JP5113494B2 - Device sealing material, sealed device and manufacturing method thereof - Google Patents

Description

  The present invention relates to a device sealing material comprising a laminate layer having a layer (B) obtained by irradiating an unsaturated carboxylic acid metal salt with energy rays, a device sealed using the same, and a method for producing the same About.

In order to prevent damage to devices such as organic EL and solar cells, sealing for insulating from the atmosphere is performed. In particular, organic EL easily forms damaged portions called dark spots due to moisture.
Conventionally, various proposals have been made to prevent the occurrence of dark spots. For example, it has been proposed that a moisture-proof material such as zeolite is accommodated in a hermetic seal when a glass plate is sealed (Japanese Patent Laid-Open No. 10-275679).
In addition, as a drying member for preventing the organic EL material from being damaged by moisture, an organometallic compound such as aluminum oxide octylate (JP 2002-33187, JP 2005-298598, JP 2006-297380), activated alumina as a moisture-proof agent Molecular sieves, calcium oxide and barium oxide (Japanese Patent Laid-Open No. 2006-66366) are known.

JP-A-10-275679 (Claims) JP 2002-33187 (Claims) JP-A-2005-298598 (Claims) JP 2006-297380 (Claims) JP 2006-66366 (Claims)

  The present invention provides a device sealing material that has a dehumidifying effect and can prevent the occurrence of dark spots in organic EL, and can seal various other devices, a device sealed by the device, and a method for manufacturing the device To do.

That is, this invention relates to the device sealing material which consists of a laminated body (C) which has a moisture-proof layer (B) obtained by irradiating an energy ray to a base material layer (A) and unsaturated carboxylic acid metal salt.
Moreover, this invention uses the laminated body (C) which has a moisture-proof layer (B) obtained by irradiating an energy beam to a base material layer (A) and unsaturated carboxylic acid metal salt, and the moisture-proof layer (B) is used. The present invention relates to a method for manufacturing a sealed device characterized in that the device is accommodated inside and sealed.
Furthermore, in the present invention, when the device is housed and sealed, the moisture content of the moisture-proof layer (B) is lower than the moisture content that is in equilibrium with the water vapor pressure in the system where it is placed. The present invention also relates to a method for producing a sealed device, wherein the device is housed and sealed with a moisture-proof layer (B) inside.

Further, the present invention provides a device sealing wherein the moisture-proof layer (B) is obtained by irradiating an energy ray to a coating solution containing a metal alkoxide and / or a hydroxyl group-containing polymer together with an unsaturated carboxylic acid metal salt. The present invention relates to a method for manufacturing a material or a device.
Furthermore, the present invention is a device material or device characterized in that the moisture-proof layer (B) is in a state in which a part or all of the moisture contained in the moisture-proof layer (B) is preliminarily heat-treated. It relates to the manufacturing method.
Furthermore, this invention relates to the manufacturing method of the device sealing material or device characterized by the laminated body (C) having the base material layer (A) which consists of a thermoplastic resin layer and an inorganic thin film layer.

  According to the present invention, it is possible to provide a sealing material suitable for sealing other devices in addition to preventing the occurrence of dark spots in organic EL.

The laminate (C) used in the present invention has a moisture-proof layer (B) obtained by irradiating the base layer (A) and the unsaturated carboxylic acid metal salt with energy rays.
Base material layer (A)
Examples of the base material layer (A) include molded products of various shapes such as plates, sheets, films made of organic materials such as synthetic resins, metals, semiconductors, and inorganic materials such as glass.
Synthetic resins include polyester, polycarbonate, polyarylate, polyamide, polyimide, polyolefin, polyether, etc., polyethylene terephthalate, polyethylene naphthalate, polylactic acid, polyglycolic acid, polycarbonate, polysulfone, polymethyl methacrylate, polycarbonate, Examples thereof include transparent resins such as polyarylate, polyacetate, 6-nylon, aromatic nylon, polycycloolefin copolymer, and polypropylene.
Among these, materials suitable for forming films and the like include polyolefin resins such as polyethylene, polypropylene, poly-4-methyl-1-pentene copolymer, polycycloolefin copolymer, polystyrene, polyethylene terephthalate, polylactic acid. Translucent resins such as polyglycolic acid, polysulfone, polyether sulfone, polyester, polymethyl methacrylate, polycarbonate, polyarylate, polyacetate, and polyamide resin are suitable. These films may be unstretched or uniaxial or biaxial stretched films.
On the other hand, examples of the inorganic material include aluminum, copper, silicon, aluminum oxide, glass, and paper.
The base material layer (A) has various shapes such as a plate shape, a sheet shape, and a film shape according to the type and use of the device. The thickness in the case of a sheet is about 250 microns (μm) to 5 millimeters (mm), and the thickness in the case of a film is usually about 10 μm to 250 μm. These can be determined in consideration of the self-supporting property, handling, impact resistance, etc. of the laminate (C) depending on the application to be used.
When the gas barrier property of the base material layer (A) is insufficient, other layers of materials having excellent gas barrier properties are also laminated. For example, laminating aluminum foil or flexible glass can be used. In particular, when a synthetic resin film is used, it is desirable to laminate the inorganic thin film layer (D).

