (A): Modified polyolefin resin)
The adhesive composition used in the present invention contains a modified polyolefin resin (A).
When the adhesive composition used in the present invention contains the modified polyolefin resin (A), a sheet-like adhesive that satisfies the above requirements (I) and (II) can be formed. Moreover, the formability of a sheet-like material (adhesive layer) having a relatively thin film thickness can be improved.
In addition, a modified polyolefin resin (A) may be used independently and may use 2 or more types together.

In the present invention, the modified polyolefin resin is a polyolefin resin having a functional group obtained by subjecting a polyolefin resin as a precursor to a modification treatment using a modifier having a functional group.
The polyolefin resin refers to a polymer having a repeating unit derived from an olefin monomer.
In the present invention, the polyolefin resin may be a polymer composed only of repeating units derived from olefinic monomers, or together with repeating units derived from olefinic monomers, an olefinic unit. It may be a copolymer having a repeating unit derived from a monomer other than a monomer.

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

Examples of the polyolefin resin include very low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene, polypropylene (PP), ethylene- Examples thereof include a propylene copolymer, an olefin elastomer (TPO), an ethylene-vinyl acetate copolymer (EVA), an ethylene- (meth) acrylic acid copolymer, and an ethylene- (meth) acrylic acid ester copolymer.
In this specification, for example, “(meth) acrylic acid” indicates both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.

The modifier used for the modification treatment of the polyolefin resin may be a compound having a functional group that can contribute to the crosslinking reaction described later in the molecule or a compound that can introduce the functional group into the polyolefin resin.
Examples of the functional group include a carboxyl group, a group derived from a carboxylic anhydride (hereinafter, also referred to as “carboxylic anhydride group”), a carboxylic ester group, a hydroxyl group, an epoxy group, an amide group, an ammonium group, a nitrile group, Examples thereof include an amino group, an imide group, an isocyanate group, an acetyl group, a thiol group, an ether group, a thioether group, a sulfone group, a phosphone group, a nitro group, a urethane group, an alkoxysilyl group, and a halogen atom.
Among these, a carboxyl group, a carboxylic acid anhydride group, a carboxylic acid ester group, a hydroxyl group, an ammonium group, an amino group, an imide group, or an isocyanate group is preferable, and a carboxyl group, a carboxylic acid anhydride group, a hydroxyl group, or an alkoxysilyl group. Are more preferable, a carboxyl group, a carboxylic acid anhydride group, or a hydroxyl group is more preferable, and a carboxylic acid anhydride group is still more preferable.
The modifying agent to be used may be a compound having one kind of the above functional group in the molecule, or may be a compound having two or more kinds of the above functional groups.
By modifying the polyolefin resin with the above modifier, a group that can contribute to the crosslinking reaction (hereinafter also referred to as “crosslinkable functional group”) can be introduced into the polyolefin resin.
Therefore, the “modified polyolefin resin (A)” is a polyolefin resin having a crosslinkable functional group.

As the modified polyolefin resin (A), it is easy to form a sheet-like adhesive satisfying the above requirements (I) and (II), and it is easy to form a sheet-like adhesive having a low gas permeability and a high gas barrier property. In view of the above, an acid-modified polyolefin resin, a hydroxyl group-modified polyolefin resin, or a silane-modified polyolefin resin is preferable, an acid-modified polyolefin resin or a hydroxyl group-modified polyolefin resin is more preferable, and an acid-modified polyolefin resin is still more preferable.

In the present invention, the acid-modified polyolefin-based resin refers to a polyolefin resin graft-modified using an acid as a modifier. Examples thereof include those obtained by reacting an unsaturated carboxylic acid and / or an anhydride thereof with a polyolefin resin to introduce a carboxyl group and / or a carboxylic anhydride group (graft modification). In other words, a polyolefin resin having a carboxyl group and / or a carboxylic anhydride group as a crosslinkable functional group can be mentioned.

Examples of the unsaturated carboxylic acid and / or anhydride thereof reacted with the polyolefin resin include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, maleic anhydride, itaconic anhydride, Examples include glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic acid anhydride, and tetrahydrophthalic anhydride.
These unsaturated carboxylic acids and / or anhydrides thereof may be used alone or in combination of two or more.
Among these, maleic anhydride is preferable from the viewpoint of forming a sheet-like adhesive that satisfies the requirements (I) and (II).

The compounding amount of the unsaturated carboxylic acid and / or anhydride thereof reacted with the polyolefin resin facilitates the formation of a sheet-like adhesive that satisfies the above requirements (I) and (II), has a low water vapor transmission rate, and has a gas barrier property. From the viewpoint of facilitating the formation of a high sheet-like adhesive, it is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, and still more preferably 100 parts by mass of the polyolefin resin before modification. 0.2 to 1.0 part by mass.

In the present invention, a commercially available product can be used as the acid-modified polyolefin resin.
Examples of commercially available acid-modified polyolefin resins include Admer (registered trademark) (manufactured by Mitsui Chemicals), Unistor (registered trademark) (manufactured by Mitsui Chemicals), BondyRam (manufactured by Polyram), and orevac (registered). Trademark) (manufactured by ARKEMA), Modic (registered trademark) (manufactured by Mitsubishi Chemical Corporation), and the like.

In the present invention, the silane-modified polyolefin resin refers to a polyolefin resin graft-modified using an unsaturated silane compound as a modifier. That is, the silane-modified polyolefin resin has a structure in which an unsaturated silane compound as a side chain is graft copolymerized with a polyolefin resin as a main chain. In other words, the silane-modified polyolefin resin is a polyolefin resin having a silane-containing group as a crosslinkable functional group.

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

The amount of the unsaturated silane compound to be reacted with the polyolefin resin is preferably 0 with respect to 100 parts by mass of the polyolefin resin before modification, from the viewpoint of forming a sheet-like adhesive that satisfies the above requirements (I) and (II). 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass, and still more preferably 0.5 to 5 parts by mass.

Specific examples of the silane-modified polyolefin resin include a silane-modified polyethylene resin and a silane-modified ethylene-vinyl acetate copolymer, such as a silane-modified low-density polyethylene, a silane-modified ultra-low-density polyethylene, and a silane-modified linear chain. A silane-modified polyethylene resin such as a low-density polyethylene is preferred.

