TW201900832A - Sheet for sealing - Google Patents

Abstract

Provided is a sheet for sealing, said sheet being capable of forming a sealed structure having high moisture-proofness without including a sealing member and a moisture-proof support body. This sheet 10 for sealing is characterized by (B) a moisture-proof inorganic covering film 2 being directly formed on one surface of (A) a pressure-sensitive adhesive resin composition layer 1, and (B) the moisture-proof inorganic covering film 2 being either (B1) a silica glass film comprising a thermally treated product of a polysilazane-containing coating film, or (B2) an inorganic vapor-deposited film.

Description

Sealing sheet

The present invention relates to a sheet for sealing, and more particularly to a sheet for sealing, which can form a sealing structure having high moisture resistance only by the sheet.

An organic EL (Electroluminescence) element is a light-emitting element in which an organic material is used as a light-emitting material, and high-luminance light emission can be obtained at a low voltage. However, the organic EL element is extremely afraid of moisture, and the luminescent material (light-emitting layer) is deteriorated by moisture, and the luminance is lowered, light is not emitted, and the interface between the electrode and the light-emitting layer is affected by moisture, peeling, metal oxidation, and high resistance. Therefore, in order to isolate the moisture in the inside and outside of the element, for example, the sealing layer is formed by the resin composition so as to cover the entire surface of the light-emitting layer of the organic EL element formed on the substrate, and the organic EL element is sealed.

For example, Patent Document 1 discloses a polyisobutylene resin, a polyisoprene resin having a functional group reactive with an epoxy group, a polyisobutylene resin, an adhesion-providing resin, and a resin composition for sealing. A resin composition of an epoxy resin. Further, Patent Document 2 discloses a resin composition containing a styrene-isobutylene-modified resin and an adhesion-imparting resin. Further, in order to improve the moisture permeability resistance of the sealing layer, a hygroscopic filler may be blended into the resin composition.

The sealing of the organic EL element is carried out by such a resin composition, and it is carried out by a sheet for sealing which forms a resin composition layer on a support from the viewpoint of productivity, sealing workability and the like. Further, in order to form a highly moisture-proof sealing structure, not only the moisture permeability resistance of the resin composition layer but also the moisture-proof support or the sealing substrate may be used. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2011/62167 [Patent Document 2] International Publication No. 2013/108731

[Problems to be solved by the invention]

In the case where the support for the sealing sheet has a moisture-proof support when the organic EL element is sealed with the sheet for sealing, the substrate having the organic EL element is laminated with the resin composition layer covering the organic EL element. After the sheet for sealing, the support is not peeled off, and the sealing step of the organic EL element is directly completed. In the case where heat hardening is necessary after the sealing step, thermal hardening is performed.

On the other hand, when the sheet for sealing is used and the sheet having the moisture-proof property is used as the sheet, the sheet for sealing is laminated on the substrate having the organic EL element so that the resin layer is coated with the organic EL element. The support is peeled off, and the sealing substrate is pressure-bonded to the exposed resin composition layer, and the sealing step of the organic EL element is completed. Sealing the substrate, in order to improve the moisture-proof effect, it is also possible to use two or more pieces together.

In general, as the moisture-retaining support and the sealing substrate, a plastic film having moisture resistance or a metal foil such as copper foil or aluminum foil can be used. The plastic film having moisture-proof property may, for example, be a plastic film obtained by vapor-depositing an inorganic substance such as SiO ₂ , SiN, SiCN or amorphous enamel on the surface.

Incidentally, as the demand for organic EL devices has increased, it has been desired to reduce the thickness of the organic EL device, and the support having a moisture-proof property or the sealing substrate is hindered from being thinned.

The present invention has been made in view of the above circumstances, and an object to be solved is to provide a sealing sheet which does not contain a sealing substrate or a moisture-proof support, and can form a sealing structure having high moisture resistance. [Means for solving problems]

The constitution of the present invention for solving the above problems is as follows.

[1] A sheet for sealing comprising (A) a pressure-sensitive adhesive composition layer and a (B) moisture-proof inorganic film directly formed on one surface of the (A) pressure-sensitive adhesive composition layer. . [2] The sheet for sealing according to the above [1], wherein the (B) moisture-proof inorganic film is (B1) a cerium oxide glass film composed of a heat-treated product of a coating film containing polyazoxide, or (B2) An inorganic deposited film. [3] The sealing sheet according to the above [2], which comprises a polydecazane-containing perhydroxy polyazane. [4] The sheet for sealing according to the above [2], wherein the (B2) inorganic deposited film is a bismuth compound deposited film. [5] The sealing sheet according to the above [4], wherein the ruthenium compound vapor-deposited film is a SiO ₂ -SiCN multilayer deposited film containing a SiO ₂ deposited film and a SiCN deposited film. [6] The [5] The sealing sheet, wherein the SiO ₂ -SiCN multilayer deposited film forming deposited film of SiO ₂ deposited film to interact with the SiCN SiO ₂ -SiCN multilayer deposited film. [7] The sheet for sealing according to any one of the above [1], wherein the (B) moisture-proof inorganic film has a thickness of 1000 nm or less. [8] The sheet for sealing according to any one of [1] to [7] wherein (A) the pressure-sensitive adhesive composition layer has a thickness of 3 to 50 μm. [9] The sheet for sealing according to any one of [1] to [8] wherein the (A) pressure-sensitive adhesive composition layer contains a hygroscopic filler. [10] The sheet for sealing according to any one of the above [1], wherein the (A) pressure-sensitive adhesive composition layer contains an adhesion-imparting resin. [11] The sheet for sealing according to any one of [1] to [10] further comprising (C) a release-treated support and having (C) a release-treated support/(A) A pressure-sensitive adhesive composition layer/(B) a moisture-proof inorganic film is laminated. [12] The sheet for sealing according to [11] above, wherein the (C) release-treated support is a moisture-proof support. [13] The sheet for sealing according to any one of the above [1] to [12], which is used for sealing an organic EL element. [14] The sheet for sealing according to any one of the above [1] to [10], which is the surface of the (B) moisture-proof inorganic film and the side opposite to the (A) pressure-sensitive adhesive composition layer side. Further, (D) a circular polarizing plate is formed, and is a sheet for sealing of an organic EL element. [15] The sheet for sealing according to the above [11] or [12], wherein the surface of the (B) moisture-proof inorganic film opposite to the side of the (A) pressure-sensitive adhesive composition layer is further followed (D) It is a circular polarizing plate and is a sheet for sealing of an organic EL element. [16] An organic EL device obtained by sealing an organic EL element with a sheet for sealing according to any one of the above [1] to [10] or [14]. [17] A method for producing a sheet for sealing comprising forming a coating film containing polyazoxide on one side of a (A) pressure-sensitive adhesive composition layer, the coating film being in a vapor atmosphere of water The step of heating to convert into a (B1) cerium oxide glass film or the step of vapor-depositing the inorganic material on the one side of the (A) pressure-sensitive adhesive composition layer to form (B2) an inorganic deposited film. [Effects of the Invention]

According to the sealing sheet of the present invention, since the sealing substrate or the moisture-proof support is not contained, a sealing structure having high moisture resistance can be formed, so that the thickness of the sealing structure can be made thin. Therefore, for example, the sealing sheet of the present invention is used for sealing of an organic EL element, and a thin organic EL device can be obtained.

Fig. 1 is a schematic cross-sectional view showing a sheet for sealing according to an embodiment of the present invention. The sealing sheet of the present invention contains at least (A) pressure-sensitive adhesive composition layer 1 and directly formed on the (A) pressure-sensitive adhesive composition as shown in the sealing sheet 10 of the embodiment. (B) moisture-proof inorganic film 2 of one layer of the layer.

Typically, the sealing sheet of the present invention, as shown in Fig. 1, further contains (C) a release-treated support 3 having a (C) release-release support 3/(A) A sheet of the pressure-sensitive resin composition layer 1/(B) laminated with the moisture-proof inorganic film 2 is formed.

Further, (C) the release-treated support 3 is a support when the (A) pressure-sensitive adhesive composition layer 1 is formed, and (A) a pressure-sensitive adhesive resin is actually used before the sealing target is sealed. The composition layer 1 was peeled off. Therefore, the release-treated support 3 does not have to have moisture resistance, and moisture penetration is prevented during storage of the sealing sheet from the production of the sealing sheet to the sealing operation (A) pressure-sensitive adhesive composition From the viewpoint of layer 1, it is possible to use a support having moisture resistance by (C) the release-treated support 3.

Hereinafter, each constituent element of the sheet for sealing will be described in detail. [(A) Pressure-sensitive adhesive composition layer] (A) The pressure-sensitive adhesive composition layer 1 is formed by sealing a sealing sheet to an organic EL element or the like and then sealing the object. The layer of the sealing layer is formed of a pressure-sensitive adhesive resin composition.

The pressure-sensitive adhesive resin composition (hereinafter also referred to simply as "resin composition") which forms (A) the pressure-sensitive adhesive composition layer 1 is preferably a resin composition having adhesiveness and hygroscopicity, and for example, A resin composition containing (a) a polyolefin resin, (b) an adhesive resin, and (c) a hygroscopic filler. The (A) pressure-sensitive adhesive resin composition layer 1 is hygroscopic and can effectively prevent moisture from reaching the sealed object.

<(a) Polyolefin-based resin> (a) The polyolefin-based resin (hereinafter also simply referred to as "(a) component") is not particularly limited as long as it has a skeleton derived from an olefin monomer. For example, a polyolefin resin, a polypropylene resin, a polybutene resin, and a polyisobutylene resin are mentioned.

The polyolefin resin may be any of a homopolymer, a random copolymer, or a block copolymer. Further, examples of the copolymer include (i) a copolymer of two or more kinds of olefins, (ii) a copolymer of an olefin and a non-conjugated diene, or (iii) an olefin other than an olefin such as methyl methacrylate or styrene. a copolymer of a monomer other than a non-conjugated diene. Among the copolymer of (ii) and the copolymer of (iii), one or two or more kinds of olefins may be used.

Suitable examples of the homopolymer include, for example, polybutene. Suitable examples of the copolymer include an ethylene-nonconjugated diene copolymer, an ethylene-propylene copolymer, an ethylene-butylene-nonconjugated diene copolymer, an ethylene-propylene-nonconjugated diene copolymer, and ethylene. - propylene-butene copolymer, propylene-butene copolymer, propylene-butene-nonconjugated diene copolymer, isobutylene-butene copolymer, isobutylene-butene-nonconjugated diene copolymer, styrene - an isobutylene copolymer, a styrene-isobutylene-styrene copolymer, an ethylene-methyl methacrylate copolymer, or the like.

