WO2015098648A1 - Sheet-shaped sealing material, sealing sheet, electronic-device seal, and organic electroluminescent element - Google Patents

Abstract

This invention is a sheet-shaped sealing material that comprises one or more sealing-resin layers and is characterized in that (each of) said sealing-resin layer(s) satisfies the following conditions: (a) a sealing resin constitutes at least 50% of the total mass of the sealing-resin layer in question; (b) the thickness (T₁) of the sealing-resin layer is between 0.1 and 100 µm, inclusive; (c) the water-vapor transmission rate (A₁) of the sealing-resin layer at said thickness (T₁) and at a temperature of 40°C and a relative humidity of 90% is between 0.1 and 5000 g/m²/day, inclusive; and (d) A₁ and T₁ satisfy relation (I). (I) A₁×(T₁)² < 10,000 This invention provides the following: a sheet-shaped sealing material that exhibits excellent sealing performance; a sealing sheet that has both a sealing-material layer comprising said sheet-shaped sealing material and a gas-barrier layer; an electronic-device seal obtained using said sheet-shaped sealing material or sealing sheet as a sealing material; and an organic electroluminescent element that has a sealing-material layer that exhibits excellent sealing performance.

Description

Sheet-like sealing material, sealing sheet, electronic device sealing body, and organic EL element

The present invention is obtained by using a sheet-shaped sealing material having excellent sealing properties, a sealing sheet having the sheet-shaped sealing material and a gas barrier layer, and using the sheet-shaped sealing material or the sealing sheet as a sealing material. The present invention relates to an electronic device sealing body and an organic EL element having the sheet-like sealing material.

In recent years, organic EL elements have attracted attention as light-emitting elements that can emit light with high luminance by low-voltage direct current drive.
However, the organic EL element has a problem that light emission characteristics such as light emission luminance, light emission efficiency, and light emission uniformity are likely to deteriorate with time.
As a cause of the deterioration of the light emission characteristics of the organic EL element, it is conceivable that oxygen, moisture or the like enters the inside of the organic EL element and degrades the electrode or the organic layer. In order to solve this problem, several methods using a sealing material have been proposed.
For example, Patent Document 1 discloses an organic EL element in which an organic EL layer sandwiched between a transparent electrode and a back electrode is covered with a photocurable resin layer (sealing material) having moisture resistance. Patent Document 2 discloses 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 electroluminescence element.

As adhesives and pressure-sensitive adhesives that are sealing materials for organic EL elements, acrylic adhesives and pressure-sensitive adhesives (hereinafter referred to as “acrylic adhesives”) are proposed from the viewpoint of optical properties such as transparency. Has been.
For example, Patent Document 3 discloses an acrylic adhesive having an ultraviolet curing function and a room temperature curing function as a sealing material for an organic EL display.
Patent Document 4 discloses a pressure-sensitive adhesive that can form a pressure-sensitive adhesive layer that can propagate light from an organic EL display element to the display surface with excellent propagation efficiency even after receiving a thermal history. An acrylic pressure-sensitive adhesive is disclosed.

Furthermore, in recent years, an adhesive containing a polyisobutylene resin has been proposed as a sealing adhesive having good moisture barrier properties. For example, Patent Document 5 discloses an adhesive composition containing a specific hydrogenated cyclic olefin polymer and a polyisobutylene resin, which is used as an encapsulant for an organic EL element.

JP-A-5-182759 Japanese Patent Laid-Open No. 5-101884 JP 2004-87153 A Japanese Patent Application Laid-Open No. 2004-224991 Special table 2009-524705 gazette (WO2007 / 08871 pamphlet)

As described in the above documents, various sealing materials have been developed in recent years, and sheet-shaped sealing materials with low water vapor permeability have been reported. However, even if such a sealing material having a low water vapor transmission rate is used for actually sealing an organic EL element, sufficient sealing performance (function to prevent moisture and the like from entering inside) is exhibited. There were times when it was not.

The present invention has been made in view of the situation of the prior art, and is a sheet-shaped sealing material excellent in sealing properties, a sealing sheet having this sheet-shaped sealing material and a gas barrier layer, and these sheet-shaped sealing materials. It aims at providing the organic EL element which has an electronic device sealing body obtained using a stop material or a sealing sheet as a sealing material, and the said sheet-like sealing material.

As a result of intensive studies to solve the above problems, the inventors of the present invention (a) by increasing the thickness of the sheet-like sealing material, usually lowering the water vapor transmission rate in the vertical direction (perpendicular to the sheet surface). On the other hand, since moisture and the like easily enter the inside from the end portion of the sheet-like sealing material, there is a tendency to be inferior in sealing properties, (b) and water vapor of the sheet-like sealing material It has been found that a sheet-like sealing material in which the transmittance and the thickness of the sheet-like sealing material satisfy a specific relational expression is excellent in sealing properties, and the present invention has been completed.

Thus, according to the present invention, the following sheet-shaped sealing materials (1) to (3), (4) to (6) sealing sheets, (7) electronic device sealing bodies, (8) to (10) ) Organic EL device.
(1) A sheet-like sealing material comprising one or two or more sealing resin layers, wherein the sealing resin layer satisfies the following (a) to (d): Stopping material (however, when the sheet-like sealing material is composed of a plurality of sealing resin layers, all of the plurality of sealing resin layers satisfy the requirements (a) to (d)).
(A) The sealing resin layer contains 50% by mass or more of the sealing resin with respect to the entire layer.
(B) The sealing resin layer has a thickness (T ₁ ) of 0.1 to 100 μm.
(C) The sealing resin layer has a water vapor transmission rate (A ₁ ) of 0.1 to 5,000 g / (m ² · day) at a temperature of 40 ° C. at a thickness (T ₁ ) and a relative humidity of 90%. .
; (D) _{A 1} and _{T 1} is, satisfies the following relational expression (I).

(2) The sheet-like sealing according to (1), wherein at least one of the sealing resin layers contains at least one selected from a rubber-based polymer, a polyolefin-based polymer, and a styrene-based thermoplastic elastomer. Stop material.
(3) The sheet-like sealing material according to (1), which is used for sealing an electronic device.
(4) A sealing sheet having a sheet-shaped sealing material composed of one or two or more sealing resin layers and a gas barrier layer, wherein the sheet-shaped sealing material is a sheet-shaped sealing according to (1) A sealing sheet characterized by being a material.
(5) The sealing according to (4), which includes the sheet-like sealing material and a gas barrier film in which the gas barrier layer is formed directly or via another layer on the base film. Stop sheet.
(6) The sealing sheet according to (4), which is used for sealing an electronic device.
(7) An electronic device sealing body in which an electronic device is sealed with the sheet-like sealing material according to (1) or the sealing sheet according to (4).
(8) An organic EL having a first electrode, an organic EL layer, a second electrode, a sheet-like sealing material composed of one or more sealing resin layers, and a sealing substrate in this order on a transparent substrate. It is an element, The said sheet-like sealing material is a sheet-like sealing material as described in (1), The organic EL element characterized by the above-mentioned.
(9) The organic EL element according to (8), wherein the sealing substrate has a gas barrier layer.
(10) The sealing substrate has a gas barrier film, and the gas barrier film is formed by forming the gas barrier layer on the substrate film directly or through another layer. ) Organic EL element.