In the present invention, a commercially available product can be used as the silane-modified polyolefin resin.
Commercially available silane-modified polyolefin resins include, for example, Rinklon (registered trademark) (manufactured by Mitsubishi Chemical Corporation), etc., but low-density polyethylene-based linklon and linear low-density polyethylene-based linklon. Ultra low density polyethylene based rinklon and ethylene-vinyl acetate copolymer based rinklon are preferred.

In the present invention, the hydroxyl group-modified polyolefin resin means a polyolefin resin in which a hydroxyl group that is a crosslinkable functional group is introduced into the polyolefin resin. In other words, the hydroxyl group-modified polyolefin resin is a polyolefin resin having a hydroxyl group as a crosslinkable functional group.

The method for introducing a hydroxyl group into the polyolefin resin is not particularly limited. For example, a method in which a polyolefin resin and a peroxide having a hydroperoxy group (for example, hydrogen peroxide) are reacted to epoxidize a double bond site of the polyolefin resin, and then hydrolyze it.

Although the compounding quantity of the said peroxide made to react with polyolefin resin is not specifically limited, From a viewpoint of forming the sheet adhesive which satisfy | fills the said requirements (I) and (II), with respect to 100 mass parts of polyolefin resin before modification | denaturation The amount is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass, and still more preferably 0.5 to 5 parts by mass.

In the present invention, a commercially available product may be used as the hydroxyl group-modified polyolefin resin.
Examples of the commercially available hydroxyl group-modified polyolefin-based resin include Polytail (registered trademark) (manufactured by Mitsubishi Chemical Corporation).

The weight average molecular weight (Mw) of the modified polyolefin resin (A) is preferably 10,000 to 2,000,000 from the viewpoint of forming a sheet-like adhesive that satisfies the above requirements (I) and (II). More preferably, it is 20,000 to 1,500,000, more preferably 25,000 to 250,000, and still more preferably 30,000 to 150,000. When the weight average molecular weight of the modified polyolefin resin is in such a range, the adhesive composition has a sheet shape even when the content of the modified polyolefin resin in the adhesive composition is large. It is easy to maintain.

In this specification, the weight average molecular weight (Mw) of the modified polyolefin resin (A) is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method using tetrahydrofuran as a solvent. Specifically, it is a value measured based on the method described in the examples.

Even if the modified polyolefin resin (A) contains a large amount of the modified polyolefin resin (A) in the adhesive composition, the adhesive composition can easily maintain the sheet shape. From the viewpoint of being, those that are solid at room temperature (25 ° C.) are preferable.

In the adhesive composition used in the present invention, from the viewpoint of forming a sheet-like adhesive that satisfies the above requirements (I) and (II), the content of the component (A) is the total amount of active ingredients of the adhesive composition. It is preferably 15 to 95% by mass, more preferably 23 to 95% by mass, and further preferably 30 to 90% by mass with respect to (100% by mass).

<Component (B): Thermosetting component>
The adhesive composition used in the present invention contains a thermosetting component (B).
When the adhesive composition used in the present invention contains the thermosetting component (B), a sheet-like adhesive that satisfies the above requirements (I) and (II) can be formed.
In addition, a thermosetting component (B) may be used independently and may use 2 or more types together.
The content of the thermosetting component (B) is preferably 5 to 110 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the modified polyolefin resin (A). The amount is preferably 20 to 30 parts by mass.

The thermosetting component (B) is heated to react with the functional groups of the thermosetting component (B) and / or with the crosslinkable functional groups of the modified polyolefin resin (A) (crosslinking). It is sufficient that the compound has a property of forming a strong film having a three-dimensional network structure by reaction, for example, an epoxy compound, a melamine compound, a urea compound, and a maleimide compound, preferably It is an epoxy compound.
These compounds may be used alone or in combination of two or more.

Here, from the viewpoint of forming a sheet-like adhesive satisfying the above requirements (I) and (II), the thermosetting component (B) contains a polyfunctional epoxy compound. It is preferable.
In addition, a polyfunctional epoxy compound may be used independently and may use 2 or more types together.
The content of the polyfunctional epoxy compound in the thermosetting component (B) is the total amount of the thermosetting component (B) from the viewpoint of forming a sheet-like adhesive that satisfies the above requirements (I) and (II). 100 mass%), preferably 50 mass% or more, more preferably 60 to 100 mass%, still more preferably 70 to 100 mass%, still more preferably 80 to 100 mass%, still more preferably 90 to 100 mass%. % By mass, particularly preferably 100% by mass.

In the present invention, the polyfunctional epoxy compound refers to a compound having at least two epoxy groups in the molecule.
The polyfunctional epoxy compound is preferably a bifunctional epoxy compound having two epoxy groups from the viewpoint of forming a sheet-like adhesive that satisfies the requirements (I) and (II).

Bifunctional epoxy compounds include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, novolak Type epoxy resins (for example, phenol / novolac type epoxy resins, cresol / novolac type epoxy resins, brominated phenol / novolak type epoxy resins); hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether , Cycloaliphatic epoxy compounds such as hydrogenated bisphenol S diglycidyl ether; pentaerythritol polyglycidyl ether, 1,6-hexane All diglycidyl ether, hexahydrophthalic acid diglycidyl ester, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, 2,2-bis (3-glycidyl-4-glycidyloxyphenyl) propane, dimethylol tricyclode Examples include aliphatic epoxy compounds such as candiglycidyl ether.

Here, it is preferable to further improve the crosslinking density of the sheet-like adhesive from the viewpoint of improving the adhesive strength defined in the requirement (II).
From this viewpoint, it is preferable to increase the number of epoxy groups derived from the polyfunctional epoxy compound contained in the adhesive composition to promote the crosslinking reaction.
Therefore, from the viewpoint of increasing the number of epoxy groups derived from the polyfunctional epoxy compound contained in the adhesive composition, it is preferable to select a polyfunctional epoxy compound having a smaller epoxy equivalent. From the same viewpoint, it is preferable to select a polyfunctional epoxy compound having a smaller weight average molecular weight (Mw).