The polyolefin-based resin may contain an acid anhydride group (that is, a carbonyloxycarbonyl group) from the viewpoint of imparting excellent properties such as adhesion between the resin composition layer and the sealing target, and subsequent wet heat resistance of the resin composition layer. A polyolefin-based resin of -CO-O-CO-)) and/or a polyolefin-based resin having an epoxy group. Examples of the acid anhydride group include a group derived from succinic anhydride, a group derived from maleic anhydride, a group derived from glutaric anhydride, and the like. The acid anhydride group may have one type or two or more types. The polyolefin-based resin having an acid anhydride group can be obtained by graft-denatured a polyolefin-based resin under a radical reaction condition, for example, with an unsaturated compound having an acid anhydride group. Further, an unsaturated compound having an acid anhydride group may be radically copolymerized together with an olefin or the like. Similarly, the polyolefin-based resin having an epoxy group may have an epoxy group such as glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, allyl glycidyl ether or the like. The base unsaturated compound is obtained by graft denaturation of a polyolefin resin under a radical reaction condition. Further, an unsaturated compound having an epoxy group may be radically copolymerized together with an olefin or the like.

The polyolefin-based resin having an acid anhydride group is preferably, for example, liquid polybutene having an acid anhydride group, and maleic anhydride-denatured liquid polybutene is preferred. The polyolefin-based resin having an epoxy group is preferably, for example, an epoxy-modified polyethylene having an epoxy group, an epoxy-modified polypropylene, or an epoxy-modified polybutene.

The concentration of the acid anhydride group in the polyolefin resin having an acid anhydride group is preferably 0.05 to 10 mmol/g, more preferably 0.1 to 5 mmol/g. The concentration of the acid anhydride group can be obtained from the acid value defined as the number of mg of potassium hydroxide necessary for neutralizing the acid present in 1 g of the resin, in accordance with the description of JIS K 2501. Further, the amount of the polyolefin-based resin having an acid anhydride group in the component (a) is preferably from 0 to 70% by mass, preferably from 10 to 50% by mass.

Further, the concentration of the epoxy group in the polyolefin-based resin having an epoxy group is preferably 0.05 to 10 mmol/g, more preferably 0.1 to 5 mmol/g. The epoxy group concentration is determined from the epoxy equivalent obtained in accordance with JIS K 7236-1995. Further, the amount of the polyolefin-based resin having an epoxy group in the component (a) is preferably from 0 to 70% by mass, preferably from 10 to 50% by mass.

The number average molecular weight of the component (a) is not particularly limited, and from the viewpoint of imparting good coatability of the resin composition varnish and good compatibility with other components in the resin composition, it is preferably 1,000,000 or less. 750,000 or less is preferred, 500,000 or less is preferred, 400,000 or less is more preferred, 300,000 or less is more preferred, and 200,000 or less is particularly preferred, and 150,000 or less is preferred. On the other hand, from the viewpoint of preventing repulsion when the resin composition varnish is applied, the formed resin composition layer exhibits moisture permeability resistance and mechanical strength is preferably 2,000 or more, more preferably 10,000 or more. More than 30,000 is better, and more than 50,000 is especially good. Further, the number average molecular weight is measured by a gel permeation chromatography (GPC) method (in terms of polystyrene). The number average molecular weight measured by the GPC method, specifically, the LC-9A/RID-6A manufactured by Shimadzu Corporation, and the Shodex K-800P/K-804L/K-804L manufactured by Showa Denko Co., Ltd. The phase was measured at a column temperature of 40 ° C using toluene or the like, and was calculated using a calibration curve of standard polystyrene.

In addition, one of the suitable aspects of the component (a) includes a liquid polyolefin having a number average molecular weight of 1,000 or more and 3,000 or less in a range of 10% by mass or more and 90% by mass or less of the total of the component (a) (it is preferably a liquid) The aspect of polybutene and/or maleic anhydride denatured liquid polybutene. If the component (a) is in this suitable state, it is easy to obtain high adhesion strength.

The (a) polyolefin-based resin in the present invention is preferably amorphous in view of suppressing a decrease in fluidity due to viscosification of the varnish. Here, the amorphous property means that the polyolefin-based resin does not have a clear melting point, and for example, a resin in which a clear peak is not observed when the melting point is measured by DSC (differential scanning calorimetry) of the polyolefin-based resin can be used.

The component (a) may be used alone or in combination of two or more. The content of the component (a) in the resin composition is not particularly limited. However, from the viewpoint of imparting good coatability and compatibility, and ensuring good wet heat resistance and usability (suppression of sticking), the content of the non-volatile components in the resin composition is 100% by mass in total. It is preferably 80% by mass or less, more preferably 75% by mass or less, more preferably 70% by mass or less, more preferably 60% by mass or less, more preferably 55% by mass or less, and most preferably 50% by mass or less. On the other hand, from the viewpoint of improving the moisture permeability resistance and the transparency, the content of the nonvolatile components in the resin composition is preferably 1% by mass or more, and 3% by mass or more. Preferably, 5% by mass or more is more preferable, 7% by mass or more is more preferable, 10% by mass or more is more preferable, and 35% by mass or more is particularly preferable, and 40% by mass or more is most preferable.

Next, a specific example of the (a) polyolefin-based resin will be described. Specific examples of the polyisobutylene resin include "Oppanol B100" (viscosity average molecular weight: 1,110,000) manufactured by BASF Corporation, and "B50SF" (viscosity average molecular weight: 400,000) manufactured by BASF Corporation.

Specific examples of the polybutene-based resin include "HV-1900" (polybutene, number average molecular weight: 2,900) manufactured by JX Energy Co., Ltd., and "HV-300M" manufactured by Toho Chemical Industry Co., Ltd. (maleic anhydride denaturing liquid polymerization) Butene ("HV-300" (quantitative average molecular weight: 1,400) denature), number average molecular weight: 2,100, number of carboxyl groups constituting an acid anhydride group: 3.2 / one molecule, acid value: 43.4 mgKOH / g, acid anhydride group Concentration: 0.77 mmol/g).

Specific examples of the styrene-isobutylene copolymer include "SIBSTAR T102" manufactured by Kaneka Co., Ltd. (styrene-isobutylene-styrene block copolymer, number average molecular weight: 100,000, styrene content: 30% by mass), and Star PMC "T-YP757B" (maleic anhydride modified styrene-isobutylene-styrene block copolymer, acid anhydride group concentration: 0.464 mmol/g, number average molecular weight: 100,000), "T-YP766" manufactured by Starlight PMC Co., Ltd. Glyceryl methacrylate modified styrene-isobutylene-styrene block copolymer, epoxy group concentration: 0.638 mmol/g, number average molecular weight: 100,000), "T-YP8920" manufactured by Starlight PMC Co., Ltd. (maleic anhydride denaturation) Styrene-isobutylene-styrene copolymer, acid anhydride group concentration: 0.464 mmol/g, number average molecular weight: 35,800), "T-YP8930" manufactured by Starlight PMC Co., Ltd. (glycidyl methacrylate modified styrene-isobutylene-benzene Ethylene copolymer, epoxy group concentration: 0.638 mmol/g, number average molecular weight: 48,700).

Specific examples of the polyethylene resin or the polypropylene resin include "EPT X-3012P" manufactured by Mitsui Chemicals Co., Ltd. (ethylene-propylene-5-ethylidene-2-norbornene copolymer, "EPT1070" manufactured by Mitsui Chemicals Co., Ltd. (Ethylene-propylene-dicyclopentadiene copolymer), "TAFMER A4085" (ethylene-butene copolymer) manufactured by Mitsui Chemicals Co., Ltd., and the like.

Specific examples of the ethylene-methyl methacrylate copolymer include "ACRYFT CM5022" manufactured by Sumitomo Chemical Co., Ltd. (ethylene-methyl methacrylate copolymer, ethylene unit and methyl methacrylate unit total 100% by mass of A) Amount of methyl acrylate unit: 33% by mass), "T-YP429" manufactured by Starlight PMC Co., Ltd. (maleic anhydride-denatured ethylene-methyl methacrylate copolymer, ethylene unit and methyl methacrylate unit total per 100 masses % of methyl methacrylate unit: 32% by mass, acid anhydride group concentration: 0.46 mmol/g, number average molecular weight: 2,300), "T-YP430" manufactured by Starlight PMC Co., Ltd. (maleic anhydride-denatured ethylene-methacrylic acid) The amount of the methyl methacrylate copolymer, the ethylene unit and the methyl methacrylate unit per 100 mass% of the methyl methacrylate unit: 32% by mass, the acid anhydride group concentration: 1.18 mmol/g, the number average molecular weight: 4,500), starlight "T-YP431" (glycidyl methacrylate modified ethylene-methyl methacrylate copolymer, epoxy group concentration: 0.64 mmol/g, number average molecular weight: 2,400) manufactured by PMC Corporation, "T-made by Starlight PMC" -YP432" Hydroglyceryl methacrylate modified ethylene-methyl methacrylate copolymer, epoxy group concentration: 1.63 mmol/g, number average molecular weight: 3,100). Further, specific examples of the propylene-butene-based copolymer include "T-YP341" manufactured by Starlight PMC Co., Ltd. (glycidyl methacrylate-modified propylene-butene random copolymer, propylene unit and butene unit totaled per 100 Mass% of butene unit: 29% by mass, epoxy group concentration: 0.638 mmol/g, number average molecular weight: 155,000), "T-YP279" manufactured by Starlight PMC Co., Ltd. (Maleic anhydride-denatured propylene-butene random copolymerization The total amount of the butene unit per 100 mass% of the propylene unit and the butene unit: 36% by mass, the acid anhydride group concentration: 0.464 mmol/g, the number average molecular weight: 35,000), and the "T-YP276" manufactured by Starlight PMC Co., Ltd. Glycidyl methacrylate denatured propylene-butene random copolymer, propylene unit and butene unit total amount of butene unit per 100% by mass: 36% by mass, epoxy group concentration; 0.638 mmol/g, number average Molecular weight: 57,000), "T-YP312" manufactured by Starlight PMC Co., Ltd. (maleic anhydride-denatured propylene-butene random copolymer, propylene unit and butene unit total amount of butene unit per 100% by mass: 29% by mass, Anhydride group concentration of 0.464mmol/g, number average Sub-quantity: 60,900), "T-YP313" manufactured by Starlight PMC Co., Ltd. (glycidyl methacrylate modified propylene-butene random copolymer, propylene unit and butene unit total amount of butene units per 100% by mass: 29% by mass, epoxy group concentration: 0.638 mmol/g, number average molecular weight: 155,000).