Inorganic thin film layer (D)
The inorganic thin film layer (C) is made of an oxide such as silicon, aluminum, titanium, zirconium, tin, magnesium, nitride, fluoride alone, or a composite thereof. In particular, aluminum oxide is colorless and transparent, It has excellent characteristics such as boil and retort resistance and can be used in a wide range of applications.

  The method for forming the inorganic thin film layer (C) is not particularly limited, and a known method can be used. For example, there is a method of forming a film by sputtering or CVD. These inorganic thin film layers are preferably formed after undercoating such as epoxy acrylate or urethane acrylate on the base material layer (A).

Moreover, in order to obtain the inorganic thin film excellent in surface smoothness, it is preferable that the surface of the base material layer (A) and an inorganic atom or compound in the formation of the inorganic thin film are promptly performed. In order to perform these bonding reactions quickly, it is desirable that the inorganic atom or compound is a chemically active molecular species or atomic species.
Therefore, the chemical vapor deposition method (CVD method) is desirable as the film forming method. Thereby, the surface of the base material layer (A) and the chemically active molecular species containing silicon such as silicon nitride and silicon oxynitride react quickly, thereby smoothing the surface of the inorganic thin film layer (C). It is expected that the properties will be improved and the number of pores can be reduced.

Among the CVD methods, when a so-called catalytic CVD method (Cat-CVD) is performed in which gas molecules are decomposed and activated by a heating element to form a film on a substrate, a dense transparent inorganic thin film is obtained and excellent gas barrier properties are obtained. can get. Further, it is more desirable because a transparent film having lower stress, that is, a flexible film can be formed.
The film thickness of the inorganic thin film layer (C) in the present invention is usually from 5 to 500 nm, more preferably from 10 to 200 nm, from the viewpoints of gas barrier performance and bending resistance to gas barrier performance.

Moisture-proof layer (B)
The moisture-proof layer (B) is obtained by irradiating an unsaturated carboxylic acid metal salt with energy rays.
The moisture-proof layer (B) is a layer that prevents the humidity of the system from rising and has performances such as moisture absorption and water absorption. As the unsaturated carboxylic acid of the unsaturated carboxylic acid metal salt to be used, a carboxylic acid having an α, β-ethylenically unsaturated group such as acrylic acid, methacrylic acid, maleic acid and itaconic acid is preferable, and the degree of polymerization is It is desirable that it is less than 20, preferably 10 or less.
Examples of these metal salts include alkali metals such as sodium and potassium, and salts of divalent or higher metals such as magnesium, calcium, barium, zinc, copper, cobalt, nickel, aluminum, and iron.
In the present invention, as the unsaturated carboxylic acid metal salt, one kind of these metal salts may be used, or two or more kinds may be used in combination as required.

  The unsaturated carboxylic acid metal salt of the present invention is generally used in the form of a solution, and it is desirable to use it as an aqueous solution. Various additives such as a lubricant, a slip agent, an anti-blocking agent, an antistatic agent, an antifogging agent, a pigment, and a dye may be added to the base layer as long as the purpose is not impaired. In order to improve the wettability between (A) and the undercoat layer, various surfactants and the like may be added.

The moisture-proof layer (B) is preferably prepared by irradiating an energy ray to a coating solution containing not only an unsaturated carboxylic acid metal salt but also a metal alkoxide and / or a hydroxyl group-containing polymer.
When a metal alkoxide is used in combination, the gas barrier property of the moisture-proof layer (B) is improved. Moreover, when a hydroxyl group-containing polymer is used in combination, flexibility can be imparted to the moisture-proof layer (B) and gas barrier properties under low humidity can be improved.

