KR20190050968A - An adhesive composition, a sealing sheet, - Google Patents

Abstract

The present invention relates to an adhesive composition comprising a component (A): a modified polyolefin-based resin, and a component (B): a polyfunctional epoxy compound. When the outgas amount is measured at 120 ° C for 20 minutes, And an outgas amount per 1 cm 3 of solid content of not more than 20 mg, an encapsulating sheet having an adhesive layer formed using the adhesive composition, and a closure member in which the encapsulation article is encapsulated with the encapsulation sheet. According to the present invention, a low-outgassing adhesive composition which is easy to form into a sheet form, a sealing sheet formed by using the adhesive composition, a sealing sheet having a low-outgassing adhesive layer and a sealing material are sealed with the sealing sheet Is provided.

Description

An adhesive composition, a sealing sheet,

The present invention relates to an adhesive composition which is easy to form into a sheet form and which has low outgassing property, a sealing sheet formed by using the adhesive composition and having a low outgassing adhesive layer, and a sealing sheet Lt; / RTI >

In recent years, organic EL devices have attracted attention as light emitting devices capable of high luminance emission by low voltage direct current drive.

However, the organic EL device has a problem that the luminescence characteristics such as the light emission luminance, the light emission efficiency, and the light emission uniformity are likely to deteriorate over time.

As a cause of the deterioration of the luminescent characteristics, it has been considered that oxygen, water or the like intrudes into the interior of the organic EL device to deteriorate the electrodes and the organic layer. For this reason, it has been practiced to encapsulate the organic EL element using an encapsulating material to prevent intrusion of oxygen and moisture.

Further, in the case of encapsulating an organic EL device using an encapsulant, development of a low outgassing encapsulant has been conducted in view of deteriorating the organic EL device when out gas is generated from the encapsulant.

For example, Patent Document 1 describes a composition for encapsulation containing a specific cation-curable compound, a photocathode polymerization initiator, and an azole-based compound.

Patent Document 1 also discloses that the cured product of the sealing composition has a low outgassing property and a moisture-proofing property.

WO2015 / 111525

Patent Document 1 discloses that a sealing composition having low outgassing property can be obtained by using an azole compound as a curing retarder.

However, according to the study by the present inventors, it has been found that further investigation is necessary to obtain a sealing material having a low outgassing property, since the cause of outgassing in the sealing material is not only the curing retarder.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and has an object of providing a low outgassing adhesive composition which is easy to form into a sheet form and a sealing sheet having a low outgassing adhesive layer formed using the adhesive composition, And sealing the bag with the bag sheet.

The present inventors have intensively studied to solve the above problems and found that an adhesive composition containing a modified polyolefin resin and a polyfunctional epoxy compound is suitable as a material for forming a low outgassing sealing material and completes the present invention .

Thus, according to the present invention, the adhesive composition of the following (1) to (9), the sealing sheet of (10) to (13), and the sealing material of (14) or (15) are provided.

(1) An adhesive composition comprising a component (A) and a component (B) described below, wherein the amount of the outgas per 1 cm 3 of the solid content is 20 mg By weight or less.

(A) Component: Modified polyolefin-based resin

Component (B): polyfunctional epoxy compound

(2) The adhesive composition according to (1), wherein the component (A) is an acid-modified polyolefin-based resin.

(3) The adhesive composition according to (1) or (2), wherein the content of the component (B) is 25 to 200 parts by mass based on 100 parts by mass of the component (A).

(4) The adhesive composition according to any one of (1) to (3), which further contains the following component (C).

Component (C): a tackifier having a softening point of 80 ° C or higher

(5) The adhesive composition according to (4), wherein the content of the component (C) is 1 to 200 parts by mass based on 100 parts by mass of the component (A).

(6) The adhesive composition according to any one of (1) to (5), further containing the following component (D).

(D) Component: Imidazole-based curing catalyst

(7) The adhesive composition according to (6), wherein the content of the component (D) is 0.1 to 10 parts by mass relative to 100 parts by mass of the component (A).

(8) The adhesive composition according to any one of (1) to (7), further containing the following component (E).

(E) Component: Silane coupling agent

(9) The adhesive composition according to (8), wherein the content of the component (E) is 0.01 to 10 parts by mass relative to 100 parts by mass of the component (A).

(10) A sealing sheet comprising two release films and an adhesive layer sandwiched between these release films, wherein the adhesive layer is formed by using the adhesive composition according to any one of (1) to (9) .

(11) A sealing sheet comprising a release film, a gas-barrier film, and an adhesive layer sandwiched between the release film and the gas-barrier film, wherein the adhesive layer comprises the adhesive composition according to any one of (1) to (9) Wherein the sealing sheet is formed using a sealing material.

(12) The encapsulating sheet according to (11), wherein the gas barrier film is a metal foil, a resin film, or a thin film glass.

(13) The encapsulating sheet according to any one of (10) to (12), wherein the thickness of the adhesive layer is 5 to 25 占 퐉.

(14) A bag according to any one of (10) to (13), wherein the bag is sealed with a bag sheet.

(15) The bag according to (14), wherein the handpiece is an organic EL device, an organic EL display device, a liquid crystal display device, or a solar cell device.

According to the present invention, a low-outgassing adhesive composition which is easy to form into a sheet form, a sealing sheet formed by using the adhesive composition, a sealing sheet having a low-outgassing adhesive layer and a sealing material are sealed with the sealing sheet Is provided.

Hereinafter, the present invention will be described in detail with reference to 1) an adhesive composition, 2) a sealing sheet, and 3) a sealing member.

