JP5593175B2 - Sealing adhesive sheet, electronic device, and organic device - Google Patents

Description

  The present invention relates to a sealing adhesive sheet, and an electronic device and an organic device including the sealing adhesive sheet.

In recent years, organic electronics has been attracting attention as a technology that can form displays, circuits, batteries, etc. on flexible plastic substrates at low temperatures close to room temperature using coating and printing processes. Various organic devices, liquid crystal displays, Research and development of electronic paper, thin film transistors, etc. are underway.
For example, an organic EL element used in an organic device has an organic layer in which an organic charge transport layer or an organic light emitting layer is laminated between an anode and a cathode, and can emit light with high brightness by low voltage direct current drive. As a light emitting element, it is attracting attention. In addition, organic devices are also expected as displays that achieve a reduction in thickness, weight, flexibility, etc. by using a plastic film as a substrate.

By the way, when the organic EL element is driven for a certain time, there is a problem that light emission characteristics such as light emission luminance, light emission efficiency, and light emission uniformity are deteriorated as compared with the initial stage. Possible causes of this problem include oxidation of the electrode due to oxygen or water vapor entering the organic EL element, modification of organic matter, oxidative decomposition of the organic material due to heat during driving, and the like.
In addition, a phenomenon that the interface of the structure peels frequently occurs. The phenomenon is thought to be caused by stress at the interface of the structure due to the difference in thermal expansion coefficient of each component when exposed to high temperature due to the influence of oxygen, water vapor, etc. or heat generated during driving. .

In order to solve the above problems, for example, a photo-curing resin having moisture resistance with respect to an organic EL element formed on a glass substrate in order to seal the organic EL element and suppress contact with oxygen or water vapor. And a method of fixing a substrate with low water permeability to the upper part of the photocurable resin layer is disclosed (see Patent Document 1). Also, a method of sealing an opposing transparent substrate with a sealing material made of frit glass (see Patent Document 2), and when forming an airtight space with a substrate and a shield material, the two are bonded with a cationic curing type ultraviolet curing epoxy resin. A method of adhering with an agent (see Patent Document 3), a protective layer made of an insulating inorganic compound is provided on the outer surface of a laminated structure having a light emitting layer between two electrodes facing each other, and a polymer is provided outside the protective layer A method of sealing an organic EL element with a sealing film formed by an adhesive layer when the organic EL element is sealed by providing a shield layer made of a film is disclosed (see Patent Document 4).
In recent years, a method of sealing using a plastic film instead of a glass plate has been studied in order to realize reduction in thickness, weight, flexibility, and the like of an organic EL element. For example, by a method of coating a sealing film formed of a moisture-proof polymer film and an adhesive layer on the outer surface of an organic EL element (see Patent Document 5), or an adhesive sealing composition film containing an isobutylene resin Examples include a method of sealing an organic EL element (see Patent Document 6), a method of forming a smooth primary film with a photocurable resin layer on a substrate of the organic EL element (see Patent Document 7), and the like.

JP-A-5-182759 Japanese Patent Laid-Open No. 10-74583 JP-A-10-233283 Japanese Patent Laid-Open No. 5-89959 Japanese Patent Application Laid-Open No. 5-101884 Special table 2009-524705 gazette Japanese Patent No. 4419012

However, the above-described method using a conventional plastic film has a problem that water vapor, oxygen, and the like are easily transmitted and elements such as an organic EL element are easily deteriorated. In addition, the adhesive layer itself deteriorates due to exposure to high temperature or ultraviolet irradiation from a long-time driving or outdoor driving environment, and the characteristics of elements such as organic EL elements that are sealed are also associated with it. It has a problem of deterioration.
The present invention is a pressure-sensitive adhesive sheet for sealing, which has a very low water vapor transmission rate, has excellent gas barrier performance, and can suppress deterioration of the characteristics of the sealing element even when exposed to ultraviolet irradiation, And it aims at providing the electronic device and organic device which comprise this adhesive sheet for sealing.

The present inventors provide a sealing adhesive sheet having at least a gas barrier layer and an adhesive layer on a substrate, wherein the adhesive layer comprises an adhesive composition containing a specific resin and an additive. It has been found that an adhesive sheet can solve the above problems.
That is, the present invention provides the following [1] to [7].
[1] A sealing pressure-sensitive adhesive sheet having at least a gas barrier layer and a pressure-sensitive adhesive layer on a substrate, wherein the pressure-sensitive adhesive layer has a weight average molecular weight of 300,000 to 500,000 as a first component. (A), a polybutene resin (B) having a weight average molecular weight of 1,000 to 250,000 as the second component, a hindered amine light stabilizer (C) and / or a hindered phenol antioxidant (D) as the third component, A pressure-sensitive adhesive sheet for sealing, comprising a pressure-sensitive adhesive composition containing 10 to 100 parts by mass of the polybutene resin (B) with respect to 100 parts by mass of the polyisobutylene resin (A).
[2] The pressure-sensitive adhesive sheet for sealing according to the above [1], wherein a water vapor transmission rate at 40 ° C. and a relative humidity of 90% is 0.5 g / (m ² · day) or less.
[3] The pressure-sensitive adhesive sheet for sealing according to the above [1] or [2], wherein the hindered amine light stabilizer (C) is a hindered amine light stabilizer having a tertiary hindered amine group.
[4] The above [l], wherein the hindered phenol antioxidant (D) is a hindered phenol antioxidant in which both of the hindered phenol groups are substituted with tertiary butyl groups. The adhesive sheet for sealing according to any one of to [3].
[5] The sealing adhesive sheet according to any one of the above [1] to [4], which is used in an electronic device.
[6] An electronic device comprising the sealing adhesive sheet according to any one of [1] to [4].
[7] A structure having at least a pair of opposing electrodes and an organic layer disposed between the electrodes, and the structures according to [1] to [4] disposed at an upper portion, a lower portion, and / or around the structure. An organic device comprising the sealing adhesive sheet according to any one of the above.

  The pressure-sensitive adhesive sheet for sealing of the present invention has a very low water vapor transmission rate, has excellent gas barrier performance, and can suppress deterioration of the characteristics of the sealed element even when exposed to ultraviolet irradiation. . Therefore, the pressure-sensitive adhesive sheet for sealing of the present invention is suitable as a sealing member for electronic devices and organic devices. Electronic devices and organic devices provided with this pressure-sensitive adhesive sheet for sealing can be driven for a long time or outdoors. The deterioration of the characteristics of the element can also be suppressed depending on the driving environment.

It is a figure which shows an example of a structure of the adhesive sheet for sealing of this invention. It is a figure which shows an example of the organic device which comprises the adhesive sheet for sealing of this invention.