A metal alkoxide metal alkoxide, tetraethoxysilane [Si _{(OC 2} H _{5) 4],} triisopropoxyaluminum [Al _{(OC 3} H _{7) 3],} tri-n-propoxy aluminum _{[Al (O-n-C 3} H _{7) 3],} tri isopropoxide aluminum _{[Al (O-i-C 3} H 7) 3 ], tri-n-butoxy aluminum _{[Al (O-n-C 4} H 9) 3 ], tri isobutoxy aluminum Al (O _-i-C 4 _{H 9) 3],} tetramethoxy titanium [Ti _{(OCH 3) 4]} in the general formula M (OR) n (wherein such, M is Si, Ti, AL, metals such as Zr, R is an alkyl group having about 1 to 5 carbon atoms such as methyl, ethyl, etc.) and a decomposition product thereof.
Of these, tetraethoxysilane and triisopropoxyaluminum are preferable.
These metal alkoxides are used in combination in a ratio of about 1 to 50% by weight based on the weight of the unsaturated carboxylic acid metal salt in terms of weight in terms of metal oxide.

Hydroxyl-containing polymers Hydroxyl-containing polymers include natural or synthetic homopolymers and copolymers, such as polyvinyl alcohols, vinyl alcohol polymers such as hydrolysates of ethylene vinyl acetate copolymers, homopolymers of glycerol methacrylate, and glycerol acrylates. Examples thereof include homopolymers and copolymers of glycerol methacrylate and glycerol acrylate.
Of these, vinyl alcohol polymers are preferred.
The vinyl alcohol polymer is a polymer mainly composed of vinyl alcohol, and is usually a polymer obtained by saponifying polyvinyl acetate, and may contain 19 mol% or less of ethylene. Such a vinyl alcohol polymer usually has a degree of polymerization of about 100 to 3,000. Further, the saponification degree is about 70 to 99.9%, and those having a high saponification degree are suitable.

The vinyl alcohol polymer is preferably further modified.
Examples of the modified vinyl alcohol polymer include those obtained by adding various reactive groups (reactive groups) having a variety of known reactivity to the vinyl alcohol polymer, and by modifying the reactive groups by bonding or esterification. Examples include saponified copolymers obtained by copolymerizing vinyl esters such as vinyl and unsaturated compounds having reactive groups, and are particularly limited as long as they have reactive groups in the molecule. Not done.

Examples of such reactive vinyl alcohol polymer reactive groups include (meth) acrylate groups, (meth) acryloyl groups, (meth) acrylamide groups, vinyl groups, allyl groups, styryl groups, thiol groups, and silyl groups. , Acetoacetyl group, epoxy group and the like. The amount of the reactive group of the modified vinyl alcohol polymer can be determined as appropriate, but if the amount of the hydroxyl group of the vinyl alcohol polymer decreases, the gas barrier performance inherent in the vinyl alcohol polymer tends to decrease. Thus, usually the amount of reactive groups is in the range of 0.001 to 50 mol%. (The total of reactive groups and hydroxyl groups is 100 mol%.) The modified vinyl alcohol polymer is preferably soluble in water, lower alcohols, organic solvents, and the like. Those that are soluble in a lower alcohol-based mixed solvent are preferred.

By using these modified vinyl alcohol polymers together with an unsaturated carboxylic acid metal salt, when the unsaturated carboxylic acid metal salt undergoes a chemical reaction, some of the modified vinyl alcohol polymer also binds to form a low humidity. It is considered that a moisture-proof film (B) having an improved gas barrier property is obtained.
Examples of modified vinyl alcohol polymers include, for example, α, β-ethylenically unsaturated groups such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc. There is a (meth) acrylate group-modified vinyl alcohol polymer obtained by reacting with a carboxylic acid compound having a group or a derivative thereof to introduce a (meth) acrylate group.
In addition, as another example, a vinyl monomer having vinyl acetate and an isothiuronium salt or thiolate ester copolymerized with vinyl acetate, and the resulting polymer is decomposed with straw or a base to introduce a thiol group, in the presence of thiolic acid There is a thiol group-modified vinyl alcohol polymer in which a thiol group is introduced only at the end of a molecule by polymerizing a vinyl ester and saponifying the resulting polymer.