In the present specification, the term "low outgassing property" means that the amount of outgas emitted is small even when the solid content of the adhesive composition (or the adhesive layer formed of the adhesive composition) is placed under a high temperature environment, .

1) Adhesive composition

The adhesive composition of the present invention is an adhesive composition containing the following components (A) and (B), and when the amount of the outgas is measured under the condition of 120 占 폚 and 20 minutes with respect to the solid content thereof, And the gas amount is 20 mg or less.

(A) Component: Modified polyolefin-based resin

Component (B): polyfunctional epoxy compound

The modified polyolefin-based resin is a polyolefin resin into which a functional group is introduced.

The polyolefin resin is a polymer containing a repeating unit derived from an olefin-based monomer. The polyolefin resin may be a homopolymer composed of only one type of repeating unit derived from an olefin monomer or may be a copolymer composed of two or more kinds of repeating units derived from an olefin monomer and may be a copolymer comprising an olefin- Or a copolymer composed of a repeating unit derived from another monomer capable of copolymerizing with a monomer (other monomer than the olefin-based monomer).

As the olefinic monomer, an? -Olefin having 2 to 8 carbon atoms is preferable, and ethylene, propylene, 1-butene, isobutylene, and 1-hexene are more preferable, and ethylene and propylene are more preferable.

Examples of other monomers copolymerizable with the olefinic monomer include vinyl acetate, (meth) acrylic acid esters, styrene and the like. Here, (meth) acrylic acid means acrylic acid or methacrylic acid (the same applies hereinafter).

Examples of the polyolefin resin include polyolefin resins such as an ultra low density polyethylene (VLDPE), a low density polyethylene (LDPE), a medium density polyethylene (MDPE), a high density polyethylene (HDPE), a linear low density polyethylene, a polypropylene (PP), an ethylene- Based elastomer (TPO), an ethylene-vinyl acetate copolymer (EVA), an ethylene- (meth) acrylic acid copolymer, and an ethylene- (meth) acrylic acid ester copolymer.

The modified polyolefin resin can be obtained by subjecting a polyolefin resin as a precursor to a modification treatment using a modifying agent.

The modifier used in the modification treatment of the polyolefin resin is a compound having in the molecule thereof a functional group, that is, a group capable of contributing to a crosslinking reaction described later.

Examples of the functional group include a carboxyl group, a carboxylic anhydride group, a carboxylic acid ester group, a hydroxyl group, an epoxy group, an amide group, an ammonium group, a nitrile group, an amino group, an imide group, an isocyanate group, an acetyl group, a thiol group, , A sulfone group, a phosphoric acid group, a nitro group, a urethane group, and a halogen atom. Among them, 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 and an isocyanate group are preferable, a carboxylic acid anhydride group and an alkoxysilyl group are more preferable, desirable.

The compound having a functional group may have two or more functional groups in the molecule.

Examples of the modified polyolefin-based resin include an acid-modified polyolefin-based resin and a silane-modified polyolefin-based resin. Among them, an acid-modified polyolefin-based resin is preferable from the viewpoint of obtaining a more excellent effect of the present invention.

The acid-modified polyolefin-based resin refers to a polyolefin resin graft-modified with an acid. For example, a polyolefin resin is reacted with an unsaturated carboxylic acid to introduce a carboxyl group (graft modification). Further, in the present specification, the unsaturated carboxylic acid includes the concept of a carboxylic acid anhydride, and the carboxyl group includes the concept of a carboxylic acid anhydride group.

Examples of the unsaturated carboxylic acid to be reacted with the polyolefin resin include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, maleic anhydride, itaconic anhydride, Citraconic acid, anhydrous aconitic acid, norbornene dicarboxylic acid anhydride, and tetrahydrophthalic anhydride.

These may be used singly or in combination of two or more. Of these, maleic anhydride is preferable in view of obtaining an adhesive composition having an excellent adhesive strength.

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

In the present invention, a commercially available product may be used as the acid-modified polyolefin-based resin. Commercially available products include, for example, Admer (registered trademark) (manufactured by Mitsui Chemicals), Unistol (registered trademark) (manufactured by Mitsui Chemicals), BondyRam (manufactured by Polyram), orevac (registered trademark) Mordic (registered trademark) (manufactured by Mitsubishi Chemical Corporation), and the like.

The silane-modified polyolefin-based resin refers to a polyolefin resin graft-modified with an unsaturated silane compound. The silane-modified polyolefin-based resin has a structure in which an unsaturated silane compound is graft-copolymerized with a polyolefin resin as a main chain. The silane-modified polyolefin-based resin is not particularly limited, and examples thereof include silane-modified polyethylene resins and silane-modified ethylene-vinyl acetate copolymers. Of these, silane-modified polyethylene resins such as silane-modified low-density polyethylene, silane-modified ultralow-density polyethylene, and silane-modified linear low density polyethylene are preferable.

As the unsaturated silane compound to be reacted with the polyolefin resin, a vinyl silane compound is preferable. Examples of the vinylsilane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltripentyloxysilane, vinyltriphenoxysilane, vinyl Tribenzyloxysilane, vinyltrimethylenedioxysilane, vinyltriethylenedioxysilane, vinylpropionyloxysilane, vinyltriacetoxysilane, vinyltricarboxysilane, and the like. These may be used alone or in combination of two or more.

The unsaturated silane compound may be subjected to graft polymerization to the main chain polyolefin resin by a conventional method of known graft polymerization.

The amount of the unsaturated silane compound to be reacted with the polyolefin resin is preferably from 0.1 to 10 parts by mass, more preferably from 0.3 to 7 parts by mass, further preferably from 0.5 to 5 parts by mass, relative to 100 parts by mass of the polyolefin resin. When the amount of the unsaturated silane compound to be reacted is within the above range, the adhesive composition containing the obtained silane-modified polyolefin-based resin has superior adhesive strength.