<(b) Adhesive-imparting resin> (b) Adhesive-imparting resin (hereinafter also referred to as "(b) component"), which is also called a tackifier, is blended into a plastic polymer to impart adhesiveness. The component (b) is not particularly limited, and a terpene resin, a denatured terpene resin (hydrogenated terpene resin, terpene phenol copolymer resin, aromatic modified terpene resin, etc.), a coumarone resin, an anthracene resin, and the like are preferably used. Petroleum resin (aliphatic petroleum resin, hydrogenated alicyclic petroleum resin, aromatic petroleum resin, aliphatic aromatic copolymerized petroleum resin, alicyclic petroleum resin, dicyclopentadiene petroleum resin, and hydrogenated thereof) Things, etc.).

Commercially available products can be used as the component (b), and the following products can be mentioned, for example. Examples of the terpene resin include YS RESIN PX and YS RESIN PXN (all of which are manufactured by Yasuhara Chemical Co., Ltd.), and aromatic-modified terpene resins, and examples thereof include YS RESIN TO and TR series (any of them are Yasuhara Chemical Co., Ltd.). The hydrogenated terpene resin may, for example, be a Clearon P, a Clearon M or a Clearon K series (all of which is manufactured by Yasuhara Chemical Co., Ltd.), or a terpene phenol copolymer resin, and examples thereof include YS Polystar 2000, Polystar U, and Polystar. T, Polystar S, Mighty Ace G (manufactured by Yasuhara Chemical Co., Ltd.), etc., and hydrogenated alicyclic petroleum resins, such as Escorez 5300 series and 5600 series (all of which are manufactured by Exxon Mobil Co., Ltd.), etc., aromatic Examples of the petroleum resin include ENDEX 155 (manufactured by EASTMAN Co., Ltd.), and an aliphatic aromatic copolymer-based petroleum resin, and examples thereof include an alicyclic petroleum resin such as Quintone D100 (manufactured by Zeon Co., Ltd.), and examples thereof include Quintone 1325 and Quintone 1345. The cyclohexane ring contains a hydrogenated petroleum resin, and examples thereof include Alcon P100, Alcon P125, and Alcon P140 (all of which are manufactured by Arakawa Chemical Co., Ltd.), and cyclohexane. A saturated hydrocarbon resin, include TFS13-030 (Arakawa Chemical Industries, Ltd.) and the like.

The softening point of the component (b) is preferably from 50 to 200 ° C and preferably from 90 to 180 ° C from the viewpoint of softening the sheet in the lamination step of the resin composition sheet and having desired heat resistance. 100~150°C is better. Further, the softening point was measured by a ring and ball method in accordance with JIS K 2207.

The component (b) may be used alone or in combination of two or more. The content of the component (b) in the resin composition is not particularly limited. However, from the viewpoint of maintaining good moisture permeability resistance of the resin composition, when the component (b) is used, the content of the non-volatile component in the resin composition is 100% by mass or less, and 80% by mass or less. Preferably, 60% by mass or less is preferred, and 50% by mass or less is more preferably 40% by mass or less. On the other hand, in the case of using the component (b), the content of the component (b) is preferably 5% by mass or more per 100% by mass of the nonvolatile component in the resin composition, 10 The mass% or more is preferably 15% by mass or more.

In particular, petroleum resin is preferred from the viewpoints of adhesion of the resin composition, moisture permeability resistance, transparency, and the like. Examples of the petroleum resin include an aliphatic petroleum resin, an aromatic petroleum resin, an aliphatic aromatic copolymerized petroleum resin, and an alicyclic petroleum resin. In particular, an aromatic petroleum resin, an aliphatic aromatic copolymerized petroleum resin, or an alicyclic petroleum resin is preferable from the viewpoints of adhesion of the resin composition, moisture permeability resistance, compatibility, and the like. Further, from the viewpoint of improving transparency, an alicyclic petroleum resin is particularly preferred. For the alicyclic petroleum resin, a person who hydrogenates an aromatic petroleum resin can also be used. In this case, the hydrogenation rate of the alicyclic petroleum resin is preferably from 30 to 99%, preferably from 40 to 97%, more preferably from 50 to 90%. When the hydrogenation rate is too low, there is a tendency that transparency is lowered due to coloring, and if the hydrogenation rate is too high, the production cost tends to increase. The hydrogenation rate can be determined from the ratio of the ¹ H-NMR peak intensity of hydrogen on the aromatic ring after hydrogenation and after hydrogenation. The alicyclic petroleum resin preferably contains a hydrogenated petroleum resin or a dicyclopentadiene hydrogenated petroleum resin in a cyclohexane ring. The petroleum resins may be used alone or in combination of two or more. The number average molecular weight Mn of the petroleum resin is preferably from 100 to 2,000, more preferably from 700 to 1,500, still more preferably from 500 to 1,000.

<(c) Hygroscopic filler> (c) The hygroscopic filler (hereinafter also referred to as "(c) component) is not particularly limited as long as it is a filler capable of absorbing moisture, and is preferably a hygroscopic metal. Oxide. The hygroscopic metal oxide means a metal oxide which has a ability to absorb moisture and chemically reacts with the absorbed moisture to become a hydroxide. Specific examples thereof include calcium oxide, magnesium oxide, cerium oxide, aluminum oxide, cerium oxide, unfired hydrotalcite, semi-fired hydrotalcite, calcined hydrotalcite, and calcined dolomite. In particular, from the viewpoint of hygroscopicity, it is preferred to use semi-fired hydrotalcite and calcined hydrotalcite.

Hydrotalcites can be classified into unfired hydrotalcites, semi-fired hydrotalcites, and calcined hydrotalcites.

The uncalcined hydrotalcite has, for example, a metal hydroxide having a layered crystal structure typified by natural hydrotalcite (Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · 4H ₂ O), for example, a layer as a basic skeleton [ Mg _1-x Al _x (OH) ₂ ] ^x+ is composed of an intermediate layer [(CO ₃ ) _x/2 · mH ₂ O] ^x- . The unfired hydrotalcite in the present invention is a concept including a hydrotalcite-like compound such as synthetic hydrotalcite. The hydrotalcite-like compound may, for example, be represented by the following formula (I) and the following formula (II).

(wherein M ²⁺ represents a divalent metal ion such as Mg ²⁺ or Zn ²⁺ , M ³⁺ represents a trivalent metal ion such as Al ³⁺ or Fe ³⁺ , and A ^n- represents CO ₃ ^2- or Cl. ^- n-valent anion of NO ₃ ^-, etc., 0 < x < 1, 0 ≦ m < 1, n is a positive number. In the formula (I), M ^{2+ is} preferably Mg ²⁺ , and M ^{3+ is} preferably Al ³⁺ , A ^n- should be CO ₃ ^2- .

(wherein M ²⁺ represents a divalent metal ion such as Mg ²⁺ or Zn ²⁺ , A ⁿ⁻ represents an n-valent anion such as CO ₃ ^2- , Cl ⁻ or NO ₃ ^— , and x is a positive number of 2 or more, z is a positive number of 2 or less, m is a positive number, and n is a positive number. In the formula (II), M ^{2+ is} preferably Mg ²⁺ , and A ^{n- is} preferably CO ₃ ^2- .

The semi-fired hydrotalcite refers to a metal hydroxide having a layered crystal structure in which the amount of interlayer water is reduced or disappeared by firing the unfired hydrotalcite. The "interlayer water" is a "H ₂ O" described in the composition formula of the unfired natural hydrotalcite and the hydrotalcite-like compound.

On the other hand, the hydrotalcite is a metal oxide having an amorphous structure which is obtained by firing unfired hydrotalcite or semi-fired hydrotalcite, and not only interlayer water but also hydroxyl groups are lost due to condensation and dehydration.

Unburned hydrotalcite, semi-fired hydrotalcite and calcined hydrotalcite can be distinguished by saturated water absorption. The saturated water absorption rate of the semi-fired hydrotalcite is less than 20% by weight in 1% by weight or more. On the other hand, the saturated water absorption of the unfired hydrotalcite is less than 1% by weight, and the saturated water absorption of the calcined hydrotalcite is 20% by weight or more.

The "saturated water absorption rate" in the present invention means that 1.5 g of unfired hydrotalcite, semi-baked hydrotalcite or calcined hydrotalcite is weighed in a scale, and after the initial mass is measured, it is set at 60 ° C under atmospheric pressure. In the case of a small environmental tester (SH-222 manufactured by ESPEC Co., Ltd.) of 90% RH (relative humidity) for 200 hours, the mass increase rate with respect to the initial mass can be obtained by the following formula (i): Water absorption rate (% by mass) = 100 × (mass after moisture absorption - initial mass) / initial mass (i).

The saturated water absorption rate of the semi-fired hydrotalcite is preferably 3% by weight or more and less than 20% by mass, preferably 5% by weight or more and less than 20% by mass.

Further, the unfired hydrotalcite, the semi-fired hydrotalcite, and the calcined hydrotalcite can be distinguished by the thermal weight reduction rate measured by thermogravimetric analysis. The semi-calcined hydrotalcite has a thermal weight reduction rate of less than 15% by mass at 280 ° C, and its thermal weight reduction rate at 380 ° C is 12% by mass or more. On the other hand, the thermogravimetric reduction rate of the unfired hydrotalcite at 280 ° C was 15% by mass or more, and the thermal weight loss rate of the calcined hydrotalcite at 380 ° C was less than 12% by mass.

Thermogravimetric analysis, by using TG/DTA EXSTAR6300 manufactured by Hitachi High-Tech Science Co., Ltd., weighing 5 mg of hydrotalcite into a sample tray made of aluminum, without opening, in an open state, under a nitrogen flow rate of 200 mL/min. The temperature was raised from 30 ° C to 550 ° C at a temperature increase rate of 10 ° C / min. The heat weight reduction rate can be obtained by the following formula (ii): Thermal weight reduction rate (% by mass) = 100 × (mass before heating - mass at a predetermined temperature) / mass before heating (ii).

Further, the unfired hydrotalcite, the semi-fired hydrotalcite, and the calcined hydrotalcite can be distinguished by the peak and relative intensity ratio measured by powder X-ray diffraction. Semi-fired hydrotalcite, by powder X-ray diffraction, exhibits two separate peaks at 2θ of 8 to 18°, or has a shoulder peak due to the synthesis of two peaks, and a peak appearing on the low angle side Or the relative intensity ratio of the diffraction intensity of the shoulder (= low angle side diffraction intensity) to the diffraction intensity (= high angle side diffraction intensity) of the peak or shoulder appearing on the high angle side (low angle side diffraction) The intensity/high angle side diffraction intensity is 0.001 to 1,000. On the other hand, the unfired hydrotalcite has a relative intensity ratio of only one peak around 8 to 18°, or a peak or shoulder appearing on the low angle side and the diffraction intensity of the peak or shoulder appearing on the high angle side. Will be outside the aforementioned range. The hydrotalcite is fired, has no characteristic peak in the region of 8° to 18°, and has a characteristic peak at 43°. The powder X-ray diffraction measurement was performed by a powder X-ray diffraction apparatus (Empyrean, manufactured by PANalytica1 Co., Ltd.), a cathode CuKα (1.5405 Å), a voltage of 45 V, a current of 40 mA, a sampling width of 0.0260°, and a scanning speed: 0.0657 ° / s, measuring the diffraction angle range (2θ): 5.0131 ~ 79.9711 ° conditions. For peak search, the peak search function of the software attached to the diffractive device can be used to "minimum saliency: 0.50, minimum peak tip: 0.01°, maximum peak tip: 1.00 °, peak width: 2.00 °, method: 2 times. The condition of the minimum value of the differential is performed.