Further, a method of adding a silyl group by post-modification using a silylating agent such as organohalogen silane, organoacetoxy silane, organoalkoxy silane to a vinyl alcohol polymer or a vinyl acetate polymer containing a carboxyl group or a hydroxyl group, etc. Thus, a silyl group-modified vinyl alcohol-based polymer having a trimethoxysilane group, a trialkoxysilane group such as a triethoxysilane group, or a tricarbonyloxysilane group as a part of the hydroxyl group of a vinyl alcohol polymer serving as a substrate. There is a coalescence.
Furthermore, a vinyl alcohol polymer is dispersed in an acetic acid solvent, and a method of adding diketene thereto, a vinyl alcohol polymer is previously dissolved in a solvent such as dimethylformamide or dioxane, and diketene is added thereto. There is an acetoacetyl group-modified vinyl alcohol polymer having an acetoacetyl group in a part of hydroxyl groups of a vinyl alcohol polymer to be a base, which is obtained by a method of addition.

  Other reactive functional group monomers are copolymerized with vinyl acetate and then saponified to introduce reactive functional groups into the side chain, and reactive functional groups are introduced into the side chain of polyvinyl alcohol by polymer reaction. Modified vinyl alcohol polymer formed by adding other radical polymerization groups such as (meth) acrylamide group, allyl group, vinyl group, styryl group, intramolecular double bond, vinyl ether group, etc. Examples thereof include a modified vinyl alcohol polymer obtained by adding a cationic polymerization group such as an epoxy group or a glycidyl ether group.

  Among these modified vinyl alcohol polymers, a moisture-proof layer made of a polymer obtained by using a (meth) acrylate-modified vinyl alcohol polymer in combination has a gas barrier property (oxygen barrier) at high and low humidity. A laminated body (laminated film) in which a moisture barrier layer (B) is formed is used as a packaging material, etc. In this case, the heat seal strength is improved.

  As the (meth) acrylate group-modified vinyl alcohol polymer, the amount of (meth) acryloyl group (contrast with hydroxyl group; esterification rate) is preferably 0.001 to 50%, more preferably 0.1 to 40%. It is in the range. If the esterification rate is less than 0.001%, the hot water resistance and flexibility of the resulting moisture barrier layer (B) may not be improved. On the other hand, if it exceeds 50%, the hot water resistance and oxygen of the resulting moisture barrier layer will not be improved. There is a possibility that the barrier properties and the like are not improved.

  The ratio of the hydroxyl group-containing polymer including these modified polyvinyl alcohol-based polymers is usually used in a ratio of about 1 to 50% by weight with respect to the weight of the unsaturated carboxylic acid metal salt.

These unsaturated carboxylic acid metal salts are generally formed by irradiating energy rays in a solution state such as water. Therefore, generally after coating the surface of the base material layer (A) with a solution of an unsaturated carboxylic acid metal salt,
It is usual to irradiate energy rays to form a moisture-proof film (B).
Energy rays include ultraviolet rays, electron beams, α rays, β rays, γ rays and other ionizing radiations, and any unsaturated carboxylic acid metal salt that can chemically react can be used without any particular limitation. It is desirable to use ultraviolet rays.
When the energy beam is irradiated, heating or the like is performed as necessary.

  Of course, after irradiating the unsaturated carboxylic acid metal salt with energy rays, such a radically polymerized polymer may be coated on the substrate layer (A), or a solution containing the unsaturated carboxylic acid metal salt (coating) The liquid) may first be coated on the base material layer (A), and then the coating layer may be irradiated with energy rays to be radically polymerized.

  When ultraviolet rays are used as energy rays, it is desirable to add a photopolymerization initiator to the unsaturated carboxylic acid metal salt. As the photopolymerization initiator, known ones can be used. For example, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name; Darocur 1173, manufactured by Ciba Specialty Chemicals) , 1-hydroxy-cyclohexyl-phenyl ketone (trade name; Irgacure 184 manufactured by Ciba Specialty Chemicals), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (product manufactured by Ciba Specialty Chemicals) Name; Irgacure 819), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (manufactured by Ciba Specialty Chemicals) 2959), α-hydroxyketone, acylphosphite Mixture of oxide, 4-methylbenzophenone and 2,4,6-trimethylbenzophenone (Lamberty Chemical Specialty, trade name; Esacure KT046), Esacure KT55 (Lamberti Chemical Specialty), 2,4,6 -The radical polymerization initiator manufactured and sold by the brand name of a trimethyl benzoyl diphenylphosphine oxide (Ramson Fire Chemical company brand name; Speed Cure TPO) can be mentioned. Furthermore, a polymerization accelerator can be added to improve the polymerization degree or polymerization rate, and examples thereof include N, N-dimethylaminoethyl- (meth) acrylate and N- (meth) acryloyl-morpholine.