On the other hand, it is preferable to increase the weight average molecular weight (Mw) of the polyfunctional epoxy compound from the viewpoint of reducing the outgas generation amount defined in the requirement (I). Moreover, it is preferable to reduce content of the polyfunctional epoxy compound in an adhesive composition.
In other words, considering the viewpoint of improving the adhesive strength defined in the requirement (II), the adjustment of the adhesive composition for forming a sheet-like adhesive that simultaneously satisfies the requirements (I) and (II) is as follows. It's not easy. However, by adjusting the weight average molecular weight (Mw) of the polyfunctional epoxy compound, the epoxy equivalent, and the content of the polyfunctional epoxy compound relative to the modified polyolefin resin (A) in the adhesive composition as described above, An adhesive composition for forming a sheet-like adhesive that simultaneously satisfies the requirements (I) and (II) can be prepared.

Therefore, the weight average molecular weight (Mw) of the polyfunctional epoxy compound is preferably from the viewpoint of further reducing the outgas generation amount defined in the requirement (I) and further improving the adhesive strength defined in the requirement (II). Is 1,000 to 4,000, more preferably 1,200 to 3,600, still more preferably 1,400 to 3,200.

Further, from the viewpoint of further improving the adhesive strength defined in the above requirement (II), the epoxy equivalent of the polyfunctional epoxy compound is preferably 300 g / eq or less, more preferably 270 g / eq or less, and further preferably 240 g / eq or less. More preferably, it is 210 g / eq or less. Moreover, it is 100 g / eq or more normally.
In this specification, “epoxy equivalent” means the number of grams (g / eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and is a value measured according to JIS K 7236: 2009.

Furthermore, from the viewpoint of further reducing the outgas generation amount defined in the above requirement (I), the content of the polyfunctional epoxy compound is preferably 5 to 150 parts by mass with respect to 100 parts by mass of the modified polyolefin resin (A). More preferably, it is 10 to 80 parts by mass, and still more preferably 15 to 50 parts by mass.

<Component (C): Silane coupling agent>
The adhesive composition used in the present invention is a silane coupling agent (C) from the viewpoint of an adhesive composition capable of forming a sealed body having excellent adhesive strength in both normal temperature and high temperature environments. ) Is preferably contained.

From the above viewpoint, the silane coupling agent (C) is preferably an organosilicon compound having at least one alkoxysilyl group in the molecule.
Specific examples of the silane coupling agent (C) include polymerizable unsaturated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxy Silicon compounds having an epoxy structure such as silane, glycidoxyoctyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, N- (2-aminoethyl)- Amino group-containing silicon compounds such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane; 3-chloropropyltrimethoxysilane; 3-isocyanatopropyltriethoxysilane; Can be mentioned.
These silane coupling agents (C) may be used alone or in combination of two or more.

In the adhesive composition used in the present invention, the content of the component (C) is from the viewpoint of an adhesive composition capable of forming a sealed body having excellent adhesive strength in both normal temperature and high temperature environments. The amount is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 5 parts by mass, and still more preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the component (A).

<Component (D): Imidazole-based curing catalyst>
The adhesive composition used in the present invention preferably further contains an imidazole-based curing catalyst (D) from the viewpoint of an adhesive composition that can exhibit excellent adhesiveness even in a high temperature environment.

Examples of the imidazole curing catalyst (D) include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, Examples thereof include 2-phenyl-4-methyl-5-hydroxymethylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole.
These imidazole-based curing catalysts (D) may be used alone or in combination of two or more.
Of these, 2-ethyl-4-methylimidazole is preferred as component (D).

In the adhesive composition used in the present invention, the content of the component (D) is based on 100 parts by mass of the component (A) component from the viewpoint of an adhesive composition that can exhibit excellent adhesiveness even in a high temperature environment. The amount is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, and still more preferably 0.3 to 2.5 parts by mass.

<Component (E): Tackifier>
The adhesive composition used for this invention may contain a tackifier (E) further from a viewpoint of making the shape maintenance property of the sealing material formed more favorable.

Examples of the tackifier (E) include rosin resins such as polymerized rosin, polymerized rosin ester, and rosin derivatives; terpene resins such as polyterpene resins, aromatic modified terpene resins and hydrides thereof, and terpene phenol resins; Indene resins; aliphatic petroleum resins, aromatic petroleum resins and their hydrides, petroleum resins such as aliphatic / aromatic copolymer petroleum resins; styrene or substituted styrene polymers; α-methylstyrene monopolymer resins Copolymers of α-methylstyrene and styrene, copolymers of styrene monomers and aliphatic monomers, copolymers of styrene monomers, α-methylstyrene and aliphatic monomers, styrene monomers And a styrene resin such as a copolymer of a styrene monomer and an aromatic monomer.
These tackifiers (E) may be used alone or in combination of two or more.
Among these, as the component (E), a styrene resin is preferable, and a copolymer of a styrene monomer and an aliphatic monomer is more preferable.

The softening point of the tackifier (E) is preferably from the viewpoint of further improving the shape maintaining property of the sealing material to be formed and forming an adhesive composition that can exhibit excellent adhesiveness even in a high temperature environment. The temperature is 80 ° C or higher, more preferably 85 to 170 ° C, still more preferably 90 to 150 ° C.
In this specification, the softening point means a value measured according to JIS K 5902.
When using 2 or more types of several tackifier, it is preferable that the weighted average of the softening point of these several tackifiers belongs to the said range.

In the adhesive composition of the present invention, the content of the component (E) is 100 parts by mass of the component (A) from the viewpoint of making the adhesive composition having better shape maintenance of the formed sealing material. On the other hand, it is preferably 1 to 200 parts by mass, more preferably 10 to 150 parts by mass, still more preferably 15 to 100 parts by mass, and still more preferably 20 to 80 parts by mass.

<Other additives>
The adhesive composition used in the present invention may contain other additives other than the above components (A) to (E) as long as the effects of the present invention are not impaired.
Other additives are appropriately selected depending on the application, but examples include UV absorbers, antistatic agents, light stabilizers, antioxidants, resin stabilizers, fillers, pigments, extenders, softeners, etc. These additives may be mentioned.
These additives may be used alone or in combination of two or more.

