TW201903099A - Sheet adhesive, gas barrier laminate, and sealing body - 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 DEG 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 [mu]m-thick polyethylene terephthalate film is pressed onto a glass plate using a roller and conditions of a temperature of 60 DEG 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 DEG C followed by holding for 24 hours in a 23 DEG 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 DEG, is at least 10 N/25 mm.

Description

Sheet adhesive, gas barrier laminated body, and sealing body

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

In recent years, organic EL elements have attracted much attention as light-emitting elements that can generate high-brightness light emission by low-voltage DC driving. However, after a certain period of time, the organic EL element is prone to problems such as reduction in light emission brightness, light emission efficiency, and light emission uniformity. The cause of the problem of lowering the light-emitting characteristics is presumably due to the penetration of oxygen or moisture into the organic EL element, which deteriorates the electrode or the organic layer. Therefore, a sealing material is often used to seal the organic EL element to prevent oxygen or Infiltration of water, etc. Specifically, in order to form an organic EL element on a substrate, a sealing material is used to cover the surface of the organic EL element and the substrate on the periphery of the organic EL element, and the sealing material is hardened to seal the organic EL element. In addition, when an organic EL element is sealed with a sealing material, the organic EL element will be deteriorated when out gas is generated in the sealing material, so development of a sealing material with low outgassing properties is being carried out again.

For example, Patent Document 1 describes a composition for sealing an organic EL device using a specific cation-curable compound, a photocationic polymerization initiator, and an azole-based compound. Patent Document 1 describes that the use of an azole-based compound as a hardening and rolling agent for a sealing composition can form a hardened material having low outgassing property and moisture resistance. [Prior Art Literature] [Patent Literature]

[Patent Document 1] WO2015 / 111525

[Problems to be solved by the invention]

However, according to the studies of the present inventors, it is known that the amount of outgassing in the sealing material is changed not only by the hardening and rolling agent, but also by the type or content of each component contained in the composition. Therefore, a sealing material having low outgassing property and highly inhibiting the deterioration of the sealed object is further sought. Further, for example, even when a low outgassing property of the sealing material is achieved, there is still a need to further suppress the degradation of the characteristics of the electronic device of the sealed object, such as the light-emitting characteristics of the organic EL element.

In addition, in general, when a resin-containing resin layer is directly laminated on a gas-barrier layer of a gas-barrier film, the affinity of the gas-barrier layer and the resin is low, so the gas-barrier layer has low affinity. There may be a problem in the adhesion between the barrier layer and the resin layer. In particular, when a modified gas barrier layer containing a polymer compound is used, the interlayer adhesion between the gas barrier layer and the resin layer may be deteriorated. Therefore, the sealing material also needs to have excellent interlayer adhesion with the gas barrier layer.

The present invention has been made in view of the above circumstances, and proposes a sealing material having a high effect of suppressing deterioration of a sealed object, a sheet-shaped adhesive having excellent interlayer adhesion with a gas barrier layer, and a layer as an adhesive. The gas-barrier laminated body of the sheet-shaped adhesive, and a sealed body formed by sealing the to-be-sealed object such as an electronic device with the gas-barrier laminated body. [Solution to the problem]

The present inventors have found that a sheet-shaped adhesive formed from an adhesive composition containing a modified polyolefin resin (A) and a thermosetting component (B) can solve the above-mentioned problems, and thus completed the present invention.

That is, the present invention relates to the following [1] to [18]. [1] A sheet-shaped adhesive, which is a sheet-shaped adhesive formed from an adhesive composition containing a modified polyolefin-based resin (A) and a thermosetting component (B), and satisfies the following requirements (I ) And (II); ・ Requirement (I): The outgassing amount per 1 cm ³ after the sheet adhesive is left to stand at 120 ° C for 20 minutes is 20 mg / cm ³ or less; ・ Requirement (II): At a temperature of 60 ° C, a pressure of 0.2 MPa, and a speed of 0.2 m / min, using a roll, the laminate having the aforementioned sheet-shaped adhesive on a polyethylene terephthalate film having a thickness of 50 μm was pressed against the glass. The sheet is bonded to the sheet-shaped adhesive side surface of the laminated body and the glass plate, and the sheet-shaped adhesive is hardened at 100 ° C for 2 hours, and then at 23 ° C and a relative humidity of 50%. After storage for 24 hours, the adhesive force 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 ° was 10 N / 25 mm or more. [2] The sheet-shaped adhesive according to [1], wherein the thermosetting component (B) contains a polyfunctional epoxy compound. [3] The sheet-shaped adhesive according to [2], wherein the epoxy equivalent of the polyfunctional epoxy compound is 100 to 300 g / eq. [4] The sheet-shaped adhesive according to any one of [1] to [3], wherein the modified polyolefin resin (A) is an acid-modified polyolefin resin. [5] The sheet-shaped adhesive according to any one of [1] to [4], wherein the content of the modified polyolefin-based resin (A) is 15 based on the total amount of the active ingredients of the adhesive composition. ~ 95 mass%. [6] The sheet-like adhesive according to any one of [1] to [5], wherein the content of the thermosetting component (B) is 100 parts by mass of the modified polyolefin-based resin (A). 5 to 150 parts by mass. [7] The sheet-shaped adhesive according to any one of [1] to [6], further comprising a silane coupling agent (C). [8] The sheet-shaped adhesive according to [7], wherein the content of the silane coupling agent (C) is 0.01 to 10 parts by mass based on 100 parts by mass of the modified polyolefin-based resin (A). [9] A gas barrier laminate, comprising: a gas barrier film having a substrate layer and an adhesive layer, the adhesive layer is composed of a sheet adhesive, and the sheet adhesive is composed of Formed by an adhesive composition containing a modified polyolefin resin (A) and a thermosetting component (B), and satisfying the following requirements (I) and (IIa); After the adhesive is left at 120 ° C for 20 minutes, the outgassing amount per 1cm ³ is less than 20mg / cm ³ · Requirement (IIa): Conditions of temperature 60 ° C, pressure 0.2MPa, and speed 0.2m / min Next, a roll is used to press the gas-barrier laminate to a glass plate, and the sheet-shaped adhesive of the gas-barrier laminate and the glass plate are bonded, and the foregoing is made at 100 ° C for 2 hours. After the sheet-shaped adhesive is cured, it is stored in an environment with a relative humidity of 50% at 23 ° C. for 24 hours, and the peeling speed is 300 mm / min and the peeling angle is 180 ° according to JIS Z0237: 2000. The adhesive force of the laminate is 10N / 25mm or more. [10] The gas barrier laminate according to [9], wherein the thermosetting component (B) contains a polyfunctional epoxy compound. [11] The gas barrier laminate according to [10], wherein the epoxy equivalent of the multifunctional epoxy compound is 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] The gas-barrier laminate according to any one of [9] to [12], wherein the content of the modified polyolefin-based resin (A) is modified relative to the total amount of active ingredients of the adhesive composition It is 15 to 95% by mass. [14] The gas barrier laminate according to any one of [9] to [13], wherein the thermosetting component (B) is 100 parts by mass of the modified polyolefin resin (A). The content is 5 to 150 parts by mass. [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 based on 100 parts by mass of the modified polyolefin resin (A). [17] The gas barrier laminate according to any one of [9] to [16], wherein the gas barrier film has a base material layer and a gas barrier layer, and the gas barrier layer contains a polymer A modified polymer layer of a compound. [18] The gas barrier laminate according to [17], wherein the gas barrier layer and the adhesive layer are directly laminated. [19] A sealed body characterized in that the material to be sealed is a sheet-shaped adhesive as described in any one of [1] to [8], or as described in any one of [9] to [18] The adhesive layer of the gas barrier laminate is sealed 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. [Effect of the invention]

The sheet-shaped adhesive of the present invention can form a sealing material having a high effect of suppressing deterioration of an object to be sealed, and also has excellent interlayer adhesion with a gas barrier layer. [Form of Implementing Invention]

In the present specification, a preferred numerical range (for example, a range of content, etc.), a lower limit value and an upper limit value described in stages may be used independently in combination. For example, the description of "preferably 10 to 90, more preferably 30 to 60" may also be combined with "better lower limit (10)" and "better upper limit (60)" to form "10 ~ 60 "combination.