In order to coat the base material layer (A) with a coating solution containing an unsaturated carboxylic acid metal salt, the coating solution is generally coated with a coating solution of a solution containing an unsaturated carboxylic acid metal salt. The saturated metal carboxylate is formed into a moisture-proof layer (B) by energy rays such as ultraviolet rays to be irradiated.
As a method for applying a coating solution containing an unsaturated carboxylic acid metal salt, a conventionally known method such as an air knife coater, a slit die coater, or a direct gravure coater is employed.
Furthermore, when coating these coating liquids on the base layer (A), it is desirable to coat the surface of the base layer (A) with an under coating material such as epoxy acrylate or urethane acrylate in advance.

Heat treatment of the moisture- proof layer (B) The moisture-proof layer (B) is preferably heat-treated.
The heat treatment is desirably performed at a moisture-proof layer (B) in a temperature range of usually 60 to 350 ° C., preferably 100 to 300 ° C., more preferably 150 to 250 ° C., and preferably in an inert gas atmosphere. The pressure is not particularly limited, and may be any of under pressure, under reduced pressure, and normal pressure. The heat treatment time is usually about 30 seconds to 90 minutes, with 1 minute to 70 minutes being preferred, and 5 minutes to 60 minutes being particularly preferred.
The moisture-proof layer (B) to be subjected to heat treatment is usually heat-treated while being applied to the base material layer (A).

Further, the moisture-proof layer (B) obtained by irradiation with energy rays may be continuously heat-treated, or the moisture-proof layer (B) may be returned to room temperature and then subjected to heat treatment. Usually, it is desirable in terms of production efficiency that the process of forming a film by irradiation of energy rays and the process of heat treatment are continued.
It is presumed that the moisture-proof layer (B) subjected to the heat treatment has a fixed film structure by radical polymerization. By subjecting this to further heat treatment, it is presumed that the dehydration and the membrane structure become more stable by partial rearrangement, and the gas barrier property is more stable.

Device sealing A device such as an organic EL is housed and sealed using a device sealing material including the laminate (C) obtained as described above.
Generally, the sealing material of the present invention is attached to an opening of a glass or metal container that houses the device via an adhesive, and sealing is performed.
At that time, the laminate (C) is attached with the moisture-proof layer (B) inside.
Further, when the laminate (C) is in the form of a film, the film-like laminate (C) is cut and formed into a bag shape, and the opening is sealed by heat sealing or the like for storing the device therein.
When the device is housed and sealed by these methods, part or all of the moisture contained in the moisture-proof layer (B) of the laminate (C) is removed in advance, and the moisture-proof layer (B) The moisture-proof performance after sealing can be improved by setting the moisture content in the state where the moisture content is lower than the moisture content in equilibrium with the water vapor pressure in the system in which it is placed.

It is desirable that part or all of the moisture contained in the moisture-proof layer (B) is removed in advance.
When the sealing material containing the laminate (C) is manufactured, an operation for removing moisture from the moisture-proof layer (B) is performed by heat treatment, and if the moisture content is maintained at a condition that does not increase, There is no need to heat-treat the laminated film again.
However, after the heat treatment at the time of manufacturing the sealing material including the laminate (C), the sealing material is placed under humid conditions, and the moisture content of the moisture-proof layer (B) is restored to the original ratio again. In such a case, it is desirable to remove a part or all of the moisture by performing a heat treatment again.

  Thus, it is desirable that the moisture content in the moisture-proof layer (B) is in a state of a moisture content that is lower than the moisture content in equilibrium with the water vapor pressure in the system in which it is placed. Thereby, the moisture absorption performance of the moisture-proof layer (B) is enhanced.

  And the sealing material containing a laminated body needs to be shape | molded so that a base material layer (A) may become an outer side and moisture-proof (B) may become an inner side. This is because the moisture-proof layer (B) absorbs moisture that remains slightly in the inner space in which the device that is the content is stored, and moisture does not remain in the sealed space.