Moreover, the adhesive composition used for this invention may contain a dilution solvent from a viewpoint which makes moldability favorable.
The dilution solvent can be appropriately selected from organic solvents. Specifically, aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone; aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane and methylcyclohexane; .
These solvents may be used alone or in combination of two or more.
The content of the solvent can be appropriately set in consideration of applicability and the like.

<Method for producing sheet adhesive>
The sheet-like adhesive of the present invention is formed from the above-mentioned adhesive composition.
The method for producing the sheet-like adhesive of the present invention is not particularly limited. For example, the above-mentioned adhesive composition is applied to the release-treated surface of the release film described later to form a coating film. The method of making it dry and forming a sheet-like adhesive agent is mentioned.

Examples of the method for applying the adhesive composition include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
Further, from the viewpoint of improving applicability, it is preferable to add the above-described dilution solvent to the adhesive composition to form a solution.
As drying conditions for drying the coating film, for example, it is usually preferable to perform a drying treatment at 80 to 150 ° C. for 30 seconds to 5 minutes.

It should be noted that another release film may be laminated on the sheet-like adhesive formed on the release film. Thereby, both surfaces of a sheet-like adhesive are protected until use. The two release films may be the same or different from each other, but preferably have different adhesive forces.

<Use of sheet adhesive>
The sheet-like adhesive of the present invention is used, for example, as an adhesive layer of a sealing sheet that seals an object to be sealed such as an electronic device.
Next, the gas barrier laminate according to the second embodiment of the present invention will be described.

[Gas barrier laminate]
The gas barrier laminate of the present invention has a gas barrier film having a base material layer and an adhesive layer composed of a sheet-like adhesive. The sheet-like adhesive is formed from an adhesive composition containing the modified polyolefin resin (A) and the thermosetting component (B) and satisfies the above requirement (I).
And the gas-barrier laminated body of this invention satisfy | fills the following requirements (IIa).
Requirement (IIa): The gas barrier laminate is pressed against a glass plate with a roller under conditions of a temperature of 60 ° C., a pressure of 0.2 MPa, and a speed of 0.2 m / min, and the sheet of the gas barrier laminate. The sheet adhesive was bonded to the glass plate and cured at 100 ° C. for 2 hours, and then stored at 23 ° C. in an environment with a relative humidity of 50%, and then the relative humidity JIS Z0237. : Adhesive strength between the gas barrier laminate and the glass plate, measured in accordance with 2000, is 10 N / 25 mm or more.

In the gas barrier laminate of the present invention, the configuration of the adhesive composition for forming the sheet-like adhesive constituting the adhesive layer can be the same as that described above. Moreover, the adhesive force prescribed | regulated to the said requirement (IIa) can be satisfy | filled with the method similar to the above-mentioned adjustment method for satisfy | filling the adhesive force prescribed | regulated to the said requirement (II). The outgas generation amount defined in the requirement (I) can also be satisfied by the adjustment method described above.

The gas barrier film which the gas barrier laminate of the present invention has is a film having at least a base material layer and having a gas barrier function. As one aspect of the gas barrier film, one having a base material layer and a gas barrier layer can be mentioned. For example, the aspect which has the following layer structures is mentioned.
-(I) A gas barrier laminate obtained by laminating a base layer / gas barrier layer / adhesive layer / release film in this order.

Further, in the above aspect (i), in order to increase the adhesion between the base material layer and the gas barrier layer, a primer layer is provided between the base material layer and the gas barrier layer as in the following aspect (ii). It may be.
-(Ii) A gas barrier laminate obtained by laminating a base layer / primer layer / gas barrier layer / adhesive layer / release film in this order.

In addition, the aspect of said (i) and (ii) represents the state before use of a gas-barrier laminated body, and when using, a peeling film is usually peeled and removed.

Here, the gas barrier film of the gas barrier laminate of the present invention is a single layer resin film or the like in which the base material layer itself has a gas barrier function, and the base material layer also has a function as a gas barrier layer. Also good.

Here, the gas barrier laminate of the present invention preferably has a structure in which a gas barrier layer and an adhesive layer are directly laminated. In particular, when the gas barrier layer is a polymer layer that has been subjected to the modification treatment described below, the interlayer adhesion between the adhesive layer and the gas barrier layer is generally inferior, but the sheet of the present invention By using the adhesive as the adhesive layer, the interlayer adhesion between the adhesive layer and the gas barrier layer can be made excellent.

About the gas barrier film which a gas barrier laminated body has, the water-vapor-permeation rate in the environment of temperature 40 degreeC and 90% RH (relative humidity) becomes like this. Preferably it is 0.1 g / m < ² > / day or less, More preferably, it is 0.05 g / m ² / day or less, more preferably 0.005 g / m ² / day or less.
When the water vapor permeability of the gas barrier film is 0.1 g / m ² / day or less, oxygen, moisture, etc. are contained inside the element such as an organic EL element formed on the transparent substrate by using the gas barrier laminate. Can be prevented, and the electrode and the organic layer can be effectively prevented from deteriorating.
Moreover, also about the gas-barrier laminated body which has a gas-barrier film and an adhesive bond layer, it is preferable that the water-vapor-permeation rate in an environment with a temperature of 40 degreeC and 90% RH (relative humidity) is the same value as the above.
In this specification, the water vapor permeability of the gas barrier layer means a value measured using a gas permeability measuring device (manufactured by mocon, product name “PERMATRAN”), but other general-purpose water vapor permeability. The measured value using the measuring device shows the same value.
Hereinafter, as an aspect of the gas barrier laminate of the second embodiment of the present invention, a gas barrier film composed of a base material layer and a gas barrier layer is taken as an example, and the adhesive layer is used for the gas barrier laminate of the present invention. The detailed configuration other than is shown below.