Semi calcined hydrotalcite BET specific surface area to 1 ~ 250m ² / g preferably, 5 ~ 200m ² / g is preferred. The BET specific surface area of the semi-baked hydrotalcite can be calculated by a BET multipoint method using a specific surface area measuring device (manufactured by Macsorb HM Model 1210 Mountech Co., Ltd.) to adsorb nitrogen gas on the surface of the sample.

The average particle diameter of the semi-baked hydrotalcite is preferably from 1 to 1,000 nm, preferably from 10 to 800 nm. The average particle diameter of the semi-fired hydrotalcite is a median diameter diameter of the particle size distribution when a particle size distribution is produced on a volume basis by a laser diffraction scattering type particle size distribution measurement (JIS Z 8825).

The component (c) may be an article surface-treated with a surface treatment agent. As the surface treatment agent used for the surface treatment, for example, a high carbon fatty acid, an alkyl decane, a decane coupling agent or the like can be used, and particularly, it is preferably a high carbon fatty acid or a alkyl decane. The surface treatment agent may be used alone or in combination of two or more.

The high-carbon fatty acid may, for example, be a high-carbon fatty acid having 18 or more carbon atoms such as stearic acid, montanic acid, myristic acid or palmitic acid, and particularly preferably stearic acid. These may be used alone or in combination of two or more. Examples of the alkyl decanes include methyltrimethoxydecane, ethyltrimethoxydecane, hexyltrimethoxydecane, octyltrimethoxydecane, decyltrimethoxydecane, and octadecyltrimethoxydecane. Dimethyldimethoxydecane, octyltriethoxydecane, n-octadecyldimethyl(3-(trimethoxycarbinyl)propyl)ammonium chloride, and the like. These may be used alone or in combination of two or more. The decane coupling agent may, for example, be 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane or 3-glycidoxypropyl(dimethoxy)methyl group. An epoxy decane coupling agent such as decane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane; 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, a mercapto decane coupling agent such as 3-mercaptopropylmethyldimethoxydecane and 11-decylundecyltrimethoxydecane; 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxy Baseline, 3-aminopropyldimethoxymethylnonane, N-phenyl-3-aminopropyltrimethoxydecane, N-methylaminopropyltrimethoxydecane, N-(2-amine B Amino decane coupling agent such as 3-aminopropyltrimethoxydecane and N-(2-aminoethyl)-3-aminopropyldimethoxymethyl decane; 3-ureidopropyl a vinyl decane coupling agent such as a ureido coupling agent such as triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane or vinyl methyl diethoxy decane; Styrene such as trimethoxy decane Base decane coupling agent; acrylate decane coupling agent such as 3-propenyloxypropyltrimethoxydecane and 3-methylpropenyloxypropyltrimethoxydecane; 3-isocyanatepropyltrimethoxy a thioether decane coupling agent such as decane or the like, an isocyanate coupling agent such as decane, bis(triethoxymethyl sulfonylpropyl) disulfide or bis(triethoxymethyl sulfonylpropyl) tetrasulfide; Trimethoxy decane, methacryloxypropyltrimethoxy decane, imidazolium, triazine decane, and the like. These may be used alone or in combination of two or more.

The surface treatment of the component (c) can be carried out, for example, by mixing the untreated component (c) with a mixer at a normal temperature and simultaneously adding a surface treatment agent by spraying, followed by stirring for 5 to 60 minutes. As the mixer, a well-known mixer can be used, and examples thereof include a blender of a V blender, a ribbon blender, a double cone blender, a mixer such as a Henschel mixer, and a concrete mixer, and a ball mill. , milling cutter grinding machine, etc. Further, when the absorbent material is pulverized by a ball mill or the like, the surface treatment may be carried out by mixing the above-mentioned high-carbon fatty acid, alkyl decane or decane coupling agent. The amount of the surface treatment agent to be treated varies depending on the type of the component (c), the type of the surface treatment agent, and the like, and is preferably 1 to 10 parts by mass based on 100 parts by mass of the component (c).

The content of the component (c) in the resin composition is not particularly limited. However, from the viewpoint of maintaining the adhesion between the resin composition layer and the substrate such as glass and the transparency of the resin composition layer, the content of the non-volatile components in the resin composition is preferably 60% by mass per 100% by mass. The mass% or less is preferably 55 mass% or less, more preferably 50 mass% or less, and still more preferably 45 mass% or less. In addition, the content of the non-volatile component in the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, and 30% by mass, from the viewpoint of sufficiently obtaining the effect of the hygroscopicity. More than % is better.

Specific examples of the component (c) in the present invention include the following: DHT-4C (manufactured by Kyowa Chemical Industry Co., Ltd.): semi-baked hydrotalcite (average particle diameter: 400 nm, BET specific surface area: 15 m ² /g) - DHT-4A-2 (manufactured by Kyowa Chemical Industry Co., Ltd.): semi-calcined hydrotalcite (average particle size: 400 nm, BET specific surface area: 13 m ² /g) ・KW-2200 (manufactured by Kyowa Chemical Industry Co., Ltd.): firing Hydrotalcite (average particle diameter: 400 nm, BET specific surface area: 146 m ² /g) ・DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.): unfired hydrotalcite (average particle diameter: 400 nm, BET specific surface area: 10 m ² /g) )

<(d) Hardener> The resin composition may further contain (d) a curing agent (hereinafter referred to as "(d) component") from the viewpoint of improving the curing property of the resin composition. The component (d) is not particularly limited, and examples thereof include an amine-based curing agent, an oxime-based curing agent, an imidazole-based curing agent, an anthraquinone-based curing agent, and a phenol-based curing agent. The component (d) may be used alone or in combination of two or more.

The amine-based curing agent is not particularly limited, and examples thereof include a tetra-ammonium salt such as tetramethylammonium bromide or tetrabutylammonium bromide; and DBU (1,8-diazabicyclo[5.4.0]undecene- 7), DBN (1,5-diazabicyclo[4.3.0]nonene-5), DBU-phenolate, DBU-octanoate, DBU-p-toluenesulfonate, DBU-antinate, DBU- a diazabicyclo compound such as a phenol novolac resin salt; a grade 3 such as benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-ginole (diaminomethyl)phenol A dimethyl urea compound such as an amine or a salt thereof, an aromatic dimethyl urea, an aliphatic dimethyl urea or an aromatic dimethyl urea; or the like. These may be used alone or in combination of two or more.

The lanthanide hardener is not particularly limited, and examples thereof include dicyandiamide, 1-methyl hydrazine, 1-ethyl hydrazine, 1-cyclohexyl fluorene, 1-phenyl fluorene, and 1-(o-tolyl) fluorene. Dimethyl hydrazine, diphenyl hydrazine, trimethyl hydrazine, tetramethyl hydrazine, pentamethyl hydrazine, 1,5,7-triazabicyclo[4.4.0]non-5-ene, 7-methyl -1,5,7-triazabicyclo[4.4.0]non-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allyl biguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, and the like. These may be used alone or in combination of two or more.

The imidazole-based curing agent is not particularly limited, and examples thereof include 1H-imidazole, 2-methylimidazole, 2-phenyl-4-methylimidazole, and 1-cyanoethyl-2-ethyl-4-methyl-imidazole. , 2-phenyl-4,5-bis(hydroxymethyl)-imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methyl Imidazole, 2-phenylimidazole, 2-dodecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and the like. These may be used alone or in combination of two or more.

The lanthanide hardener is not particularly limited, and examples thereof include triphenylphosphine, bismuth borate compound, tetraphenylphosphonium tetraphenyl borate, n-butyl fluorene tetraphenyl borate, tetrabutyl citrate, and (4). -Methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like. These may be used alone or in combination of two or more.

The type of the phenolic curing agent is not particularly limited, and examples thereof include MEH-7700, MEH-7810, MEH-7851 (manufactured by Mingwa Kasei Co., Ltd.), NHN, CBN, GPH (manufactured by Nippon Kayaku Co., Ltd.), SN170, SN180, and SN190. SN475, SN485, SN495, SN375, SN395 (made by Dongdu Chemical Co., Ltd.), TD2090 (made by DIC Corporation), etc. Specific examples of the triazine skeleton containing a phenolic curing agent include LA3018 (manufactured by DIC Corporation). Specific examples of the triazine skeleton containing a phenol phenolic curing agent include LA7052, LA7054, and LA1356 (manufactured by DIC Corporation). These may be used alone or in combination of two or more.

The content of the component (d) in the resin composition is not particularly limited. However, in the case of using the component (d), the content of the non-volatile component in the resin composition is preferably 5% by mass or less, and the mass is preferably 5% by mass or less. % below is preferred. On the other hand, in the case of using the component (d), the content of the component (d) is preferably 0.01% by mass or more per 100% by mass of the nonvolatile component in the resin composition, and 0.05% by mass. The above is preferred.

<(e) Resin having a functional group reactive with an epoxy group> Among the resin compositions of the present invention, when a polyolefin-based resin having an epoxy group is used as the component (a), it is desirable to use (e) A resin having a functional group reactive with an epoxy group (hereinafter, simply referred to as "(e) component") is a component for forming a structure in association with the component (a). The functional group reactive with the epoxy group may, for example, be a hydroxyl group, a phenolic hydroxyl group, an amine group, a carboxyl group or an acid anhydride group, and the like is preferably an acid anhydride group. Examples of the acid anhydride group include a group derived from succinic anhydride, a group derived from maleic anhydride, a group derived from glutaric anhydride, and the like. The resin may, for example, be a polyolefin resin (except for a polyolefin resin having an acid anhydride group as the component (a)), an acrylic resin, a melamine resin, a phenol resin, a urea resin, a polyester resin, an alkyd resin, or a polyamic acid. The ethyl ester, the polyimide resin, and the like are preferably a polyolefin resin. The polyolefin-based resin of the component (e) is a polyolefin-based resin similar to the component (a) except that it has a hydroxyl group, a phenolic hydroxyl group, an amine group, a carboxyl group or the like as a functional group. Polybutene is preferred.