According to the present invention, a sheet-shaped sealing material having excellent sealing properties, a sealing sheet having the sheet-shaped sealing material and a gas barrier layer, and using these sheet-shaped sealing material or sealing sheet as a sealing material The electronic device sealing body obtained by this and the organic EL element which has the said sheet-like sealing material are provided.

It is a schematic diagram which shows the usage aspect of the sheet-like sealing material of this invention. It is a schematic diagram which shows an example of the sheet-like sealing material of this invention.

Hereinafter, the present invention will be described in detail by dividing it into 1) a sheet-like encapsulant, 2) an encapsulating sheet, 3) an electronic device encapsulant, and 4) an organic EL element.

1) Sheet-like encapsulant The sheet-like encapsulant of the present invention is a sheet-like encapsulant comprising one or two or more encapsulating resin layers, and the encapsulating resin layer comprises the following (a) to ( d) is satisfied.
(A) The sealing resin layer contains 50% by mass or more of the sealing resin with respect to the entire layer.
(B) The sealing resin layer has a thickness (T ₁ ) of 0.1 to 100 μm.
(C) The water vapor permeability (A ₁ ) of the sealing resin layer at a temperature of 40 ° C. and a relative humidity of 90% is 0.1 to 5,000 g / (m ² · day).
(D) A ₁ and T ₁ satisfy the relational expression (I).

In the present specification, “low water vapor transmission rate” means that the amount of moisture passing through the upper and lower surfaces of the sheet-like sealing material under a predetermined condition is small. The “sealing property” refers to the moisture barrier property of the sheet-like sealing material when actually used as the sealing material. For example, it refers to the moisture barrier property when a planar object to be sealed placed on a glass plate or the like is covered with a sheet-like sealing material.
That is, “sealing performance” is based on both the function of blocking moisture entering through the upper and lower surfaces of the sheet-like sealing material and the function of blocking moisture entering from the end of the sheet-like sealing material. This is the function of the sealing material.

The sheet-like sealing material of the present invention comprises one or two or more sealing resin layers.
Hereinafter, the sealing resin layer will be described for each requirement.

<Requirement (a)>
The sealing resin layer contains 50% by mass or more of the sealing resin with respect to the entire layer.
The sealing resin is not particularly limited as long as the effects of the present invention can be obtained.

Examples of the sealing resin include rubber polymers, styrene thermoplastic elastomers, (meth) acrylic polymers, polyolefin polymers, polyester polymers, silicone polymers, and the like.

The rubber-based polymer is a polymer having rubber elasticity such as natural rubber or synthetic rubber. For example, natural rubber (NR), butadiene homopolymer (butadiene rubber, BR), chloroprene homopolymer (chloroprene rubber, CR), isoprene homopolymer, acrylonitrile-butadiene copolymer (nitrile rubber), Examples thereof include an ethylene-propylene-nonconjugated diene terpolymer, an isobutylene polymer, or a modified product thereof. Of the rubber polymers, isobutylene polymers are more preferable.

The isobutylene polymer refers to a polymer having repeating units derived from isobutylene in the main chain and / or side chain. The amount of the isobutylene-derived repeating unit is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70 to 99% by mass.
Examples of the isobutylene polymer include a homopolymer of isobutylene (polyisobutylene), a copolymer of isobutylene and isoprene (butyl rubber), a copolymer of isobutylene and n-butene, a copolymer of isobutylene and butadiene, and these polymers And an isobutylene polymer such as a halogenated polymer obtained by brominating or chlorinating a benzene. Among these, a copolymer of isobutylene and isoprene (butyl rubber) is preferable.

The styrene-based thermoplastic elastomer is a polymer having a repeating unit derived from styrene or a modified one thereof. For example, styrene-butadiene-styrene block copolymer (SBS), SBS hydrogenated styrene-ethylene-butene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), SIS hydrogenated styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-butadiene copolymer (styrene-butadiene rubber, SBR), styrene-isoprene copolymer, styrene-isobutylene diblock Examples thereof include a copolymer (SIB) and a styrene-isobutylene-styrene triblock copolymer (SIBS).

The (meth) acrylic polymer is a polymer having a repeating unit derived from a (meth) acrylic monomer in the main chain and / or side chain. For example, homopolymers or copolymers of (meth) acrylic monomers, or modified ones thereof may be mentioned. Here, (meth) acryl means acryl or methacryl (the same applies hereinafter).

The amount of the repeating unit derived from the (meth) acrylic monomer in the (meth) acrylic polymer is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70 to 99% by mass with respect to all the repeating units. .
(Meth) acrylic monomers include: (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2- (meth) acrylic acid 2- (Meth) acrylic acid ester having 1 to 20 carbon atoms in the alkyl group such as ethylhexyl; (meth) acrylic acid ester having a reactive functional group such as 2-hydroxyethyl (meth) acrylate.

The polyolefin polymer refers to a polymer having a repeating unit derived from an olefin monomer in the main chain and / or side chain. For example, homopolymers or copolymers of olefinic monomers, or modified ones thereof may be mentioned.
Examples of olefin monomers include ethylene; α-olefins having 3 to 20 carbon atoms such as propylene, 1-butene, 4-methyl-1-pentene, 3-methyl-1-butene, 1-hexene, 1-octene; cyclobutene And cyclic olefins having 4 to 20 carbon atoms such as tetracyclododecene and norbornene; or modified ones thereof.

The polyester polymer is a polymer obtained by polycondensation of a polyvalent carboxylic acid and a polyol, or a modification thereof.
Examples of the polyvalent carboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, succinic acid, adipic acid, sebacic acid, cyclohexanedicarboxylic acid, trimellitic acid and the like. Examples of the polyol include aliphatic alcohols such as ethylene glycol and propylene glycol, and polyether polyols such as polyethylene glycol and polypropylene glycol.

The silicone-based polymer is a polymer having a (poly) siloxane structure in the main chain and / or side chain, or a modification thereof.
Examples of the silicone polymer include dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and the like.

These sealing resins can be used alone or in combination of two or more.
Among these, a rubber-based polymer, a polyolefin-based polymer, and a styrene-based thermoplastic elastomer are preferable as the sealing resin because a sheet-shaped sealing material having a low water vapor transmission rate and excellent sealing properties is easily obtained. A polymer is more preferable.

The number average molecular weight (Mn) of the sealing resin is preferably 100,000 to 2,000,000, more preferably 100,000 to 1,500,000, and still more preferably 100,000 to 1,000,000.
When the number average molecular weight (Mn) of the sealing resin is within the above range, a sheet-like sealing material having sufficient adhesiveness and excellent sealing properties can be obtained.
The number average molecular weight (Mn) of the sealing resin can be obtained as a standard polystyrene equivalent value by performing gel permeation chromatography using tetrahydrofuran as a solvent.

The sealing resin layer may be formed with a crosslinked structure. By forming the cross-linked structure, the sealing resin layer has a sufficient cohesive force, and the sheet-like sealing material has excellent adhesiveness and excellent sealing properties.
When a crosslinked structure is formed in the sealing resin layer, a known crosslinked structure forming method using an adhesive or the like can be used.

For example, when a sealing resin having a hydroxyl group or a carboxyl group is used, a crosslinked structure is formed by using a crosslinking agent such as an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, or a metal chelate crosslinking agent. Can do.