The sealing pressure-sensitive adhesive sheet of the present invention has at least a gas barrier layer and a pressure-sensitive adhesive layer on a substrate.
FIG. 1 is a diagram showing an example of the configuration of the sealing adhesive sheet of the present invention. Although the pressure-sensitive adhesive sheet for sealing of the present invention has at least a base material, a gas barrier layer, and a pressure-sensitive adhesive layer, the order of lamination is not particularly limited. For example, as shown in FIG. 1 (A1), a sealing adhesive sheet 1 in which a gas barrier layer 3 is laminated on one side of a substrate 2 and an adhesive layer 4 is laminated on the gas barrier layer 3 is used. May be. In addition, like the sealing adhesive sheet 1a of FIG. 1 (A2), the gas barrier layer 3 is laminated on one surface of the substrate 2, and the surface opposite to the surface of the substrate 2 on which the gas barrier layer 3 is laminated. Alternatively, the pressure-sensitive adhesive layer 4 may be formed.
Further, as shown in FIG. 1 (B), the gas barrier layer 3 and the pressure-sensitive adhesive layer 4a are laminated on one surface of the base material 2, and the pressure-sensitive adhesive layer 4b is provided on the opposite base material. It can also be set as the adhesive sheet 1a for sealing which has a layer.
Furthermore, it is good also as the adhesive sheet 1b for sealing which has an adhesive layer on both surfaces laminated | stacked through the adhesive layer 4a with respect to two gas barrier layers 3a and 3b like (C) of FIG. In the sealing adhesive sheet 1b, the adhesive layer 4a not only bonds the two gas barrier layers 3a and 3b, but also absorbs an impact and protects the gas barrier layers 3a and 3b when an impact is applied from the outside. It can also play a role.
Although not shown in FIG. 1, “other layers” other than the base material, the gas barrier layer, and the pressure-sensitive adhesive layer may be provided. The position where other layers are laminated is not particularly limited.
Hereinafter, (1) pressure-sensitive adhesive layer, (2) base material, (3) gas barrier layer, and (4) other layers constituting the sealing pressure-sensitive adhesive sheet of the present invention will be described.

[(1) Adhesive layer]
Although an adhesive layer is laminated | stacked on the below-mentioned base material, a gas barrier layer, or another layer, you may have on one side or both surfaces with respect to a base material.

The pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer of the present invention comprises a polyisobutylene resin (A) having a weight average molecular weight of 300,000 to 500,000 as a first component and a polybutene resin having a weight average molecular weight of 1,000 to 250,000 as a second component. (B) As a 3rd component, a hindered amine light stabilizer (C) and / or a hindered phenolic antioxidant (D) are included.
Since the pressure-sensitive adhesive composition of the present invention contains these specific resins, the pressure-sensitive adhesive layer to be formed has a very low water vapor permeability and is excellent in durability under high temperature or ultraviolet irradiation.
The pressure-sensitive adhesive composition of the present invention may contain other resins and additives in addition to these specific resins. Hereinafter, components (A) to (D) included in the pressure-sensitive adhesive composition of the present invention, and other resins and additives will be described.

<Polyisobutylene resin (A)>
The polyisobutylene-based resin (A) (hereinafter also referred to as “resin (A)”) is a resin having a polyisobutylene skeleton in the main chain or side chain, and a resin having the following structural unit (a).

  Examples of the resin (A) include polyisobutylene which is a homopolymer of isobutylene, isobutylene and isoprene, isobutylene and n-butene, a copolymer of isobutylene and butadiene, and a halogenated halogenated chlorinated copolymer of these copolymers. A copolymer etc. are mentioned. In addition, when resin (A) is a copolymer, the structural unit which consists of isobutylene shall be contained most among all the monomers.

  Examples of the method for synthesizing the resin (A) include a method in which a monomer component such as isobutylene is polymerized in the presence of a Lewis acid catalyst such as aluminum chloride or boron trifluoride. Moreover, a commercial item can also be used for resin (A). Examples of commercially available products include Vistanex (manufactured by Exxon Chemical Co.), Hycar (manufactured by Goodrich), Opanol (manufactured by BASF), and the like. These resins (A) may be used alone or in combination of two or more.

The weight average molecular weight of the resin (A) is from 300,000 to 500,000, preferably from 320,000 to 480,000, more preferably from 330,000 to 450,000, from the viewpoint of reducing the water vapor transmission rate and improving the cohesive force. It is. If the weight average molecular weight is less than 300,000, the cohesive force of the pressure-sensitive adhesive composition cannot be sufficiently obtained, and the adherend may be contaminated. On the other hand, if it exceeds 500,000, the cohesive force of the pressure-sensitive adhesive composition becomes too high, and the flexibility and fluidity become low, and it is difficult to sufficiently obtain wetness with the adherend. Moreover, when preparing an adhesive composition, when molecular weight is too high, the solubility with respect to a solvent may fall.
In addition, the weight average molecular weight as used in this application is the value of polystyrene conversion measured by a gel permeation chromatography (GPC) method (the same applies to the following description).

<Polybutene resin (B)>
The polybutene resin (B) (hereinafter also referred to as “resin (B)”) is a copolymer having a long-chain hydrocarbon molecular structure. Resin (B) is well compatible with resin (A) and plasticizes resin (A) appropriately, thereby improving wettability to the adherend and improving adhesive properties, flexibility, holding power, etc. Can be made.
Examples of the resin (B) include polybutene copolymer, ethylene / 1-butene copolymer elastomer, ethylene / propylene / 1-butene copolymer elastomer, propylene / 1-butene copolymer elastomer, ethylene / 1-butene- Examples thereof include ethylene-propylene rubber such as non-conjugated diene copolymer elastomer and ethylene / propylene / 1-butene-non-conjugated diene copolymer elastomer.
Among these, a polybutene copolymer is preferable from the viewpoint of being well compatible with the resin (A), appropriately plasticizing the resin (A), and increasing flexibility and fluidity. Examples of the polybutene copolymer include those obtained by copolymerizing at least two of isobutene, 1-butene, and 2-butene, and more preferred is an isobutene / 1-butene copolymer.

Examples of the method for synthesizing the resin (B) include a method of polymerizing a monomer component constituting the resin (B) in the presence of a Lewis acid catalyst such as aluminum chloride or boron trifluoride.
Moreover, a commercial item can also be used for resin (B). Examples of commercially available products include Idemitsu polybutene (manufactured by Idemitsu Kosan Co., Ltd.), Nissan polybutene (manufactured by Nippon Oil & Fats Co., Ltd.), Nisseki Polybutene (manufactured by Nippon Oil & Petroleum Corporation), and the like. These resins (B) may be used alone or in combination of two or more.

The weight average molecular weight of the resin (B) is 1000 from the viewpoint that it is well compatible with the resin (A), plasticizes the resin (A) appropriately, and does not affect physical properties such as water vapor permeability of the pressure-sensitive adhesive layer. Although it is -250,000, Preferably it is 1200-220,000, More preferably, it is 1500-200,000.
If the weight average molecular weight is less than 1000, the resin (B) may be separated as a low molecular component to contaminate the adherend, or the outgas generated at high temperatures may increase, which may adversely affect physical properties. On the other hand, if it is larger than 250,000, the resin (A) cannot be sufficiently plasticized, and it is difficult to obtain sufficient wettability with the adherend.

The content of the polybutene resin (B) is 10 to 100 parts by mass with respect to 100 parts by mass of the polyisobutylene-based resin (A) from the viewpoint of balance with adhesive force, cohesive force, and water vapor permeability. Preferably it is 15-100 mass parts, More preferably, it is 25-100 mass parts.
If it is less than 10 parts by mass, the resin (A) cannot be sufficiently plasticized, and the wettability with the adherend is not sufficient. On the other hand, if it exceeds 100 parts by mass, the cohesive force is lowered and the durability against ultraviolet irradiation is inferior, which is not preferable.

<Hindered amine light stabilizer (C)>
In the present invention, a hindered amine light stabilizer (C) (hereinafter also referred to as “light stabilizer (C)”) is used as the light stabilizer. The hindered amine light stabilizer has at least one group (hindered amine group) represented by the following formula (c) in one molecule.

In the formula (c), R ¹ represents a hydrogen atom, an alkyl group, or an alkoxy group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkoxy group include a methoxy group and an ethoxy group.
When there are a plurality of groups represented by the formula (c) in one molecule, R ¹ in the plurality of groups may be the same or different.