[Flake Adhesive] The sheet adhesive according to the first embodiment of the present invention is a sheet adhesive formed from an adhesive composition containing a modified polyolefin resin (A) and a thermosetting component (B). Agent and satisfies the following requirements (I) and (II); ・ Requirement (I): The amount of outgassing per 1 cm ³ after the sheet adhesive is left to stand at 120 ° C for 20 minutes is 20 mg / cm ³ or less.・ Requirement (II): Under the conditions of a temperature of 60 ° C, a pressure of 0.2 MPa, and a speed of 0.2 m / min, a 50 μm-thick polyethylene terephthalate film is affixed with a roll by a roller. The laminated body was pressed against a glass plate to adhere the sheet-shaped adhesive side surface of the laminated body to the glass plate, and the sheet-shaped adhesive was cured at 100 ° C for 2 hours, and then the relative humidity was 23 ° C. After 24 hours of storage in a 50% environment, the adhesive force of the aforementioned laminated body from the aforementioned glass plate as measured in accordance with JIS Z0237: 2000 under conditions of a peeling speed of 300 mm / min and a peeling angle of 180 ° was 10 N / 25 mm or more.

Since the amount of outgassing required by the requirement (I) is 20 mg / cm ³ or less, the sheet-shaped adhesive of the present invention can be called a sealing material having excellent low outgassing properties. Moreover, since the adhesive force prescribed | regulated by the requirement (II) is 10 N / 25mm or more, the sheet-shaped adhesive agent of this invention can be said to be a sealing material which does not peel easily from a to-be-sealed surface after hardening. That is, the sheet-shaped adhesive of the present invention can be adjusted in a manner that satisfies the requirements (I) and (II) described above, so it can have excellent low outgassing properties, and it is not easy to peel off from the sealed surface after curing. A sealing material having a high effect of suppressing deterioration of a sealed object.

In the sheet-shaped adhesive of the present invention, it is preferable that the outgassing amount prescribed by the requirement (I) has a better low outgassing property and has a higher effect of suppressing deterioration of the sealed object. of 18mg / cm ³ or less, more preferably 15mg / cm ³ or less, and particularly preferably 10mg / cm ³ or less, most preferably 8mg / cm ³ or less, more preferably 7mg / cm ³ or less, particularly preferably 4mg / cm ³ or less, most preferably 1 mg / cm ³ or less, and usually 0.1 mg / cm ³ or more. In addition, in this specification, the outgassing amount of the sheet-like article specified in the requirement (I) means the value measured by the method described in the examples.

In the sheet-shaped adhesive of the present invention, from the viewpoint that the adhesive force specified by the requirement (II) can reliably suppress peeling from the sealed surface after curing, it is preferably 12N / 25mm or more, and more preferably 14N. Above / 25mm, particularly preferably above 16N / 25mm, most preferably above 18N / 25mm, more preferably above 20N / 25mm, particularly preferably above 22N / 25mm, and usually below 30N / 25mm.

In the sheet-shaped adhesive of the present invention, the polyethylene terephthalate film used in the requirement (II) is a film formed substantially of polyethylene terephthalate, which is made of polyterephthalic acid. Ethylene glycol is the main component. Polyethylene terephthalate film can be added with common additives. Polyethylene terephthalate film can usually be stretched, and the stretching method is generally a biaxial stretching method.

From the viewpoint of improving the adhesion when a sheet-shaped adhesive is laminated on a polyethylene terephthalate film, the surface of the resin film can be easily adhered by an oxidation method or an uneven method. The hafnium oxidation method includes, for example, a corona discharge treatment, a plasma discharge treatment, a chromic acid treatment (wet), a hot air treatment, ozone, and an ultraviolet irradiation treatment, and a bumping method such as a sandblasting method, a solvent treatment method, and the like.

The thickness of the sheet-shaped adhesive of the present invention can be appropriately set according to the application, and is preferably 2 to 50 μm, more preferably 5 to 25 μm, and particularly preferably 10 to 20 μm. In addition, the shape of the sheet-shaped adhesive of the present invention can also be appropriately set according to the application. For example, the shape can be a square, a rectangle, a polygon, a circle, and an ellipse.

The sheet-shaped adhesive of the present invention is formed from an adhesive composition containing a modified polyolefin resin (A) and a thermosetting component (B). When the adhesive composition contains a combination of a modified polyolefin resin (A) and a thermosetting component (B), the sheet-shaped adhesive can be obtained in a manner that satisfies the requirements (I) and (II) described above.剂 组合 物。 Composition. Hereinafter, the present invention will be described in detail using a specific method for producing an adhesive composition capable of forming a sheet-shaped adhesive satisfying the requirements (I) and (II) using the adhesive composition of the present invention.

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

The adhesive composition used in the present invention may contain ingredients other than the components (A) and (B) in a range in which the sheet-shaped adhesive of the present invention satisfies the above requirements (I) and (II) without impairing the effects of the present invention. Other ingredients.其他 The other components are, for example, one or more selected from a silane coupling agent (C), an imidazole-based hardening catalyst (D), and a thickener (E). In the following description, "silane coupling agent (C)", "imidazole-based hardening catalyst (D)", and "tackifier (E)" are also referred to as "ingredient (C)" and "ingredient" (D) ", and" ingredient (E) ".

In the adhesive composition used in the present invention, the total content of the 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. It is more preferably 80% by mass or more, particularly preferably 90% by mass or more, most preferably 95% by mass or more, more preferably 99% by mass or more, and usually 100% by mass or less.

In the adhesive composition used in the present invention, the components (A), (B), (C), (D), and (E) are relative to the total amount (100% by mass) of the active ingredients of the adhesive composition. The total content is preferably 80 to 100% by mass, more preferably 85 to 100% by mass, particularly preferably 90 to 100% by mass, and most preferably 95 to 100% by mass. In addition, in the present invention, the effective component of the adhesive composition refers to a component obtained by removing an irrelevant physical solvent and a diluting solvent contained in the adhesive composition.

(Component (A): Modified polyolefin resin) 的 The adhesive composition used in the present invention contains a modified polyolefin resin (A).接着 Since the adhesive composition used in the present invention contains a modified polyolefin resin (A), it can form a sheet-shaped adhesive that satisfies the requirements (I) and (II) described above. Moreover, the sheet-form (adhesive layer) with a thin film thickness can also be made more favorable. In addition, the modified polyolefin resin (A) may be used alone or in combination of two or more kinds.

In the present invention, the modified polyolefin-based resin means a polyolefin resin having a functional group, which is obtained by subjecting the polyolefin resin as a precursor to a modification treatment using a modifier having a functional group. The term “polyolefin resin” refers to a polymer having a repeating unit derived from an olefin-based monomer. In the present invention, the polyolefin resin may be a polymer composed of only repeating units generated from an olefin-based monomer, or may have a repeating unit generated from an olefin-based monomer. A copolymer of a repeating unit generated from a monomer other than the monomer may be used.

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

Polyolefin resins, for example, very 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-based elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene- (meth) acrylic copolymer, ethylene- (meth) acrylate copolymer, and the like. In addition, in this specification, for example, "(meth) acrylic acid" means both "acrylic acid" and "methacrylic acid", and other similar terms have the same meaning.