The isocyanate-based crosslinking agent is a compound having an isocyanate group as a crosslinkable group.
As isocyanate-based crosslinking agents, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate; And biuret bodies, isocyanurate bodies, and adduct bodies that are reaction products with low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor oil.

The epoxy-based crosslinking agent is a compound having an epoxy group as a crosslinkable group.
Epoxy crosslinking agents include 1,3-bis (N, N'-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, ethylene glycol diglycidyl ether 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidylaniline, diglycidylamine and the like.

An aziridine-based crosslinking agent is a compound having an aziridine group as a crosslinkable group.
Examples of the aziridine-based crosslinking agent include diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane tri-β-aziridinylpropionate, tetramethylolmethanetri-β-aziridinylpro Pionate, toluene-2,4-bis (1-aziridinecarboxamide), triethylenemelamine, bisisophthaloyl-1- (2-methylaziridine), tris-1- (2-methylaziridine) phosphine, tri And methylolpropane tri-β- (2-methylaziridine) propionate.

Examples of the metal chelate-based crosslinking agent include chelate compounds in which the metal atom is aluminum, zirconium, titanium, zinc, iron, tin, etc. Among them, aluminum chelate compounds are preferable.
Aluminum chelate compounds include diisopropoxy aluminum monooleyl acetoacetate, monoisopropoxy aluminum bis oleyl acetoacetate, monoisopropoxy aluminum monooleate monoethyl acetoacetate, diisopropoxy aluminum monolauryl acetoacetate, diisopropoxy aluminum mono Examples include stearyl acetoacetate and diisopropoxyaluminum monoisostearyl acetoacetate.

These crosslinking agents can be used alone or in combination of two or more.
When a crosslinked structure is formed using these crosslinking agents, the amount used is that the crosslinking group of the crosslinking agent (in the case of a metal chelate crosslinking agent, the metal chelate crosslinking agent) is the hydroxyl group and carboxyl of the sealing resin. The amount is preferably 0.1 to 5 equivalents, more preferably 0.2 to 3 equivalents, based on the group.

Further, when a sealing resin having a polymerizable functional group such as a (meth) acryloyl group is used, a crosslinked structure can be formed by using a photopolymerization initiator or a thermal polymerization initiator.

Examples of the photopolymerization initiator include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin benzoic acid methyl, benzoin dimethyl ketal, 2,4-diethylthioxanthone, 1 -Hydroxycyclohexyl phenyl ketone, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, 2-chloroanthraquinone, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, bis (2,4,6 -Trimethylbenzoyl) -phenyl-phosphine oxide.

Examples of the thermal polymerization initiator include hydrogen peroxide; peroxodisulfates such as ammonium peroxodisulfate, sodium peroxodisulfate, and potassium peroxodisulfate; 2,2′-azobis (2-amidinopropane) dihydrochloride, 4,4 Azo compounds such as' -azobis (4-cyanovaleric acid), 2,2'-azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide Organic peroxides such as lauroyl peroxide, peracetic acid, persuccinic acid, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, and the like.

These polymerization initiators can be used alone or in combination of two or more.
When a crosslinked structure is formed using these polymerization initiators, the amount used is preferably 0.1 to 100 parts by mass and more preferably 1 to 100 parts by mass with respect to 100 parts by mass of the sealing resin.

The content of the sealing resin in the sealing resin layer (including a crosslinked structure when a crosslinked structure is formed) is 50% by mass or more based on the entire sealing resin layer, and is 55 to 95. More preferably, it is more preferably 60 to 90% by weight.

The sealing resin layer may further contain a tackifier.
By including a tackifier in the sealing resin layer, it becomes easy to obtain a sheet-like sealing material that is excellent in moisture barrier properties and excellent in adhesive strength.

A tackifier will not be specifically limited if it improves the adhesiveness of a sealing material, A well-known thing can be used. For example, alicyclic petroleum resin, aliphatic petroleum resin, terpene resin, ester resin, coumarone-indene resin, rosin resin, epoxy resin, phenol resin, acrylic resin, butyral resin, olefin resin, chlorinated olefin resin , Vinyl acetate resins, and these modified resins or hydrogenated resins. Among these, aliphatic petroleum resins, terpene resins, rosin ester resins, rosin resins and the like are preferable.
A tackifier can be used individually by 1 type or in combination of 2 or more types.

The weight average molecular weight of the tackifier is preferably 100 to 10,000, more preferably 500 to 5,000.
The softening point of the tackifier is preferably 50 to 160 ° C, more preferably 60 to 140 ° C, still more preferably 70 to 130 ° C.

Moreover, a commercially available product can be used as it is as a tackifier. For example, commercially available products include aliphatic petroleum resins such as Escolets 1000 Series (Exxon Chemical Co., Ltd.), Quinton A, B, R, CX Series (Zeon Japan Co., Ltd.); Alcon P, M Series (Arakawa Chemical Co., Ltd.) ), ESCOREZ series (manufactured by Exxon Chemical), EASTOTAC series (manufactured by Eastman Chemical), ILARV series (manufactured by Idemitsu Kosan Co., Ltd.); ), Clearon P series (manufactured by Yashara Chemical), picolite A, C series (manufactured by Hercules), etc .; Foal series (manufactured by Hercules), Pencel A series, ester gum, super ester, pine crystal Ester resins such as Arakawa Chemical Industries, etc .;

When the sealing resin layer contains a tackifier, the content of the tackifier in the sealing resin layer is preferably 0.1 to 40% by mass with respect to the entire sealing resin layer, and 1 to 35% by mass. % Is more preferable.

The sealing resin layer may contain other components as long as the effects of the present invention are not hindered.
Other components include additives such as silane coupling agents, antistatic agents, light stabilizers, antioxidants, UV absorbers, resin stabilizers, fillers, pigments, extenders, softeners, getter materials, etc. It is done.
These can be used singly or in combination of two or more.
When the sealing resin layer contains other components, the content thereof is preferably 0.01 to 5% by mass and more preferably 0.01 to 2% by mass with respect to the entire sealing resin layer.

<Requirement (b)>
The sealing resin layer has a thickness (T ₁ ) of 0.1 to 100 μm.
The thickness (T ₁ ) of the sealing resin layer is preferably 0.5 to 50 μm, and more preferably 1 to 10 μm.
It becomes easy to form the sealing resin layer which satisfy | fills relational formula (I) because the thickness of a sheet-like sealing material exists in the said range.

<Requirement (c)>
The sealing resin layer has a water vapor transmission rate (A ₁ ) at a temperature of 40 ° C. and a relative humidity of 90% at a thickness (T ₁ ) of 0.1 to 5,000 g / (m ² · day).
The sealing resin layer preferably has a water vapor transmission rate (A ₁ ) at a temperature of 40 ° C. and a relative humidity of 90% at a thickness (T ₁ ) of 0.5 to 1,000 g / (m ² · day), 1.0 It is more preferably from 500 to 500 g / (m ² · day), and further preferably from 1.0 to 50 g / (m ² · day).
When the water vapor transmission rate (A ₁ ) is within the above range, it becomes easy to form a sealing resin layer that satisfies the relational expression (I).