  Examples of the light stabilizer (C) include dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1 , 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {( 2,2,6,6-tetramethyl-4-piperidyl) imino, poly [{6-morpholino-s-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) ) Imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino, N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl-)) (N-methyl-2,2,6,6-tetramethyl Piperidin-4-yl) -4,7-diazadecane-1,10-diamine, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethyl) Ethyl) -4-hydroxyphenyl] methyl] butyl malonate, cyclohexane and N-butyl peroxide 2,2,6,6-tetramethyl-4-piperidineamine-2,4,6-trichloro 1,3,5- Reaction product of triazine with reaction product of 2-aminoethanol, decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, 1,1- Reaction products of dimethylethyl hydroperoxide and octane, bis (1,2,2,6,6-pentamethyl-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl- Piperidyl sebacate (mixture), N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine) -4-yl) -4,7-diazadecane-1,10-diamine, bis (1,2,2,6,6-pentamethyl-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4 -Piperidyl sebacate (mixture), bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like.

Among these, it is a tertiary hindered amine group in which R ¹ in the formula (c) is an alkyl group from the viewpoint of excellent performance as a light stabilizer and improving the durability of the pressure-sensitive adhesive composition to ultraviolet rays. Is preferred. The hindered amine light stabilizer having a tertiary hindered amine group is particularly excellent in performance as a light stabilizer.
Examples of such a light stabilizer (C) include N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6). , 6-Tetramethylpiperidin-4-yl) -4,7-diazadecane-1,10-diamine, bis (1,2,2,6,6-pentamethyl-piperidyl) sebacate and methyl 1,2,2,6 , 6-pentamethyl-4-piperidyl sebacate (mixture), bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like.
In addition, you may use these light stabilizers (C) individually or in combination of 2 or more types.

  The content of the light stabilizer (C) is based on 100 parts by mass of the polyisobutylene resin (A) from the viewpoint of improving the durability of the pressure-sensitive adhesive composition to ultraviolet rays by exhibiting the performance as a light stabilizer. Preferably it is 0.25-1.0 mass part, More preferably, it is 0.3-0.9 mass part, More preferably, it is 0.4-0.8 mass part. If the content of the light stabilizer (C) is 0.25 part by mass or more, the durability of the pressure-sensitive adhesive composition can be sufficiently improved, and if it is 1.0 part by mass or less, other components and Separation can also be suppressed.

<Hindered phenolic antioxidant (D)>
In the present invention, a hindered phenolic antioxidant (D) (hereinafter also referred to as “antioxidant (D)”) is used as the antioxidant. The hindered phenol antioxidant has at least one group (hindered phenol group) represented by the following formula (d) in one molecule.

In formula (d), R ² and R ³ each represent a hydrogen atom, a linear alkyl group, or a branched alkyl group. Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the branched alkyl group include isopropyl group, isobutyl group, tertiary butyl group and the like.
When there are a plurality of groups represented by the formula (d) in one molecule, R ² and R ³ may be the same or different in the plurality of groups.

  Examples of the antioxidant (D) include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythrityl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio -Diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N '-Hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydroxynamamide, 1,3,5-trimethyl-2,4,6-tri (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 2,4-bis- (n-octylthio) ) -6- (4-hydroxy-3,5-di-t-butylanilino) 1,3,5-triazine, 2,4-bis [(octylthio) methyl] -o-cresol, 2,6-di-t -Butyl-p-cresol, 4,4'-butylidenebis- (6-t-butyl-3-methylphenol), 2,2'-methylenebis- (4-methyl-6-t-butylphenol), 2,2 ' -Methylenebis- (4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-ethylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t) -Butylpheny ) Butane, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) trione, isooctyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythris Lithyl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxy Phenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-tert-butyl) 4-hydroxy-hydroxynamamide, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris- (3,5 -Di-t-butyl-4-hydroxybenzyl) -isocyanurate, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) 1,3,5 -Triazine, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, 1,3,5-tris (3,5-di-t-butyl- 4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) trione, isooctyl (3,5-di-t-butyl-4-hydroxyphenyl) propionate and the like. .

Among these, the antioxidant (D) is a hindered in which R ² and R ³ in the formula (d) are branched alkyl groups from the viewpoint of improving the durability of the pressure-sensitive adhesive composition to high-humidity heat. Phenol-based antioxidants are preferable, and hindered phenol-based antioxidants in which both of the beta positions of the hindered phenol group are tertiary butyl groups are more preferable. The hindered phenol antioxidants in which both of the hindered phenol groups are in a tertiary butyl group are particularly antioxidants when used in a long-time driving or outdoor driving environment as in the present invention. Excellent performance as an agent.
Examples of such antioxidant (D) include 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythrityl tetrakis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] , Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydroxynnamamide 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4 -Hydroxybenzyl) -isocyanurate, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) 1,3,5-triazine, 2,6-di -T-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -1, 3,5-triazine-2,4,6 (1H, 3H, 5H) trione, isooctyl (3,5-di-t-butyl-4-hydroxyphenyl) propionate, etc. In addition, antioxidant (D ) Commercially available products include Yoshinox BHT (manufactured by Yoshitomi Fine Chemical), IRGANOX 565 (manufactured by Ciba Specialty Chemicals), IRGANOX 1010, and the like.
These antioxidants (D) may be used alone or in combination of two or more.

  The content of the antioxidant (D) is preferably 0.25 to 1.0 with respect to 100 parts by mass of the polyisobutylene resin (A) from the viewpoint of improving the durability of the pressure-sensitive adhesive composition to high-humidity heat. It is a mass part, More preferably, it is 0.3-0.9 mass part, More preferably, it is 0.4-0.8 mass part. If the content of the antioxidant (D) is 0.25 parts by mass or more, the durability of the pressure-sensitive adhesive composition can be sufficiently improved, and if it is 1.0 parts by mass or less, other components and Separation can also be suppressed. The pressure-sensitive adhesive composition of the present invention contains at least one of a hindered amine light stabilizer (C) and a hindered phenol antioxidant (D). Moreover, you may use together according to a use.

<Other resins>
The pressure-sensitive adhesive composition of the present invention preferably contains a cyclic olefin polymer (E) (hereinafter also referred to as “polymer (E)”) as the other resin in addition to the above (A) to (D). . The polymer (E) is useful in the adjustment of the viscosity at the time of coating, the improvement of the flexibility due to the plasticity effect, the improvement of the initial adhesive force due to the improvement of the wettability, the increase of the cohesive force, etc. Have.
The polymer (E) contains a repeating unit derived from a cyclic olefin monomer. The bonding mode of the cyclic olefin monomer is not particularly limited as long as a cyclic structure can be introduced into the main chain, and a polymer obtained by polymerizing a carbon-carbon unsaturated bond of the monomer, or a cyclic conjugated diene. Addition-polymerized products and the like can be mentioned. The polymer (E) includes a polymer obtained by addition polymerization of an alicyclic monomer having a norbornene ring, a polymer copolymerized with a copolymerizable monomer other than a cyclic olefin, and a norbornene ring. Examples thereof include a ring-opening polymer obtained by ring-opening polymerization of an alicyclic monomer. In addition, a polymer obtained by addition polymerization of a monocyclic olefin monomer, a polymer obtained by 1,4-addition polymerization of a cyclic conjugated diene monomer such as cyclopentadiene or cyclohexadiene, a monocyclic olefin The polymer which copolymerized the monomer and cyclic conjugated diene type monomer, and the copolymerizable monomer other than cyclic olefin is also mentioned.