In the present invention, a commercially available product may be used as the silane-modified polyolefin-based resin. Examples of commercially available products include ring clones (registered trademark) (manufactured by Mitsubishi Chemical Corporation) and the like. Of these, low-density polyethylene-based ring clones, linear low-density polyethylene-based ring clones and ultra low-density polyethylene- A ring clone, and a ring clone of an ethylene-vinyl acetate copolymerization system can be preferably used.

The modified polyolefin resins may be used singly or in combination of two or more.

The number average molecular weight (Mn) of the modified polyolefin-based resin is not particularly limited, but is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000 from the viewpoint of obtaining a more excellent effect of the present invention.

The number average molecular weight (Mn) of the modified polyolefin-based resin can be determined as a standard polystyrene conversion value by performing gel permeation chromatography using tetrahydrofuran as a solvent.

The content of the modified polyolefin-based resin is not particularly limited, but the total amount of the modified polyolefin-based resin and the following component (B) is preferably 30% by mass or less, Or more, more preferably 50 mass% or more.

Component (B): polyfunctional epoxy compound

The adhesive composition of the present invention contains, as the component (B), a polyfunctional epoxy compound.

Since the adhesive composition of the present invention contains a polyfunctional epoxy compound, the cured product is excellent in water vapor barrier property.

The polyfunctional epoxy compound means a compound having at least two epoxy groups in the molecule.

Examples of the epoxy compound having two or more epoxy groups include bisphenol diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl (For example, phenol novolak type epoxy resin, cresol novolak type epoxy resin, brominated phenol novolak type epoxy resin), hydrogenated bisphenol S type epoxy resin A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, pentaerythritol polyglycidyl ether, 1,6-hexanediol diglycidyl ether, hexahydro Phthalic acid diglycidyl ester, neopentyl glycol diglycidyl ether, trimethylol propane polyglycidyl ether, 2,2-bis (3-glycidyl-4-glycidyloxyphenyl) propane, dimethylol Tricyclodecane diglycidyl ether, and the like.

These polyfunctional epoxy compounds may be used singly or in combination of two or more.

The lower limit of the weight average molecular weight of the polyfunctional epoxy compound is preferably 1,000, more preferably 1,200. The upper limit of the weight average molecular weight of the polyfunctional epoxy compound is preferably 5,000, more preferably 4,500. By using an adhesive composition having a weight average molecular weight of 1,000 or more of the polyfunctional epoxy compound, a sealing material having a low outgassing ability can be formed. The adhesive composition having a weight-average molecular weight of the polyfunctional epoxy compound of 5,000 or less is more excellent in fluidity, and can sufficiently fill irregularities caused by the irregularities on the surface of the article to be encapsulated and the thickness of the article to be encapsulated.

The epoxy equivalent of the polyfunctional epoxy compound is preferably 100 g / eq or more and 500 g / eq or less, more preferably 150 g / eq or more and 300 g / eq or less. By using an adhesive composition having an epoxy equivalent of 100 g / eq or more and 500 g / eq or less of the polyfunctional epoxy compound, it is possible to form a sealing material having a low outgassing property.

The content of the polyfunctional epoxy compound in the adhesive composition of the present invention is preferably 25 to 200 parts by mass, more preferably 50 to 150 parts by mass based on 100 parts by mass of the component (A). The cured product of the adhesive composition having a content of the polyfunctional epoxy compound within this range is superior in the water vapor barrier property.

The adhesive composition of the present invention may contain components other than the components (A) and (B).

Examples of the components other than the component (A) and the component (B) include the following components (C), (D), and (E)

Component (C): a tackifier having a softening point of 80 ° C or higher

(D) Component: Imidazole-based curing catalyst

(E) Component: Silane coupling agent

Component (C): a tackifier having a softening point of 80 ° C or higher

The adhesive composition containing the component (B) has a low storage modulus before curing and excellent follow-up irregularity. However, such an adhesive composition is difficult to maintain a constant shape, and it may be difficult to form the sheet into a sheet form. In such a case, the moldability can be improved by containing the component (C).

Examples of the tackifier include rosin-based resins such as polymerized rosin, polymerized rosin esters and rosin derivatives; Terpene resins such as polyterpene resins, aromatic modified terpene resins and hydrogenated products thereof, and terpene phenol resins; Coumarone-indene resin; Petroleum resins such as aliphatic petroleum resins, aromatic petroleum resins and hydrides thereof, and aliphatic / aromatic copolymer petroleum resins; Low molecular weight polymers of styrene or substituted styrene; styrene monomer / aliphatic monomer copolymer resin, a styrene monomer /? -methylstyrene / aliphatic monomer copolymer resin, a single styrene monomer copolymer, a? -methylstyrene copolymer, Styrene-based resins such as a styrene-based monomer / aromatic monomer-based resin; And the like. Among these, a styrene-based resin is preferable, and a styrene-based monomer / aliphatic monomer-copolymer-based resin is more preferable.

These tackifiers may be used alone or in combination of two or more.

The softening point of the tackifier is 80 DEG C or higher. Since the softening point of the tackifier is 80 占 폚 or higher, an adhesive composition excellent in tackiness at high temperature is obtained. Further, the workability in molding the adhesive composition into a sheet form is improved.