As the modifier used for the modification treatment of the polyolefin resin, any compound having a functional group capable of performing a cross-linking reaction described later or a compound having the functional group may be introduced into the polyolefin resin. The functional group is, for example, a carboxyl group, a group derived from a carboxylic acid anhydride (hereinafter, also referred to as a "carboxylic acid anhydride group"), a carboxylic acid ester group, a hydroxyl group, an epoxy group, a sulfonylamino group, an ammonium group, a nitrile group, or an amine group. , Fluorenimine, isocyanate, ethenyl, thiol, ether, thioether, fluorenyl, phosphoric group, nitro, carbamate, alkoxysilyl, and Halogen atom, etc. Among these, a carboxyl group, a carboxylic acid anhydride group, a carboxylic acid ester group, a hydroxyl group, an ammonium group, an amine group, an imino group, or an isocyanate group are more preferable, and a carboxyl group, a carboxylic acid anhydride group, a hydroxyl group, or an alkoxysilane The group is more preferable, and a carboxyl group, a carboxylic acid anhydride group, or a hydroxyl group is more preferable, and a carboxylic acid anhydride group is more preferable.质 The modifier used may be a compound having one kind of the above-mentioned functional group in the molecule, or a compound having two or more kinds of the above-mentioned functional group.结果 As a result of the modification treatment of the polyolefin resin using the above-mentioned modifier, a group capable of performing a 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.

The modified polyolefin resin (A) can easily form a sheet-shaped adhesive that satisfies the above requirements (I) and (II), and also easily form a sheet-shaped adhesive with low water vapor transmission rate and high gas barrier properties. From the viewpoint of the agent, it is preferable to use an acid-modified polyolefin resin, a hydroxy-modified polyolefin resin, or a silane-modified polyolefin resin, and an acid-modified polyolefin resin or a hydroxy-modified polyolefin resin. More preferably, an acid-modified polyolefin resin is more preferred.

In the present invention, the term "acid-modified polyolefin resin" refers to a polyolefin resin that has been graft-modified using an acid as a modifier. For example, it is obtained by reacting a polyolefin resin with an unsaturated carboxylic acid and / or its anhydride, and introducing a carboxyl group and / or a carboxylic anhydride group (graft modification). In other words, for example, a polyolefin resin having a carboxyl group and / or a carboxylic acid anhydride group as a crosslinkable functional group.

Unsaturated carboxylic acids and / or anhydrides thereof that can react with polyolefin resins, such as maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaric acid, tetrahydrophthalic acid, aconitic acid, horse Maleic anhydride, itaconic anhydride, glutaric anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride and the like. These unsaturated carboxylic acids and / or their anhydrides can be used alone or in combination of two or more. Among these, maleic anhydride is preferable from the viewpoint that the sheet-like adhesives that can form the above-mentioned requirements (I) and (II) are satisfied.

The blending amount of the unsaturated carboxylic acid and / or its anhydride reacted with the polyolefin resin can easily form a sheet-shaped adhesive that satisfies the above requirements (I) and (II), and also easily form a low water vapor transmission rate. From the viewpoint of sheet adhesive with high gas barrier properties, it is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, and still more preferably 0.2 to 100 parts by mass of the polyolefin resin before modification. ~ 1.0 part by mass.

In the present invention, a commercially available product may be used as the acid-modified polyolefin resin. Commercially available acid-modified polyolefin resins include, for example, ADMER (registered trademark) (manufactured by Mitsui Chemicals Co., Ltd.), UNISTOLE (registered trademark) (manufactured by Mitsui Chemicals Co., Ltd.), Bondy Ram (manufactured by Polyram Corporation), orevac (registered trademark) (made by ARKEMA), MODIC (registered trademark) (made by Mitsubishi Chemical Corporation), and the like.

In the present invention, the silane-modified polyolefin resin refers to a polyolefin resin obtained by graft-modifying an unsaturated silane compound with a modifier. That is, the silane-modified polyolefin resin is a polyolefin resin having a main chain having a structure that forms a graft copolymerization with an unsaturated silane compound as a side chain. In other words, the silane-modified polyolefin resin is a polyolefin resin having a silane-containing group as a crosslinkable functional group.

Unsaturated silane compounds that react with polyolefin resins are preferably ethylene silane compounds, for example, ethylene trimethoxysilane, ethylene triethoxysilane, ethylene tripropoxysilane, ethylene triisopropoxysilane, ethylene Tributoxysilane, ethylenetripentyloxysilane, ethylenetriphenoxysilane, ethylenetribenzyloxysilane, ethylenetrimethyldioxysilane, ethylenetriethyldioxysilane, ethylenepropyloxy Silane, ethylene triethoxysilane, ethylene tricarboxysilane, etc. These unsaturated silane compounds can be used alone or in combination of two or more. In addition, for a polyolefin resin having an unsaturated silane compound as a main chain, the conditions for performing graft polymerization may be a generally known graft polymerization method.

From the viewpoint that the amount of the unsaturated silane compound to be reacted with the polyolefin resin forms a sheet-shaped adhesive that satisfies the requirements (I) and (II) described above, compared with 100 parts by mass of the polyolefin resin before the modification, It is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass, and particularly preferably 0.5 to 5 parts by mass.

Specific silane-modified polyolefin resins, for example, silane-modified polyethylene resins, silane-modified ethylene-vinyl acetate copolymers, etc., and silane-modified low-density polyethylene, silane-modified ultra-low-density polymer Silane-modified polyethylene resins such as ethylene and silane-modified linear low-density polyethylene are preferred.

In the present invention, commercially available products may be used as the silane-modified polyolefin resin. Commercially available silane-modified polyolefin resins, for example, LINKLON (registered trademark) (manufactured by Mitsubishi Chemical Co., Ltd.), and other low-density polyethylene-based LINKLON, linear low-density polyethylene-based LINKLON, Ultra low density polyethylene based LINKLON and ethylene-vinyl acetate copolymer based LINKLON are preferred.

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

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

There is no particular limitation on the amount of the peroxide to be reacted with the polyolefin resin. From the viewpoint of forming a sheet-like adhesive that satisfies the above requirements (I) and (II), it is relative to the polymerization before the modification. The olefin resin is 100 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass, and particularly preferably 0.5 to 5 parts by mass.

In the present invention, a commercially available hydroxy-modified polyolefin resin may be used. A commercially available hydroxy-modified polyolefin-based resin is, for example, POLYTAIL (registered trademark) (manufactured by Mitsubishi Chemical Corporation).

The weight average molecular weight (Mw) of the modified polyolefin-based resin (A) is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000 from the viewpoint of forming a sheet-shaped adhesive that satisfies the requirements (I) and (II) described above. Particularly preferred is 25,000-250,000, and the best is 30,000-150,000. When the weight average molecular weight of the modified polyolefin-based resin is within this range, it is easy to maintain the sheet-like shape of the adhesive composition even when the content of the adhesive composition of the modified polyolefin resin is large.

In this specification, the weight average molecular weight (Mw) of the modified polyolefin-based resin (A) is a value converted into a 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.

In view of the fact that the modified polyolefin-based resin (A) has a large content in the adhesive composition of the modified polyolefin-based resin (A), it is also easy to maintain the sheet-like shape of the adhesive composition, It is better to be solid at room temperature (25 ° C).

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

<Component (B): Thermosetting component> 的 The adhesive composition used in the present invention contains a thermosetting component (B).的 The adhesive composition used in the present invention can form a sheet-shaped adhesive that satisfies the above-mentioned requirements (I) and (II) because it contains a thermosetting component (B). The thermosetting component (B) may be used alone or in combination of two or more kinds. The content of the thermosetting component (B) is preferably 5 to 110 parts by mass, more preferably 10 to 50 parts by mass, and particularly preferably 20 to 100 parts by mass of the modified polyolefin-based resin (A). 30 parts by mass.

As long as the thermosetting component (B) is heated, it can react with each other via the functional groups of the thermosetting component (B) and / or via the functional group possessed by the modified polyolefin resin (A). The crosslinkable functional group is allowed to react (crosslinking reaction), and a compound having a property of forming a strong film having a three-dimensional mesh structure may be sufficient, for example, epoxy-based compound, melamine-based compound, urea-based compound, and maleam The imine-based compound and the like are preferably epoxy-based compounds. These compounds may be used singly or in combination of two or more kinds.