The content of the component (e) in the resin composition is not particularly limited. However, in the case of using the component (e), the content of the non-volatile component in the resin composition is preferably 30% by mass or less, and the mass is 20% by mass. % below is preferred. On the other hand, in the case of using the component (e), the content of the component (e) is preferably 5% by mass or more per 100% by mass of the nonvolatile component in the resin composition, and 10% by mass. The above is preferred.

<(f) Resin having a functional group reactive with an acid anhydride group> Among the resin compositions, when a polyolefin-based resin having an acid anhydride group is used as the component (a), it is desirable to use (f) with an acid anhydride. The resin of the functional group of the radical reaction (hereinafter referred to as "(f) component) is referred to as a component for forming a crosslinked structure with the component (a). The functional group reactive with the acid anhydride group may, for example, be a hydroxyl group, a primary or secondary amine group, a thiol group, an epoxy group or an oxetanyl group, and an epoxy group is preferred. The resin may, for example, be a polyolefin resin (except for a polyolefin resin having an epoxy group as the component (a)), an acrylic resin, a melamine resin, a phenol resin, a urea resin, a polyester resin, an alkyd resin, or a polyamine. For example, ethyl formate or polyimide resin is preferably a polyolefin resin. The polyolefin-based resin of the component (f) includes, as a functional group, an amino group having a hydroxyl group, a first-order or a second-order, a thiol group, an epoxy group, an oxetane group, or the like, other than an epoxy group. In addition, the polyolefin resin similar to the component (a) above is preferably polybutene.

The content of the component (f) in the resin composition is not particularly limited. However, in the case of using the component (f), the content of the non-volatile component in the resin composition is preferably 30% by mass or less, and the mass is 20% by mass. % below is preferred. On the other hand, in the case of using the component (f), the content of the component (f) is preferably 5% by mass or more per 100% by mass of the nonvolatile component in the resin composition, and 10% by mass. The above is preferred.

<(g) Plasticizer> The resin composition may further contain (g) a plasticizer (hereinafter referred to as "(g) component"). By using the component (g), the flexibility or formability of the resin composition can be improved. The component (g) is not particularly limited, and a material which is liquid at room temperature is suitably used. Specific examples of the plasticizer include paraffin-based processing oil, naphthenic processing oil, flowing paraffin, polyethylene wax, polypropylene wax, petroleum oil such as petrolatum, castor oil, cottonseed oil, vegetable oil, soybean oil, and palm oil. A vegetable polyaniene such as vegetable oil such as coconut oil or olive oil, liquid polybutene, hydrogenated liquid polybutene, liquid polybutadiene or hydrogenated liquid polybutadiene. The plasticizer used in the present invention is preferably a liquid polyalphaolefin, and particularly preferably a liquid polybutadiene. Further, from the viewpoint of adhesion, the liquid polyalphaolefin preferably has a lower molecular weight, and preferably has a weight average molecular weight of 500 to 5,000 or even 1,000 to 3,000. These plasticizers may be used alone or in combination of two or more. In addition, "liquid" here means the state of the plasticizer at room temperature (25 degreeC). In the case of using the component (g), the content of the non-volatile component in the resin composition is preferably 50% by mass or less per 100% by mass or less, from the viewpoint of not adversely affecting the organic EL device.

<Other Additives> The resin composition may optionally contain various additives other than the above components to the extent that the effects of the present invention are not inhibited. Examples of such an additive include resins other than the above components (a), (e) and (f) (for example, epoxy resin, urethane resin, acrylic resin, polyamide resin, etc.), cerium oxide. , barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, boron nitride, aluminum borate, barium titanate, barium titanate, calcium titanate, magnesium titanate, titanic acid Inorganic fillers such as barium, strontium zirconate and calcium zirconate (except for hygroscopic fillers); organic fillers such as rubber particles, polyfluorene oxide powder, nylon powder, and fluororesin powder; increase in ORBEN, bentonite, etc. An adhesive; an anthraquinone, a fluorine-based, a polymer-based antifoaming agent or a leveling agent; a adhesion imparting agent such as a triazole compound, a thiazole compound, a triazine compound or a porphyrin compound.

<Preparation of Resin Composition> The method of preparing the resin composition is not particularly limited, and a method of mixing the compounded component, adding a solvent or the like as necessary, and mixing using a kneading roll or a rotary mixer, or the like is exemplified.

In the sealing sheet of the present invention, the thickness of the (A) pressure-sensitive adhesive composition layer 1 is not particularly limited, and is preferably 1 μm or more and 3 μm or more from the viewpoint of stable sealing performance and workability. It is better. In addition, from the viewpoints of thickness reduction and embedding property of the sealing structure, it is preferably 100 μm or less, and preferably 50 μm or less.

In addition, the moisture resistance (water vapor shielding property) of the (A) pressure-sensitive adhesive composition layer 1 may vary depending on, for example, the constituent material or thickness of the pressure-sensitive adhesive resin composition layer 1 . When the thickness is within the above-mentioned suitable range (3 to 50 μm), the water vapor permeability in 1 m ² is measured under the measurement conditions of temperature 40 ° C, humidity 90% RH, and 24 hours according to the method of JIS Z 0208:1976. Generally, it is 0.1 to 100 g / (m ² · 24 h), preferably 0.1 to 50 g / (m ² · 24 h).

[(B) Moisture-Retaining Inorganic Film] The sheet for sealing of the present invention has a structure in which (B) the moisture-proof inorganic film 2 is directly formed on one surface of the (A) pressure-sensitive adhesive composition layer. (B) The moisture-proof inorganic film (hereinafter also referred to as "inorganic film") 2 refers to a film which is formed of an inorganic substance and has moisture resistance, and the "inorganic substance" is an organic substance (a substance which generates carbon dioxide or coke black during combustion and becomes carbon) Other than ).

(B) The moisture-proof inorganic film 2 is preferably a heat-treated product of a coating film containing polyazide, from the viewpoint of imparting excellent moisture resistance to the sheet for sealing even if the thickness is thin. The cerium oxide glass film (hereinafter also referred to simply as "(B1) cerium oxide glass film") or (B2) inorganic deposited film.

<(B1) cerium oxide glass film composed of a heat-treated product of a coating film containing polyazane> The (B1) cerium oxide glass film can be formed by (A) pressure-sensitive adhesive resin The polyxaazene-containing coating film on one side of the composition layer 1 is obtained by heating in a gas atmosphere containing water vapor.

As the polyazane, for example, a compound having a repeating unit represented by the formula (1) (hereinafter also referred to as "polyazide compound of the formula (1)") can be used.

(wherein, n represents an arbitrary natural number, and Rx and Ry are each independently, and represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group; a non-hydrolyzable group of an unsubstituted or substituted aryl group, etc., Rz represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted group An alkenyl group, an unsubstituted or substituted aryl group or a non-hydrolyzable group such as an alkylcarboxyalkyl group).

The alkyl group of the above unsubstituted or substituted alkyl group may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a second butyl group, a third butyl group or a positive group. An alkyl group having 1 to 10 carbon atoms such as a pentyl group, an isopentyl group, a neopentyl group, a n-hexyl group, a n-heptyl group or an n-octyl group.

The cycloalkyl group of the above-mentioned unsubstituted or substituted cycloalkyl group may, for example, be a cycloalkyl group having 3 to 10 carbon atoms such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or a cycloheptyl group.

The alkenyl group of the above unsubstituted or substituted alkenyl group may, for example, be a carbon such as a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group or a 3-butenyl group. A few 2 to 10 alkenyl groups.

Examples of the substituent of the alkyl group, the cycloalkyl group and the alkenyl group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a hydroxyl group; a thiol group; an epoxy group; a glycidyl etheroxy group; Alkyl acryloxy; an unsubstituted or substituted aryl group such as phenyl, 4-methylphenyl or 4-chlorophenyl;

The aromatic group of the above-mentioned unsubstituted or substituted aryl group may, for example, be an aryl group having 6 to 10 carbon atoms such as a phenyl group, a 1-naphthyl group or a 2-naphthyl group.

Examples of the substituent of the above-mentioned aromatic group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group; and a methoxy group or an ethoxy group. Alkoxy group having 1 to 6 carbon atoms; nitro group; cyano group; hydroxyl group; thiol group; epoxy group; glycidyl etheroxy group; (meth) propylene oxime group; phenyl group, 4-methylphenyl group An unsubstituted or substituted aryl group such as 4-chlorophenyl;

The alkylcarboalkyl group may, for example, be trimethylformamidinyl group, triethylcarbenyl group, triisopropylcarbenyl group, tri-tert-butylformamyl group, methyldiethylformamidine group or dimethyl group. Alkylalkyl, diethylformamidinyl, methylformamidinyl, ethylformamidinyl, and the like.

Among these, Rx, Ry, and Rz are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

The polyazane of the formula (1) can be produced by a conventionally known method. For example, it can be obtained by reacting a reaction product of an unsubstituted or substituted halogenated decane compound represented by the following formula (2) with a secondary amine with ammonia or a primary amine.

(wherein m represents 2 or 3, X represents a halogen atom, and R ¹ represents any of Rx, Ry, and Rz in the formula (1)).

The secondary amine, the ammonia, and the primary amine may be appropriately selected in accordance with the structure of the target polyazane compound.

The polyazane may be a perhydroxypolyazane having all of Rx, Ry, and Rz in the formula (1) being a hydrogen atom, or an organopolyazane having at least one of Rx, Ry, and Rz which is not a hydrogen atom. In the case of the stability of conversion to polyoxyalkylene (hydrolysis reaction), perhydroxyl polyazane is preferred.

Further, the molecular weight of the polyazane is not particularly limited, and usually the number average molecular weight is about 100 to 50,000. Further, the number average molecular weight can be measured by VPO (vapor pressure drop method) using a toluene solution of a polymer or the like.

The polyazide compound may be used alone or in combination of two or more.

The coating film containing polyazane can be formed, for example, by applying a coating liquid containing polyazide and a solvent onto (A) the pressure-sensitive adhesive composition layer 1 and drying it. Drying can be natural drying or heat drying. Further, in the case where the coating liquid after application is dried by heating, drying and drying of the coating liquid can be continuously performed by heating and drying in a gas atmosphere containing water vapor (heat treatment) in a gas atmosphere containing water vapor (heat treatment) ) The formation of a cerium oxide glass film.