  In addition, in the heat seal of the peripheral part for the shaping | molding of the bag-shaped article using the sealing material containing a film-form laminated body (C), and the heat seal for sealing of an opening part, a laminated body (C In addition, a heat-sealable thermoplastic resin layer (E) can be laminated and the portions are butted and heat-sealed.

The thermoplastic resin used in the heat-sealable thermoplastic resin layer (E) is not particularly limited, but among them, low density polyethylene, LLDPE, which is a random copolymer of ethylene and an α-olefin having 4 to 8 carbon atoms, ethylene・ Ethylene / α-olefin copolymer elastomer such as propylene copolymer, ethylene / 1-butene copolymer, ethylene-1-hexene copolymer, 1-octene copolymer, propylene / ethylene copolymer, propylene・ Propylene elastomer such as ethylene / 1-butene copolymer, Butene elastomer such as butene / ethylene copolymer, Ethylene / vinyl acetate copolymer, Ethylene / acrylic acid copolymer, etc. A copolymer is exemplified as a preferred example.
These may be further modified with polar group-containing monomers such as acrylic acid, maleic acid, maleic anhydride, and epoxy group-containing monomers.
The thickness of the heat-sealable thermoplastic resin layer (E) is usually about 5 μm to 300 μm, usually about 10 μm to 100 μm.

  The laminate (C) is a moisture-proof material obtained by irradiating an inorganic thin film layer (C) and then an unsaturated carboxylic acid metal salt with energy rays as the outermost layer as a base material layer (A) and then as required. Layer (B) Further, the heat-sealable thermoplastic resin layer (E) can be laminated and integrated in this order at the peripheral edge or opening of the bag-like material.

Even if the sealing material containing the laminated body (C) used by this invention contains the other layer in the range which does not impair the objective, the other layer may be formed.
For example, a tris (8-quinolinolato) aluminum-based moisture-proofing agent that has been conventionally known for use in moisture-proofing inside a sealed interior, and an organometallic compound that can be further selected by reacting a metal alkoxide with a polyol. A moisture-proof film made of SiN, a moisture-proof layer made of SiN, a moisture-proof layer made of SiOF, and the like may be used in combination.
In addition, an inert gel film containing a hygroscopic agent such as calcium oxide, barium oxide, calcium chloride, alumina silica alumina gel, or zeolite can be used as the inner surface layer, or these hygroscopic agents can be stored in a sealed space. It may be left.
Furthermore, it is desirable to provide an inorganic thin film layer (C) such as a transparent metal thin film layer or a transparent metal oxide layer between the base material layer (A) and the moisture-proof layer (B). Furthermore, functional transparent layers, such as a light-diffusion layer, an antifouling layer, a hard-coat layer, an antistatic layer, an ultraviolet absorption layer, are mentioned. Further, the base material layer (A) and the moisture-proof layer (B) may be subjected to corona treatment or plasma treatment. By suitably combining these, antireflection performance and antiglare performance can be imparted.

The visible light transmittance of the laminate (C) used in the sealing material of the present invention is preferably 70% or more, and more preferably 85% or more. The upper limit of the visible light transmittance is 100%, but in reality, it is often 95% or less because of surface reflection and absorption by the material. In addition, the average roughness Ra of the surface of the device sealing material of the present invention is preferably 0 to 1 nm, and more preferably 0 to 0.5 nm, for example, in a 1 square micron (μm ² ) area.

According to the present invention, a device such as an organic EL is accommodated between the two laminated film-like laminates (C) or the folded laminate-like film (C). The portion of the heat-sealable thermoplastic resin layer (E) can be heat-sealed and sealed.
At that time, the moisture-proof layer (B) of the film-like laminate (C) was hermetically sealed by using the moisture-proof layer (B) so as to be on the inner side in contact with the stored item while the moisture content was reduced. Absorbs the water portion of the space containing the stored items, and moisture does not remain in the sealed space.
Furthermore, it can also be set as a flexible sealing material by setting it as the sealing material which has a film-form laminated body (C).

