WO2018174116A1 - Sheet for sealing - Google Patents

Sheet for sealing Download PDF

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Publication number
WO2018174116A1
WO2018174116A1 PCT/JP2018/011245 JP2018011245W WO2018174116A1 WO 2018174116 A1 WO2018174116 A1 WO 2018174116A1 JP 2018011245 W JP2018011245 W JP 2018011245W WO 2018174116 A1 WO2018174116 A1 WO 2018174116A1
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Prior art keywords
resin composition
sealing
moisture
group
composition layer
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PCT/JP2018/011245
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French (fr)
Japanese (ja)
Inventor
達也 本間
学 増山
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味の素株式会社
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Priority to JP2019507726A priority Critical patent/JP7099441B2/en
Publication of WO2018174116A1 publication Critical patent/WO2018174116A1/en

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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a sealing sheet, and more particularly to a sealing sheet that can form a highly moisture-proof sealing structure by itself.
  • organic EL (Electroluminescence) element is a light-emitting element using an organic substance as a light-emitting material, and has recently attracted attention because it can emit light with high luminance at a low voltage.
  • organic EL elements are extremely vulnerable to moisture, and the light emitting material (light emitting layer) is altered by moisture, resulting in a decrease in luminance, no light emission, or peeling of the interface between the electrode and the light emitting layer due to moisture. There is a problem that the metal is oxidized to increase the resistance.
  • a sealing layer made of a resin composition is formed so as to cover the entire surface of the light emitting layer of the organic EL element formed on the substrate. The element is sealed.
  • Patent Document 1 discloses a polyisobutylene resin, a polyisoprene resin having a functional group capable of reacting with an epoxy group and / or a polyisobutylene resin, a tackifying resin, and an epoxy.
  • a resin composition containing a resin is disclosed.
  • Patent Document 2 discloses a resin composition containing a styrene-isobutylene-modified resin and a tackifier resin.
  • a hygroscopic filler may be mix
  • Sealing of the organic EL element with such a resin composition may be performed by a sealing sheet in which a resin composition layer is formed on a support from the viewpoints of productivity, sealing workability, and the like.
  • a sealing sheet in which a resin composition layer is formed on a support from the viewpoints of productivity, sealing workability, and the like.
  • a moisture-proof support or a sealing substrate may be used.
  • thermosetting is performed.
  • a moisture-proof plastic film a metal foil such as a copper foil or an aluminum foil, or the like is used.
  • the moisture-proof plastic film include a plastic film in which an inorganic material such as SiO 2 , SiN, SiCN, and amorphous silicon is deposited on the surface.
  • the present invention has been made in view of the above circumstances, and the problem to be solved is to form a sealing structure having high moisture resistance without including a sealing substrate and a moisture-proof support. It is in providing the sheet
  • the configuration of the present invention for solving the above problems is as follows.
  • a sealing sheet comprising (A) a pressure-sensitive adhesive resin composition layer and (B) a moisture-proof inorganic coating formed directly on one side of the (A) pressure-sensitive adhesive resin composition layer.
  • (B) the moisture-proof inorganic coating is a silica glass coating made of a heat-treated product of (B1) a polysilazane-containing coating, or (B2) is an inorganic vapor deposition coating.
  • Sealing sheet [3] The sealing sheet according to the above [2], wherein the polysilazane contains perhydroxypolysilazane.
  • the silicon compound vapor deposited film is a SiO 2 -SiCN multilayered vapor deposition film comprising SiO 2 deposited film and SiCN deposited film, sheet for sealing the [4], wherein.
  • SiO 2 -SiCN multilayer deposition film, a SiO 2 -SiCN multilayered vapor deposition film SiO 2 deposited film and SiCN deposited film are alternately formed, the [5] encapsulating sheet according.
  • a circularly polarizing plate is further adhered to the surface of the moisture-proof inorganic coating on the side opposite to the side of the (A) pressure-sensitive adhesive resin composition layer, thereby sealing the organic EL device
  • the sealing sheet according to any one of the above [1] to [10], which is a sheet for use.
  • a circularly polarizing plate is further bonded to the surface of the moisture-proof inorganic coating on the side opposite to the side of the (A) pressure-sensitive adhesive resin composition layer, thereby sealing the organic EL device
  • the sealing sheet of the present invention it is possible to form a sealing structure having high moisture resistance without including a sealing substrate or a moisture-proof support, and therefore, the sealing structure can be made thin. it can. Therefore, for example, a thin organic EL device can be obtained by using the sealing sheet of the present invention for sealing an organic EL element.
  • FIG. 1 is a diagram schematically showing a cross section of a sealing sheet according to an embodiment of the present invention.