The solvent is not particularly limited as long as it can dissolve the polyazane and deactivate the polyazane, and from the viewpoint of volatility and environmental hygiene, for example, dimethyl ether, diethyl ether, and An ether-based organic solvent such as propyl ether or dibutyl ether is preferred. The ether organic solvent may be used alone or in combination of two or more. In addition, an aromatic hydrocarbon solvent such as anisole may be mixed in an amount of 10% by mass or less based on the ether organic solvent. The concentration of polyazane in the coating liquid is preferably from about 1 to 30% by mass. Further, the coating liquid may contain various additives such as a hydrolysis catalyst.

In addition, such a coating liquid containing polyazane is commercially available as a general term such as "glass coating agent" or "cerium oxide coating agent", and a commercially available product can be used as it is. For example, "Olam Z" manufactured by Artbreed Co., Ltd., "Olam OZ", "NAX110" manufactured by Merck Co., Ltd., "NAX120", "NL110A", "NN110", and the like can be cited.

The method of applying the coating liquid to the (A) pressure-sensitive adhesive composition layer 1 can be applied to the coating liquid as long as it is spin coating, spray coating, dip coating, bar coating or the like. The method of the liquid film of a uniform thickness is not particularly limited. Further, the coating amount of the coating liquid is not particularly limited, and the coating amount is generally 0.01 to 100 g/m ² in terms of solid content, preferably 0.05 to 10 g/m ² . By setting the coating amount in such a range, it is possible to form a coating film of a ceria glass film which is thin and exhibits sufficiently high moisture resistance (water vapor shielding property).

The polyazoxide-containing coating film is heated (heat-treated) in a vapor-containing gas atmosphere in order to produce a cerium oxide glass film, and examples of the vapor-containing gas atmosphere include air, humidified air, and humidified inert gas (for example, nitrogen). , argon, helium, etc.).

The heating (heat treatment) temperature of the coating film is preferably 200 ° C or less, and more preferably 50 to 150 ° C from the viewpoint of preventing (A) denaturation or deterioration of the pressure-sensitive adhesive resin composition layer. The heating time is generally 30 minutes to 5 hours. For example, air having a humidity of 20 to 100% RH or humidified air is a suitable aqueous vapor atmosphere.

Further, the composition of the cerium oxide glass film can be changed stepwise by changing the heating temperature or the water vapor concentration in the gas atmosphere containing water vapor.

The heating means applied to the drying of the coating liquid applied to the (A) pressure-sensitive adhesive composition layer and the heating (heat treatment) of the coating film for producing the ceria glass coating film are not particularly limited, and for example, heat can be used. Circulating oven, hot plate, etc.

Further, various ceramic coating agents containing cerium oxide (SiO ₂ ) as a main component are known, and as shown in the comparative example described later, a ceramic coating is formed on one side of the (A) pressure-sensitive adhesive composition layer. The thermosetting film of the coating film of the coating agent does not impart moisture-proof property to the (A) pressure-sensitive adhesive composition layer, and (A) the water vapor transmission amount of the single-layer sheet of the pressure-sensitive adhesive resin layer. The amount of water vapor permeation of the sheet forming the thermosetting film ((A) pressure-sensitive adhesive composition layer/thermosetting film) is rather increased.

<(B2) Inorganic Material Deposited Film> (B2) The inorganic deposited film is formed by vapor-depositing an inorganic material on one side of the (A) pressure-sensitive adhesive composition layer 1. Examples of the inorganic material include ruthenium compounds such as SiC, SiO ₂ , Si ₃ N ₄ , SiCN, SiOC, SiOCN, polyazane, alkoxy decane, alumina, indium oxide, tin oxide, gallium oxide, and indium tin oxide. (ITO), one or more selected from the group consisting of aluminum-added zinc oxide (AZO), zinc-tin composite oxide (ZTO), aluminum nitride, and zirconia. In particular, it is preferable to use a ruthenium compound from the viewpoint of forming a vapor deposition film which is excellent in adhesion to the (A) pressure-sensitive adhesive composition layer 1 and has high moisture resistance. In other words, the (B2) inorganic deposited film is preferably a vapor deposited film of a ruthenium compound.

(B2) The inorganic deposited film may be a deposited film formed by any one of a chemical vapor deposition method and a physical vapor deposition method.

Further, the (B2) inorganic deposited film may be a single layer film or a multilayer film. In the case where the (B2) inorganic deposited film is a ruthenium compound deposited film, a suitable form of SiO ₂ -SiCN multilayer deposited film containing one or more SiO ₂ deposited films and one or more SiCN deposited films may be mentioned. The thickness of each of the SiO ₂ layer and the SiCN layer in the SiO ₂ -SiCN multilayer deposited film is preferably 10 to 100 nm. Further, the total number of layers is preferably two or more, and six or more layers are preferable. Further, it is preferably 20 or less, and 12 or less is preferable. Further, the SiO ₂ -SiCN multilayer deposited film preferably has an SiO ₂ deposited layer and an SiCN deposited layer alternately laminated from the viewpoint of excellent water vapor shielding properties. Further, each of the SiO ₂ vapor-deposited layer and the SiCN vapor-deposited layer may be a physical vapor-deposited layer or a chemical vapor-deposited layer, and chemical vapor deposition may form a film at a low temperature, from the viewpoints of properties of the sealing sheet and shape stability. It is preferred to alternately laminate the SiO ₂ chemical vapor deposition layer with the SiCN chemical vapor deposition layer.

In the case of forming a SiO ₂ -SiCN multiple vapor-deposited film in which an SiO ₂ chemical vapor deposition layer and an SiCN chemical vapor deposition layer are alternately laminated, a suitable embodiment is as follows.

The pressure in the vapor deposition chamber was maintained at about 1 Pa, the temperature was maintained at about 100 ° C, and SiO ₂ was vapor-deposited using hexamethyldioxane and oxygen as source gases. After the vapor deposition was carried out for about 1 minute, the material gas was switched to hexamethyldioxane and hydrogen gas, and SiCN was further vapor-deposited for about 1 minute. The SiO ₂ -SiCN multiple vapor deposited film in which the SiO ₂ chemical vapor deposition layer and the SiCN chemical vapor deposition layer are alternately laminated is formed until the desired layer structure is repeated.

(B) The thickness of the moisture-proof inorganic film ((B1) cerium oxide glass film, (B2) inorganic material vapor-deposited film) 2 is preferably 1000 nm or less, 500 nm from the viewpoint of thinning the thickness of the sealing structure. The following is preferable, and 400 nm or less is more preferable. Further, from the viewpoint of obtaining a sufficiently high moisture-proof property, it is preferably 10 nm or more, more preferably 20 nm or more, and still more preferably 30 nm or more.

In addition, when the moisture-proof inorganic film 2 has a thickness of 1000 nm or less, the pressure-sensitive adhesive composition layer 1 and the moisture-proof property are prevented from being wet-proof (water vapor-shielding property) by the moisture-proof inorganic film 2 . The two-layer sheet composed of the inorganic inorganic film 2 has a water vapor permeability per 1 m ² under the measurement conditions of a temperature of 40 ° C, a humidity of 90% RH, and a measurement of 24 hours in accordance with the method of JIS Z 0208:1976, with only the resin. the same single composition layer sheet 1 and by the same process conditions as measured per 1m ² of the water vapor permeability of 70% or less (preferably 65% or less, preferably 60% or less) of the moisture-proof property (water vapor Covering) is preferred.

In the sealing sheet of the present invention, the moisture resistance (water vapor shielding property) of the two-layer sheet composed of the resin composition layer 1 and the moisture-proof inorganic coating 2 obtained by peeling the support 3 is based on It is preferable that the water vapor permeability per 1 m ² is 40 g/(m ² · 24 h) or less under the measurement conditions of the temperature of 40 ° C and the humidity of 90% RH and 24 hours measured by the method of JIS Z 0208: 1976, 30 g / (m ² · 24h) The following is preferable, and 20g / (m ² · 24h) or less is more preferable.

[(C) Release-Retained Support] The release-treated support 3 is a support for performing a release treatment on the side on which the resin composition layer 1 is formed, and is used for sealing the sheet for actual use. The support is peeled off before the formation of the structure. Therefore, the release-treated support 3 does not have to have moisture resistance, and it is preferable to have moisture resistance from the viewpoint of preventing moisture from entering the resin composition layer 1 during storage during which the sealing sheet is sealed. .

Examples of the moisture-retaining support include a plastic film having moisture resistance, a metal foil such as copper foil or aluminum foil, and the like. The plastic film having moisture-proof property may, for example, be a plastic film obtained by vapor-depositing an inorganic material such as SiO ₂ , Si ₃ N ₄ , SiCN or amorphous ruthenium on the surface. Here, the plastic film on which the inorganic material is vapor-deposited is suitably, for example, a polyolefin (for example, polyethylene, polypropylene, polyvinyl chloride, etc.) or a polyester (for example, polyethylene terephthalate may be abbreviated as "PET". A plastic film such as a case, a polyethylene naphthalate or the like, a polycarbonate or a polyimide, is particularly preferred as a PET film. Examples of the commercially available moisture-proof plastic film include Techbarrier HX, AX, LX, L series (manufactured by Mitsubishi Plastics Co., Ltd.), or further improved moisture resistance compared with the Techbarrier HX, AX, LX, and L series. The effect of X-BARRIER (made by Mitsubishi Plastics Co., Ltd.). Further, as the support having moisture resistance, an article having a multilayer structure of two or more layers may be used, for example, an article obtained by bonding the plastic film and the metal foil through an adhesive. This item is inexpensive and advantageous from an operational point of view.

Further, as the support 3 for the release treatment, a support having no moisture resistance (for example, a monomer having a plastic film on which the inorganic material is not vapor-deposited on the surface) may be used. The thickness of the support is not particularly limited, and is preferably from 10 to 150 μm, and preferably from 20 to 100 μm, from the viewpoint of usability of the sheet for sealing and the like.

Specific examples of the release agent used for the release treatment include a fluorine-based release agent, a polyoxymethylene-based release agent, and an alkyd-based release agent. The release agent can also be mixed with different types of products.

[(D) Circular Polarizing Plate] A circular polarizing plate is generally composed of a polarizing plate and a quarter-wave plate. In the case where a circularly polarizing plate is used as the support, the quarter-wavelength plate is generally disposed on the side of the resin composition layer for sealing. In the case of using a support including both a circular polarizing plate and a moisture-proof support, the moisture-proof support is preferably disposed on the side of the resin composition layer for sealing, and the quarter-wave plate of the circularly polarizing plate is preferably disposed. Moisture-proof support side. The moisture-proof support and the circularly polarizing plate can be followed by an adhesive or the like. The sheet for sealing of the present invention is directed to a sheet for sealing which is suitable for sealing of an organic EL element, for example, as shown in Fig. 2, and can be made by (B) a moisture-proof inorganic film 2 (A) The surface on the opposite side to the one side of the pressure-sensitive resin composition layer 1 is followed by (D) the circularly polarizing plate 4, and the sealing sheet 11 of the organic EL element having a circular polarizing plate integrated sealing structure can be formed.