When the adhesive composition of the present invention contains a tackifier having a softening point of 80 ° C or higher, the content thereof is preferably 1 to 200 parts by mass, more preferably 10 to 200 parts by mass, per 100 parts by mass of the component (A) 150 parts by mass. If the tackifier having a softening point of 80 deg. C or higher is excessively small, it may be difficult to form the adhesive composition into a sheet. On the other hand, if the tackifier having a softening point of 80 deg. C or more is too large, there is a fear that the adhesive layer will be retracted.

(D) Component: Imidazole-based curing catalyst

The imidazole-based curing catalyst is a compound having an imidazole skeleton and has an action of promoting the curing reaction of the adhesive composition.

Examples of the imidazole-based curing catalyst include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl- Phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole. Of these, 2-ethyl-4-methylimidazole is preferable.

These imidazole-based curing catalysts can be used singly or in combination of two or more.

By using an adhesive composition containing an imidazole-based curing catalyst, it is easy to obtain a cured product having excellent adhesion even at a high temperature.

When the adhesive composition of the present invention contains an imidazole-based curing catalyst, its content is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, per 100 parts by mass of the component (A) . The cured product of the adhesive composition in which the content of the imidazole-based curing catalyst is within this range has excellent adhesiveness even at a high temperature.

(E) Component: Silane coupling agent

The silane coupling agent is an organosilicon compound having both a functional group that reacts with an organic material in the molecule and a functional group that reacts with the inorganic material (hydrolyzable group) at the same time.

As the silane coupling agent, a known silane coupling agent can be used, and among them, an organosilicon compound having at least one alkoxysilyl group in the molecule is preferable.

Examples of the silane coupling agent include a polymerizable unsaturated group-containing silicon compound such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane; Silicon compounds having an epoxy structure such as 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; Containing silicon compounds such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane. ; 3-chloropropyltrimethoxysilane; 3-isocyanate propyl triethoxysilane; And the like.

These silane coupling agents may be used alone or in combination of two or more.

By using an adhesive composition containing a silane coupling agent, it is easy to obtain a cured product having an excellent bonding strength under normal temperature (15 ° C to 30 ° C) and high temperature (40 ° C to 100 ° C) environment.

When the adhesive composition of the present invention contains a silane coupling agent, the content thereof is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 10 parts by mass, per 100 parts by mass of the component (A) More preferably 0.02 to 5 parts by mass.

The adhesive composition of the present invention may contain a solvent.

Examples of the solvent include aromatic hydrocarbon solvents such as benzene and toluene; Ester solvents such as ethyl acetate and butyl acetate; Ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-heptane; Alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane and methylcyclohexane; And the like.

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

The content of the solvent can be suitably determined in consideration of the coatability and the like.

The adhesive composition of the present invention may contain other components as long as the effect of the present invention is not hindered.

Examples of the other components include additives such as an ultraviolet absorber, an antistatic agent, a light stabilizer, an antioxidant, a resin stabilizer, a filler, a pigment, an extender and a softening agent.

These may be used singly or in combination of two or more.

When the adhesive composition of the present invention contains these additives, the content thereof can be appropriately determined in accordance with the purpose.

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

The adhesive composition of the present invention preferably has an outgas amount of 20 mg or less per 1 cm 2 of solid content, preferably 18 mg or less, and 15 mg or less when the outgas amount is measured at 120 캜 for 20 minutes with respect to the solid content thereof Particularly preferably 10 mg or less, and most preferably 8 mg or less. The lower limit value is not particularly specified, but is usually 0.1 mg or more. In the present specification, the term "solid component" refers to a solid portion excluding a volatile substance such as a solvent from an adhesive composition.

Further, by using the multifunctional epoxy compound having a weight average molecular weight of 1,000 to 5,000, a low outgassing adhesive layer can be more easily formed.

The amount of outgassing with respect to the solid content of the adhesive composition can be measured, for example, by using the film having the sheet-like adhesive attached thereto, obtained by coating the adhesive composition of the present invention on a base film (or a release film) Can be measured according to the method described in "

An adhesive composition having a small outgassing amount can be efficiently obtained by using a polyfunctional epoxy compound having a relatively high molecular weight.

The adhesive composition of the present invention is easy to be formed into a sheet form and has a low outgassing property. For this reason, the adhesive composition of the present invention is preferably used when forming an encapsulating material.

2) Seal sheet

The encapsulating sheet of the present invention is the following encapsulating sheet (?) Or encapsulating sheet (?).

Encapsulation sheet (?): An encapsulation sheet comprising two release films and an adhesive layer sandwiched between these release films, characterized in that the adhesive layer is formed using the adhesive composition of the present invention

Sealing sheet (?): A sealing sheet comprising a release film, a gas-barrier film, an adhesive layer sandwiched between the release film and the gas-barrier film, wherein the adhesive layer is formed using the adhesive composition of the present invention Characterized by that

These seal sheets show the state before use, and when the seal sheet of the present invention is used, the release film is usually peeled off.

[Seal sheet (?)]

The release film constituting the sealing sheet? Functions as a support in the production process of the sealing sheet? And also functions as a protective sheet of the adhesive layer until the sealing sheet? Is used.

As the release film, conventionally known ones can be used. For example, a release layer having a release layer formed on a substrate for a release film by a release agent may be mentioned.

Examples of the base material for the release film include paper base materials such as a gloss paper, a coat paper, and a top paper; A laminate paper in which a thermoplastic resin such as polyethylene is laminated on these paper substrates; A polyethylene terephthalate resin, a polybutylene terephthalate resin, a polyethylene naphthalate resin, a polypropylene resin, and a polyethylene resin; And the like.

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

The two sheets of release film in the sealing sheet? May be the same or different, but it is preferable that the two sheets of release films have different peeling forces. By making the peeling force of the two peeling films different from each other, the step of peeling the peeling film for the first time can be performed more efficiently.