The water vapor transmission rate (A ₁ ) of the sealing resin layer can be controlled by appropriately selecting the sealing resin to be used and appropriately determining the thickness of the sealing resin layer. For example, a sealing resin layer having a low water vapor transmission rate can be easily formed by containing a large amount of a rubber-based polymer or a polyolefin-based polymer as a sealing resin in the sealing resin layer.
The water vapor transmission rate (A ₁ ) of the sealing resin layer can be measured by the method described in the Examples after actually forming a sealing resin layer having a thickness (T ₁ ).
Further, the water vapor transmission rate (A ₁ ) of the sealing resin layer can also be obtained by a conversion formula. The water vapor transmission rate of the encapsulating resin layer depends on the thickness, and decreases when the thickness is thick, and increases when the thickness is thin. For example, if the thickness of the sealing resin layer is α (μm) and the water vapor transmission rate is β [g / (m ² · day)], the thickness is changed to γ (μm) and the sealing resin layer is When produced, the water vapor transmission rate δ [g / (m ² · day)] is obtained by the following equation.

Thus, if the thickness γ (μm) and the water vapor transmission rate β [g / (m ² · day)] of a certain sealing resin layer are first measured, then the sealing resin layer is expressed as γ in the above formula. by substituting a thickness of (T _1), can be calculated in the sealing resin layer, the value of water vapor permeability at a thickness _{(T 1) (a 1)} .

<Requirement (d)>
A ₁ and T ₁ satisfy the following relational expression (I).

In relational expression (I), A ₁ × (T ₁ ) ² encapsulates an object to be sealed such as an electronic device using the sheet-like sealing material of the present invention comprising one or two or more sealing resin layers. When stopped, this is a parameter related to the amount of moisture entering from the end of the sealing resin layer in the thickness (T ₁ ).

Below, the mode when sealing to-be-sealed bodies, such as an electronic device, using the sheet-like sealing material of this invention, and the derivation | leading-out method of relational expression (I) are used for FIG. 1, FIG. I will explain.

FIG. 1 is a schematic view of an electronic device sealing body (5) obtained by sealing an element (1) using a sheet-like sealing material (4).
1A and 1B are a front view and a top view, respectively, of an electronic device sealing body (5).
An electronic device sealing body (5) includes a substrate (3), an element (1) formed on the substrate (3), and a sheet-like sealing material (4) for sealing the element (1). And a sealing substrate (2).

FIG. 2 is a schematic view of a single sealing resin layer (100) constituting the sheet-like sealing material.
The encapsulating resin layer (100) is an encapsulating resin layer having a two-side length of 1 m (1 × 10 ⁶ μm) and a thickness of T ₁ μm.
Water vapor permeability of the sealing resin layer (100) [passes in a direction from the upper surface (6) to the lower surface (7) of the sealing resin layer (100) (in the direction of arrow (8) in the figure) under a predetermined condition. Water amount] is A ₁ g / (m ² · day), moisture passes in the direction from the first surface (9) to the second surface (10) (the direction of arrow (11) in the figure). The water vapor transmission rate (X) is determined by the following equation.

In addition, since the area of the _first surface is T ₁ × 10 ⁻⁶ m ² , the amount of moisture entering from the first surface [Y (g / day)] is obtained by the following equation.

As shown from the above formula, by obtaining A ₁ × (T ₁ ) ² , it is possible to grasp the degree of moisture intrusion from the end portion of the sealing resin layer in the thickness (T ₁ ). Then, as shown in the _{Examples, A 1 × (T 1)} 2 is sealed to be sealing body such as an electronic device by a sheet-like sealing material made of a sealing resin layer is less than 10,000 In this case, the balance between the function of blocking the moisture entering through the upper and lower surfaces of the sheet-shaped sealing material and the function of blocking the moisture entering from the end of the sheet-shaped sealing material is optimal. Become. Thus, the sheet-like sealing material of the present invention is such that moisture or the like is difficult to enter inside, and has excellent sealing properties.

The lower limit of A ₁ × (T ₁ ) ² is not particularly limited and is preferably as small as possible, but is usually 100 or more. The value of A ₁ × (T ₁ ) ² is preferably 500 or more and less than 10,000, more preferably 500 or more and less than 5,000, and even more preferably 500 or more and less than 3,000.

The value of A ₁ × (T ₁ ) ² can be controlled by appropriately determining the thickness T ₁ and A ₁ of the sealing resin layer within the range of the requirement (b) and the requirement (c) described above. .

The sheet-like sealing material of the present invention comprises one or two or more sealing resin layers. Therefore, it may consist of one sealing resin layer or may consist of two or more sealing resin layers. The upper limit of the number of sealing resin layers is not particularly limited, but is usually 10 layers or less.
When the sheet-like sealing material of the present invention is composed of a plurality of sealing resin layers, all of the plurality of sealing resin layers satisfy the requirements (a) to (d).

When the sheet-like sealing material of the present invention is composed of a plurality of sealing resin layers, as such a sheet-like sealing material, two or more of the same sealing resin layers may be laminated, Two or more different sealing resin layers may be laminated.
Examples of the different sealing resin layers include layers having different sealing resins, components other than the sealing resin, layers having different contents, and the like.

The thickness of the sheet-like sealing material is not particularly limited as long as it satisfies the requirement (b) regarding the sealing resin layer. The thickness of the sheet-like sealing material is usually 0.1 to 500 μm, preferably 0.2 to 300 μm.

The sheet-like sealing material of the present invention is composed of one or two or more sealing resin layers, and this represents a state functioning as a sealing material. That is, the sheet-like sealing material of the present invention may have a layer that is peeled off before use, such as a peeling sheet. When the sheet-like sealing material of the present invention has a release sheet, the water vapor transmission rate and the thickness of the sheet-like sealing material described below are the values excluding the release sheet (sealing resin layer).

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

In addition, although the sheet-form sealing material of this invention consists of 1 or 2 or more sealing resin layers, this represents the state which is functioning as a sealing material. When the sheet-like sealing material of the present invention has a release sheet, the water vapor transmission rate and the thickness of the sheet-like sealing material described below are the values excluding the release sheet (sealing resin layer).

The manufacturing method of the sheet-like sealing material of the present invention is not particularly limited. For example, the sheet-like sealing material of the present invention can be produced using a casting method or an extrusion method.
When the sheet-like sealing material of the present invention is produced by a casting method, for example, a resin composition containing a predetermined component such as a sealing resin is prepared, and this resin composition is prepared by a known method using a release sheet. It is possible to form a sealing resin layer with a release sheet (the sheet-like sealing material of the present invention with a release sheet) by applying to the release-treated surface and drying the obtained coating film.

The resin composition can be prepared by appropriately mixing and stirring predetermined components, a solvent and the like according to a conventional method.
Solvents 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; n-pentane, n-hexane, n- And aliphatic hydrocarbon solvents such as heptane; alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane; and the like.
These solvents can be used alone or in combination of two or more.

The solid content concentration of the resin composition is preferably 10 to 60% by mass, more preferably 10 to 45% by mass, and further preferably 15 to 30% by mass.

Examples of the method for applying the resin composition include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
The drying conditions for drying the coating film include, for example, 80 to 150 ° C. for 30 seconds to 5 minutes.
After performing the drying treatment, the sealing resin layer may be cured by leaving it still for about one week. By curing the sealing resin layer, a crosslinked structure can be sufficiently formed.