Example

<Preparation of coating solution (X)>
Zinc acrylate (Zn salt of acrylic acid) aqueous solution (manufactured by Asada Chemical Co., Ltd., concentration 30 wt% (acrylic acid component: 20 wt%, Zn component 10 wt%)) and photopolymerization diluted to 25 wt% with methyl alcohol Initiator [1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name; Irgacure 2959, manufactured by Ciba Specialty Chemicals)] and A surfactant (trade name; Emulgen 120, manufactured by Kao Corporation) was mixed so that the molar fractions were 98.5%, 1.2%, and 0.3%, respectively, and consisted of a Zn acrylate solution (X). An unsaturated carboxylic acid compound polyvalent metal salt solution was prepared.

<Preparation of moisture-proof laminated film>
Epoxy acrylate UV curable coating (manufactured by Nippon Kakko Paint Co., Ltd.) on the corona-treated surface of a substrate made of biaxially stretched polyethylene terephthalate (product name; Emblet S-50 manufactured by Unitika Ltd.) with a thickness of 50 microns (μm) Name: FA-18) was diluted with ethyl acetate, coated to 1.2 g / m ² (solid content) using a Mayer bar, and dried at 100 ° C. for 15 seconds. Thereafter, the coated surface is fixed on a stainless steel plate, and using a UV irradiation device (EYE GRANDAGE model ECS 301G1 manufactured by Eye Graphic Co., Ltd.) under the conditions of UV intensity: 250 mW / cm ² and integrated light quantity: 117 mJ / cm ² . The coat film was polymerized by irradiating with ultraviolet rays to obtain a coat film. Furthermore, a film in which a SiN film having a thickness of 75 nm was formed on the coated surface of the coated film by the CatCVD method was obtained. After corona treatment is applied to this surface, the solution (X) is applied using a slit die coater so that the solid content is 1.5 g / m ² , fixed to a stainless steel plate with the coated surface facing upward, and UV Using an irradiation apparatus (EYE GRANDAGE model ECS 301G1 manufactured by Eye Graphic Co., Ltd.), a coating film is obtained by irradiating ultraviolet rays under the conditions of UV intensity: 250 mW / cm ² and integrated light quantity: 117 mJ / cm ^2. It was. Thereafter, heat treatment was performed in an oven at 200 ° C. for 1 hour to obtain a moisture-proof laminated film.

Example 1
<Preparation of organic EL sealing cap>
The moisture-proof laminated film is cut to 19 mm x 19 mm, and the barrier surface is made of a quartz glass frame (outer diameter 19 mm x 19 mm, inner diameter 13 mm x 13 mm, thickness 2 mm) and UV curable epoxy adhesive (manufactured by Nagase ChemteX Corporation, UV The organic EL sealing cap was prepared by bonding using RESIN XNR5570). The ultraviolet irradiation conditions at this time were an illuminance of 150 mW / cm ² and an integrated light amount of 12000 mJ / cm ² . The thickness of the adhesive was about 60 microns (μm).

<Sealing of organic EL>
The produced sealing cap is put in a glass tube that can be depressurized with a vacuum pump, the glass tube is heated and dried at 130 ° C. for 1 hour, and then the inside of the glass tube is depressurized with a vacuum pump, and further 1 is left in a heated state. Held for hours. Then, the bulb of the glass tube was closed and brought into the glove box while maintaining the reduced pressure state, and the glass cap on which the sealing cap and the organic EL element were formed was bonded with an ultraviolet curable epoxy adhesive (manufactured by Nagase ChemteX Corporation, UV RESIN XNR5570). The ultraviolet irradiation conditions at this time were an illuminance of 150 mW / cm ² and an integrated light amount of 12000 mJ / cm ² . The thickness of the adhesive was about 60 microns (μm).
In this way, an organic EL device sealed with a moisture-proof laminated film was obtained.

<Evaluation of sealing performance>
The organic EL device sealed with a moisture-proof laminated film is placed in a low-temperature constant temperature and humidity chamber (Advantech: THN-052PB) set to 40 ° C. and 90% RH, and samples are taken out every week, and driving conditions are set. Was 10 mA / cm ² to emit light and observe dark spots.
Evaluation is made by observing the light emitting part with a stereomicroscope at a magnification of 25 times, ○ when the dark spot is not recognized, △ when slightly spotted, × when scattered over the entire surface, no light emission -.

Comparative Example 1
A sample was prepared in the same manner except that a 100 micron (μm) glass plate was used instead of the moisture-proof film used in Example 1, and the sealing performance was evaluated.
Comparative Example 2
Instead of the moisture-proof film used in Example 1, a sample was prepared in the same manner except that a 30 micron (μm) aluminum foil was used, and the sealing performance was evaluated.
These results are shown in Table 1.