Among them, the thermosetting component (B) is preferable from the viewpoint of forming a sheet-shaped adhesive that satisfies the above requirements (I) and (II). The adhesive composition used in the present invention is preferably one containing a polyfunctional epoxy compound. . The polyfunctional epoxy compound may be used alone or in combination of two or more kinds. The content of the polyfunctional epoxy compound in the thermosetting component (B) is from the viewpoint of forming a sheet-shaped adhesive that satisfies the requirements (I) and (II) above, relative to the total amount of the thermosetting component (B) ( 100% by mass), preferably 50% by mass or more, more preferably 60 to 100% by mass, particularly preferably 70 to 100% by mass, most preferably 80 to 100% by mass, and more preferably 90 to 100% by mass, It is particularly preferably 100% by mass.

In the present invention, the polyfunctional epoxy compound means a compound having at least two epoxy groups in the molecule. (2) A polyfunctional epoxy compound is preferably a bifunctional epoxy compound having at least two epoxy groups from the viewpoint of forming a sheet-shaped adhesive that satisfies the requirements (I) and (II).

Bifunctional epoxy compounds, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether Ether, brominated bisphenol S diglycidyl ether, novolac-type epoxy resin (e.g., phenol, novolac-type epoxy resin, cresol, novolac-type epoxy resin, brominated phenol-novolac-type epoxy resin) And other aromatic epoxy compounds; alicyclic epoxy compounds such as hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether; pentaerythritol polyglycidyl ether, 1 , 6-hexanediol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, 2,2-bis (3-glycidyl- Aliphatic epoxy compounds such as 4-glycidyloxyphenyl) propane, dimethylol tricyclodecane diglycidyl ether, and the like.

Among them, from the viewpoint of increasing the adhesion force prescribed by the above-mentioned requirement (II), it is preferable to increase the cross-linking density of the sheet-shaped adhesive further upward. From this viewpoint, the more the number of epoxy groups generated by the polyfunctional epoxy compound contained in the adhesive composition, the better the purpose of promoting the crosslinking reaction. Therefore, from the viewpoint of increasing the number of epoxy groups generated from the polyfunctional epoxy compound contained in the adhesive composition, it is preferable to select a polyfunctional epoxy compound having a small epoxy equivalent. From the same viewpoint, it is preferable to select a polyfunctional epoxy compound having a small weight average molecular weight (Mw).

From the viewpoint of reducing the amount of outgassing specified in the above requirement (I), the larger the weight average molecular weight (Mw) of the polyfunctional epoxy compound is preferred. The content of the polyfunctional epoxy compound in the adhesive composition is preferably smaller. That is, in the past, when the viewpoint of improving the adhesive force specified in the above-mentioned requirement (II) was considered at the same time, it would not be easy to adjust the adhesive composition that can be used to form a sheet-shaped adhesive agent that satisfies the requirements (I) and (II). However, the weight-average molecular weight (Mw) of the polyfunctional epoxy compound, the epoxy equivalent, and the content of the polyfunctional epoxy compound with respect to the modified polyolefin-based resin (A) in the adhesive composition are adjusted in the following manner. In this case, an adhesive composition that can be used to form a sheet adhesive that satisfies the above requirements (I) and (II) can be obtained.

Therefore, it is achieved that the outgassing amount is lower than that specified in the above requirement (I), and at the same time, the adhesive force specified in the above requirement (II) can be raised upward, the weight average molecular weight (Mw) of the polyfunctional epoxy compound, It is preferably 1,000 to 4,000, more preferably 1,200 to 3,600, and particularly preferably 1,400 to 3,200.

From the viewpoint of further increasing the adhesive force specified 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 particularly preferably 240 g / eq. eq or less, preferably 210 g / eq or less. It is usually 100 g / eq or more. 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 it is a value measured based on JIS K 7236: 2009.

From the viewpoint of reducing the outgassing amount specified in the above requirement (I), the content of the polyfunctional epoxy compound is preferably 5 to 150 parts by mass relative to 100 parts by mass of the modified polyolefin resin (A). Parts, more preferably 10 to 80 parts by mass, and particularly preferably 15 to 50 parts by mass.

<Component (C): Silane coupling agent> 的 The adhesive composition used in the present invention is an adhesive composition capable of forming a sealing body having excellent adhesive strength regardless of normal temperature and high temperature environments. Containing a silane coupling agent (C) is preferred.

The silane coupling agent (C) is preferably an organosilicon compound having at least one alkoxysilyl group in the molecule from the above viewpoint. Specific silane coupling agent (C), for example, a silicon compound containing a polymerizable unsaturated group such as ethylenetrimethoxysilane, ethylenetriethoxysilane, methacryloxypropyltrimethoxysilane, etc .; Silicon compounds with epoxy structure, such as oxypropyloxypropyltrimethoxysilane, glycidoxyoctyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3 -Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethyl Amine-containing silicon compounds such as oxysilane; 3-chloropropyltrimethoxysilane; 3-isocyanatopropyltriethoxysilane; etc. These silane coupling agents (C) may be used alone or in combination of two or more kinds.

In the adhesive composition used in the present invention, the content of the component (C) is an adhesive composition that can form a sealed body having excellent adhesive strength regardless of the environment at normal temperature and high temperature. 100 parts by mass of the component (A) is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 5 parts by mass, and particularly preferably 0.05 to 2 parts by mass.

<Ingredient (D): imidazole-based hardening catalyst> 的 The adhesive composition used in the present invention contains an imidazole-based hardening catalyst from the viewpoint that the adhesive composition can exhibit excellent adhesion even in a high temperature environment ( D) is better.

Imidazole-based hardening catalyst (D), for example, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dimethylolimidazole, and the like. These imidazole-based hardening catalysts (D) may be used alone or in combination of two or more kinds. Among these, the component (D) is preferably 2-ethyl-4-methylimidazole.

The content of the component (D) in the adhesive composition used in the present invention is preferably from 100 parts by mass of the component (A) from the viewpoint that the adhesive composition can exhibit excellent adhesion even in a high-temperature environment. It is 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, and particularly preferably 0.3 to 2.5 parts by mass.

<Component (E): Tackifier> The adhesive composition used in the present invention may further contain a tackifier (E) from the viewpoint that the shape-maintaining property of the formed sealing material is better.

Tackifier (E), for example, turpentine resins such as polymerized turpentine, polymerized turpentine esters, and turpentine derivatives; polyterpene resins, aromatic modified terpene resins and their hydrides, and terpenes such as terpene phenol resins Resins; benzofuran and indene resins; petroleum resins such as aliphatic petroleum resins, aromatic petroleum resins and their hydrides, aliphatic / aromatic copolymer petroleum resins; styrene or substituted styrene polymers ; Α-methylstyrene single polymer resin, copolymer of α-methylstyrene and styrene, copolymer of styrene monomer and aliphatic monomer, styrene monomer and α-methyl A styrene resin such as a copolymer of styrene and an aliphatic monomer, a homopolymer formed of a styrene monomer, a copolymer of a styrene monomer and an aromatic monomer, and the like; and the like. These thickeners (E) may be used alone or in combination of two or more kinds. Among these, the component (E) is preferably a styrene resin, and a copolymer of a styrene monomer and an aliphatic monomer is more preferable.

The softening point of the tackifier (E) improves the shape retention of the formed sealing material, and at the same time, it is an adhesive composition that can exhibit excellent adhesiveness under a high temperature environment, and is preferably 80 ° C or higher. , More preferably 85 to 170 ° C, and particularly preferably 90 to 150 ° C. In this specification, the softening point means a value measured in accordance with JIS K 5902.时 When two or more types of tackifiers are used, the weighted average of the softening points of the plurality of tackifiers is preferably within the above range.

The content of the component (E) in the adhesive composition of the present invention is preferably from 100 mass parts of the component (A) from the viewpoint that the sealing material to be formed is an adhesive composition having better shape retention. It is 1 to 200 parts by mass, more preferably 10 to 150 parts by mass, particularly preferably 15 to 100 parts by mass, and most preferably 20 to 80 parts by mass.