The thickness of the adhesive layer of the sealing sheet (?) Is not particularly limited, but is preferably 5 to 25 占 퐉, more preferably 10 to 20 占 퐉.

Since the adhesive layer is formed by the adhesive composition of the present invention as described above, the adhesive layer is excellent in conformity with irregularity and can sufficiently fill the unevenness of the adherend.

The adhesive layer of the sealing sheet? Is preferably thermosetting. The adhesive layer having a thermosetting property is excellent in adhesive strength after curing.

The conditions for thermally curing the adhesive layer are not particularly limited.

The heating temperature is usually 80 to 200 占 폚, preferably 90 to 150 占 폚.

The heating time is usually 30 minutes to 12 hours, preferably 1 to 6 hours.

The peel adhesion strength of the adhesive layer after curing treatment at 23 ° C is usually 1 to 100 N / 25 mm, preferably 10 to 50 N / 25 mm, and the peel adhesion strength at 85 ° C is usually 1 to 100 N / 25 mm, preferably 5 to 50 N / 25 mm.

The peel adhesion strength was measured according to the method described in the examples.

The water vapor permeability of the adhesive layer after the curing treatment is usually 0.1 to 200 g / m 2 / day, preferably 1 to 150 g / m 2 / day.

The production method of the sealing sheet (?) Is not particularly limited. For example, a known casting method can be used to produce the sealing sheet (?). More specifically, the adhesive composition of the present invention is coated on the exfoliated surface of a release film by using a known method, and the obtained film is dried to prepare an adhesive layer having a release film adhered thereon, By laminating the release film on the adhesive layer, the sealing sheet (?) Can be obtained.

Examples of the method for applying the adhesive composition include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, gravure coating and the like.

The drying conditions for drying the coating film are not particularly limited. For example, the drying temperature is 80 to 150 占 폚 and the drying time is 30 seconds to 5 minutes.

[Seal sheet (?)]

The release film and the adhesive layer constituting the sealing sheet (?) Are the same as those shown as the release film and the adhesive layer constituting the sealing sheet (?), Respectively.

The gas barrier film constituting the sealing sheet (?) Is not particularly limited as long as it is a film having moisture barrier property.

The gas barrier film preferably has a water vapor transmission rate of 0.1 g / m < 2 > / day or less in an environment of a temperature of 40 DEG C and a relative humidity of 90% (hereinafter abbreviated as 90% RH) day or less, and more preferably 0.005 g / m 2 / day or less.

Oxygen, moisture, and the like intrude into devices such as organic EL devices formed on a transparent substrate, because the vapor permeability of the gas barrier film under an environment of 40 ° C and 90% RH is 0.1 g / m 2 / day or less , It is possible to effectively suppress deterioration of the electrode and the organic layer.

The transmittance of water vapor or the like of the gas barrier film can be measured using a known gas permeability measuring apparatus.

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

Examples of the metal of the metal foil include metal materials such as copper, nickel, and aluminum; Alloy materials such as stainless steel or aluminum alloy; And the like.

The composition and composition of the thin film glass are not particularly limited, but a non-alkali borosilicate glass is preferable in view of obtaining more stable flexibility.

Thin film glass may be used as a single body, but a metal foil such as an aluminum foil or a resin film may be laminated or laminated on a thin glass.

It is preferable that the thin film glass has a flexibility of about 10 to 200 탆 in thickness.

Examples of the resin component constituting the base material of the gas barrier film include polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyetheretherketone, polyolefin, polyester, polycarbonate, polysulfone, poly Ether sulfone, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin-based polymer, aromatic polymer, and polyurethane-based polymer.

The thickness of the substrate is not particularly limited, but is preferably from 0.5 to 500 μm, more preferably from 1 to 200 μm, and still more preferably from 5 to 100 μm from the viewpoint of ease of handling.

The material or the like of the gas barrier layer is not particularly limited as long as it can give a desired gas barrier property. Examples of the gas barrier layer include an inorganic film and a layer obtained by subjecting a layer containing a polymer compound to a modification treatment. Among them, the gas barrier layer is preferably a gas barrier layer made of an inorganic film, and a gas barrier layer made of a layer containing a polymer compound, which are obtained by performing a modifying treatment on a gas barrier layer made of an inorganic film A gas barrier layer is preferred.

The inorganic film is not particularly limited, and examples thereof include an inorganic vapor deposited film.

As the inorganic vapor deposition film, a vapor deposition film of an inorganic compound or a metal may be mentioned.

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

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

Examples of the method for forming the inorganic film include a vacuum deposition method, an EB deposition method, a sputtering method, an ion plating method, a lamination method, and a plasma vapor deposition method (CVD method).

The thickness of the inorganic film is appropriately selected depending on the kind and composition of the inorganic material, but is usually 1 to 500 nm, preferably 2 to 300 nm.

As the polymer compound to be used in the gas barrier layer obtained by ion implantation into a layer containing a polymer compound (hereinafter also referred to as a " polymer layer "), a silicon compound such as a polyorganosiloxane, A polyimide, a polyimide, a polyamide, a polyamideimide, a polyphenylene ether, a polyether ketone, a polyether ether ketone, a polyolefin, a polyester, a polycarbonate, a polysulfone, a polyether sulfone, a polyphenylene sulfide, , An acrylic resin, a cycloolefin-based polymer, and an aromatic polymer. These polymer compounds may be used singly or in combination of two or more.

Among them, a silicon-containing polymer is preferable from the viewpoint of forming a gas barrier layer having excellent gas barrier properties, and a polysilazane-based compound is more preferable.