<Base material layer>
As a base material layer which a gas barrier film has, a resin film containing a resin component is preferable.
The resin component includes polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin Examples include polymers, aromatic polymers, and polyurethane polymers.
These resins may be used alone or in combination of two or more.
Moreover, when using the resin film containing a resin component, it is preferable to perform the easy adhesion process by the oxidation method, the uneven | corrugated method, etc. with respect to the surface of a resin film. Specific examples of the oxidation method and the unevenness method are as described above.
The thickness of the base material layer possessed by the gas barrier film is not particularly limited, but is preferably 0.5 to 500 μm, more preferably 1 to 200 μm, and still more preferably 5 to 100 μm from the viewpoint of ease of handling.

<Gas barrier layer>
The gas barrier layer of the gas barrier film includes an inorganic film and a polymer compound, and has been subjected to a modification treatment from the viewpoint that the thickness of the gas barrier film can be reduced and has an excellent gas barrier property. A polymer layer is preferable, and the polymer layer is more preferable. When the polymer layer is a gas barrier layer, the gas barrier layer is rich in flexibility, and the durability to bending of the gas barrier film can be improved.

Examples of the polymer compound contained in the polymer layer include silicon-containing polymer compounds such as polyorganosiloxane and polysilazane compounds, polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, Examples thereof include polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin polymer, and aromatic polymer.
These high molecular compounds may be used independently and may use 2 or more types together.
Among these, from the viewpoint that a gas barrier layer having excellent gas barrier properties can be formed, the polymer compound contained in the polymer layer is preferably a silicon-containing polymer compound, and more preferably a polysilazane compound.
The number average molecular weight of the polysilazane compound is preferably 100 to 50,000.

The polysilazane compound is a polymer having a repeating unit containing —Si—N— bond (silazane bond) in the molecule, specifically, a polymer having a repeating unit represented by the following general formula (1) It is preferable that

In the general formula (1), n represents the number of repeating units and represents an integer of 1 or more.
Rx, Ry, and Rz each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, unsubstituted or substituted An aryl group or alkylsilyl group having a group is represented.
Among these, as Rx, Ry, and Rz, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group is preferable, and a hydrogen atom is more preferable.
The polymer compound contained in the gas barrier layer may be an inorganic polysilazane in which Rx, Ry, and Rz in the general formula (1) are all hydrogen atoms, and at least one of Rx, Ry, and Rz is hydrogen. Organic polysilazanes which are groups other than atoms may be used.

A polysilazane compound may be used independently and may use 2 or more types together.
Moreover, a polysilazane modified material can also be used as a polysilazane compound, and a commercial item can also be used.

In addition to the polymer compound described above, the polymer layer may further contain other components as long as the effects of the present invention are not impaired.
Examples of other components include curing agents, other polymers, anti-aging agents, light stabilizers, flame retardants, and the like.
The content of the polymer compound in the polymer layer is preferably 50 to 100 with respect to the total amount (100% by mass) of the components in the polymer layer from the viewpoint of obtaining a gas barrier layer having better gas barrier properties. The mass is more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass.

The thickness of the polymer layer of the gas barrier film is preferably 50 to 300 nm, more preferably 50 to 200 nm.
In the present invention, even if the thickness of the polymer layer is nano-order, a gas barrier laminate having a sufficient gas barrier property can be obtained.

As a method for forming a polymer layer, for example, a solution for forming a polymer layer containing at least one polymer compound, optionally other components, a solvent, etc., is applied to a spin coater, knife coater, gravure coater, etc. A method of forming a coating film by applying using a known apparatus and drying the coating film is exemplified.

Examples of the polymer layer modification treatment include ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, and heat treatment. These processes can be performed alone or in combination of two or more.
The ion implantation process is a method of modifying the polymer layer by implanting ions into the polymer layer, as will be described later.
The plasma treatment is a method for modifying the polymer layer by exposing the polymer layer to plasma. For example, plasma treatment can be performed according to the method described in Japanese Patent Application Laid-Open No. 2012-106421.
The ultraviolet irradiation treatment is a method for modifying the polymer layer by irradiating the polymer layer with ultraviolet rays. For example, the ultraviolet modification treatment can be performed according to the method described in JP2013-226757A.
Among these, from the viewpoint that a gas barrier layer that can be efficiently modified to the inside without roughening the surface of the polymer layer and that has a better gas barrier property can be formed, the polymer layer is modified by ion implantation. Treatment is preferred.

Examples of ions implanted into the polymer layer during the ion implantation process include ions of rare gases such as argon, helium, neon, krypton, and xenon; fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine Ions of alkane gases such as methane and ethane; ions of alkene gases such as ethylene and propylene; ions of alkadiene gases such as pentadiene and butadiene; ions of alkyne gases such as acetylene Ions; ions of aromatic hydrocarbon gases such as benzene and toluene; ions of cycloalkane gases such as cyclopropane; ions of cycloalkene gases such as cyclopentene; metal ions; ions of organosilicon compounds; Is mentioned.
These ions may be used alone or in combination of two or more.
Among these, ions of rare gases such as argon, helium, neon, krypton, xenon are preferable from the viewpoint that ions can be more easily implanted and a gas barrier layer having particularly excellent gas barrier properties can be obtained. Argon ions are more preferred.

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

<Primer layer>
In the gas barrier laminate of the present invention, a primer layer may be provided between the base material layer and the gas barrier layer from the viewpoint of further improving the adhesion between the base material layer and the gas barrier layer.
Examples of the primer layer include a layer obtained by curing a composition containing an ultraviolet curable compound. The composition containing the ultraviolet curable compound may contain an inorganic filler such as silica particles.
The thickness of the primer layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm.

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

<Method for producing gas barrier laminate>
The method for producing the gas barrier laminate is not particularly limited. For example, in the method for producing a sheet-like adhesive described above, a gas barrier laminate can be produced by replacing one of the release films with a gas barrier film.
In addition, after manufacturing the sheet-like adhesive, one of the two release films of the sheet-like adhesive is peeled off, and the exposed surface of the sheet-like adhesive and the gas barrier layer of the gas barrier film are adhered. Thus, a gas barrier laminate can be produced. In this case, when the sheet-like adhesive has two release films having different adhesive strengths, it is preferable to release the release film having the smaller adhesive strength from the viewpoint of handleability.