<Other additives> 的 The adhesive composition used in the present invention may contain other additives other than the above-mentioned components (A) to (E), as long as the effect of the present invention is not impaired. Other additives can be appropriately selected according to the application, for example, additives such as ultraviolet absorbers, antistatic agents, light stabilizers, antioxidants, resin stabilizers, fillers, pigments, extenders, softeners and the like. These additives may be used alone or in combination of two or more.

The adhesive composition used in the present invention may further contain a diluent solvent from the viewpoint of good moldability. The diluting solvent can be appropriately selected from organic solvents, and specific examples include aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone, and methyl isobutyl Ketone solvents such as ketones; aliphatic hydrocarbon solvents such as n-pentane, n-hexane, and n-heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, and methylcyclohexane ;Wait. These solvents may be used alone or in combination of two or more. In addition, the content of the solvent can be appropriately set in consideration of coating properties and the like.

<The manufacturing method of a sheet-shaped adhesive> The sheet-shaped adhesive of this invention is formed from the said adhesive composition. The method for producing the sheet-shaped adhesive of the present invention is not particularly limited. For example, the adhesive composition can be applied on the release-treated surface of a release film described later to form a coating film, and the coating film can be dried. A method for forming a sheet-like adhesive.

The coating method of the adhesive composition is, for example, a spin coating method, a spray coating method, a strip coating method, a blade coating method, a roll coating method, a panel coating method, or a die coating method. , Gravure coating method, etc. Furthermore, from the viewpoint of better coating properties, it is preferable to add the above-mentioned diluent solvent to the adhesive composition to form a solution form. The drying conditions used when the coating film is dried are, for example, usually 80 to 150 ° C., and a drying treatment is preferably performed for 30 seconds to 5 minutes.

Further, another sheet of release film may be laminated on the sheet-shaped adhesive formed on the release film. In this way, both sides of the sheet-shaped adhesive can be protected until use. The two peeling films may be the same or different from each other, and it is preferable that they have mutually different adhesion.

<Application of Sheet Adhesive> The sheet adhesive of the present invention can be used, for example, as an adhesive layer of a sealing sheet for sealing an object to be sealed such as an electronic device. Next, a gas barrier laminate according to a second embodiment of the present invention will be described.

[Gas Barrier Laminate] The gas barrier laminate of the present invention is a gas barrier film having a substrate layer and an adhesive layer composed of a sheet-shaped adhesive. The sheet-shaped adhesive is formed from an adhesive composition containing a modified polyolefin resin (A) and a thermosetting component (B), and satisfies the above-mentioned requirement (I). In addition, the gas barrier laminate of the present invention satisfies the following requirement (IIa).・ Requirement (IIa): At a temperature of 60 ° C, a pressure of 0.2 MPa, and a speed of 0.2 m / min, the gas barrier laminate is pressed against a glass plate with a roller, and the gas barrier is bonded to the glass barrier. Laminate the sheet-shaped adhesive and the glass plate, and harden the sheet-shaped adhesive at 100 ° C for 2 hours, and then store the sheet-shaped adhesive at 23 ° C and 50% relative humidity according to the relative humidity JIS Z0237 : The adhesion between the gas barrier laminate and the glass plate measured at 2000 is 10N / 25mm or more.

In the gas barrier laminate of the present invention, the constitution of the adhesive composition forming a sheet-like adhesive capable of constituting the adhesive layer is the same as that described above. In addition, when the adhesive force specified in the above-mentioned requirement (IIa) satisfies the adhesive force specified in the above-mentioned requirement (II), the same method as the above-mentioned adjustment method can be used. The outgassing amount specified in the above requirement (I) can also be satisfied through the above-mentioned adjustment method.

The gas barrier film included in the gas barrier laminate of the present invention is a film having a gas barrier function having at least a base material layer. One aspect of the gas barrier film includes, for example, a substrate layer and a gas barrier layer. For example, it has the aspect of the following layer constitution content. (I) A gas barrier laminate obtained by laminating a base material layer, a gas barrier layer, an adhesive layer, and a release film in this order.

In addition, in the aspect (i), from the viewpoint of improving the adhesion between the base material layer and the gas barrier layer, it can be applied to the base material layer and the gas barrier layer as in the following aspect (ii). There is a primer layer in between. (Ii) A gas barrier laminate obtained by laminating a base material layer, a primer layer, a gas barrier layer, an adhesive layer, and a release film in this order.

In addition, the aspects (i) and (ii) above indicate the state of the gas barrier laminate before use, and when used, the peeled film is usually removed and removed.

Among them, the gas barrier film of the gas barrier laminate of the present invention has a gas barrier function in the substrate layer body, so the substrate layer can be used as a single-layer resin film that also has the function of the gas barrier layer. Wait.

Among them, in the gas-barrier laminate of the present invention, it is preferable that the gas-barrier layer and the adhesive layer are directly laminated. In particular, when the gas barrier layer is a polymer layer to be modified as described later, generally, the adhesiveness between the adhesive layer and the gas barrier layer is not good, so the sheet-shaped adhesive of the present invention is used as When the adhesive layer is used, the adhesive layer and the gas barrier layer can have excellent interlayer adhesion.

The gas-barrier film of the gas-barrier laminate has a water vapor transmission rate of 40 ° C and 90% RH (relative humidity), preferably 0.1 g / m ² / day or less, more preferably It is 0.05 g / m ² / day or less, and particularly preferably 0.005 g / m ² / day or less. When the gas barrier film has a water vapor transmission rate of 0.1 g / m ² / day or less, when a gas barrier laminate is used, it is possible to suppress the penetration of oxygen, moisture, and the like into an organic EL element formed on a transparent substrate. Inside the device, it can effectively suppress the deterioration of the electrode or the organic layer. In addition, the gas-barrier laminate having a gas-barrier film and an adhesive layer has a water vapor transmission rate of 40 ° C and 90% RH (relative humidity), and preferably has the same value as above. . In this specification, the water vapor transmission rate of the gas barrier layer is a value measured using a gas transmission rate measuring device (manufactured by Mocon Corporation, product name "PERMATRAN"), and other widely used water vapor transmission rates are used. The measured value of the measuring device also shows the same value. Hereinafter, one aspect of the gas barrier laminate according to the second embodiment of the present invention is, for example, a gas barrier film composed of a base material layer and a gas barrier layer. In the gas barrier laminate of the present invention, The details of the structure other than the adhesive layer are as follows.

<Base material layer> The base material layer included in the gas barrier film is preferably a resin film containing a resin component. Examples of the resin component include polyimide, polyimide, polyimide, polyphenylene ether, polyetherketone, polyetheretherketone, polyolefin, polyester, polycarbonate, polyfluorene, Polyether fluorene, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin polymer, aromatic polymer, polyurethane polymer, etc. These resins may be used alone or in combination of two or more. When a resin film containing a resin component is used, it is preferable that the surface of the resin film be subjected to an easy-adhesion treatment using an oxidation method or an uneven method. Specific examples of the oxidation method and the unevenness method are as described above. The thickness of the base material layer of the gadolinium gas barrier film is not particularly limited, and from the viewpoint of easy handling, it is preferably 0.5 to 500 μm, more preferably 1 to 200 μm, and still more preferably 5 to 100 μm.

<Gas barrier layer> The gas barrier layer of a gas barrier film can reduce the thickness of the gas barrier film and have excellent gas barrier properties. From the viewpoint of an inorganic film and a polymer compound A polymer layer that has been subjected to modification treatment is preferable, and the polymer layer is more preferable. When the polymer layer is a gas barrier layer, the gas barrier layer can be filled with flexibility, and the gas barrier film can have excellent buckling durability.