  • the sealing sheet of the present invention includes (A) the pressure-sensitive adhesive resin composition layer 1 and (A) the pressure-sensitive adhesive resin composition layer, as shown in the sealing sheet 10 of one embodiment. (B) at least the moisture-proof inorganic coating 2 formed directly on one side.
  • the sealing sheet of the present invention further includes (C) a release-treated support 3 as shown in FIG. 1, and (C) a release-treated support 3 / ( A) A sheet having a laminated structure of a pressure-sensitive adhesive resin composition layer 1 / (B) a moisture-proof inorganic coating 2.
  • the release-treated support 3 is a support for forming the (A) pressure-sensitive adhesive resin composition layer 1, and before actually sealing the sealing target, A) It peels from the pressure-sensitive-adhesive resin composition layer 1. Therefore, the release-treated support 3 does not necessarily have moisture resistance, but after the production of the sealing sheet, during the storage period of the sealing sheet until the sealing operation is performed ( A) From the viewpoint of preventing moisture from entering the pressure-sensitive adhesive resin composition layer 1, (C) a support having moisture resistance can be used as the support 3 subjected to the release treatment.
  • the pressure-sensitive adhesive resin composition layer 1 is a layer for forming a sealing layer adhered to a sealing target by laminating a sealing sheet on the sealing target such as an organic EL element. It is formed by a pressure-bonding resin composition.
  • the pressure-sensitive adhesive resin composition forming the pressure-sensitive adhesive resin composition layer 1 (hereinafter also simply referred to as “resin composition”) is preferably a resin composition having adhesiveness and hygroscopicity,
  • the resin composition containing (a) polyolefin resin, (b) adhesive resin, and (c) hygroscopic filler is mentioned. Since the (A) pressure-sensitive adhesive resin composition layer 1 has hygroscopicity, it is possible to effectively prevent moisture from reaching the object to be sealed.
  • the (a) polyolefin resin (hereinafter also abbreviated as “component (a)”) is not particularly limited as long as it has a skeleton derived from an olefin monomer.
  • examples of polyolefin resins include polyethylene resins, polypropylene resins, polybutene resins, and polyisobutylene resins.
  • the polyolefin resin may be a homopolymer, a random copolymer, or a block copolymer.
  • the copolymer includes (i) a copolymer of two or more olefins, (ii) a copolymer of an olefin and a non-conjugated diene, or (iii) a monomer other than an olefin such as an olefin and methyl methacrylate or styrene. And a copolymer thereof (excluding non-conjugated dienes).
  • the olefin can use 1 type (s) or 2 or more types.
  • a preferred example of a homopolymer is polybutene, for example.
  • Preferred examples of the copolymer include ethylene-nonconjugated diene copolymer, ethylene-propylene copolymer, ethylene-butene-nonconjugated diene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-propylene- Butene copolymer, propylene-butene copolymer, propylene-butene-nonconjugated diene copolymer, isobutylene-butene copolymer, isobutylene-butene-nonconjugated diene copolymer, styrene-isobutylene copolymer, styrene- Examples include isobutylene-styrene copolymer and ethylene-methyl methacrylate copolymer.
  • the polyolefin-based resin has an acid anhydride group (that is, a carbonyloxycarbonyl group (that is, a carbonyloxycarbonyl group) from the viewpoint of imparting excellent physical properties such as adhesion of the resin composition layer to an object to be sealed and adhesion and heat resistance of the resin composition layer.
  • an acid anhydride group that is, a carbonyloxycarbonyl group (that is, a carbonyloxycarbonyl group) from the viewpoint of imparting excellent physical properties such as adhesion of the resin composition layer to an object to be sealed and adhesion and heat resistance of the resin composition layer.
  • -CO-O-CO-) and / or polyolefin resins having an epoxy group.
  • 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 can have one type or two or more types.
  • the polyolefin resin having an acid anhydride group can be obtained, for example, by an unsaturated compound having an acid anhydride group and graft-modifying the polyolefin resin under radical reaction conditions. Moreover, you may make it carry out radical copolymerization of the unsaturated compound which has an acid anhydride group with an olefin.
  • the polyolefin resin having an epoxy group is an unsaturated compound having an epoxy group such as glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, allyl glycidyl ether, etc. It can be obtained by graft modification with Moreover, you may make it carry out radical copolymerization of the unsaturated compound which has an epoxy group with an olefin.
  • polyolefin resin having an acid anhydride group for example, liquid polybutene having an acid anhydride group is preferable, and maleic anhydride-modified liquid polybutene is more preferable.
  • polyolefin-based resin having an epoxy group for example, an epoxy-modified polyethylene having an epoxy group, an epoxy-modified polypropylene, an epoxy-modified polybutene and the like are preferable.
  • 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 is obtained from the value of the acid value defined as the number of mg of potassium hydroxide necessary to neutralize the acid present in 1 g of resin according to the description of JIS K 2501.