(Sealed body)
The sealing body of the present invention is formed by sealing an object to be sealed with the sheet-like adhesive according to the first embodiment of the present invention or the gas barrier laminate according to the second embodiment of the present invention. .
The sealing body of the present invention includes, for example, a substrate such as a transparent substrate, an element (an object to be sealed) formed on the substrate, and a sealing material for sealing the element. Then, the sealing material is an adhesive layer constituting the gas barrier laminate according to the second embodiment of the present invention, or a sheet-like adhesive according to the first embodiment of the present invention. is there.

The transparent substrate is not particularly limited, and various substrate materials can be used. In particular, it is preferable to use a substrate material having a high visible light transmittance. In addition, a material having a high blocking performance for blocking moisture and gas to enter from the outside of the element and having excellent solvent resistance and weather resistance is preferable.
Specifically, transparent inorganic materials such as quartz and glass; polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, polyphenylene sulfide, polyvinylidene fluoride, acetyl cellulose, brominated phenoxy, aramids, polyimides, Examples thereof include transparent plastics such as polystyrenes, polyarylates, polysulfones, and polyolefins, and the gas barrier film described above.
The thickness of the transparent substrate is not particularly limited, and can be appropriately selected in consideration of light transmittance and performance for blocking the inside and outside of the element.

Examples of the objects to be sealed include electronic devices such as organic EL elements, organic EL display elements, liquid crystal display elements, and solar cell elements.
That is, the sealing body of the present invention seals an electronic device such as an organic EL element, an organic EL display element, a liquid crystal display element, or a solar cell element, for example, with the gas barrier laminate according to the second embodiment of the present invention. It is preferable to stop.

The manufacturing method of the sealing body of this invention is not specifically limited. For example, by covering the surface of the object to be sealed and the substrate surface in the periphery of the object to be sealed with the adhesive layer of the gas barrier laminate according to the second embodiment of the present invention, the gas barrier property is obtained by heating. The adhesive layer of the laminate is bonded to the surface of the object to be sealed and the substrate surface around the object to be sealed.
Further, for example, the sheet-like adhesive is heated by coating the surface of the object to be sealed and the substrate surface in the peripheral portion of the object to be sealed with the sheet-like adhesive according to the first embodiment of the present invention. Are bonded to the surface of the object to be sealed and the substrate surface in the periphery of the object to be sealed. Under the present circumstances, the sheet-like adhesive of the sealing sheet which laminated | stacked the gas barrier layer mentioned above on the sheet-like adhesive, for example, the sealing sheet which has a layer structure of peeling film / gas barrier layer / sheet-like adhesive / release film After removing the release film on the side, sealing may be performed.
Subsequently, the sealing body of this invention can be manufactured by hardening this adhesive bond layer.

There are no particular restrictions on the bonding conditions when the adhesive layer or sheet adhesive of the gas barrier laminate and the object to be sealed are bonded. The bonding temperature is, for example, 23 to 100 ° C., preferably 40 to 80 ° C. This adhesion treatment may be performed while applying pressure. The curing conditions for curing the adhesive layer or the sheet-like adhesive are not particularly limited, and the crosslinking reaction between the crosslinkable functional group of the modified polyolefin resin (A) and the thermosetting component (B) proceeds. It is set as appropriate in consideration. For example, when the modified polyolefin resin (A) is an acid-modified polyolefin resin, the heating temperature is usually 80 to 200 ° C. (preferably 90 to 150 ° C.), and the heating time is usually 30 minutes to 12 hours ( Preferably 1 to 6 hours).

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
In addition, the weight average molecular weight (Mw) of the polyfunctional epoxy compound which is the modified polyolefin resin (A) and the thermosetting component (B) is a value measured by the following method.
<Weight average molecular weight (Mw) of modified polyolefin resin (A)>
The weight average molecular weight (Mw) of the modified polyolefin resin (A) was measured using a gel permeation chromatograph (GPC) apparatus (product name “HLC-8320” manufactured by Tosoh Corporation) under the following conditions: The value converted into the weight average molecular weight of standard polystyrene was used.
(Measurement condition)
・ Measurement sample: Tetrahydrofuran solution with a sample concentration of 1 mass% ・ Column: Two “TSK gel Super HM-H” and one “TSK gel Super H2000” (both manufactured by Tosoh Corporation), sequentially connected Column temperature: 40 ° C
・ Developing solvent: Tetrahydrofuran ・ Flow rate: 0.60 mL / min
<Weight average molecular weight of polyfunctional epoxy compound (Mw)>
The weight average molecular weight (Mw) of the polyfunctional epoxy compound is measured under the above conditions using the gel permeation chromatograph (GPC) apparatus, and the peak having the largest area among the plurality of observed peaks. It is the value converted into the weight average molecular weight of standard polystyrene corresponding to the retention time of the peak top.

Examples 1 to 4 and Comparative Examples 1 to 2
(1) Preparation of Adhesive Composition Each component shown below is added in the blending amounts (active ingredient ratio) shown in Table 1, diluted with methyl ethyl ketone, and an adhesive composition having an active ingredient concentration of 18% by mass. Were prepared respectively.
The details of each component used are as follows.
Modified polyolefin resin (A): manufactured by Mitsui Chemicals, product name “Unistor H-200”, acid-modified α-olefin polymer, solid at 25 ° C., weight average molecular weight (Mw) = 47,000.
-Thermosetting component (B):
Multifunctional epoxy compound (1): manufactured by Mitsubishi Chemical Corporation, product name “YX8034”, hydrogenated bisphenol A diglycidyl ether, epoxy equivalent = 270 g / eq, weight average molecular weight (Mw) = 3,200.
Polyfunctional epoxy compound (2): manufactured by Mitsubishi Chemical Corporation, product name “YX8000”, hydrogenated bisphenol A diglycidyl ether, epoxy equivalent = 205 g / eq, weight average molecular weight (Mw) = 1,400.
Multifunctional epoxy compound (3): manufactured by Mitsubishi Chemical Corporation, product name “YX8040”, hydrogenated bisphenol A diglycidyl ether, epoxy equivalent = 1100 g / eq, weight average molecular weight (Mw) = 4,200.
Polyfunctional epoxy compound (4): manufactured by Kyoeisha Chemical Co., Ltd., product name “Epolite 4000”, hydrogenated bisphenol A diglycidyl ether, epoxy equivalent = 215 to 245 g / eq, weight average molecular weight (Mw) = 800.
Silane coupling agent (C): manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM-4803”, glycidoxyoctyltrimethoxysilane.
Imidazole-based curing catalyst (D): manufactured by Shikoku Kasei Kogyo Co., Ltd., product name “CURESOL 2E4MZ”, 2-ethyl-4-methylimidazole.
Tackifier (E): manufactured by Mitsui Chemicals, product name “FTR6100”, copolymer of styrene monomer and aliphatic monomer, softening point = 95 ° C.