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

[Chemical Formula 1]

Is preferably a compound having a repeating unit represented by the following formula The number average molecular weight of the polysilazane compound to be used is not particularly limited, but is preferably 100 to 50,000.

In the above formula (1), n represents an arbitrary natural number.

Rx, Ry and Rz each independently represents a hydrogen atom, an alkyl group having an unsubstituted or substituted group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group or an alkyl Silyl group and the like. Among them, as Rx, Ry and Rz, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group is preferable, and a hydrogen atom is particularly preferable. Examples of the polysilazane compound having a repeating unit represented by the above formula (1) include inorganic polysilazanes in which all of Rx, Ry and Rz are hydrogen atoms, organic polysilazanes in which at least one of Rx, Ry and Rz is not a hydrogen atom .

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

The polymer layer may contain other components in addition to the above-described polymer compound within the range not hindering the object of the present invention. Other components include a curing agent, another polymer, an antioxidant, a light stabilizer, and a flame retardant.

The content of the polymer compound in the polymer layer is preferably 50% by mass or more, more preferably 70% by mass or more, from the viewpoint of obtaining a gas barrier layer having better gas barrier properties.

The thickness of the polymer layer is not particularly limited, but is preferably in the range of 50 to 300 nm, and more preferably in the range of 50 to 200 nm.

In the present invention, even if the thickness of the polymer layer is nano, a sealing sheet having sufficient gas barrier properties can be obtained.

As a method of forming the polymer layer, for example, there can be used a method of forming a layer-forming solution containing at least one kind of polymer compound, another component according to a desired amount, and a solvent, in a known manner such as spin coater, knife coater, Coating method using an apparatus, and drying the resultant coating film appropriately.

Examples of the modifying treatment of the polymer layer include ion implantation treatment, plasma treatment, irradiation with radiation, heat treatment and the like, and a treatment for changing the bonding structure of the polymer layer is preferable. These treatments may be carried out singly or in combination of two or more.

The ion implantation treatment is a method of modifying the polymer layer by implanting ions into the polymer layer as described later.

The plasma treatment is a method of modifying the polymer layer by exposing the polymer layer to the plasma. For example, the plasma treatment can be carried out according to the method described in JP-A-2012-106421.

The radiation irradiation treatment is a method of modifying the polymer layer by irradiating the polymer layer with radiation. The radiation is preferably a short wavelength having a high effect of changing the bonding structure of the polymer layer, and it is preferable to use ultraviolet rays, in particular, vacuum ultraviolet rays. For example, the vacuum ultraviolet light modifying treatment can be carried out according to the method described in JP-A-2013-226757.

Of these, the ion implantation treatment is preferable in that the surface of the polymer layer is not roughened, the gas barrier layer is efficiently reformed to the inside thereof, and the gas barrier layer having excellent gas barrier properties can be formed.

Examples of ions implanted into the polymer layer include ions of rare gases such as argon, helium, neon, krypton, and xenon; Ions such as fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur;

Ions of alkane-based gases such as methane and ethane; Ions of alkene-based gases such as ethylene and propylene; Ions of alkadienic gases such as pentadiene and butadiene; Ions of alkyne-based gases such as acetylene; Ions of aromatic hydrocarbon gases such as benzene and toluene; Ions of a cycloalkane-based gas such as cyclopropane; Ions of a cycloalkane gas such as cyclopentene; Ion of metal; Ions of organosilicon compounds; And the like.

These ions may be used singly or in combination of two or more.

Of these, rare-earth ions such as argon, helium, neon, krypton, xenon and the like are preferable in that a gas barrier layer having more excellent gas barrier properties can be obtained, which can more easily inject ions.

The method of implanting ions is not particularly limited. For example, a method of irradiating ions (an ion beam) accelerated by an electric field, a method of injecting ions (ions of a plasma generation gas) in a plasma, and the like. From the viewpoint of easily obtaining a gas barrier layer, A method of implanting plasma ions is preferable. In the plasma ion implantation method, for example, a plasma is generated in an atmosphere containing a plasma generation gas, and a negative high voltage pulse is applied to a layer into which ions are implanted to convert ions (positive ions) in the plasma into ions And then injected into the surface portion of the layer to be implanted.

The method for producing the sealing sheet (?) Is not particularly limited. For example, in the above-described method of producing the sealing sheet (?), The sealing sheet (?) Can be produced by replacing one of the release films with a gas-barrier film.

The sealing sheet (?) May also be produced by producing the sealing sheet (?), Peeling the single sheet of the release film, and sticking (sticking) the exposed adhesive layer to the gas barrier film. In this case, when the sealing sheet (a) has two peeling films having different peeling forces, it is preferable to peel off the peeling films having a smaller peeling force from the viewpoint of handling.

As described above, the adhesive layer of the sealing sheet of the present invention has a low outgassing property. Therefore, when the organic EL element is encapsulated, deterioration thereof can be suppressed.

3)

The bag body of the present invention is one in which the handpiece is sealed with the bag sheet of the present invention.

The encapsulant of the present invention includes, for example, a transparent substrate, an element (pickled object) formed on the transparent substrate, and an encapsulation material for encapsulating the encapsulation material, Of the adhesive layer.

The transparent substrate is not particularly limited, and various substrate materials can be used. Particularly, it is preferable to use a substrate material having a high transmittance of visible light. It is preferable to use a material having a high barrier performance for preventing water or gas from intruding from the outside of the device and excellent in solvent resistance and weather resistance. Specifically, transparent inorganic materials such as quartz and glass; Polyvinylidene fluoride, acetyl cellulose, phenoxy bromide, aramids, polyimides, polystyrenes, polyarylates, polyesters such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, Transparent plastic such as sulfone, polyolefin and the like; the above-mentioned gas barrier film; .