After the sealing resin layer is formed, another sheet of release sheet is laminated on the sealing resin layer, whereby a sheet-like sealing material having release sheets as both outermost layers can be obtained.
Moreover, the sheet-like sealing material consisting of two or more sealing resin layers can be obtained by forming a plurality of sealing resin layers and laminating them so that the sealing resin layers face each other. it can.
Also, after forming the sealing resin layer, a sheet-like sealing composed of two or more sealing resin layers can be obtained by applying a resin composition on the sealing resin layer and drying the obtained coating film. A material can be obtained.

When producing the sheet-like sealing material of the present invention by an extrusion molding method, for example, by dry blending a sealing resin and other components, and using this as a raw material, a film is formed by an extrusion film forming method. A sheet-like sealing material can be obtained.
At this time, the sheet-like sealing material which consists of two or more sealing resin layers can be obtained by forming into a film by the multilayer extrusion film forming method.
When manufacturing the sheet-like sealing material of this invention by a multilayer extrusion film forming method, the well-known method used when manufacturing a co-extrusion multilayer film can be utilized.

The sealing resin layer constituting the sheet-like sealing material of the present invention satisfies the above-mentioned requirements (a) to (d), and therefore reduces the amount of moisture entering from the end when used as a sealing material. It is possible. Therefore, the sheet-like sealing material of the present invention has excellent sealing properties, and is suitably used as a sealing material for sealing an electronic device, as will be described later.

2) Sealing sheet The sealing sheet of this invention is a sealing sheet which has the sheet-like sealing material which consists of 1 or 2 or more sealing resin layers, and a gas barrier layer, Comprising: The said sheet-like sealing material is, It is a sheet-like sealing material of the present invention.

The gas barrier layer of the sealing sheet of the present invention is not particularly limited. Examples thereof include a gas barrier layer obtained by implanting ions into a layer containing an inorganic film or a polymer compound, plasma treatment, ultraviolet irradiation treatment, and the like. The “gas barrier layer” is a layer having a property that it is difficult for gas such as air, oxygen, and water vapor to pass therethrough.

The inorganic film is not particularly limited, and examples thereof include an inorganic vapor deposition film.
Examples of the inorganic vapor deposition film include vapor deposition films of inorganic compounds and metals.
As the raw material for the vapor-deposited 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 oxynitrides such as silicon oxynitride; inorganic oxide carbides; inorganic nitride carbides; inorganic oxynitride carbides and the like.
Examples of the raw material for the metal vapor deposition film include aluminum, magnesium, zinc, and tin.
These can be used singly or in combination of two or more.
Among these, an inorganic vapor-deposited film using an inorganic oxide, inorganic nitride or metal as a raw material is preferable from the viewpoint of gas barrier properties, and further, an inorganic material using an inorganic oxide or inorganic nitride as a raw material from the viewpoint of transparency. A vapor deposition film is preferred.

As a method of forming an inorganic vapor deposition film, a PVD (physical vapor deposition) method such as a vacuum vapor deposition method, a sputtering method, or an ion plating method, a thermal CVD (chemical vapor deposition) method, a plasma CVD method, a photo CVD method, etc. The CVD method is mentioned.

Examples of the polymer compound used for the layer containing the polymer compound (hereinafter sometimes referred to as “polymer layer”) include polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, Examples include polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin polymer, aromatic polymer, and silicon-containing polymer compound. These polymer compounds can be used alone or in combination of two or more.
Among these, a silicon-containing polymer compound is preferable from the viewpoint of forming a gas barrier layer having excellent gas barrier properties. A well-known thing can be used as a silicon-containing high molecular compound. Examples thereof include polysilazane compounds, polycarbosilane compounds, polysilane compounds, and polyorganosiloxane compounds. Among these, a polysilazane compound is preferable.

The polysilazane compound is a polymer compound having a repeating unit represented by (—Si—N—) in the molecule, and examples thereof include organic polysilazane, inorganic polysilazane, and modified polysilazane.
As the polysilazane compound, a commercially available product as a glass coating material or the like can be used as it is.
Polysilazane compounds can be used alone or in combination of two or more.

The polymer layer may contain other components in addition to the above-described polymer compound as long as the object of the present invention is not impaired. Examples of other components include curing agents, other polymers, anti-aging agents, light stabilizers, and flame retardants.

As a method for forming a polymer layer, for example, a known device such as a spin coater, a knife coater, a gravure coater, or the like is used to form a layer forming solution containing at least one kind of a polymer compound, and optionally other components and a solvent. The method of using and apply | coating and forming the coating film obtained by drying moderately is mentioned.

As ions implanted into the inorganic film or polymer layer, 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 gases such as methane and ethane; Ions of alkene gases such as ethylene and propylene; Ions of alkadiene gases such as pentadiene and butadiene; Ions of alkyne gases such as acetylene; Benzene, toluene, etc. Ions of aromatic hydrocarbon gases such as: ions of cycloalkane gases such as cyclopropane; ions of cycloalkene gases such as cyclopentene; ions of metals; ions of organosilicon compounds;
These ions can be used alone or in combination of two or more.
Among these, ions of rare gases such as argon, helium, neon, krypton, and xenon are preferable because ions can be more easily implanted and a gas barrier layer having particularly excellent gas barrier properties can be obtained.

The method for implanting ions is not particularly limited. For example, there are a method of irradiating ions accelerated by an electric field (ion beam), a method of implanting ions in plasma (plasma ion implantation method), etc., and a gas barrier film can be easily obtained. Plasma ion implantation is preferred. Specifically, the plasma ion implantation method generates plasma in an atmosphere containing a plasma generating gas and applies a negative high-voltage pulse to an inorganic film or a polymer layer, thereby generating ions (positive ions) in the plasma. Ion) is injected into the surface of the inorganic film or polymer layer.

In the sealing sheet of the present invention, the thickness of the gas barrier layer is not particularly limited. From the viewpoint of gas barrier properties and handleability, it is usually in the range of 10 to 2000 nm, preferably 20 to 1000 nm, more preferably 30 to 500 nm, and still more preferably 40 to 200 nm.
Further, the arrangement position of the gas barrier layer is not particularly limited, and may be formed directly on the sealing resin layer or may be formed through another layer.

The sealing sheet of the present invention is a sealing sheet having a sheet-shaped sealing material composed of one or more sealing resin layers and a gas barrier film, wherein the sheet-shaped sealing material is the sheet of the present invention. What is a shape sealing material is mentioned.
The gas barrier film is formed by forming a gas barrier layer on a base film directly or via another layer.
In a sealing sheet having a sheet-shaped sealing material composed of one or more sealing resin layers and a gas barrier film, the sheet-shaped sealing material is preferably laminated on the gas barrier layer side surface of the gas barrier film. .

Base film includes polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin A resin film such as a polymer, an aromatic polymer, or a polyurethane polymer can be used.
The thickness of the base film is not particularly limited, but is preferably 0.5 to 500 μm, more preferably 1 to 200 μm, and further preferably 5 to 100 μm from the viewpoint of ease of handling.

As a gas barrier layer of a gas barrier film, the thing similar to what was demonstrated previously is mentioned. Moreover, the preferable thickness of the gas barrier layer of a gas barrier film is also the same value as what was demonstrated previously.
The gas barrier layer may be a single layer or a plurality of layers.