(2) Preparation of sheet-like adhesive On the release-treated surface of a release film (product name “SP-PET382150” manufactured by Lintec Corporation), the prepared adhesive composition was applied to form a coating film, The film was dried at 100 ° C. for 2 minutes to produce a sheet adhesive having a thickness of 10 μm. Furthermore, the exposed surface of the said sheet-like adhesive and the release treatment surface of the release film similar to the above were bonded together to obtain a sheet-like adhesive sandwiched between the release films.

(3) Preparation of test piece for measuring adhesive strength One of the release films of the sheet-like adhesive sandwiched between the release films obtained in (2) above was removed, and a 50 μm-thickness subjected to double-sided easy adhesion treatment Using a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., product name “PET50A4300”) as a base film, the base film and the exposed surface of the sheet-like adhesive are heated at 60 ° C. using a heat roller heat laminator. Bonding was performed under the conditions of a pressure of 0.2 MPa and a speed of 0.2 m / min to prepare a test piece for measuring adhesive force.

The following measurements and evaluations were performed using the above-described sheet-like adhesives prepared in Examples and Comparative Examples and test pieces for measuring adhesive strength. These results are shown in Table 1.

[Measurement of outgas generation amount of sheet adhesive]
The sheet-like adhesive produced in Examples and Comparative Examples was removed so that one release film of the sheet-like adhesive sandwiched between the release films was removed, and the exposed surface of the sheet-like adhesive was opposed to the glass plate. Was placed on a glass plate and adhered at 60 ° C. using a heat laminator. And the other peeling film of the said sheet-like adhesive was removed, and the sample for outgas generation amount measurement was obtained.
The outgas generation amount when this outgas generation amount measurement sample was allowed to stand for 20 minutes in an environment of 120 ° C. was measured using the following apparatus.
Apparatus: Gas chromatograph mass spectrometer (manufactured by Shimadzu Corporation, product name “GCMS-QP2010”).
Column: 5MS column (manufactured by Shimadzu Corporation, product name “SH-Rtx (registered trademark) -5MS”, 5% diphenyl / 95% dimethylpolysiloxane).
-Calibration curve: Toluene.

[Adhesion measurement]
The test pieces for measuring the adhesive force produced in Examples and Comparative Examples were cut into strips having a width of 25 mm, and then the release film was removed. And using the laminator apparatus, the test piece for measuring the adhesive force is pressed against the glass plate with a roller under the conditions of a temperature of 60 ° C., a pressure of 0.2 MPa, and a speed of 0.2 m / min. The exposed surface of the sheet-like adhesive and the glass plate were pasted to produce a laminate of the glass plate and the test specimen for measurement. Then, the said laminated body was heated at 100 degreeC for 2 hours, the sheet adhesive was hardened, and the sample for adhesive force measurement was obtained.
After the produced laminate was stored for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity), this adhesive strength measurement sample was subjected to the measurement method described in JIS Z0237: 2000 except for the above-mentioned pasting conditions and the like. The adhesive strength was measured in accordance with the standard. Specifically, the test piece for measuring adhesive strength was peeled off from the glass plate at a peeling speed of 300 mm / min by a 180 ° peeling method, and the adhesive strength was measured.

[Sealability evaluation]
(I) Production of organic EL element An organic EL element was produced by the following method using a glass substrate on which an indium tin oxide (ITO) film (thickness: 100 nm, sheet resistance: 50Ω / □) was formed as an anode. did.
On the ITO film of the glass substrate, N, N′-bis (naphthalen-1-yl) -N, N′-bis (phenyl) -benzidine (manufactured by Luminescence Technology) was 0.1 to 0.2 nm / min. The hole transport layer having a thickness of 50 nm was formed by vapor deposition at a rate of 5 nm.
Then, tris (8-hydroxy-quinolinate) aluminum (manufactured by Luminescence Technology) is deposited on the formed hole transport layer at a rate of 0.1 to 0.2 nm / min to form a light emitting layer having a thickness of 50 nm. did.
Further, on the formed light emitting layer, lithium fluoride (LiF) (manufactured by High Purity Chemical Research Laboratories) was deposited at a rate of 0.1 nm / min to form an electron injection layer having a thickness of 4 nm.
Finally, aluminum (Al) (manufactured by Kojundo Chemical Laboratory Co., Ltd.) is vapor-deposited on the formed electron injection layer at a rate of 0.1 nm / min to form a cathode having a thickness of 100 nm to obtain an organic EL element. It was.
The degree of vacuum at the time of vapor deposition was 1 × 10 ⁻⁴ Pa or less.

(Ii) Production of electronic device Remove one release film of the sheet-like adhesive sandwiched between the release films produced in Examples and Comparative Examples, and overlay the exposed surface of the sheet-like adhesive on the metal foil film, Adhesion was performed at 40 ° C. using a heat laminator.
Then, the other release film of the sheet-like adhesive is removed, and the surface of the sheet-like adhesive is laminated so as to cover the organic EL element formed on the glass substrate including the surface of the glass substrate. Bonding was performed at 40 ° C. using a laminator. Subsequently, it heated at 100 degreeC for 2 hours, the sheet-like adhesive was hardened, and the bottom emission type electronic device which is the sealing body which sealed the organic EL element was obtained.