The thickness of the transparent substrate is not particularly limited and can be appropriately selected in consideration of the light transmittance and the ability to block the inside and outside of the device.

Examples of the picking material include organic EL devices, organic EL display devices, liquid crystal display devices, and solar cell devices.

The method for producing the plug of the present invention is not particularly limited. For example, the adhesive layer of the encapsulation sheet of the present invention is superimposed on the clasp followed by heating, thereby bonding the adhesive layer of the encapsulation sheet to the clasp.

Then, the plug material of the present invention can be produced by curing the adhesive layer.

The bonding condition at the time of bonding the adhesive layer of the sealing sheet to the peeling member is not particularly limited. The bonding temperature is, for example, 23 to 100 占 폚, preferably 40 to 80 占 폚. This adhesion treatment may be performed while pressurizing.

As the curing conditions for curing the adhesive layer, the conditions described above can be used.

The bag body of the present invention is one in which the handpiece is sealed with the bag sheet of the present invention.

Therefore, in the bag according to the present invention, the performance of the article to be sealed is maintained over a long period of time.

Example

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

In each example, parts and% are based on mass unless otherwise specified. The weight-average molecular weight (Mw) of the modified polyolefin-based resin and the polyfunctional epoxy compound is a value measured by the following method.

≪ Weight-average molecular weight (Mw) of modified polyolefin-based resin &

The weight average molecular weight (Mw) of the modified polyolefin resin was measured under the following conditions using a gel permeation chromatograph (GPC) apparatus (product name: "HLC-8320" .

(Measuring conditions)

Measured sample: a solution of a modified polyolefin-based resin having a concentration of 1% by mass in tetrahydrofuran

Column: Two TSK gel Super HM-Hs and one TSK gel Super H2000 (both manufactured by Tosoh Corporation), which are connected in series

Column temperature: 40 ° C

· Developing (developing) solvent: tetrahydrofuran

Flow rate: 0.60 ml / min

<Weight average molecular weight (Mw) of polyfunctional epoxy compound>

The weight average molecular weight (Mw) of the polyfunctional epoxy compound was measured under the following conditions using a gel permeation chromatograph (GPC) apparatus (product name: "HLC-8320" Average molecular weight of the standard polystyrene corresponding to the retention time of the peak top of the maximum area.

(Measuring conditions)

Measurement sample: a tetrahydrofuran solution of 1% by mass of polyfunctional epoxy compound concentration

Column: Two TSK gel Super HM-Hs and one TSK gel Super H2000 (both manufactured by Tosoh Corporation), which are connected in series

Column temperature: 40 ° C

· Developing solvent: tetrahydrofuran

Flow rate: 0.60 ml / min

[Example 1]

100 parts of an acid-modified polyolefin resin (? -Olefin polymer, product of Mitsui Chemicals, Inc., trade name: Unistol H-200, weight average molecular weight: 52,000), polyfunctional epoxy compound (1) (bisphenol A diglycidyl ether, 50 parts of a tackifier (styrene-based monomer aliphatic monomer copolymer, softening point 95 ° C, manufactured by Mitsui Chemicals, Inc., trade name: FTR6100), 100 parts of a polyester resin (trade name: YL980, epoxy equivalent: 180 to 190 g / And 1 part of an imidazole-based curing catalyst (trade name: Kyouzol 2E4MZ, 2-ethyl-4-methylimidazole, manufactured by Shikoku Chemical Co., Ltd.) were dissolved in methyl ethyl ketone to prepare an adhesive composition 1 having a solid concentration of 30%.

This adhesive composition 1 was coated on a release treatment surface of a release film (trade name: SP-PET382150, manufactured by Lin Tec Co., Ltd.) and the resulting coating film was dried at 100 캜 for 2 minutes to form an adhesive layer having a thickness of 12 탆, , Another release film (manufactured by Lin Tec Corporation, trade name: SP-PET381031) was peeled off to obtain a sealing sheet 1.

[Example 2]

(Hydrogenated bisphenol A diglycidyl ether, product of Mitsubishi Chemical Corporation, trade name: YX8000, epoxy equivalent: 205 g / eq, weight average molecular weight: 1,400 ) Was used in place of the polypropylene resin composition obtained in Example 1.

[Example 3]

(3) (hydrogenated bisphenol A diglycidyl ether, product of Mitsubishi Chemical Corporation, trade name: YX8034, epoxy equivalent: 270 g / eq, weight average molecular weight: 3,200 ) Was used in place of the polyolefin-based resin (B).

[Example 4]

(4) (hydrogenated bisphenol A diglycidyl ether, product of Mitsubishi Chemical Corporation, trade name: YX8040, epoxy equivalent: 1100 g / eq, weight average molecular weight: 4,200 ) Was used in place of the polypropylene-based resin (B).

[Comparative Example 1]

(Example 1) A polyfunctional epoxy compound (5) (hydrogenated bisphenol A diglycidyl ether, manufactured by Kyowa Chemical Industry Co., Ltd., trade name: Epolite 4000, epoxy equivalents 215 to 245 g / eq , Weight average molecular weight: 800) was used instead of the polyolefin resin (A).

[Comparative Example 2]

(Adducted with hydrogenated bisphenol A diglycidyl ether, manufactured by ADEKA, trade name: ADEKA RESIN, EP-4080E, epoxy equivalent weight 215 g / eq , Molecular weight: 800) was used in place of the ethylene-propylene copolymer (A).

The following tests were performed on the encapsulation sheets 1 to 6 obtained in Examples 1 to 4 and Comparative Examples 1 and 2.