Further, these polymers (E) may be further hydrogenated. Specifically, what is called hydrogenated petroleum resin etc. which hydrogenated petroleum resin known as a tackifier is mentioned. Examples of the hydrogenated petroleum resin include a partially hydrogenated resin having a different hydrogenation rate to a fully hydrogenated resin. However, the compatibility with the resin (A) and the resin (B), water vapor transmission rate, high From the viewpoint of durability against wet heat and ultraviolet rays, a completely hydrogenated resin is preferred.
Examples of hydrogenated petroleum resins include hydrogenated terpene resins, hydrogenated rosins and hydrogenated rosin ester resins, disproportionated rosins, disproportionated rosin ester resins, pentenes generated by thermal decomposition of petroleum naphtha, and isoprene. Hydrogenated dicyclopentadiene resin which is a hydrogenated resin of C5 petroleum resin obtained by copolymerizing C5 fractions such as piperine and 1.3-pentadiene, partially hydrogenated aromatic modified dicyclopentadiene resin, Resin obtained by hydrogenation of C9 petroleum resin obtained by copolymerizing C9 fraction such as indene, vinyltoluene, α- or β-methylstyrene produced by thermal decomposition of petroleum naphtha, C5 fraction and C9 fraction described above For example, a resin obtained by hydrogenation of a copolymerized petroleum resin. Among these, hydrogenated dicyclopentadiene resins are used from the viewpoint of low moisture permeability and from the viewpoint of preventing the discoloration (yellowing) of the resin (A) and the resin (B) by high humidity heat or ultraviolet rays and ensuring transparency. preferable.
In addition, you may use these polymers (E) individually or in combination of 2 or more types.

The weight average molecular weight of the polymer (E) is preferably 200 to 5,000, more preferably 500 to 3,000. When the weight average molecular weight is 5,000 or less, excellent adhesiveness can be imparted and sufficient wetting with the adherend can be obtained. Moreover, compatibility with resin (A) also becomes favorable.
The content of the polymer (E) is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the polyisobutylene resin (A) from the viewpoints of viscosity, flexibility, wettability, cohesive force, and water vapor transmission rate reduction effect. 300 mass parts, More preferably, it is 10-100 mass parts, More preferably, it is 20-80 mass parts. When the content of the polymer (E) is 10 parts by mass or more, excellent adhesiveness can be imparted, and sufficient wettability with the adherend can be obtained. The cohesive strength of the object can be sufficiently obtained, and when being attached to an adherend, peeling can be prevented.

<Other additives>
The pressure-sensitive adhesive composition of the present invention includes a light stabilizer, an antioxidant, an ultraviolet absorber, a resin stabilizer, a filler, a pigment, a bulking agent, etc. May be included. These additives may be used alone or in combination of two or more.
Examples of light stabilizers other than the hindered amine light stabilizer (C) include benzophenone-based and benzotriazole-based light stabilizers. Examples of the antioxidant other than the hindered phenol antioxidant (D) include phosphate ester compounds. Each content of these light stabilizers other than (C) and antioxidants other than (D) is preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the polyisobutylene resin (A). is there.
Examples of ultraviolet absorbers include benzotriazole compounds, oxazolyac acid amide compounds, benzophenone compounds, and the like. The content of these ultraviolet absorbers is preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the polyisobutylene resin (A).
Examples of the resin stabilizer include an imidazole resin stabilizer, a dithiocarbamate resin stabilizer, a phosphorus resin stabilizer, and a sulfur ester resin stabilizer. The content of these resin stabilizers is preferably 0.01 to 3 masses per 100 mass parts of the polyisobutylene resin (A).

  The pressure-sensitive adhesive composition of the present invention may further contain an organic solvent such as toluene, ethyl acetate, or methyl ethyl ketone. When mix | blending an organic solvent, solid content concentration of an adhesive composition becomes like this. Preferably it is 10-60 mass%, More preferably, it is 10-45 mass%, More preferably, it is 15-30 mass%. If it is 10% by mass or more, the amount of the solvent used is sufficient, and if it is 60% by mass or less, it has an appropriate viscosity and can be a solution having excellent coating workability.

  There is no restriction | limiting in particular in the method of forming the adhesive layer of this invention, It can manufacture by a well-known method. For example, a pressure-sensitive adhesive composition (solution) containing an organic solvent can be produced by a known coating method. For example, the pressure-sensitive adhesive composition on the release layer surface of the substrate or release sheet by a known method such as spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, or gravure coating. In order to prevent the solvent and low-boiling components from remaining, the solution can be produced by heating at a temperature of 80 to 150 ° C. for 30 seconds to 5 minutes.

  The thickness of the pressure-sensitive adhesive layer to be formed is not particularly limited and is appropriately selected according to the use of the pressure-sensitive adhesive sheet for sealing, etc., preferably 0.5 to 100 μm, more preferably 1 to 60 μm, still more preferably. Is 3-40 μm. If it is 0.5 μm or more, good adhesive force can be obtained for the adherend, and if it is 100 μm or less, it is advantageous in terms of productivity and can be an easy-to-handle pressure-sensitive adhesive sheet.

The water vapor transmission rate at a thickness of 50 μm of the pressure-sensitive adhesive layer of the present invention is preferably 10 g / (m ² · day) or less, more preferably 8 g / (m ² · m) at 40 ° C. and 90% RH (RH: relative humidity). day) or less, more preferably 6 g / (m ² · day) or less. When the water vapor transmission rate is 10 g / (m ² · day) or less, when used for sealing an organic EL element or the like, the entry of water vapor from the end of the pressure-sensitive adhesive layer can be suppressed. The water vapor transmission rate can be measured by a known method.
Further, the pressure-sensitive adhesive layer of the present invention has high adhesive force even when the pressure-sensitive adhesive layer itself is thin. The adhesive strength of the pressure-sensitive adhesive layer is preferably 3 N / 25 mm or more, more preferably 5 N / 25 mm or more.

In the sealing adhesive sheet of the present invention, a release sheet may be provided on the adhesive layer as desired. Examples of the release sheet include paper substrates such as glassine paper, coated paper, and high-quality paper, Laminated paper obtained by laminating a thermoplastic resin such as polyethylene or polypropylene to these paper base materials, or a paper base material obtained by sealing the base material with cellulose, starch, polyvinyl alcohol, acrylic-styrene resin, or polyethylene. Polyester films such as terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc., plastic films such as polyethylene films such as polyethylene and polypropylene, and films obtained by applying an adhesive to these plastic films, etc. Can be mentioned.
Examples of the release agent used to form the release agent layer include rubber elastomers such as olefin resins, isoprene resins, butadiene resins, long chain alkyl resins, alkyd resins, fluorine resins, silicone resins, etc. Is used.
The thickness of the release agent layer is not particularly limited, but when the release agent is applied in a solution state, it is preferably 0.05 to 2.0 μm, more preferably 0.1 to 1.5 μm. When the release agent layer is formed using a thermoplastic resin such as polyethylene or polypropylene, the thickness of the release agent layer is preferably 3 to 50 μm, more preferably 5 to 40 μm.

[(2) Base material]
The substrate of the present invention is not particularly limited as long as it meets the object of the present invention. For example, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyimides, polyamideimides, wholly aromatic polyamides, nylon 6, nylon 66, nylon copolymers and other polyamides, rubornene polymers, monocyclic Cyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, cycloolefin polymers such as hydrides thereof, polyphenylene ether, polyether ketone, polyether ether ketone, polycarbonate, Examples thereof include a sheet made of a resin of polysulfone, polyethersulfone, polyphenylene sulfide, or polyarylate. Moreover, you may use aluminum foil, metal foil, such as copper foil and iron foil, glass, etc. as a base material.
Among these, polyester, polyamide or cycloolefin polymer is preferable, and polyester or cycloolefin polymer is more preferable from the viewpoint of excellent transparency and versatility.