(Iii) Evaluation of sealing property After the produced electronic device was allowed to stand for 240 hours in an environment of 85 ° C. and 85% RH (relative humidity), the electronic device was started up and dark spots (non-light emitting) of the organic EL element was measured area _{S 1} point).
The area S ₀ of the dark spot of the organic EL element before standing in the above environment was also measured in advance, and the dark spot magnification (Sm) was calculated from the following formula.
・ Sm (%) = S ₁ / S ₀ × 100
And the sealing property of the sealing sheet was evaluated from the following criteria.
A: The dark spot enlargement ratio (Sm) is less than 150%.
B: The dark spot enlargement ratio (Sm) is 150% or more.
Note that the larger the value of the dark spot enlargement ratio (Sm), the more the deterioration of the electrode and the organic layer proceeds.

 

 

Table 1 shows the following.
From the outgas amounts of Examples 3 and 4 and Comparative Example 2, even if the content of the polyfunctional epoxy compound in the sheet adhesive is the same, the outgas amount increases if the weight average molecular weight (Mw) is small. I understand that.
Moreover, even if the polyfunctional epoxy compound in a sheet-like adhesive is the same from the outgas amount of Example 1, 2 and Example 3, 4, it turns out that the amount of outgas will become small if the content is small. .
Further, from the adhesive strength after curing of Examples 1 and 2 and Comparative Example 1, when the epoxy equivalent of the polyfunctional epoxy compound is small and the weight average molecular weight (Mw) of the polyfunctional epoxy compound is small, the adhesive strength after curing is increased. In particular, it can be seen that the adhesive strength after curing tends to increase when the epoxy equivalent of the polyfunctional epoxy compound decreases.

Claims (20)

A sheet-like adhesive formed from an adhesive composition containing a modified polyolefin resin (A) and a thermosetting component (B),
A sheet-like adhesive that satisfies the following requirements (I) and (II).
Requirement (I): The amount of outgas generated per cm ³ when the sheet-like adhesive is allowed to stand for 20 minutes in an environment of 120 ° C. is 20 mg / cm ³ or less. Requirement (II): Thickness The laminate in which the sheet-like pressure-sensitive adhesive is stuck on a 50 μm polyethylene terephthalate film is pressed against a glass plate with a roller at a temperature of 60 ° C., a pressure of 0.2 MPa, and a speed of 0.2 m / min. The surface of the sheet-like pressure-sensitive adhesive side of the body and the glass plate are bonded together, the sheet-like adhesive is cured at 100 ° C. for 2 hours, and then 24 ° C. at 23 ° C. and 50% relative humidity. After storage for a period of time, the adhesive strength of the laminate from the glass plate measured according to JIS Z0237: 2000 under conditions of a peeling speed of 300 mm / min and a peeling angle of 180 ° is 10 N / 2. 5mm or more The sheet-like adhesive according to claim 1, wherein the thermosetting component (B) contains a polyfunctional epoxy compound. The sheet adhesive according to claim 2, wherein an epoxy equivalent of the polyfunctional epoxy compound is 100 to 300 g / eq. The sheet-like adhesive according to any one of claims 1 to 3, wherein the modified polyolefin resin (A) is an acid-modified polyolefin resin. The sheet-like adhesive according to any one of claims 1 to 4, wherein the content of the modified polyolefin resin (A) is 15 to 95% by mass with respect to the total amount of active ingredients of the adhesive composition. Agent. The sheet according to any one of claims 1 to 5, wherein a content of the thermosetting component (B) is 5 to 150 parts by mass with respect to 100 parts by mass of the modified polyolefin resin (A). Adhesive. The sheet adhesive according to any one of claims 1 to 6, further comprising a silane coupling agent (C). The sheet adhesive according to claim 7, wherein the content of the silane coupling agent (C) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the modified polyolefin resin (A). A gas barrier having a gas barrier film having a base material layer and an adhesive layer composed of a sheet-like adhesive formed from an adhesive composition containing a modified polyolefin resin (A) and a thermosetting component (B) A laminated body,
A gas barrier laminate satisfying the following requirements (I) and (IIa).
Requirement (I): The amount of outgas generated per cm ³ when the sheet-like adhesive is allowed to stand for 20 minutes in an environment of 120 ° C. is 20 mg / cm ³ or less Requirement (IIa): the gas barrier The sheet laminate adhesive of the gas barrier laminate and the glass plate are pressed against the glass plate with a roller under the conditions of a temperature of 60 ° C., a pressure of 0.2 MPa, and a speed of 0.2 m / min. After the sheet adhesive was cured at 100 ° C. for 2 hours and stored at 23 ° C. in an environment with a relative humidity of 50% for 24 hours, the peeling speed was 300 mm / min and the peeling angle was 180 °. The adhesive strength of the laminate from the glass plate is 10 N / 25 mm or more, measured in accordance with JIS Z0237: 2000 under the conditions of The gas barrier laminate according to claim 9, wherein the thermosetting component (B) contains a polyfunctional epoxy compound. The gas barrier laminate according to claim 10, wherein an epoxy equivalent of the polyfunctional epoxy compound is 100 to 300 g / eq. The gas barrier laminate according to any one of claims 9 to 11, wherein the modified polyolefin resin (A) is an acid-modified polyolefin resin. The gas barrier laminate according to any one of claims 9 to 12, wherein the content of the modified polyolefin resin (A) is 15 to 95% by mass with respect to the total amount of active ingredients of the adhesive composition. body. The gas barrier according to any one of claims 9 to 13, wherein the content of the thermosetting component (B) is 5 to 150 parts by mass with respect to 100 parts by mass of the modified polyolefin resin (A). Laminate. The gas barrier laminate according to any one of claims 9 to 14, further comprising a silane coupling agent (C). The gas barrier laminate according to claim 15, wherein the content of the silane coupling agent (C) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the modified polyolefin resin (A). The gas barrier film has the base material layer and the gas barrier layer,
The gas barrier laminate according to any one of claims 9 to 16, wherein the gas barrier layer is a polymer layer containing a polymer compound and subjected to a modification treatment. The gas barrier laminate according to claim 17, wherein the gas barrier layer and the adhesive layer are directly laminated. The sheet-like adhesive according to any one of claims 1 to 8 or the adhesive layer possessed by the gas barrier laminate according to any one of claims 9 to 18 is sealed. A sealed body that is sealed as a stopper. The sealing body according to claim 19, wherein the object to be sealed is an organic EL element, an organic EL display element, a liquid crystal display element, or a solar cell element.