The gas barrier film may further have other layers such as a protective layer, a conductor layer, and a primer layer. The position where these layers are laminated is not particularly limited.

Of the gas barrier film, the temperature 40 ° C., water vapor permeability at 90% relative humidity, preferably 0.1g ^/ (m 2 · day) or ^{less, 0.05g / (m 2 · day} ) , more preferably less, 0.005 g / (M ² · day) or less is more preferable.
When the water vapor transmission rate is 0.1 g / (m ² · day) or less, the amount of water passing through the upper and lower surfaces of the sheet-shaped sealing material can be sufficiently reduced.
The water vapor permeability of the gas barrier film can be measured using a known gas permeability measuring device.

The total light transmittance of the gas barrier film is preferably 80% or more, and more preferably 85% or more.
When the total light transmittance of the gas barrier film is 80% or more, the sealing sheet of the present invention can be suitably used as a sealing material for an element formed on a transparent substrate that requires transparency. .
The total light transmittance of the gas barrier film can be measured using a known integrating sphere light transmittance measuring device in accordance with JIS K7105-1981.

The thickness of the gas barrier film is not particularly limited. From the viewpoint of gas barrier properties and handling properties, it is usually in the range of 0.5 to 500 μm, preferably 1 to 100 μm, more preferably 5 to 50 μm.

Examples of the method for producing the sealing sheet of the present invention using a gas barrier film include the following production method 1 and production method 2.

(Manufacturing method 1)
First, a release sheet is prepared, and a resin composition for forming a sealing resin layer is applied onto the release-treated surface of the release sheet, and the resulting coating film is dried to form a sheet-like sealing material By doing, the sheet-like sealing material with a release sheet (the sheet-like sealing material of this invention with a release sheet) is obtained. Subsequently, the sealing sheet with a peeling sheet can be obtained by laminating | stacking the obtained sheet-like sealing material with a peeling sheet and a gas barrier film.
The method for laminating the sheet-shaped sealing material with release sheet and the gas barrier film is not particularly limited. For example, a sheet-like sealing material with a release sheet and a gas barrier film can be laminated and pressed by using a roller or the like. When pressing, it may be performed at room temperature or while heating. When pressing while heating, the temperature is not particularly limited, but is usually 150 ° C. or lower.

(Manufacturing method 2)
First, a gas barrier film is prepared, and a resin composition for forming a sealing resin layer is applied onto the gas barrier layer of the gas barrier film by a known method, and the obtained coating film is dried to form a sheet-like sealing By forming the material, a target sealing sheet can be obtained. Moreover, after forming a sealing sheet, in order to protect the sheet-like sealing material of the obtained sealing sheet, by laminating | stacking a peeling sheet on this sheet-like sealing material, sealing with a peeling sheet A sheet can be obtained.

As the resin composition for forming the sealing resin layer used in the production methods 1 and 2, the coating method of the resin composition, the drying conditions, etc., the resin composition described above in the sheet-like sealing material, The same coating method, drying conditions and the like can be mentioned.
Moreover, you may form the sheet-like sealing material which has a some sealing resin layer with the method similar to what was shown with the manufacturing method of the sheet-like sealing material of this invention.

The sealing sheet of the present invention has a sheet-like sealing material in which moisture hardly enters from an end portion and a gas barrier layer having excellent gas barrier properties. Therefore, the sealing sheet of the present invention is particularly excellent in both the performance of blocking moisture passing through the upper and lower surfaces of the sealing sheet and the performance of blocking moisture entering from the end of the sheet-shaped sealing material. Therefore, it has excellent sealing properties. Therefore, the sealing sheet of this invention is used suitably when sealing an electronic device so that it may mention later.

3) Electronic device sealing body The electronic device sealing body of the present invention is obtained by sealing an electronic device with the sheet-shaped sealing material of the present invention or the sealing sheet of the present invention.

As an electronic device sealing body of the present invention, for example, an electronic device sealing comprising a transparent substrate, an element formed on the transparent substrate, a sealing material for sealing the element, and a sealing base material The sealing material is a sheet-like sealing material of the present invention, or a transparent substrate, an element formed on the transparent substrate, and a seal laminated so as to cover the element An electronic device sealing body provided with a stop sheet, wherein the sealing sheet is the sealing sheet of the present invention.

Electronic devices include organic devices such as organic transistors, organic memories, and organic EL devices; liquid crystal displays; electronic paper; thin film transistors; electrochromic devices; electrochemiluminescence devices; touch panels; solar cells; Device; and the like.

As elements, elements that convert electric energy into light (light emitting diodes, semiconductor lasers, etc.), and photoelectric conversion elements that are elements that convert light into electric energy (photodiodes, solar cells, etc.); organic EL elements, etc. And the like.
There are no particular restrictions on the type, size, shape, number, etc. of the elements formed on the transparent substrate.

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

A transparent conductive layer may be provided on the transparent substrate. The sheet resistance of the transparent electrode layer is preferably 500Ω / □ or less, and more preferably 100Ω / □ or less.
As the material for forming the transparent conductive layer, known materials can be used. Specifically, indium-tin composite oxide (ITO), fluorine-doped tin oxide (IV) SnO2 (FTO), oxidation Examples thereof include tin (IV) SnO ₂ , zinc (II) ZnO, and indium-zinc composite oxide (IZO).
These materials can be used alone or in combination of two or more.

4) Organic EL element The organic EL element of the present invention comprises a sheet-like sealing material comprising a first electrode, an organic EL layer, a second electrode, and one or two or more sealing resin layers on a transparent substrate. An organic EL element having a stop base material in this order, wherein the sheet-like sealing material is the sheet-like sealing material of the present invention (organic EL element 1), on a transparent substrate An organic EL element having a first electrode, an organic EL layer, a second electrode, a sheet-shaped sealing material composed of one or more sealing resin layers, and a gas barrier layer in this order, What is characterized in that the sealing material is the sheet-like sealing material of the present invention (organic EL element 2), or on the transparent substrate, the first electrode, the organic EL layer, the second electrode, 1 Or the organic EL element which has a sheet-like sealing material which consists of two or more sealing resin layers, and a gas barrier film in this order And the said sheet-like sealing material is the sheet-like sealing material of this invention (organic EL element 3).

As the transparent substrate, the first electrode, the organic EL layer, the second electrode, and the sealing substrate constituting the organic EL elements 1 to 3 of the present invention, conventionally known materials can be appropriately used. In particular, it is preferable to use a sealing substrate selected from the above-described transparent substrate, gas barrier layer, and gas barrier film.
As the gas barrier layer and the gas barrier film constituting the organic EL elements 2 and 3 of the present invention, those similar to the gas barrier layer and the gas barrier film of the sealing sheet of the present invention can be used.

The sealing resin layer constituting the organic EL element of the present invention satisfies the requirements (a) to (d). Therefore, the organic EL element of the present invention has a configuration excellent in sealing properties.
Since it becomes easy to become the structure which is excellent in sealing performance, what contains the rubber-type polymer for at least 1 layer of a sealing resin layer is preferable.