  Although there is no restriction | limiting in particular in the thickness of a base material, From a viewpoint of ease of handling, Preferably it is 2-200 micrometers, More preferably, it is 10-150 micrometers, More preferably, it is 20-100 micrometers.

[(3) Gas barrier layer]
The material for the gas barrier layer is not limited as long as it prevents the permeation of oxygen and water vapor. For example, metal such as aluminum, magnesium, zinc, tin, silicon nitride, silicon oxide, silicon oxynitride, polysilazane compound, polycarbosilane compound, polysilane compound, polyorganosiloxane compound, silicon compound such as tetraorganosilane compound, aluminum oxide , Aluminum compounds such as aluminum oxynitride, inorganic oxides such as magnesium oxide, zinc oxide, indium oxide, tin oxide, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl chloride, polyvinylidene chloride, polychlorotrifluoroethylene And the like.
Among these, as the material of the gas barrier layer, from the viewpoint of gas barrier properties, metals such as aluminum, magnesium, zinc and tin, silicon nitride, silicon oxide, silicon oxynitride, polysilazane compound, polycarbosilane compound, polysilane compound, polyorgano Preferred are silicon compounds such as siloxane compounds and tetraorganosilane compounds, aluminum compounds such as aluminum oxide and aluminum oxynitride, and inorganic oxides such as magnesium oxide, zinc oxide, indium oxide and tin oxide. Among these, from the viewpoint of transparency, polysilazane compounds, polycarbosilane compounds, polysilane compounds, polyorganosiloxane compounds, and tetraorganosilane compounds are more preferable.

(Polysilazane compound)
The polysilazane compound is a polymer having a repeating unit containing a (—Si—N—) bond in the molecule, and examples thereof include a compound having a repeating unit represented by the following formula (1).

In formula (1), R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted group. Represents a non-hydrolyzable group such as an alkenyl group having a substituent, an unsubstituted or substituted aryl group or an alkylsilyl group.
Among these, as R < ⁴ > -R < ⁶ >, a hydrogen atom, a C1-C6 alkyl group, or a phenyl group is preferable, and a hydrogen atom is especially preferable.
Moreover, as a polysilazane compound having a repeating unit represented by the formula (1), an inorganic polysilazane in which R ^{4 to} R ⁶ are all hydrogen atoms from the viewpoint of easy availability and formation of an excellent gas barrier property, Alternatively, organic polysilazane in which at least one of R ^{4 to} R ⁶ is not a hydrogen atom is preferable, inorganic polysilazane is more preferable, and perhydropolysilazane is further preferable.
The number average molecular weight of the polysilazane compound is not particularly limited, but is preferably 100 to 50,000.

(Polycarbosilane compound)
The polycarbosilane compound is a polymer compound having a repeating unit containing a (—Si—C—) bond in the main chain in the molecule, and includes a compound having a repeating unit represented by the following formula (2). .

In the formula (2), R ⁷ and R ⁸ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, or a monovalent heterocyclic group. R ⁷ and R ⁸ may be the same or different from each other. R ⁹ represents an alkylene group, an arylene group or a divalent heterocyclic group.

Among these, as a polycarbosilane compound having a repeating unit represented by the formula (2), R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group or an aryl group, and R ⁹ is an alkylene. A group or an arylene group is preferred, R ⁷ and R ⁸ are each independently a hydrogen atom or an alkyl group, R ⁹ is preferably an alkylene group, and R ⁷ and R ⁸ are each independently And a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁹ is more preferably an alkylene group having 1 to 6 carbon atoms.
The weight average molecular weight of the polycarbosilane compound is usually 400 to 12000.

(Polysilane compound)
The polysilane compound is a polymer compound having a repeating unit containing a (—Si—Si—) bond in the molecule. Examples of such polysilane compounds include compounds having at least one repeating unit selected from structural units represented by the following formula (3).

In formula (3), R ¹⁰ and R ¹¹ are each independently a hydrogen atom, hydroxyl group, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, alkoxy group, cycloalkyloxy group, aryl An oxy group, an aralkyloxy group, an amino group optionally having a substituent, a silyl group, or a halogen atom is represented.

As the polysilane compound to be used, in the formula (3), R ¹⁰ and R ¹¹ are preferably each independently a hydrogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group, an amino group, or a silyl group, R ¹⁰ and R ¹¹ are each independently a hydrogen atom, more preferably those wherein the alkyl group or aryl group, R ¹⁰ and R ¹¹ are each independently an alkyl group or an aryl group having from 1 to 4 carbon atoms Is more preferred.

The form of the polysilane compound to be used is not particularly limited, and it may be a random copolymer, a block even if it is a homopolymer such as acyclic polysilane (linear polysilane, branched polysilane, network polysilane, etc.) or cyclic polysilane. Copolymers such as copolymers, alternating copolymers, and comb copolymers may also be used.
When the polysilane compound is an acyclic polysilane, the terminal group (terminal substituent) of the polysilane compound is a hydrogen atom, a halogen atom (such as a chlorine atom), an alkyl group, a hydroxyl group, an alkoxy group, a silyl group, etc. It may be.

  Although the weight average molecular weight of a polysilane compound is not specifically limited, Preferably it is 300-100,000, More preferably, it is 400-50000, More preferably, it is 500-30000.

(Polyorganosiloxane compound)
The polyorganosiloxane compound is not limited in the main chain structure, and may be any of a straight chain, a ladder, and a cage.
For example, the structure represented by the following formula (4) as a linear main chain structure, and the structure represented by the following formula (5) as a ladder main chain structure are Is exemplified by the structure represented by the following formula (6).

In formulas (4) to (6), Rx, Ry, and Rz each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted group. Represents a non-hydrolyzable group such as an aryl group having Rx, Ry, and Rz in the formula may be the same or different from each other, but both Rx in the formula (1) are not hydrogen atoms.
Among these, as Rx, Ry, and Rz, each independently, an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms or a phenyl group is preferable, and a methyl group, an ethyl group, a propyl group, 3- A glycidoxypropyl group or a phenyl group is particularly preferred.

(Tetraorganosilane compound)
The tetraorganosilane compound is a compound in which four hydrolyzable groups are bonded to a silicon element. Specifically, the tetraorganosilane compound is a compound represented by the formula (7): SiX ₄ .
Formula (7): In SiX ₄ , X represents a hydrolysis substituent and may be the same or different from each other.
X is a group represented by the formula (8): OR (R represents a hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group), and the formula (9): OSi (R ^a ) (R ^b ) A group represented by (R ^c ) (R ^a , R ^b , and R ^c each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group), a chlorine atom, a bromine atom, etc. And the like.

Examples of the tetraorganosilane compound include tetra (C1-C10) alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetrabutoxysilane; trimethoxychlorosilane, triethoxychlorosilane, and tripropoxy Tri (C1-C10) alkoxyhalogenosilanes such as chlorosilane; Di (C1-C10) dihalogenoalkoxysilanes such as dimethoxycyclosilane, diethoxydichlorosilane, dipropoxydichlorosilane; methoxytrichlorosilane, ethoxytrichlorosilane, propoxytri Mono (C1-C10) alkoxytrihalogenosilanes such as chlorosilane; tetrahalogenosilanes such as tetrachlorosilane and tetrabromosilane; Here, (C1 to C10) represents that the carbon number is 1 to 10.
These tetraorganosilane compounds can be used alone or in combination of two or more.

  Among these, tetra (C1-C10) alkoxysilane is preferable from the viewpoint of excellent handleability and gas barrier properties. These tetraorganosilane compounds are preferably hydrolyzed and dehydrated in a suitable solvent in the presence of water and optionally a catalyst.