Polymer compounds contained in the polymer layer, for example, silicon-containing polymer compounds such as polyorganosiloxane and polysilazane-based compounds, polyimide, polyimide, polyimide, imide, and polybenzene Ether, polyetherketone, polyetheretherketone, polyolefin, polyester, polycarbonate, polyfluorene, polyetherfluorene, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin polymer, aromatic system Polymer, etc. These polymer compounds may be used alone or in combination of two or more kinds. Among these, from the viewpoint of forming a gas barrier layer having excellent gas barrier properties, the polymer compound contained in the polymer layer is preferably a polymer compound containing silicon, and a polysilazane-based compound is used as Better. The number average molecular weight of the polysilazane-based compound is preferably 100 to 50,000.

The polysilazane-based compound is a polymer having a repeating unit containing -Si-N-bond (silazane bond) in the molecule, and specifically, it has a repeating formula represented by the following general formula (1) Units of polymer are preferred.

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

The polysilazane-based compound may be used alone or in combination of two or more kinds. As the polysilazane-based compound, a polysilazane modified product may be used, or a commercially available product may be used.

The polymer layer may further contain other components in addition to the polymer compound as long as the effect of the present invention is not impaired. Other ingredients, such as hardeners, other polymers, anti-aging agents, light stabilizers, flame retardants, etc. The content of the polymer compound in the polymer layer is preferably 50 to 50% of the total amount of the components in the polymer layer (100% by mass) from the viewpoint of being a gas barrier layer having more excellent gas barrier properties. 100% by mass, more preferably 70 to 100% by mass, and particularly preferably 80 to 100% by mass.

The thickness of the polymer layer included in the gas barrier film is preferably 50 to 300 nm, and more preferably 50 to 200 nm. In the present invention, even when the thickness of the polymer layer is in the order of nanometers, a gas barrier laminate having sufficient gas barrier properties can be obtained.

The method for forming a polymer layer is, for example, using a spin coater or a doctor blade coater to form a polymer layer forming solution containing at least one of a polymer compound, other components expected, and a solvent. A method of applying a known device such as a gravure coater (Coater) to form a coating film, and drying the coating film to form a polymer layer.

Polymer layer modification treatments, such as ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, and heat treatment. These processes can be performed by using one type alone or by combining two or more types. As the ion implantation treatment, as described later, for example, a method of implanting ions into a polymer layer to modify the polymer layer. Plasma treatment is a method to modify the polymer layer in order to expose the polymer layer to the plasma. For example, plasma processing can be performed according to the method described in JP 2012-106421. Ultraviolet irradiation treatment is a method of irradiating ultraviolet rays to a polymer layer to modify the polymer layer. For example, the method described in Japanese Unexamined Patent Application Publication No. 2013-226757 can be used to perform ultraviolet modification treatment. Among these, from the viewpoint that the surface of the polymer layer is not rough and can be efficiently modified to the inside thereof, a gas barrier layer having better gas barrier properties is formed, and the polymer layer is modified. An ion implantation process is preferred.

During ion implantation, ions that can be implanted into the polymer layer, for example, ions of rare gases such as argon, helium, neon, krypton, xenon, etc .; carbon fluoride, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, Ions such as sulfur; Ions of paraffinic gases such as methane and ethane; Ions of olefin gases such as ethylene and propylene; Ions of diene gases such as pentadiene and butadiene; acetylene and others Ion of acetylene gas; ion of aromatic hydrocarbon gas such as benzene and toluene; ion of cycloalkane gas such as cyclopropane; ion of cycloolefin gas such as cyclopentene; metal ion ; Ions of organosilicon compounds; etc.离子 These ions may be used alone or in combination of two or more kinds. Among these, ions can be implanted more easily, and in particular, a gas barrier layer having excellent gas barrier properties can be prepared, and ions of rare gases such as argon, helium, neon, krypton, and xenon can be used. Preferably, argon ions are more preferred.

The method of implanting ions is not particularly limited. For example, a method of irradiating ions (ion beams) accelerated by an electric field, a method of implanting ions in a plasma (ions in a plasma-generating gas), and the like can be used to easily produce a gas barrier layer for use. The method of implanting ions in the plasma is preferred. A method for implanting ions in a plasma. For example, in a plasma-containing atmosphere, a plasma is generated, a negative high-voltage pulse is applied to the ion-implanted layer, and the ions (cations) in the plasma are generated. , Implant the surface portion of the implanted ion layer.

<Primer layer> 中 In the gas barrier laminate of the present invention, from the viewpoint of improving the adhesion between the base material layer and the gas barrier layer, a base can be provided between the base material layer and the gas barrier layer. Paint layer. (2) The primer layer is, for example, 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, and more preferably 0.5 to 5 μm.

<Release film> As a release film, a conventionally known thing can be used. For example, there is a release layer on a base material for a release film, which can be subjected to a release treatment via a release agent. Substrates for release films, for example, paper substrates such as cellophane, coated paper, and high-quality paper; laminated papers made of thermoplastic resins such as polyethylene laminated on these paper substrates; and polyethylene terephthalate Plastic film formed from resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polypropylene resin, polyethylene resin, etc .; etc. Releasing agents include, for example, rubber-based elastomers such as silicone resins, olefin-based resins, isoprene-based resins, and butadiene-based resins, long-chain alkane-based resins, alkyd-based resins, and fluorine-based resins.

<The manufacturing method of a gas barrier laminated body> The manufacturing method of a gas barrier laminated body is not specifically limited. For example, in the method for producing a sheet-shaped adhesive described previously, a gas barrier film can be replaced with one release film to form a gas barrier laminate. After the sheet-shaped adhesive is manufactured, one of the two release films included in the sheet-shaped adhesive is peeled off, and the exposed surface of the sheet-shaped adhesive is adhered to the gas barrier layer of the gas barrier film. Method, a gas barrier laminate can also be prepared. In this case, if the sheet-shaped adhesive is two peeling films having different adhesive strengths, it is preferable to peel the peeling film on the side with a smaller adhesive strength from the viewpoint of handleability.

[Sealing Body] The sealing body of the present invention is formed by sealing the object to be sealed with the sheet-shaped adhesive of the first embodiment of the present invention or the gas barrier laminate of the second embodiment of the present invention. The sealing body of the present invention includes, for example, a substrate including a transparent substrate, a component (an object to be sealed) formed on the substrate, and a sealing material for sealing the component, and the sealing material is the first aspect of the present invention. A person constituting the adhesive layer of the gas barrier laminate according to the second embodiment, or a sheet adhesive according to the first embodiment of the present invention.

The transparent substrate is not particularly limited, and various substrate materials can be used. In particular, it is preferable to use a substrate material having high transmittance to visible light. In addition, it is preferable to use a material having a high blocking performance that can block moisture or gas infiltrated from the outside of the device and has excellent solvent resistance or weather resistance. Specifically, for example, transparent inorganic materials such as quartz or glass; polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, polyphenylene sulfide, polyfluorinated Transparent plastics such as vinylene, ethyl cellulose, phenoxy bromide, aromatic polyamines, polyimides, polystyrenes, polyarylates, polyfluorenes, polyolefins, etc. Gas barrier film; etc. The thickness of the transparent substrate is not particularly limited, and it can be appropriately selected in consideration of the light transmittance or the performance of blocking the inside and outside of the element.

The object to be sealed is, for example, an electronic device such as an organic EL element, an organic EL display element, a liquid crystal display element, or a solar cell element. That is, the sealing body of the present invention is obtained by sealing an electronic device such as an organic EL element, an organic EL display element, a liquid crystal display element, or a solar cell element with the gas barrier laminate of the second embodiment of the present invention. Those are better.