The organic EL element of this invention can be formed using the sheet-like sealing material or sealing sheet of this invention mentioned above.
The manufacturing method of the organic EL element of the present invention is not particularly limited. For example, after preparing the first electrode, the organic EL layer, and the second electrode on a transparent substrate by a known method, the sheet-shaped sealing material of the present invention is placed, and a sealing substrate is formed thereon. The organic EL element of the present invention can be obtained by placing materials and bonding them by thermocompression bonding. Also, the organic EL element of the present invention can be obtained by laminating the sealing sheet of the present invention after preparing the first electrode, the organic EL layer, and the second electrode on the transparent substrate by a known method. Can be obtained.

Since the organic EL element of the present invention has a sheet-like sealing material or sealing sheet with excellent sealing properties, even if time elapses, the light emitting characteristics such as light emission luminance, light emission efficiency, and light emission uniformity are obtained. It is difficult to decrease.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
Unless otherwise indicated, the part and% in each example are based on mass.

(Compound)
The compounds and materials used in each example are shown below.
Sealing resin (1): copolymer of isobutylene and isoprene (manufactured by Nippon Butyl Co., Exxon Butyl 268, number average molecular weight 260,000, isoprene content 1.7 mol%)
Sealing resin (2): polyisoprene rubber having a carboxylic acid functional group (manufactured by Kuraray Co., Ltd., LIR410, number average molecular weight 30,000, average number of carboxyl groups per molecule: 10)
Sealing resin (3): styrene-isobutylene-butylene copolymer (manufactured by Kaneka Corporation, SIBSTAR 062M)
Sealing resin (4): Isoprene rubber (Clayton, Califlex IR310)
Sealing resin (5): Styrenic thermoplastic elastomer (SEBS) (manufactured by Nippon Zeon Co., Ltd., Quinton G1726)
Sealing resin (6): polyisoprene rubber containing methacryloyl group (manufactured by Kuraray Co., Ltd., UC-203)

The number average molecular weight of the sealing resin was obtained as a standard polystyrene equivalent value by performing gel permeation chromatography under the following conditions.
Equipment: HLC-8020 manufactured by Tosoh Corporation
Column: manufactured by Tosoh Corporation, TSK guard column HXL-H, TSK gel GMHXL (× 2), TSK gel G2000HXL
Column temperature: 40 ° C
Developing solvent: Tetrahydrofuran Flow rate: 1.0 mL / min

Tackifier (1): Aliphatic petroleum resin (manufactured by Nippon Zeon Co., Ltd., Quinton A100, softening point 100 ° C.)
The softening point of the tackifier (1) was measured according to JIS K2531.

Crosslinking agent (1): (epoxy compound, manufactured by Mitsubishi Chemical Corporation, TC-5)
Polymerization initiator (1): Phosphorous photopolymerization initiator (BASF, Lucirin TPO)
Release sheet (1): Polyethylene terephthalate film subjected to silicone release treatment (SP-PET381130, thickness 38 μm, manufactured by Lintec Corporation)
Release sheet (2): Silicone release-treated polyethylene terephthalate film (Lintec Corp., SP-PET38T103-1, thickness 38 μm)

[Production Example 1] Resin composition A
100 parts of the sealing resin (1), 5 parts of the sealing resin (2), 20 parts of the tackifier (1) and 1 part of the crosslinking agent (1) are dissolved in toluene, and the resin composition A has a solid content concentration of 25%. Got.

[Production Example 2] Resin composition B
100 parts of the sealing resin (3) and 10 parts of the tackifier (1) were dissolved in toluene to obtain a resin composition B having a solid content concentration of 25%.

[Production Example 3] Resin composition C
100 parts of the sealing resin (4) and 20 parts of the tackifier (1) were dissolved in toluene to obtain a resin composition C having a solid content concentration of 25%.

[Production Example 4] Resin composition D
100 parts of the sealing resin (5) and 20 parts of the tackifier (1) were dissolved in toluene to obtain a resin composition D having a solid content concentration of 25%.

[Production Example 5] Resin composition E
100 parts of the sealing resin (6) and 5 parts of the polymerization initiator (1) were dissolved in toluene to obtain a resin composition E having a solid content concentration of 25%.

[Production Example 6] Resin composition F
100 parts of the sealing resin (2), 20 parts of the tackifier (1) and 1 part of the crosslinking agent (1) were dissolved in toluene to obtain a resin composition F having a solid content concentration of 25%.

[Production Example 7] Gas barrier film A polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., Cosmo Shine A4100, thickness 50 μm) is used as a base film, and a polysilazane compound (perhydropolysilazane is the main component) A coating material (Clariant Japan, Aquamica NL110-20) is applied by spin coating, and the resulting coating is heated at 120 ° C. for 1 minute to form a polysilazane layer having a thickness of 150 nm and containing perhydropolysilazane. Next, argon (Ar) was ion-implanted into the surface of the polysilazane layer using a plasma ion implantation apparatus under the following conditions to form a gas barrier layer, thereby producing a gas barrier film.

The plasma ion implantation apparatus and ion implantation conditions used for forming the gas barrier layer are as follows.
(Plasma ion implantation system)
RF power source: 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 generation gas: Ar
Gas flow rate: 100sccm
Duty ratio: 0.5%
Applied voltage: -15 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): 200 seconds

[Examples 1 to 22, Comparative Examples 1 to 23]
The resin compositions A to D and F obtained in Production Examples 1 to 4 and 6 are provided on the release-treated surface of the release sheet (1), and the thicknesses after drying are shown in Tables 1 to 4 and Table 6. Each of the sealing resin layers was coated to have a thickness (T ₁ ), and the obtained coating film was dried at 120 ° C. for 2 minutes to form a sealing resin layer. Next, the release sheet (2) was bonded to the sealing resin layer on the release treatment surface to obtain a sheet-like sealing material in which the release sheets were laminated on both sides.

The resin composition E obtained in Production Example 5 was coated on the release sheet (1) so as to have the thickness (T ₁ ) of the sealing resin layer described in Table 5, and the resulting coating film was obtained. Was dried at 120 ° C. for 2 minutes, and then a release sheet (2) was bonded to obtain a bonded body. Next, the obtained bonded body was irradiated with ultraviolet rays from the release sheet (1) side using a metal halide lamp (ultraviolet irradiation conditions: illuminance: 400 mW / cm ² , light amount: 1000 mJ / cm ² , illuminance / light meter (eye UV-PF 36)) manufactured by Graphics Co., Ltd.) was cured to obtain a sheet-like sealing material having release sheets laminated on both sides.

(Water vapor transmission rate measurement)
The release sheets (1) and (2) of the sheet-like sealing material obtained by laminating release sheets on both sides obtained in Examples 1 to 22 and Comparative Examples 1 to 23 were each peeled off, and the resulting two sheets of polyethylene A sample for measuring water vapor transmission rate was obtained by sandwiching with a terephthalate film (manufactured by Mitsubishi Plastics, thickness 6 μm). Subsequently, the water vapor transmission rate at a temperature of 40 ° C. and a relative humidity of 90% was measured using a water vapor transmission rate measuring device (manufactured by LYSSY, L80-5000).
The water vapor permeability (A ₁ ) of the sealing resin layer, the thickness (T ₁ ) of the sealing resin layer, and the value of A ₁ × (T ₁ ) ² are shown in Tables 1 to 6, respectively.