  The weight average molecular weight of the hydrolysis / dehydration condensate of the tetraorganosilane compound is not particularly limited, but is preferably 200 to 50000, more preferably 200 to 30000, and still more preferably from the viewpoint of obtaining a gas barrier layer having excellent mechanical strength. Is 200-10000. If the weight average molecular weight is 200 or more, it has sufficient film forming ability, and if it is 50000 or less, a film having sufficient mechanical strength is formed.

The method for forming the gas barrier layer is not particularly limited. For example, a method in which a solution in which the above-described material is dissolved in an organic solvent is applied on the substrate, and the obtained coating film is appropriately dried. Is mentioned. The coating method is not particularly limited, and examples thereof include known coating methods such as spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
As another forming method, a method of forming the above-mentioned material on a substrate by vapor deposition, sputtering, ion plating, thermal CVD, plasma CVD, or the like can be given.
In the following, a gas barrier layer formed on a substrate is also referred to as a “gas barrier film”.

  The thickness of the formed gas barrier layer is preferably 20 nm to 100 μm, more preferably 30 to 500 nm, and still more preferably 40 to 200 nm, from the viewpoint of gas barrier performance and handleability. In addition, in this invention, even if a gas barrier layer is nano order, the adhesive sheet for sealing which has sufficient gas barrier performance can be obtained.

  Furthermore, it is preferable to implant ions into the surface of the gas barrier layer. By implanting ions, gas barrier performance can be improved while maintaining high transparency. The step of implanting ions is not particularly limited, and examples thereof include a method of forming a gas barrier layer on a substrate and then implanting ions into the gas barrier layer.

Examples of implanted ions include rare gases such as argon, helium, neon, krypton, and xenon; ions such as fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur; gold, silver, copper, and platinum And ions of metals such as nickel, palladium, chromium, titanium, molybdenum, niobium, tantalum, tungsten, and aluminum.
Among these, hydrogen, nitrogen, oxygen, argon, helium, neon, xenon, and krypton can be injected more easily and from the viewpoint of obtaining a pressure-sensitive adhesive sheet having excellent gas barrier performance and transparency. At least one ion selected from the group consisting of
The ion implantation amount is appropriately determined in consideration of the purpose of use of the sealing sheet for sealing (necessary gas barrier properties, transparency, etc.).

Examples of the ion implantation method include a method of irradiating ions accelerated by an electric field (ion beam), a method of implanting ions in plasma (plasma ion implantation method), and the like. Among these, the plasma ion implantation method is preferable from the viewpoint of obtaining a pressure-sensitive adhesive sheet for sealing having excellent gas barrier properties and the like.
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 the gas barrier layer, so that ions (positive ions) in the plasma are changed to the surface of the gas barrier layer. It can be performed by injecting into the part.

  The thickness of the portion into which ions are implanted can be controlled by implantation conditions such as ion type, applied voltage, treatment time, etc., and can be determined according to the thickness of the gas barrier layer, the purpose of use of the sealing adhesive sheet, etc. Although it is good, it is usually 10 to 1000 nm, preferably 10 to 200 nm.

The gas barrier film thus obtained has a water vapor transmission rate at a gas barrier layer thickness of 75 nm of 40 g and 90% RH, preferably 0.5 g / (m ² · day) or less, more preferably 0.05 g. / (M ² · day) or less. In addition, the transmittance | permeability, such as water vapor | steam, of a gas barrier film can be measured using a well-known gas-permeability measuring apparatus. For example, the water vapor transmission rate of the gas barrier film can be measured using the apparatus described in the examples.

[(4) Other layers]
Examples of other layers other than the above (1) to (3) include a conductor layer and a primer layer. In addition, the position where another layer is laminated | stacked is not limited, According to the objective, it selects suitably.
<Conductor layer>
Examples of the material constituting the conductor layer include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specifically, tin oxide (ATO) doped with antimony; tin oxide (FTO) doped with fluorine; conductive such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO) Metal such as gold, silver, chromium and nickel; mixtures of these metals and conductive metal oxides; inorganic conductive materials such as copper iodide and copper sulfide; organic conductive materials such as polyaniline, polythiophene and polypyrrole Material, etc. The conductor layer may be a laminate in which a plurality of layers made of these materials are laminated.
Among these, a conductive metal oxide is preferable from the viewpoint of transparency, and ITO is particularly preferable.

Examples of the method for forming the conductor layer include a vapor deposition method, a sputtering method, an ion plating method, a thermal CVD method, a plasma CVD method, and the like. Among these, the sputtering method is preferable because the conductor layer can be easily formed.
The sputtering method introduces a discharge gas (such as argon) into a vacuum chamber, applies a high-frequency voltage or a direct current voltage between the target and the substrate to turn the discharge gas into plasma, and collides the plasma with the target material. This is a method of obtaining a thin film by skipping and attaching to a substrate. As the target, a target made of a material for forming the conductor layer is used.

  The thickness of the conductor layer may be appropriately selected according to the application and the like, but is preferably 10 nm to 50 μm, more preferably 20 nm to 20 μm. The surface resistivity of the obtained conductor layer is preferably 1000Ω / □ or less.

  The formed conductor layer may be patterned as necessary. Examples of the patterning method include chemical etching by photolithography and the like, physical etching using a laser and the like, vacuum deposition method using a mask, sputtering method, lift-off method, printing method, and the like.

(Primer layer)
A primer layer plays the role which improves the interlayer adhesiveness of a base material layer and a gas barrier layer. By providing the primer layer, it is possible to obtain an adhesive sheet for sealing that is extremely excellent in interlayer adhesion and surface smoothness.
It does not specifically limit as a material which comprises a primer layer, A well-known thing can be used. For example, a photopolymerizable composition comprising a silicon-containing compound; a photopolymerizable compound comprising a photopolymerizable monomer and / or a photopolymerizable prepolymer, and a polymerization initiator that generates radicals at least in the visible light region; Resin, polyurethane resin (especially two-part curable resin of polyacryl polyol, polyester polyol, polyether polyol, etc. and isocyanate compound), acrylic resin, polycarbonate resin, vinyl chloride / vinyl acetate copolymer, polyvinyl butyral Resins such as resins and nitrocellulose resins; alkyl titanates; ethyleneimines; These materials can be used alone or in combination of two or more.

For the primer layer, a primer layer forming solution obtained by dissolving or dispersing the material constituting the primer layer in an appropriate solvent is applied to one or both sides of the base material layer, and the obtained coating film is dried to obtain a desired layer. It can form by heating by.
As a method of applying the primer layer forming solution to the substrate, a normal wet coating method can be used. Examples include dipping method, roll coating, gravure coating, knife coating, air knife coating, roll knife coating, die coating, screen printing method, spray coating, gravure offset method and the like.
As a method for drying the coating film of the primer layer forming solution, conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation can be employed. The thickness of the primer layer is preferably 10 to 1000 nm.

  Moreover, you may ion-implant into the obtained primer layer similarly to the above-mentioned gas barrier layer. By performing ion implantation also on the primer layer, better gas barrier performance can be obtained.

[Characteristics of sealing adhesive sheet]
The shape of the sealing adhesive sheet of the present invention is not particularly limited, and examples thereof include a sheet shape, a rectangular parallelepiped shape, a polygonal column shape, and a cylindrical shape. For example, when it is used as a member for an electronic device, it is preferably a sheet.