実施例２
実施例１において用いた防湿性積層フィルムを作成の際の塗工液の溶液（Ｘ）の組成を表２とする以外は同様にして防湿性積層フィルムを作成し、その飽和水分量を測定した。
ただし、２種類の金属塩を併用する場合は各金属を等モルずつ用いた。
また、防湿性積層フィルムの飽和水分量は以下の方法により測定した。
すなわち、各防湿性積層フィルムを２００℃で１時間熱処理し、その後直ちに２３℃、０％ＲＨのデシケータ中に移し、常温となった各防湿性積層フィルムの初期重量を測定した。
次に、各防湿性積層フィルムを２３℃、９０％ＲＨの恒温恒湿に維持し、その重量が平衡に他達した時点の重量を測定して、重量の増加量の割合（％）を飽和水分量とした。
同様にして、４０℃９０％ＲＨにおいても測定した。
結果を表２に示す。

表２から、アクリル酸ナトリウム、アクリル酸カリウムは、アクリル酸亜鉛に比べてその吸水量が大きく、優れた防湿性を有し、有機ＥＬの封止材としてダークスポットの防止に大きな効果がある。

Example 2
A moisture-proof laminated film was prepared in the same manner as in Table 2 except that the composition of the solution (X) of the coating solution used to produce the moisture-proof laminated film used in Example 1 was measured, and the saturated water content was measured. .
However, when using two types of metal salts together, equimolar amounts of each metal were used.
Moreover, the saturated water content of the moisture-proof laminated film was measured by the following method.
That is, each moisture-proof laminated film was heat-treated at 200 ° C. for 1 hour, and then immediately transferred into a desiccator at 23 ° C. and 0% RH, and the initial weight of each moisture-proof laminated film at room temperature was measured.
Next, each moisture-proof laminated film is maintained at a constant temperature and humidity of 23 ° C. and 90% RH, and the weight when the weight reaches equilibrium is measured to saturate the rate of increase in weight (%). The amount of water.
Similarly, it was measured at 40 ° C. and 90% RH.
The results are shown in Table 2.

From Table 2, sodium acrylate and potassium acrylate have larger water absorption than zinc acrylate, have excellent moisture resistance, and have a great effect on prevention of dark spots as an organic EL sealing material.

According to the present invention, a sealing material including the film-like laminate (C) is attached to an opening of a glass or metal container that houses a device such as an organic EL via an adhesive for sealing. A device such as an organic EL is accommodated between and encapsulated between the encapsulant or the folded encapsulant including the two film-like laminates (C) that are attached and sealed. The portion of the heat-sealable thermoplastic resin layer (E) can be heat-sealed and sealed.
At that time, the moisture-proof layer (B) of the laminate (C) is used so that the moisture-proof layer (B) is on the inner side in contact with the stored material while the moisture content is reduced, so that the moisture-proof layer (B) is sealed. The water part of the space containing water is absorbed, and moisture does not remain in the sealed space. Thereby, even when a flexible sealing material is used, it is possible to manufacture a sealed device that can prevent the occurrence of dark spots.
Furthermore, the moisture-proof layer (B) of the present invention can also have performance as a gas barrier layer.

Claims (4)

Using the laminate (C) having the moisture-proof layer (B) obtained by irradiating the base layer (A) and the unsaturated carboxylic acid metal salt with energy rays, the device is formed with the moisture-proof layer (B) inside. When storing and sealing , the moisture-proof layer (B) is in a state where the moisture content in the moisture-proof layer (B) is lower than the moisture content that is in equilibrium with the water vapor pressure in the system where it is placed. A method for producing a sealed device, wherein the device is housed and sealed with the inside facing. Proof layer (B) is, according to claim 1 Symbol mounting device characterized in that it is obtained by irradiating an energy beam to the coating liquid containing a metal alkoxide and / or a hydroxyl group-containing polymer with unsaturated carboxylic acid metal salt Production method. By moisture barrier (B) is pre-heated, the manufacture of claim 1 Symbol placement device, characterized in that its is a moisture barrier in the state in which a part or all of the water contained is removed (B) Method. The process according to claim 1 Symbol mounting device and having a substrate layer laminate (C) is formed of a thermoplastic resin layer and an inorganic thin film layer (A).