The manufacturing method of the sealing body of this invention is not specifically limited. For example, the adhesive layer of the gas barrier laminate according to the second embodiment of the present invention can be coated on the surface of the sealed object and the substrate surface of the peripheral portion of the sealed object and then heated to block the gas. The adhesive layer of the laminated body is adhered to the surface of the object to be sealed and the substrate surface at the peripheral portion of the object to be sealed. In addition, for example, the sheet-shaped adhesive of the first embodiment of the present invention covers the surface of the object to be sealed and the substrate surface of the peripheral portion of the object to be sealed, and then heats the sheet-shaped adhesive to the object to be sealed. The surface and the substrate surface of the periphery of the object to be sealed are adhered. At this time, a sheet of a sealing sheet (for example, a sealing sheet having a release film / gas barrier layer / sheet-shaped adhesive / release film layer) laminated on the sheet-shaped adhesive may be used as the sheet. After the release film on the adhesive side is removed, sealing is performed. Secondly, the adhesive layer of the present invention can be obtained by hardening the adhesive layer.

There are no particular restrictions on the bonding conditions for bonding the adhesive layer or sheet-shaped adhesive of the gas barrier laminate to the object to be sealed. The next temperature is, for example, 23 to 100 ° C, and preferably 40 to 80 ° C. This subsequent treatment can be performed under pressure. The curing conditions for curing the adhesive layer or the sheet-shaped adhesive are not particularly limited, and the crosslinkable functional group and the thermosetting component (B) of the modified polyolefin resin (A) can be considered in consideration of the modification. The degree to which the crosslinking reaction proceeds is appropriately set. 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 (compared with It is preferably 1 to 6 hours).

[Example]

Hereinafter, the present invention will be described in more detail with examples. However, the present invention is not limited in any way by the following examples. In addition, the weight average molecular weight (Mw) of the polyfunctional epoxy compound of 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)> Weight average molecular weight (Mw) of modified polyolefin resin (A) is a gel permeation chromatography (GPC) device (East (Product name: "HLC-8320", manufactured by Cao Co., Ltd.), measured under the following conditions, and converted to a value obtained by weight average molecular weight of standard polystyrene. (Measuring conditions) Measurement sample: Tetrahydrofuran solution with a sample concentration of 1% by mass. Column: 2 tubes "TSK gel Super HM-H", 1 tube "TSK gel Super H2000" (all manufactured by Tosoh Corporation), Those obtained by sequential connection. • Column temperature: 40 ° C. • Development solvent: Tetrahydrofuran. • Flow rate: 0.60mL / min. <Weight average molecular weight (Mw) of polyfunctional epoxy compound> 之 Weight average molecular weight (Mw) of polyfunctional epoxy compound. ), Measured using the above-mentioned gel permeation chromatography (GPC) device under the above conditions, and among the observed peaks, the retention time of the peak corresponding to the peak with the largest area is converted into standard polystyrene Weight average molecular weight.

Examples 1 to 4 and Comparative Examples 1 to 2 (1) Manufacture of the adhesive composition According to the addition amount (effective ingredient ratio) described in Table 1, each component shown below was added, diluted with methyl ethyl ketone, and separately prepared. An adhesive composition having an active ingredient concentration of 18% by mass was obtained. The details of each component used are shown below. • Modified polyolefin resin (A): manufactured by Mitsui Chemicals Co., Ltd., product name "UNISTOLEH-200", acid modified α-olefin polymer, solid at 25 ° C, weight average molecular weight (Mw) = 47,000.・ Thermosetting component (B): Polyfunctional epoxy compound (1): Mitsubishi Chemical Corporation, product name "YX8034", hydrogenated bisphenol A diglycidyl ether, epoxy equivalent weight = 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. Polyfunctional epoxy compound (3): manufactured by Mitsubishi Chemical Corporation, product name "YX8040", hydrogenated bisphenol A diglycidyl ether, epoxy equivalent weight = 1100 g / eq, weight average molecular weight (Mw) = 4,200. Polyfunctional epoxy compound (4): manufactured by Kyoeisha Chemical Co., Ltd., product name "EPOLIGHT 4000", hydrogenated bisphenol A diglycidyl ether, epoxy equivalent weight = 215 to 245 g / eq, weight average molecular weight (Mw) = 800.矽 Silane coupling agent (C): manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-4803", glycidyl octyl trimethoxysilane. · Imidazole-based hardening catalyst (D): manufactured by Shikoku Chemical Industry Co., Ltd., product name "QAZO 2E4MZ", 2-ethyl-4-methylimidazole. Tackifier (E): Made by Mitsui Chemicals Co., Ltd., product name "FTR6100", copolymer of styrene monomer and aliphatic monomer, softening point = 95 ° C.

(2) Production of a sheet-like adhesive on a release-treated surface of a release film (manufactured by Linde Corporation, product name "SP-PET382150"), applying the prepared adhesive composition to form a coating film, The coating film was dried at 100 ° C. for 2 minutes to obtain a sheet-shaped adhesive having a thickness of 10 μm. In addition, the release-treated surface of the release film was bonded to the exposed surface of the sheet-shaped adhesive in the same manner as described above, and a sheet-shaped adhesive held by the release film was obtained.

(3) Manufacture of test piece for measuring adhesive force The peeling film on one side of the sheet-shaped adhesive held by the peeling film obtained in the above (2) was removed, and 50 μm-thick polyparaphthalein was easily applied on both sides. Ethylene glycol film (manufactured by Toyobo Co., Ltd., product name "PET50A4300") as a base film, using a hot-roller heating laminator, at a temperature of 60 ° C, a pressure of 0.2MPa, and a speed of 0.2m / min Then, the base film and the exposed surface of the sheet-shaped adhesive were bonded to each other to prepare a test piece for measuring adhesion.

The following measurement and evaluation were performed using the above-mentioned sheet-like adhesives prepared in the examples and comparative examples and the test pieces for measuring the adhesive force. These results are shown in Table 1.

[Measurement of outgassing amount of sheet adhesive] 状 Remove the release film on one side of the sheet adhesive held by the release film held in the examples and comparative examples, and use the exposed surface of the sheet adhesive This sheet-shaped adhesive was placed on the glass plate so as to face the glass plate, and was bonded at 60 ° C. using a heating laminator. Subsequently, the release film on the other side of the sheet-shaped adhesive was removed to prepare a sample for measuring outgassing amount. (2) The sample for measuring the outgassing amount was measured using the following device, and the amount of outgassing when the sample was left standing at 120 ° C for 20 minutes. Equipment: Gas chromatography analysis mass analyzer (manufactured by Shimadzu Corporation, product name "GCMS-QP2010").管 ・ Column: 5MS series column (Shimadzu Corporation has limited shares, product name "SH-Rtx (registered trademark)-5MS", 5% diphenyl / 95% dimethylpolysiloxane).检 ・ Calibration line: Toluene.

[Adhesion measurement] (1) A test piece for adhesion measurement prepared in accordance with the examples and comparative examples was cut out into a booklet shape having a width of 25 mm, and then the release film was removed. Subsequently, at a temperature of 60 ° C., a pressure of 0.2 MPa, and a speed of 0.2 m / min, using a laminator device, the test piece for measuring the adhesive force was pressed against the glass plate with a roller, and the test piece for measuring the adhesive force was pressed. The exposed surface of the sheet-shaped adhesive was bonded to a glass plate to obtain a laminate of the glass plate and a test piece for measurement. Then, this laminated body was heated at 100 degreeC for 2 hours, the sheet-like adhesive was hardened, and the sample for adhesive force measurement was prepared. After the prepared laminate was stored in an environment of 23 ° C and 50% RH (relative humidity) for 24 hours, the adhesion measurement sample was removed from the above-mentioned attaching conditions, and the others were described in accordance with JIS Z0237: 2000 Measurement method to measure adhesion. Specifically, in order to measure the adhesive force, a test piece for measuring adhesive force was peeled from a glass plate at a peeling speed of 300 mm / minute using a 180 ° tensile peeling method.