In FIG. 2, the same reference numerals as in FIG. 1 denote the same or corresponding portions, and 4 denotes a circularly polarizing plate. The circularly polarizing plate 4 has a retardation film 41 that functions as a quarter-wavelength plate and a polarizing plate (polarizing plate) 42 that directly follows the retardation film 41, and passes through the adhesive layer 5 and then (B) moisture-proof inorganic The surface of the film 2 opposite to (A) the pressure-sensitive adhesive composition layer side. The circularly polarizing plate 4 composed of the retardation film 41 and the polarizing plate (polarizing plate) 42 can be used, and the circularly polarized light described in, for example, Japanese Laid-Open Patent Publication No. 2016-105166, the International Publication No. 2014/003189, and the like can be used. board.

The adhesive agent used in the adhesive layer 5 is not particularly limited as long as it is a highly transparent adhesive, and for example, an acrylic adhesive or a polyvinyl alcohol-based adhesive can be used.

Further, a protective film (not shown) that protects the polarizing plate (polarizing plate) 42 may be provided on the circular polarizing plate 4. As the protective film, a protective film described in, for example, JP-A-2016-105166 or International Publication No. 2014/003189 can be used.

[Production of Sheet for Sealing] The sheet for sealing of the present invention is formed on (A) pressure-sensitive adhesive composition layer 1 formed on (C) release-supported support 3 (B) moisture-proof The inorganic inorganic film 2 can be used.

(A) The pressure-sensitive adhesive resin composition layer 1 may be formed by a method known to a person skilled in the art. For example, a varnish in which a resin composition is dissolved in an organic solvent can be prepared, and a varnish can be applied to the support. It is dried to form. The drying of the organic solvent can be carried out by hot air blowing or the like. In the case where the resin composition of the present invention contains a curable component such as a polyolefin-based resin having an epoxy group, the resin composition layer may be further heated to form a cured resin composition layer.

Examples of the organic solvent include acetone, methyl ethyl ketone (hereinafter referred to as "MEK" for short), and ketones such as cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol. Acetate such as methyl ether acetate or carbitol acetate; carbitol such as cellulite or butyl carbitol; aromatic hydrocarbon such as toluene or xylene; dimethylformamide; An aromatic mixed solvent such as dimethylacetamide or N-methylpyrrolidone; or a solvent oil. Examples of the aromatic mixed solvent include "Swasol" (trade name, manufactured by Maruzen Oil Co., Ltd.) and "Ipzole" (manufactured by Idemitsu Kosan Co., Ltd., trade name). The organic solvent may be used alone or in combination of two or more.

The drying conditions are not particularly limited, and it is preferably 50 to 100 ° C and 1 to 60 minutes. By setting it at 50 ° C or more, it is easy to reduce the amount of solvent remaining in the resin composition layer.

(1) The component (a) uses a polyolefin-based resin having an acid anhydride group and a polyolefin-based resin having an epoxy group, and (2) the component (a) is a polyolefin-based resin having an epoxy group, and The component (e) (that is, a resin having a functional group reactive with an epoxy group) or the component (3) (a) is a polyolefin resin having an acid anhydride group, and the component (f) is used (that is, The resin which can react with the acid anhydride group can heat the resin composition to form a crosslinked structure before the sealing step, or can be heated after the sealing step to form a crosslinked structure. For example, in the case of sealing a member (for example, an organic EL device) by using the sealing sheet of the present invention, the resin composition layer may be preheated to form a crosslinked structure before the sealing step, or the resin composition layer may be heated after the sealing step. And a crosslinked structure is formed. From the viewpoint of heat deterioration of the mitigating element (for example, the organic EL element), it is preferable to form a crosslinked structure by preheating before the sealing step.

In the case where (A) the pressure-sensitive adhesive composition layer 1 is heated before the sealing step, the heating condition is not particularly limited, and the temperature is preferably 50 to 200 ° C, preferably 100 to 180 ° C, and 120 to 160 ° C. Better. The heating time is preferably 15 to 120 minutes, and 30 to 100 minutes is preferred.

In the case where (A) the pressure-sensitive adhesive resin composition layer 1 is thermally cured after the sealing step, the curing temperature is preferably 50 to 150 ° C from the viewpoint of preventing thermal deterioration of the element (for example, an organic EL element), 60~ 100 ° C is preferred, and 60 to 80 ° C is more preferred.

After the (A) pressure-sensitive adhesive composition layer 1 is formed, the (B) moisture-proof inorganic film 2 ((B1) cerium oxide glass film or (B2) inorganic material vapor-deposited film) is formed by the above method. Further, in the case of producing a sealing sheet having the (D) circular polarizing plate 4, it is formed on the surface of (B) the moisture-proof inorganic coating 2 ((B1) cerium oxide glass film or (B2) inorganic vapor-deposited film) The layer of the adhesive or the layer of adhesive 5 is then applied to the circular polarizing plate 4.

<Application of the sheet for sealing> As the sealing sheet of the present invention, an electronic component such as a semiconductor, a solar cell, a high-brightness LED, an LCD, or an EL element can be used, and it is preferable to seal the optical semiconductor such as a solar cell or an organic EL element. It is particularly suitable for use in the sealing of organic EL elements. Specifically, in order to apply the light-emitting portion of the organic EL element to the upper portion and/or the periphery (side portion) of the light-emitting portion of the organic EL element, the sealing sheet of the present invention can be used.

<Organic EL device> The present invention also provides an organic EL device which seals the organic EL element with the above-described sheet for sealing of the present invention. For example, the organic EL device of the present invention can be obtained by laminating the sealing sheet of the present invention on a substrate having an organic EL element. In the sealing operation, the release-treated support 3 is peeled off from the sealing sheet, and the pressure-sensitive adhesive composition layer 1 is directly bonded to the substrate, and the sealing sheet is laminated on the substrate. The lamination method can be batch or continuous in a drum. Further, in the case where the seal is required to be thermally hardened, thermal hardening is performed.

When the organic EL element is sealed by the sealing sheet of the present invention, the thickness of the moisture-proof inorganic film 2 is thin, and the rigidity is lower than that of the sealing substrate (plastic film having an inorganic vapor deposited film, metal foil, etc.). Therefore, the damage to the organic EL element during the sealing operation can be significantly reduced. Further, the sheet for sealing has excellent moisture resistance (water vapor barrier property) by the moisture-proof inorganic film 2, and the pressure-sensitive adhesive composition layer 1 contains a hygroscopic filler, so that a thin thickness can be formed. A sealing structure that is low in water absorption and excellent in moisture permeability. Therefore, it is possible to reduce the thickness and performance of the organic EL device. In addition, an organic EL device that can achieve a function of preventing thinning and high performance, and providing a function of preventing reflection of external light can be easily obtained by using a sealing sheet in which a circular polarizing plate is integrated. [Examples]

The invention is illustrated in more detail below by the examples, but the invention is not limited by these examples. In addition, in the following description, "parts" and "%" in the amounts of the components and the copolymerization units mean "mass parts" and "mass%" unless otherwise specified.

The materials used in the examples and comparative examples are as follows. 1. Pressure-sensitive adhesive composition layer forming material (a) Polyolefin resin ・ACRYFT CM5022 (manufactured by Sumitomo Chemical Co., Ltd.): ethylene-methyl methacrylate copolymer, ethylene unit and methyl methacrylate The total amount of methyl methacrylate units (33%) and the number average molecular weight of 71,000 in the total of 100% of the units. ・Tafthren X1102 (manufactured by Sumitomo Chemical Co., Ltd.): propylene-butene copolymer, propylene unit and butene unit The amount of the butene unit per 100 mass% (29%), the number average molecular weight of 658,000) ・HV-300M (manufactured by Toho Chemical Industry Co., Ltd.): maleic anhydride denatured liquid polybutene (anhydride group concentration: 0.77 mmol/g) , number average molecular weight 2,100) ・HV-1900 (manufactured by JX Energy): polybutene (quantitative molecular weight 2,900)

(b) Adhesive-imparting resin ・Alcon P125 (made by Arakawa Chemical Co., Ltd.): The cyclohexane ring contains a hydrogenated petroleum resin (softening point: 125 ° C)

(c) hygroscopic filler, DHT-4C (manufactured by Kyowa Chemical Industry Co., Ltd.); semi-fired hydrotalcite (average particle diameter: 400 nm, BET specific surface area: 15 m ² /g)

(d) Hardener ・Amine-based hardener (2,4,6-glycol (diaminomethyl)phenol, hereinafter referred to as "TAP")

Organic solvent ・Toluene ・Swasol #1000 (made by Maruzen Oil Co., Ltd.): aromatic mixed solvent

2. Coating agent for inorganic film formation (1) OlamZ (Artbreed Co., Ltd.) polyazane-based glass coating agent (perhydroxylated polyazane) (2) SSG HB21N (Nittobo Medical Co., Ltd.) alkoxy Alkane-based glass coating agent (tetraethoxydecane) (3) G401 (Nikken Co., Ltd.) Alkoxy metal salt-based ceramic coating agent (main component: SiO ₂ , ZrO ₃ ) (4) SZ- 90 (Nikken Co., Ltd.) Alkoxy metal salt ceramic coating agent (main component: polyoxyl resin, ZrO ₃ ) (5) GA1-92-52 (Nikken Co., Ltd.) Alkoxy metal salt・Resin composite ceramic coating agent (main component: SiO ₂ , Al ₂ O ₃ , Ag, acrylic resin) (6) GB1-92 (Nikken Co., Ltd.) Alkoxy metal salt/resin composite ceramic coating (Main component: SiO ₂ , Al ₂ O ₃ , butyral resin) (7) G1-90 (Nikken Co., Ltd.) Alkoxy metal salt ceramic coating agent (main component: SiO ₂ , alkyl alkane) Oxydecane

[Examples 1 to 9 and Comparative Examples 1 to 6] The resin compositions of the formulations shown in Tables 1 and 2 were prepared, and only a pressure-sensitive adhesive was formed on the PET film (support) subjected to the release treatment. The sealing sheet (sheet 1) of the resin composition layer and the pressure-sensitive adhesive composition layer on the release-treated PET film (support) are further formed of the inorganic film shown in Tables 1 and 2. A sealing sheet (sheet 2) of an inorganic film is formed on one surface of the pressure-sensitive adhesive resin composition layer with a coating agent. In addition, among the formulations of the resin composition described in Tables 1 and 2, the amount of components other than the organic solvent is a value in terms of nonvolatile content.