The water vapor permeability of the sealing adhesive sheet of the present invention is preferably 0.5 g / (m ² · day) or less, more preferably 0.05 g / (at 40 ° C. and 90% RH (RH: relative humidity). m ² · day) or less, more preferably 0.005 g / (m ² · day) or less, and particularly preferably 0.0005 g / (m ² · day) or less. When the water vapor transmission rate is 0.5 g / (m ² · day), when used for sealing an organic EL element or the like, the organic EL element or the like is sealed even by long-time driving or driving environment. Deterioration of element characteristics can be suppressed. The transmittance of water vapor or the like of the sealing adhesive sheet can be measured using a known gas permeability measuring device. In this invention, it measures by the method as described in an Example.

The sealing pressure-sensitive adhesive sheet of the present invention has an organic device such as an organic transistor, organic memory, or organic EL as a sealing member; liquid crystal display; electronic paper; thin film transistor; electrochromic; electrochemiluminescence device; It can be used for electronic devices such as batteries; thermoelectric conversion devices; piezoelectric conversion devices; For example, in FIG. 2, the example of the organic device which has an organic EL element sealed with the adhesive sheet for sealing of this invention is shown. The organic EL element 11 includes a glass substrate 12 and a structure 13 on the glass substrate 12. The structure includes at least a pair of opposed electrodes and an organic layer such as a hole transport layer or a light emitting layer disposed between the electrodes. For example, the structure 13 in FIG. 2 includes an organic layer 15 between a pair of opposed electrodes 14a and 14b. On the other hand, the pressure-sensitive adhesive sheet 1 for sealing of the present invention in which the gas barrier layer 3 and the pressure-sensitive adhesive layer 4 are laminated on the base material 2 is disposed on the upper portion, the lower portion, and / or the periphery of the structure 13. The organic EL element 11 is sealed by the pressure-sensitive adhesive layer 4 of the pressure-sensitive adhesive sheet 1 for sealing, and is bonded to the structure 14 and the glass substrate 12 to form the organic device 10. As a sealing method, after forming the structure 14 on the glass substrate 12, the sealing adhesive sheet 1 of the present invention is pasted and sealed. If the sealing adhesive sheet of this invention is used, it can seal easily.
As described above, the organic device having the organic EL element sealed with the sealing adhesive sheet of the present invention has a sealing adhesive sheet having an excellent gas barrier property, and the adhesive layer is under ultraviolet irradiation. Since the durability under the environment is excellent, the deterioration of the characteristics of the organic EL element can be suppressed even by a long-time driving or driving environment.
In addition, the said effect is show | played not only in an organic device but the same effect also in various electronic device uses as mentioned above.

  The water vapor transmission rate measuring apparatus, measurement conditions, and evaluation criteria for organic devices used in the following examples are as follows.

<Water vapor transmission rate measuring device>
About the pressure-sensitive adhesive sheet for sealing obtained in the following Examples and Comparative Examples, the water vapor transmission rate was measured using the following apparatus under the conditions of 40 ° C. and relative humidity of 90%.
When the water vapor transmission rate is 0.01 g / (m ² · day) or more: product name “L89-500” (manufactured by LYSSY),
・ When water vapor transmission rate is less than 0.01 g / (m ² · day): Product name “deltaperm” (manufactured by TECHNOLOX)

<Evaluation criteria for organic devices>
The organic device produced using the adhesive sheet for sealing obtained in Examples and Comparative Examples was left in a standard environment (temperature 23 ° C., relative humidity 50%) for 200 hours, and then the organic EL element was activated. A dark spot (non-light emitting portion) was observed.
In addition, with the surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet for sealing obtained in Examples and Comparative Examples exposed, using an ultraviolet fade meter U-48 (manufactured by Suga Test Instruments Co., Ltd.), 500 W After continuously irradiating UV light of / m ² (wavelength 300-700 nm) for 50 hours (hereinafter also referred to as FOM), an organic device was similarly produced. Then, after being allowed to stand for 200 hours in a standard environment (temperature 23 ° C., relative humidity 50%), the organic EL element was activated, and dark spots (non-light emitting portions) were observed.
Evaluation criteria for the observed elements are as follows.
-“◎”: When dark spots are not observed at all (the dark spot occurrence suppressing effect is very excellent).
“◯”: When the occurrence of dark spots is less than 5% of the light emitting area (the effect of suppressing the occurrence of dark spots is excellent).
“X”: When dark spots are generated by 5% or more of the light emitting area (the effect of suppressing dark spots is poor).
"-": When the embedding property of the pressure-sensitive adhesive layer is low, lamination to the organic EL element cannot be performed, and a uniform light emitting surface cannot be obtained.

[Example 1]
<Preparation of pressure-sensitive adhesive composition>
100 parts by weight of “OPanol B50 (manufactured by BASF, Mw: 340,000)” as polyisobutylene resin (A), and “Nisseki Polybutene Grade HV-1900 (manufactured by Nippon Oil Corporation, Mw: 1900) as polybutene resin (B) 30 parts by weight, 0.5 parts by weight of “TINUVIN 765 (manufactured by Ciba Japan, having a tertiary hindered amine group)” as a hindered amine light stabilizer (C), “IRGANOX 1010 as a hindered phenolic antioxidant (D)” (Ciba Japan, both β-positions of hindered phenol groups have a tertiary butyl group) 0.5 parts by mass, and cyclic olefin polymer (E) “Eastotac H-100L Resin (Eastman Chemical Co.) ”50 parts by mass dissolved in toluene and concentrated in solids About 25% by weight of the adhesive composition was prepared.

<Preparation of sealing sheet for sealing>
As the gas barrier layer, a polyethylene terephthalate film “Alpet 12/34 (produced by Asia Aluminum Co., Ltd.)” on which aluminum (Al) is deposited is used as a gas barrier film, and the prepared pressure-sensitive adhesive composition solution is formed after drying. The pressure-sensitive adhesive layer was coated on the aluminum side (gas barrier layer side) so as to have a thickness of 20 μm, and dried at 120 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. Next, the release treatment surface of a polyethylene terephthalate film having a thickness of 38 μm was applied as a release sheet to the pressure-sensitive adhesive layer surface to prepare an adhesive sheet for sealing.

<Production of organic EL elements and organic devices>
As an anode, the surface of a glass substrate provided with an indium tin oxide (ITO) film (thickness: 150 nm, sheet resistance: 30 Ω / square) by sputtering was cleaned by solvent cleaning and UV / Osson treatment. Thereafter, N, N′-bis (naphthalen-1-yl) -N, N′-bis (phenyl) -benzidene), which is an organic material, is 60 nm and tris (8-hydroxy-quinolinate) aluminum on the ITO film. 40 nm, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 10 nm, (8-hydroxy-quinolinolate) lithium was sequentially deposited at a rate of 10 nm, 0.1-0.2 nm / s to emit light. A layer was formed. All organic materials are “made by Luminescence Technology Corp.”. Finally, aluminum (Al) (manufactured by Kojundo Chemical Laboratory Co., Ltd.) was deposited as a cathode at a rate of 100 nm at a rate of 0.1 nm / s to produce an organic EL device. Note that the degree of vacuum at the time of vapor deposition was 1 × 10 ⁻⁴ Pa or less.
Here, the sealing pressure-sensitive adhesive sheet produced by the above-described method was dried for 10 minutes on a hot plate heated to 120 ° C. in a nitrogen atmosphere, and then confirmed to decrease to room temperature. An organic device was manufactured by laminating the cathode completely.