(Moisture penetration test)
Except that the thickness of the sealing resin layer was changed to a predetermined thickness (1 to 50 μm), a sealing material with a release sheet was obtained using the resin compositions A to F by the same method as described above.
A calcium layer having a thickness of 35 mm and a width of 35 mm and a thickness of 100 nm was formed on an alkali-free glass substrate (Corning Corp., 45 mm × 45 mm) by vacuum deposition.
The release sheet is peeled from the release sheet-attached sealing material, and the exposed sheet-like sealing material and the aluminum foil surface of the sealing base material (sheet obtained by laminating a 7 μm aluminum foil on a 38 μm thick PET film) are opposed to each other. Then, the laminate was laminated using a laminator to prepare a laminate of a sealing substrate and a sheet-like sealing material. Next, the release sheet is peeled from the laminate of the sealing substrate and the sheet-shaped sealing material, and the calcium layer on the glass substrate and the sheet-shaped sealing material are bonded using a laminator in a nitrogen atmosphere. A test piece for moisture penetration test in which the layer was sealed was obtained.
The obtained test piece is allowed to stand for 170 hours in an environment of a temperature of 60 ° C. and a relative humidity of 90%, and the rate of discoloration of the calcium layer (the rate of moisture ingress) is visually confirmed. evaluated. The evaluation results are shown in Tables 1 to 6.

〔Evaluation criteria〕
A: The area of the discolored calcium layer is less than 20% of the whole B: The area of the discolored calcium layer is 20% or more of the whole

(Durability evaluation of organic EL elements)
After the glass substrate was washed with a solvent and then subjected to UV / ozone treatment, aluminum (Al) (manufactured by Kojundo Chemical Laboratory Co., Ltd.) was deposited on the surface at a rate of 100 nm at a rate of 0.1 nm / s to form a cathode 1 electrode).
On the obtained cathode (Al film), (8-hydroxy-quinolinolate) lithium (manufactured by Luminescence Technology) was added to 10 nm, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (manufactured by Luminescence Technology). ) 10 nm, Tris (8-hydroxy-quinolinate) aluminum (manufactured by Luminescence Technology) 40 nm, N, N′-bis (naphthalen-1-yl) -N, N′-bis (phenyl) -benzidene (Lumescence Technology) Were sequentially deposited at a rate of 60 nm and a rate of 0.1 to 0.2 nm / s to form a light emitting layer (organic EL layer).
On the obtained light emitting layer, an indium tin oxide (ITO) film (thickness: 100 nm, sheet resistance: 50Ω / □) was formed by a sputtering method to produce an anode (second electrode). Note that the degree of vacuum during the deposition is 1 × 10 ⁻⁴ Pa or less.

Next, a sealing material with a release sheet similar to that used in the moisture penetration test is prepared, and the sheet-like sealing material obtained by peeling the double-sided release sheet is used in a nitrogen atmosphere using a hot plate. After drying by heating at 120 ° C. for 10 minutes, the mixture was allowed to stand and cooled to room temperature.
Next, a sheet-like sealing material is placed so as to cover the first electrode, the organic EL layer, and the second electrode formed on the glass substrate, and the gas barrier layer is opposed to the second electrode side thereon. Thus, a gas barrier film was placed, thermocompression bonded at 100 ° C., and sealed to obtain a top emission type electronic device (organic EL element).
Next, after leaving the organic EL element for 200 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50%, the organic EL element is activated, and the presence or absence of dark spots (non-light emitting portions) is observed and evaluated according to the following criteria: did. The evaluation results are shown in Tables 1 to 6.

〔Evaluation criteria〕
A: There was no dark spot, or it occurred in less than 5% of the light emitting area.
B: Dark spots occurred in 5% or more and less than 10% of the light emitting area.
C: Dark spots were generated in 10% or more and less than 90% of the light emitting area.
D: Dark spots were generated in 90% or more of the light emitting area.

From Tables 1 to 6, the following can be understood.
The sheet-like sealing material of the present invention in which A ₁ × (T ₁ ) ² is less than 10,000 is from the end of the sheet-like sealing material as shown in the moisture penetration test using a calcium layer. Moisture penetration is sufficiently suppressed. In addition, the organic EL sealed with the sheet-like sealing material of the present invention is excellent in durability because the occurrence of dark spots is suppressed to less than 10% of the light emitting area.
On the other hand, in the sheet-shaped sealing material having A ₁ × (T ₁ ) ² of 10,000 or more, the moisture is easy from the end of the sheet-shaped sealing material as shown in the moisture penetration test using the calcium layer. The organic EL sealed with such a sheet-like sealing material has many dark spots and is inferior in durability.

DESCRIPTION OF SYMBOLS 1 ... Element 2 ... Sealing base material 3 ... Transparent substrate 4 ... Sheet-like sealing material 5 ... Electronic device sealing body 6 ... Upper surface 7 of sealing resin layer ... The bottom surface 8 of the sealing resin layer ... the direction of moisture passage 9 when measuring the water vapor transmission rate of the sealing resin layer ... the first surface 10 ... the second surface 11 ... from the end of the sealing resin layer Moisture ingress direction 100 when moisture enters, sealing resin layer

Claims (10)

A sheet-like sealing material comprising one or more sealing resin layers,
The encapsulating resin layer satisfies the following (a) to (d): a sheet-like encapsulating material (provided that the sheet-like encapsulating material comprises a plurality of encapsulating resin layers; All of the sealing resin layers satisfy the requirements (a) to (d)).
(A) The sealing resin layer contains 50% by mass or more of the sealing resin with respect to the entire layer.
(B) The sealing resin layer has a thickness (T ₁ ) of 0.1 to 100 μm.
(C) The sealing resin layer has a water vapor transmission rate (A ₁ ) of 0.1 to 5,000 g / (m ² · day) at a temperature of 40 ° C. at a thickness (T ₁ ) and a relative humidity of 90%. .
; (D) _{A 1} and _{T 1} is, satisfies the following relational expression (I).

The sheet-like sealing material according to claim 1, wherein at least one of the sealing resin layers contains at least one selected from a rubber-based polymer, a polyolefin-based polymer, and a styrene-based thermoplastic elastomer. The sheet-like sealing material according to claim 1, which is used for sealing an electronic device. A sealing sheet having a sheet-like sealing material composed of one or more sealing resin layers and a gas barrier layer,
The said sheet-like sealing material is the sheet-like sealing material of Claim 1, The sealing sheet characterized by the above-mentioned. The sealing sheet according to claim 4, comprising the sheet-like sealing material and a gas barrier film in which the gas barrier layer is formed directly or via another layer on the base film. The sealing sheet according to claim 4, which is used for sealing an electronic device. The electronic device sealing body by which an electronic device is sealed with the sheet-like sealing material of Claim 1, or the sealing sheet of Claim 4. An organic EL element having a first electrode, an organic EL layer, a second electrode, a sheet-like sealing material composed of one or more sealing resin layers, and a sealing substrate in this order on a transparent substrate. And
The said sheet-like sealing material is the sheet-like sealing material of Claim 1, The organic EL element characterized by the above-mentioned. The organic EL element according to claim 8, wherein the sealing substrate has a gas barrier layer. 9. The sealing substrate according to claim 8, wherein the sealing substrate has a gas barrier film, and the gas barrier film is formed by forming a gas barrier layer on the substrate film directly or via another layer. Organic EL element.

Images