  • the amount of the polyolefin resin having an acid anhydride group in the component (a) is preferably 0 to 70% by mass, more preferably 10 to 50% by mass.
  • the concentration of the epoxy group in the polyolefin 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 based on JIS K 7236-1995.
  • the amount of the polyolefin resin having an epoxy group in the component (a) is preferably 0 to 70% by mass, more preferably 10 to 50% by mass.
  • the number average molecular weight of the component (a) is not particularly limited, but is 1,000 from the viewpoint of providing good coatability of the varnish of the resin composition and good compatibility with other components in the resin composition. , 000 or less, more preferably 750,000 or less, even more preferably 500,000 or less, still more preferably 400,000 or less, even more preferably 300,000 or less, particularly preferably 200,000 or less, 000 or less is most preferable. On the other hand, it is preferably 2,000 or more from the viewpoint of preventing repelling during coating of the varnish of the resin composition, expressing moisture resistance of the formed resin composition layer, and improving mechanical strength. 000 or more is more preferable, 30,000 or more is even more preferable, and 50,000 or more is particularly preferable.
  • the number average molecular weight is measured by gel permeation chromatography (GPC) method (polystyrene conversion).
  • GPC gel permeation chromatography
  • the number average molecular weight by the GPC method is specifically determined by moving LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex® K-800P / K-804L / K-804L manufactured by Showa Denko KK as a column. Using toluene or the like as a phase, the measurement can be made at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.
  • a liquid polyolefin preferably liquid polybutene and / or maleic anhydride-modified liquid polybutene
  • a number average molecular weight of 1000 or more and 3000 or less is added in an amount of 10 mass of the component (a).
  • the aspect contained in% or more and 90 mass% or less is mentioned.
  • the (a) polyolefin resin in the present invention is preferably amorphous from the viewpoint of suppressing a decrease in fluidity due to thickening of the varnish.
  • amorphous means that the polyolefin resin does not have a clear melting point.
  • DSC differential scanning calorimetry
  • the component may be used alone or in combination of two or more.
  • the content is about 100% by mass in total of the non-volatile content in the resin composition, 80 mass% or less is preferable, 75 mass% or less is more preferable, 70 mass% or less is still more preferable, 60 mass% or less is further more preferable, 55 mass% or less is further more preferable, 50 mass% or less is especially preferable.
  • the content is preferably 1% by mass or more, more preferably 3% by mass or more per 100% by mass of the total nonvolatile content in the resin composition.
  • 5% by mass or more is more preferable, 7% by mass or more is more preferable, 10% by mass or more is further more preferable, 35% by mass or more is particularly preferable, and 40% by mass or more is most preferable.
  • polystyrene resin examples include “OPanol B100” (viscosity average molecular weight: 11,110,000) manufactured by BASF, and “B50SF” (viscosity average molecular weight: 400,000) manufactured by BASF.
  • polybutene resin examples include “HV-1900” (polybutene, number average molecular weight: 2,900) manufactured by JX Energy, and “HV-300M” (maleic anhydride-modified liquid polybutene (“HV”) manufactured by Toho Chemical Industry Co., Ltd. -300 "(modified product of number average molecular weight: 1,400)), number average molecular weight: 2,100, number of carboxy groups constituting acid anhydride group: 3.2 / 1 molecule, acid value: 43. 4 mg KOH / g, acid anhydride group concentration: 0.77 mmol / g).
  • HV-1900 polybutene, number average molecular weight: 2,900
  • HV-300M maleic anhydride-modified liquid polybutene (“HV”) manufactured by Toho Chemical Industry Co., Ltd. -300 "(modified product of number average molecular weight: 1,400)
  • number average molecular weight: 2,100 number of carboxy groups constituting acid anhydride group
  • styrene-isobutylene copolymer examples include “SIBSTAR T102” manufactured by Kaneka (styrene-isobutylene-styrene block copolymer, number average molecular weight: 100,000, styrene content: 30% by mass), manufactured by Starlight 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 Seiko PMC (Glycidyl methacrylate-modified styrene-isobutylene-styrene block copolymer, epoxy group concentration: 0.638 mmol / g, number average molecular weight: 100,000
  • T-YP8920 maleic anhydride modified styrene-isobutylene, manufactured by Seiko PMC) -Styrene copolymer, acid anhydride base concentration : 0.464 mmol / g, number average molecular weight: 35,800
  • T-YP8930 glycidyl methacrylate modified styrene-isobutylene-st
  • polyethylene resin or polypropylene resin examples include “EPT X-3012P” (ethylene-propylene-5-ethylidene-2-norbornene copolymer manufactured by Mitsui Chemicals, “EPT1070” manufactured by Mitsui Chemicals (ethylene-propylene). -Dicyclopentadiene copolymer), “Tuffmer A4085” (ethylene-butene copolymer) manufactured by Mitsui Chemicals, and the like.