[Example 2]
In Example 1, except that the hindered amine light stabilizer (C) was not added, an adhesive sheet for sealing and an organic device were produced in the same manner as in Example 1.
Example 3
In Example 1, the adhesive sheet for sealing and the organic device were produced like Example 1 except not adding a hindered phenolic antioxidant (D).
Example 4
In Example 2, the adhesive sheet for sealing and the organic device were produced like Example 2 except having changed the hindered phenolic antioxidant (D) into 1.0 mass part.
Example 5
In Example 3, the sealing adhesive sheet and the organic device were produced like Example 3 except having changed the hindered amine light stabilizer (C) into 1.0 mass part.

Example 6
In the same manner as in Example 1, except that “Alpet 12/34” used as the gas barrier layer in Example 1 was changed to a gas barrier film produced as follows, an adhesive sheet for sealing, and an organic device Was made.

<Production of gas barrier film>
As a base material, a polyethylene terephthalate film “PET50 A-4100 (manufactured by Toyobo Co., Ltd., thickness 50 μm, hereinafter also referred to as“ PET film ”) and a gas barrier layer forming material, a polysilazane compound (manufactured by Clariant Japan, trade name“ AQUAMICA NL110-20 ", a coating material mainly composed of perhydropolysilazane) was applied and heated at 120 ° C for 1 minute to form a 75 nm thick layer containing a polysilazane compound on the PET film.
Next, using a plasma ion implantation apparatus, argon (Ar) was plasma ion implanted into the surface of the obtained layer to produce a gas barrier film having a gas barrier layer on the substrate.
<Plasma ion implantation system>
The plasma ion implantation apparatus used is an apparatus for implanting ions using an external electric field.
・ RF power supply: JEOL Ltd., model number “RF” 56000
・ High voltage pulse power supply: “PV-3-HSHV-0835” manufactured by Kurita Manufacturing Co., Ltd.
<Plasma ion implantation conditions>
・ Plasma generated gas: Ar
・ Gas flow rate: 100sccm
・ Duty ratio: 0.5%
・ Repetition frequency: 1000Hz
-Applied voltage: -10 kV
-RF power supply: frequency 13.56 MHz, applied power 1000 W
-Chamber internal pressure: 0.2 Pa
・ Pulse width: 5μsec
・ Processing time (ion implantation time): 5 minutes ・ Conveying speed: 0.2 m / min

Example 7
In Example 6, instead of the polysilazane compound, a polyorganosiloxane compound (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KS358”, silicone resin containing polydimethylsiloxane as a main component) was used. Similarly, an adhesive sheet for sealing and an organic device were produced.

[Comparative Example 1] In Example 1, "Alpet 12/34" used as a gas barrier film was replaced with a polyethylene terephthalate film having no gas barrier layer (trade name "PET50 A-4100" manufactured by Toyobo Co., Ltd., thickness 50 µm). The sealing adhesive sheet and the organic device were produced in the same manner as in Example 1 except that the above was changed.
[Comparative Example 2]
In Example 1, the adhesive sheet for sealing and the organic device were produced like Example 1 except not adding a hindered amine light stabilizer (C) and a hindered phenolic antioxidant (D). .
[Comparative Example 3]
In Example 1, except that 150 parts by mass of the polybutene resin (B) was added, an adhesive sheet for sealing and an organic device were produced in the same manner as in Example 1.

[Comparative Example 4]
In Example 1, instead of Opanol B50, sealing was performed in the same manner as in Example 1 except that 100 parts by mass of “Opanol B100 (manufactured by BASF, Mw: 1.1 million)” was added as the polyisobutylene resin (A). A pressure-sensitive adhesive sheet for stopping and an organic device were produced.
[Comparative Example 5]
In Example 1, instead of Opanol B50, sealing was performed in the same manner as in Example 1 except that 100 parts by mass of “Opanol B80SF (manufactured by BASF, Mw: 750,000)” was added as the polyisobutylene resin (A). A pressure-sensitive adhesive sheet for stopping and an organic device were produced.
[Comparative Example 6]
In Example 1, instead of Opanol B50, sealing was performed in the same manner as in Example 1 except that 100 parts by mass of “Opanol B30 (manufactured by BASF, Mw: 200,000)” was added as the polyisobutylene resin (A). A pressure-sensitive adhesive sheet for stopping and an organic device were produced.

  Table 1 shows the sealing adhesive sheets of Examples 1 to 7 and Comparative Examples 1 to 6 and the evaluation of the organic devices.

  From Table 1, it can be seen that the sealing pressure-sensitive adhesive sheets of Examples 1 to 7 have a very low water vapor transmission rate as compared with Comparative Example 1 and have excellent barrier performance. Moreover, it turns out that the adhesive sheet for sealing of Examples 1-7 has a favorable lamination to an organic EL element compared with Comparative Examples 4-6. Furthermore, the organic device using the pressure-sensitive adhesive sheet for sealing of Examples 1 to 7 is a comparative example of the sealed organic EL element even in the case of FOM exposed to ultraviolet irradiation as compared with Comparative Examples 2 and 3. It can be seen that the deterioration of characteristics is suppressed.

  The sealing pressure-sensitive adhesive sheet of the present invention has an organic device such as an organic transistor, organic memory, or organic EL as a sealing member; liquid crystal display; electronic paper; thin film transistor; electrochromic; electrochemiluminescence device; Suitable for applications of electronic devices such as batteries; thermoelectric conversion devices; piezoelectric conversion devices;

1, 1a, 1b, 1c Sealing adhesive sheet 2, 2a, 2b Base material 3, 3a, 3b Gas barrier layer 4, 4a, 4b, 4c Adhesive layer 10 Organic device 11 Organic EL element 12 Glass substrate 13 Structure 14a 14b Electrode 15 Organic layer

Claims (8)

On a base material, a pressure-sensitive adhesive sheet for sealing with a least also gas gas barrier layer and the adhesive layer,
The pressure-sensitive adhesive layer comprises a polyisobutylene resin (A) having a weight average molecular weight of 300,000 to 500,000 as a first component, a polybutene resin (B) having a weight average molecular weight of 1,000 to 250,000 as a second component, and a hindered amine as a third component. A light stabilizer (C) and / or a hindered phenol antioxidant (D) , and a polymer (E) selected from a cyclic olefin polymer having a weight average molecular weight of 200 to 5,000 and a hydrogenated product thereof , against polyisobutylene-based resin (a) 100 parts by mass of a polybutene resin (B) seen from 10 to 100 parts by mass including, and comprised of polymer (E) a pressure-sensitive adhesive composition comprising 10 to 100 parts by mass, sealing Stop adhesive sheet. The pressure-sensitive adhesive sheet for sealing according to claim 1, wherein the water vapor transmission rate at 40 ° C. and 90% RH is 0.5 g / (m ² · day) or less.   The pressure-sensitive adhesive sheet for sealing according to claim 1 or 2, wherein the hindered amine light stabilizer (C) is a hindered amine light stabilizer having a tertiary hindered amine group.   The hindered phenol antioxidant (D) is a hindered phenol antioxidant in which both of the beta positions of the hindered phenol group are substituted with tertiary butyl groups. The sealing pressure-sensitive adhesive sheet according to claim 1. The pressure-sensitive adhesive sheet for sealing according to any one of claims 1 to 4, wherein the pressure-sensitive adhesive composition does not contain any of a curing agent, a thermal reaction initiator, and a photoinitiator. The pressure-sensitive adhesive sheet for sealing according to any one of claims 1 to 5 , which is used for an electronic device. An electronic device comprising the sealing adhesive sheet according to any one of claims 1 to 6 . At least a structure having an organic layer disposed between a pair of opposed electrodes and the electrode, and the upper portion of the structure, the lower, claim 1 disposed in any one or more及BiAmane circumference An organic device comprising the sealing adhesive sheet according to any one of 6 .

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