[Low outgassing evaluation test]

One release film of the encapsulation sheet obtained in the Example or Comparative Example was peeled off and the encapsulation sheet was placed on a glass plate so that the exposed adhesive layer was opposed to the glass plate and adhered at 60 DEG C using a heat laminator.

Subsequently, the remaining release film was peeled off as a measurement sample, and outgas was generated under the conditions of 120 DEG C for 20 minutes, and the amount of the outgas was quantified.

The amount of outgassing was quantified using a gas chromatograph mass spectrometer (GCMS-QP2010, manufactured by Shimadzu Corporation) and a column using 5% -diphenyl-95% dimethylpolysiloxane (HP-5ms). At this time, a calibration curve was prepared using toluene.

[Evaluation test of organic EL device]

An organic EL device was produced by the following method using a glass substrate on which an indium tin oxide (ITO) film (thickness: 100 nm, sheet resistance: 50? /?) Was formed as an anode.

N, N'-bis (phenyl) -benzidine) (manufactured by Luminescence Technology) was coated on the ITO film of the glass substrate at a rate of 0.1 to 0.2 nm / min (8-hydroxy-quinolinate) aluminum (manufactured by Luminescence Technology) was deposited on the hole transport layer at a rate of 0.1 to 0.2 nm / min to form a hole transport layer having a thickness of 50 nm. Subsequently, Thereby forming a light emitting layer having a thickness of 50 nm. Lithium fluoride (LiF) (manufactured by Kojundo Chemical Laboratory Co., Ltd.) was vapor-deposited on the light-emitting layer at a rate of 0.1 nm / min to form an electron injection layer having a thickness of 4 nm. Subsequently, (Al) (manufactured by Kojundo Chemical Laboratory Co., Ltd.) was vapor-deposited at a rate of 0.1 nm / min to form a cathode having a thickness of 100 nm to obtain an organic EL device. In addition, the degree of vacuum at the time of vapor deposition was 1 x 10 &lt; ^-4 &gt;

Each of the release films of the encapsulation sheets 1 to 6 obtained in the Examples and Comparative Examples was peeled off one by one and the exposed adhesive layers were superimposed on the metal foil film and they were adhered at 40 DEG C using a heat laminator. Then, another peeling film was peeled off, and the exposed adhesive layer was superimposed so as to cover the organic EL device formed on the glass substrate, and these were adhered at 40 占 폚 using a heat laminator. Subsequently, the adhesive layer was cured by heating at 100 占 폚 for 2 hours to obtain a bottom emission type electronic device in which the organic EL device was sealed.

This electronic device was allowed to stand for 240 hours in an environment of 85 캜 and 85% relative humidity, and then the organic EL device was activated to measure the area of a dark spot (non-light emitting point).

The enlargement ratio of dark spots based on the area of the dark spots of the electronic device before being left in an environment of 85 DEG C and 85% relative humidity was calculated and evaluated according to the following criteria.

<Standard>

○: Magnification ratio of dark spot is less than 150%

×: An enlargement ratio of a dark spot is 150% or more

The evaluation results are shown in Table 1.

From Table 1 it can be seen that:

The sealing sheets of Examples 1 to 4 have low outgassing properties and are excellent in the evaluation test of organic EL devices.

On the other hand, the encapsulation sheets of Comparative Examples 1 and 2 are outgassed in the evaluation test of the organic EL element because a large amount of outgas is generated.

Claims (15)

The adhesive composition comprising the following components (A) and (B) is characterized in that the amount of outgas per 1 cm 3 of solids is 20 mg or less when the outgas amount is measured under the conditions of 120 ° C and 20 minutes for the solid content thereof .
(A) Component: Modified polyolefin-based resin
Component (B): polyfunctional epoxy compound The method according to claim 1,
Wherein the component (A) is an acid-modified polyolefin-based resin. 3. The method according to claim 1 or 2,
Wherein the content of the component (B) is 25 to 200 parts by mass based on 100 parts by mass of the component (A). 4. The method according to any one of claims 1 to 3,
Further, the adhesive composition contains the following component (C).
Component (C): a tackifier having a softening point of 80 ° C or higher 5. The method of claim 4,
Wherein the content of the component (C) is 1 to 200 parts by mass based on 100 parts by mass of the component (A). 6. The method according to any one of claims 1 to 5,
Further, the adhesive composition contains the following component (D).
(D) Component: Imidazole-based curing catalyst The method according to claim 6,
Wherein the content of the component (D) is 0.1 to 10 parts by mass relative to 100 parts by mass of the component (A). 8. The method according to any one of claims 1 to 7,
Further, the adhesive composition contains the following component (E).
(E) Component: Silane coupling agent 9. The method of claim 8,
Wherein the content of the component (E) is 0.01 to 10 parts by mass relative to 100 parts by mass of the component (A). Two release films and an adhesive sheet sandwiched between these release films,
Wherein the adhesive layer is formed using the adhesive composition according to any one of claims 1 to 9. A sealing sheet comprising a release film, a gas barrier film, and an adhesive layer sandwiched between the release film and the gas barrier film,
Wherein the adhesive layer is formed using the adhesive composition according to any one of claims 1 to 9. 12. The method of claim 11,
Wherein the gas barrier film is a metal foil, a resin film, or a thin film glass. 13. The method according to any one of claims 10 to 12,
Wherein the thickness of the adhesive layer is 5 to 25 占 퐉. A bag according to any one of claims 10 to 13, wherein the bag is sealed with a bag sheet. 15. The method of claim 14,
Wherein the handpiece is an organic EL element, an organic EL display element, a liquid crystal display element, or a solar cell element.