[Evaluation of Sealability] (i) Manufacture of organic EL element An organic EL element was prepared by using a glass substrate with an indium tin oxide (ITO) film (thickness: 100 nm, sheet resistance: 50 Ω / □) as the anode to form a film. . N, N'-bis (naphthalene-1-yl) -N, N'-bis (phenyl) -benzidine was deposited on the ITO film of the glass substrate at a rate of 0.1 to 0.2 nm / minute (Luminescence Technology (Manufactured by the company) to form a hole transport layer having a thickness of 50 nm. Subsequently, on the formed hole-transporting layer, ginseng (8-hydroxy-quinolinate) aluminum (manufactured by Luminescence Technology) was vapor-deposited at a rate of 0.1 to 0.2 nm / minute to form a light-emitting layer having a thickness of 50 nm. Subsequently, lithium fluoride (LiF) (manufactured by High Purity Chemical Research Institute) was vapor-deposited on the formed light emitting layer at a rate of 0.1 nm / minute to form an electron injection layer having a thickness of 4 nm. Finally, on the formed electron injection layer, aluminum (Al) (manufactured by High Purity Chemical Research Institute) was vapor-deposited at a rate of 0.1 nm / minute to form a cathode having a thickness of 100 nm, thereby obtaining an organic EL device. The degree of vacuum at the time of vapor deposition was all 1 × 10 ^-4 Pa or less.

(ii) Manufacturing of electronic devices Remove the release film on one side of the sheet-shaped adhesive held by the release film prepared in the examples and comparative examples, overlap the exposed surface of the sheet-shaped adhesive with the metal foil film, and apply heat Laminator, followed at 40 ° C. Subsequently, the release film on the other side of the sheet-shaped adhesive is removed, and the exposed surface of the sheet-shaped adhesive is laminated so as to cover the organic EL element formed on the glass substrate and also include the surface of the glass substrate, and is heated using Laminator, followed at 40 ° C. Next, the sheet-shaped adhesive was hardened by heating at 100 ° C for 2 hours to obtain a bottom-emission type electronic device that sealed the sealing body of the organic EL element.

(iii) Evaluation of tightness The obtained electronic device was left to stand in an environment of 85 ° C. and 85% RH (relative humidity) for 240 hours, and then the electronic device was started to measure the dark point (Dark Sport) of the organic EL element. (No light emitting area) area S ₁ . Before leaving in the above environment, the area S ₀ of the black dots of the organic EL element was measured in advance, and the enlargement ratio (Sm) of the black dots was calculated according to the following formula.・ Sm (%) = S ₁ / S ₀ × 100 The sealability of the sealing sheet was evaluated based on the following criteria. A: The enlargement rate (Sm) of the black dot is less than 150%. B: The enlargement ratio (Sm) of the black dot is 150% or more. In addition, the larger the value of the black dot expansion ratio (Sm), the higher the value, indicating that the deterioration of the electrode or the organic layer is in progress.

The following conclusions are obtained from Table 1. It is known from the outgassing amounts of Examples 3, 4 and Comparative Example 2 that even if the content of the polyfunctional epoxy compound in the sheet-shaped adhesive is the same, the smaller the weight average molecular weight (Mw), the greater the outgassing amount. In addition, it is known from the outgassing amounts of Examples 1 and 2 and Examples 3 and 4 that even if the polyfunctional epoxy compound in the sheet-shaped adhesive is the same, the smaller the content, the smaller the outgassing amount. In addition, from the adhesive strength after curing in Examples 1, 2 and Comparative Example 1, it is known that the smaller the epoxy equivalent of the polyfunctional epoxy compound and the smaller the weight average molecular weight (Mw) of the polyfunctional epoxy compound, the harder the polyfunctional epoxy compound is after curing. The greater the adhesive strength of the epoxy resin, especially the smaller the epoxy equivalent of the multifunctional epoxy compound, the more easily the adhesive strength becomes larger after curing.

Claims (20)

A sheet-shaped adhesive formed from an adhesive composition containing a modified polyolefin resin (A) and a thermosetting component (B), and satisfying the following requirements (I) and (II); (I): The amount of outgassing per 1 cm ³ after the sheet adhesive is left to stand at 120 ° C for 20 minutes is 20 mg / cm ³ or less; requirement (II): at a temperature of 60 ° C, a pressure of 0.2 MPa, Under the condition of a speed of 0.2 m / min and a roll, a laminate having a thickness of 50 μm on a polyethylene terephthalate film to which the aforementioned sheet-shaped adhesive has been pasted is pressed onto a glass plate to adhere the aforementioned laminate. After the sheet-shaped adhesive side surface and the glass plate were cured at 100 ° C for 2 hours, the sheet-shaped adhesive was cured for 24 hours at 23 ° C and 50% relative humidity, and then the peeling speed was 300 mm / The adhesive force of the aforementioned laminated body from the aforementioned glass plate as measured in accordance with JIS Z0237: 2000 under the conditions of min and a peeling angle of 180 ° is 10 N / 25 mm or more. The sheet-shaped adhesive according to claim 1, wherein the thermosetting component (B) contains a polyfunctional epoxy compound. The sheet-like adhesive according to claim 2, wherein the epoxy equivalent of the aforementioned multifunctional epoxy compound is 100 to 300 g / eq. The sheet-shaped adhesive according to any one of claims 1 to 3, wherein the modified polyolefin resin (A) is an acid-modified polyolefin resin. The sheet-shaped adhesive according to any one of claims 1 to 3, wherein the content of the modified polyolefin-based resin (A) is 15 to 95% by mass based on the total amount of the active ingredients of the adhesive composition. The sheet-shaped adhesive according to any one of claims 1 to 3, wherein the content of the thermosetting component (B) is 5 to 150 parts by mass based on 100 parts by mass of the modified polyolefin-based resin (A). The sheet-shaped adhesive according to any one of claims 1 to 3, further comprising a silane coupling agent (C). The sheet-shaped adhesive according to claim 7, wherein the content of the silane coupling agent (C) is 0.01 to 10 parts by mass based on 100 parts by mass of the modified polyolefin resin (A). A gas barrier laminate comprising a gas barrier film having a substrate layer and an adhesive layer, the adhesive layer is composed of a sheet adhesive, and the sheet adhesive is modified A polyolefin resin (A) and a thermosetting component (B) adhesive composition formed, and satisfy the following requirements (I) and (IIa); requirement (I): the aforementioned sheet-shaped adhesive is 120 After standing for 20 minutes at ℃, the outgassing amount per 1cm ³ is below 20mg / cm ³ (IIa): under the conditions of a temperature of 60 ° C, a pressure of 0.2MPa, and a speed of 0.2 m / min, using a roller, The gas barrier laminate is pressed onto a glass plate, the sheet adhesive and the glass plate of the gas barrier laminate are bonded, and the sheet adhesive is cured at 100 ° C for 2 hours. After 24 hours of storage in an environment with a relative humidity of 50% at 23 ° C, the adhesion force of the aforementioned laminated body from the aforementioned glass plate measured according to JIS Z0237: 2000 under the conditions of a peeling speed of 300 mm / min and a peeling angle of 180 ° is 10N / 25mm or more. 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 the epoxy equivalent of the aforementioned multifunctional 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 11, wherein the content of the modified polyolefin-based resin (A) is 15 to 95% by mass based on the total amount of the active ingredients of the adhesive composition. . The gas barrier laminate according to any one of claims 9 to 11, wherein the content of the thermosetting component (B) is 5 to 150 masses based on 100 parts by mass of the modified polyolefin resin (A). Serving. The gas barrier laminate according to any one of claims 9 to 11, 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 based on 100 parts by mass of the modified polyolefin resin (A). For example, the gas barrier laminate according to any one of claims 9 to 11, wherein the gas barrier film has the substrate layer and the gas barrier layer, and the gas barrier layer is a modified compound containing a polymer compound. Quality polymer layer. The gas barrier laminate according to claim 17, wherein the gas barrier layer and the adhesive layer are directly laminated. A sealed body characterized in that the material to be sealed will have a sheet-like adhesive as in any of claims 1 to 3, or a gas barrier laminate as in any of claims 9 to 11 The adhesive layer serves as a sealing material and is sealed. The sealing body according to claim 19, wherein the sealed object is an organic EL element, an organic EL display element, a liquid crystal display element, or a solar cell element.