<Example 1> Ethylene-methyl methacrylate copolymer (CM5022, 20% toluene) was used in a three-roll machine in 130 parts of a hydrogenated petroleum resin (Alcon P125, 60% Swasol #1000 solution) containing a cyclohexane ring. 210 parts of solution, 94 parts of polybutene (HV-1900), and semi-baked hydrotalcite (DHT-4C) were dispersed in 100 parts to obtain a mixture. To the obtained mixture, 0.5 parts of an amine-based curing agent (TAP) and 100 parts of toluene were blended, and the obtained mixture was uniformly dispersed in a high-speed rotary mixer to obtain a varnish of a resin composition. The obtained varnish was uniformly coated on a release-treated surface of a PET film (thickness: 38 μm) treated with a polyfluorene-based release agent by a die coater, and heated at 130 ° C for 60 minutes to obtain a varnish. A sheet for sealing (sheet 1) having a pressure-sensitive adhesive composition layer having a thickness of 45 μm.

In the same manner as described above, 10 g of a polyazide-based glass coating agent ("OlamZ", Artbreed Co., Ltd.) was applied onto the pressure-sensitive adhesive resin composition layer of the obtained sealing sheet. Then, film formation was performed by a spin coater at 2000 rpm for 1 minute (coating amount: 1 g/m ² (solid content conversion)). The sheet obtained in this manner was heated at 60 ° C for 30 minutes and then heated at 130 ° C for 60 minutes to obtain a heat treatment of a coating film containing a polyxazane on one side of the pressure-sensitive adhesive resin composition layer. A sheet for sealing (sheet 2) covered with a product (cerium oxide glass film).

<Example 2> Sheets 1 and 2 were produced in the same manner as in Example 1 except that ACRYFT CM5022 was changed to propylene-butene copolymer (X1102).

<Example 3> In addition to changing ACRYFT CM5022 to 40 parts of propylene-butene copolymer (X1102) and 35 parts of maleic anhydride denatured liquid polybutene (HV-300M), and polybutene (HV-1900) Sheets 1 and 2 were produced in the same manner as in Example 1 except that the amount was changed to 60 parts.

<Example 4> On the sheet 1 obtained in Example 1, SiO ₂ was chemically deposited at 30 nm, and then SiCN was chemically deposited to 30 nm. By repeating this operation, a sheet 2 having a SiO ₂ -SiCN multilayer deposited film composed of 6 layers of SiO ₂ chemical vapor-deposited layer + 6 layers of SiCN chemical vapor-deposited layer (total thickness: 360 nm) was obtained. The sheet 1 is the same as in the first embodiment.

<Example 5> Chemical vapor deposition of SiO and SiCN was carried out in the same manner as in Example 4 except that the SiO ₂ chemical vapor deposition layer 3 layer + the SiCN chemical vapor deposition layer 3 layer (total thickness: 180 nm) was changed, and the sheet 2 was obtained. The sheet 1 is the same as in the first embodiment.

<Example 6> A sheet 1 was produced in the same manner as in Example 4 except that the semi-baked hydrotalcite (DHT-4C) was removed, and the same SiO ₂ -SiCN multilayer deposited film (SiO _{2 )} as in Example 4 was formed. 6 layers of a chemical vapor deposition layer + 6 layers of a SiCN chemical vapor deposition layer and a total thickness of 360 nm) were used to obtain a sheet 2.

<Example 7> A sheet 2 was obtained in the same manner as in Example 6 except that the SiO ₂ chemical vapor deposition layer 3 layer + the SiCN chemical vapor deposition layer 3 layer (total thickness: 180 nm) was changed. The sheet 1 is the same as in the sixth embodiment.

<Example 8> Sheets 1 and 2 were produced in the same manner as in Example 4 except that the ethylene-methyl methacrylate copolymer (CM5022) was changed to the propylene-butene copolymer (X1102).

<Example 9> A sheet 2 was obtained in the same manner as in Example 8 except that the SiO ₂ chemical vapor deposition layer 3 layer + the SiCN chemical vapor deposition layer 3 layer (total thickness: 180 nm) was changed. The sheet 1 is the same as in the eighth embodiment.

<Comparative Example 1> A sheet 2 was obtained in the same manner as in Example 1 except that the coating agent was changed from OlamZ to SSG HB21N. The sheet 1 is the same as in the first embodiment.

<Comparative Example 2> A sheet 2 was obtained in the same manner as in Example 1 except that the coating agent was changed from OlamZ to G401. The sheet 1 is the same as in the first embodiment.

<Comparative Example 3> A sheet 2 was obtained in the same manner as in Example 1 except that the coating agent was changed from OlamZ to SZ-90. The sheet 1 is the same as in the first embodiment.

<Comparative Example 4> A sheet 2 was obtained in the same manner as in Example 1 except that the coating agent was changed from OlamZ to SA1-92-52. The sheet 1 is the same as in the first embodiment.

<Comparative Example 5> A sheet 2 was obtained in the same manner as in Example 1 except that the coating agent was changed from OlamZ to GB1-92. The sheet 1 is the same as in the first embodiment.

<Comparative Example 6> A sheet 2 was obtained in the same manner as in Example 1 except that the coating agent was changed from OlamZ to G1-90. The sheet 1 is the same as in the first embodiment.

The moisture permeability (water vapor transmission amount) of the sealing sheets of the examples and the comparative examples obtained in the above manner was evaluated as described below. The results are disclosed in Tables 1 and 2. In addition, the fraction of Alcon P125 and CM5022 in the material composition of the pressure-sensitive adhesive composition layer in Tables 1 and 2 is a solid content conversion value.

[Evaluation of moisture permeability (water vapor transmission amount) of the sheet for sealing] (1) Measurement of the sheet 1 by the method of JIS Z 0208: 1976 under the conditions of a temperature of 40 ° C, a humidity of 90% RH and 24 hours The water vapor permeation amount per 1 m ² of the pressure-sensitive adhesive resin composition layer (thickness; 45 μm) without the inorganic film peeled off by the support (PET film). This water vapor permeation amount was defined as the water vapor permeation amount I. (2) A pressure-sensitive adhesive composition having an inorganic film peeled off from a support (PET film) of the sheet 2 at a temperature of 40 ° C, a humidity of 90% RH, and a condition of 24 hours in accordance with JIS Z 0208:1976 The water vapor permeation amount per 1 m ² of the layer (thickness: 45 μm). This water vapor permeation amount was defined as the water vapor permeation amount II.

(Evaluation) The water vapor transmission amount (water vapor transmission amount I) of the sheet 1 and the water vapor transmission amount (water vapor transmission amount II) of the sheet 2 were compared in accordance with the following criteria. Very good (◎): When the water vapor transmission amount I is set to 1, the water vapor transmission amount II is less than 0.7 (water vapor transmission amount II / water vapor transmission amount I < 0.7). Good (○): water vapor permeation amount When the amount I is set to 1, the water vapor permeation amount II is 0.7 or more and less than 1 (0.7 ≦ water vapor transmission amount II / water vapor transmission amount I < 1). (X): When the water vapor transmission amount I is set to 1, The water vapor transmission amount II is 1 or more (1 ≦ water vapor transmission amount II / water vapor transmission amount I)

As shown in Tables 1 and 2, in comparison with Examples 1 to 9 and Comparative Examples 1 to 6, it was found that a coating film containing polyazoxide was formed on one surface of the pressure-sensitive adhesive resin composition layer. The vapor-deposited film of the cerium oxide glass film or the cerium compound which consists of a heat-processed product, and the moisture-proof property of the sealing sheet is remarkably improved.

The present application is based on Japanese Patent Application No. 2017-058073, the entire contents of which are incorporated herein by reference.

1‧‧‧ Pressure-sensitive adhesive resin layer

2‧‧‧Moisture-proof inorganic film

3‧‧‧Removed support

4‧‧‧Polar polarizer

5‧‧‧ adhesive layer

41‧‧‧ phase difference film

42‧‧‧Polarizer

10, 11‧‧‧Seal sheet

Fig. 1 is a schematic cross-sectional view showing a sheet for sealing according to an embodiment of the present invention. Fig. 2 is a schematic cross-sectional view showing a sheet for sealing according to another embodiment of the present invention.

Claims (16)

A sheet for sealing comprising (A) a pressure-sensitive adhesive composition layer and a (B) moisture-proof inorganic film directly formed on one surface of the (A) pressure-sensitive adhesive composition layer. The sealing sheet according to claim 1, wherein the (B) moisture-proof inorganic film is (B1) a cerium oxide glass film composed of a heat-treated product of a coating film containing polyazoxide, or (B2) an inorganic substance. The film is evaporated. A sealing sheet according to claim 2, which is a polyhydroxyazane containing polydecazane. The sealing sheet of claim 2, wherein the (B2) inorganic deposited film is a ruthenium compound deposited film. The sealing sheet according to claim 4, wherein the ruthenium compound vapor-deposited film is a SiO ₂ -SiCN multilayer deposited film containing a SiO ₂ deposited film and a SiCN deposited film. Item 5 of the sealing sheet for the request, wherein the SiO ₂ -SiCN evaporated multilayer film of SiO ₂ -SiCN SiO ₂ multilayer film vapor deposited film forming deposited film to interact with SiCN. The sealing sheet according to any one of claims 1 to 6, wherein (B) the moisture-proof inorganic film has a thickness of 1000 nm or less. The sealing sheet according to any one of claims 1 to 7, wherein the (A) pressure-sensitive adhesive composition layer has a thickness of 3 to 50 μm. The sealing sheet according to any one of claims 1 to 8, wherein the (A) pressure-sensitive adhesive composition layer contains a hygroscopic filler. The sealing sheet according to any one of claims 1 to 9, wherein the (A) pressure-sensitive adhesive composition layer contains an adhesion-imparting resin. The sealing sheet according to any one of claims 1 to 10, further comprising (C) a release-treated support, and having (C) a release-treated support/(A) pressure-sensitive adhesive resin The composition layer/(B) is formed by laminating a moisture-proof inorganic film. The sealing sheet according to claim 11, wherein the (C) release-treated support is a moisture-proof support. The sealing sheet according to any one of claims 1 to 12, which is used for sealing an organic EL element. The sheet for sealing according to any one of claims 1 to 10, wherein the surface of the (B) moisture-proof inorganic film opposite to the side of the (A) pressure-sensitive adhesive composition layer is further followed by (D) circularly polarized light. The sheet is formed and is a sheet for sealing of an organic EL element. The sealing sheet according to claim 11 or 12, wherein the surface of the (B) moisture-proof inorganic film opposite to the side of the (A) pressure-sensitive adhesive composition layer is further followed by a (D) circular polarizing plate. Further, it is a sheet for sealing of an organic EL element. An organic EL device obtained by sealing an organic EL element with a sheet for sealing according to any one of claims 1 to 10 and 14.