  • ethylene-methyl methacrylate copolymer examples include “ACRYFT CM5022” manufactured by Sumitomo Chemical Co., Ltd. (ethylene-methyl methacrylate copolymer, the amount of methyl methacrylate units per 100% by mass in total of ethylene units and methyl methacrylate units: 33 % By mass), “T-YP429” (maleic anhydride-modified ethylene-methyl methacrylate copolymer, amount of methyl methacrylate units per 100% by mass in total of ethylene units and methyl methacrylate units: 32% by mass, acid Anhydride group concentration: 0.46 mmol / g, number average molecular weight: 2,300), “T-YP430” (maleic anhydride modified ethylene-methyl methacrylate copolymer, total of ethylene units and methyl methacrylate units) manufactured by Seiko PMC 100% by weight Of methyl methacrylate unit: 32% by mass, acid anhydride group concentration: 1.18 mmol /
  • propylene-butene copolymer examples include “T-YP341” (glycidyl methacrylate-modified propylene-butene random copolymer manufactured by Seiko PMC Co., Ltd., butene units per 100% by mass in total of propylene units and butene units).
  • T-YP279 maleic anhydride modified propylene-butene random copolymer, propylene unit, manufactured by Seiko PMC
  • T-YP276 manufactured by Seiko PMC
  • T-YP312 maleic anhydride modified propylene- Butene random copolymer, amount of butene units per 100% by mass of
  • Tackifying resin (hereinafter also abbreviated as “component (b)”) is also called a tackifier and is a resin that is added to a plastic polymer to impart tackiness.
  • the component (b) is not particularly limited, and is not limited to terpene resin, modified terpene resin (hydrogenated terpene resin, terpene phenol copolymer resin, aromatic modified terpene resin, etc.), coumarone resin, indene resin, petroleum resin ( Aliphatic petroleum resins, hydrogenated alicyclic petroleum resins, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, alicyclic petroleum resins, dicyclopentadiene petroleum resins and their hydrides) Preferably used.
  • Examples of commercially available products that can be used as the component (b) include the following.
  • Examples of terpene resins include YS resin PX and YS resin PXN (both manufactured by Yasuhara Chemical Co.), and examples of aromatic modified terpene resins include YS resin TO and TR series (both manufactured by Yasuhara Chemical Co., Ltd.).
  • Examples of terpene resins include Clearon P, Clearon M, and Clearon K series (all manufactured by Yashara Chemical Co., Ltd.).
  • Examples of terpene phenol copolymer resins include YS Polystar 2000, Polyster U, Polyster T, Polyster S, and Mighty Ace (any) And the like.
  • Examples of hydrogenated alicyclic petroleum resins include Escorez 5300 series and 5600 series (both manufactured by ExxonMobil).
  • ENDEX155 (manufactured by Eastman) is an aromatic petroleum resin.
  • Quintone D100 (manufactured by Nippon Zeon Co., Ltd.) and the like as an aliphatic aromatic copolymer petroleum resin, and Quintone 1325 and Quintone 1345 (both manufactured by Nippon Zeon Co., Ltd.) as an alicyclic petroleum resin, cyclohexane
  • Examples of the ring-containing hydrogenated petroleum resin include Alcon P100, Alcon P125, and Alcon P140 (all manufactured by Arakawa Chemical Co.), and examples of the cyclohexane ring-containing saturated hydrocarbon resin include TFS13-030 (manufactured by Arakawa Chemical Co., Ltd.).
  • the softening point of the component (b) is preferably 50 to 200 ° C., more preferably 90 to 180 ° C., more preferably 100 to 100 ° C. from the viewpoint that the sheet softens in the resin composition sheet lamination step and has the desired heat resistance. 150 ° C. is more preferable.
  • the softening point is measured by the ring and ball method according to JIS K2207.
  • component (B) Component may be used alone or in combination of two or more.
  • the content of component (b) in the resin composition is not particularly limited. However, from the viewpoint of maintaining good moisture resistance of the resin composition, when the component (b) is used, its content is 80% by mass or less per 100% by mass of the total nonvolatile content in the resin composition. Is preferable, 60 mass% or less is more preferable, 50 mass% or less is more preferable, and 40 mass% or less is particularly preferable. On the other hand, from the viewpoint of having sufficient adhesiveness, when the component (b) is used, its content is preferably 5% by mass or more per 100% by mass of the total nonvolatile content in the resin composition, and is preferably 10% by mass. The above is more preferable, and 15% by mass or more is more preferable.
  • petroleum resins are preferred from the viewpoints of the adhesiveness, moisture permeability resistance, transparency and the like of the resin composition.
  • Examples of petroleum resins include aliphatic petroleum resins, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, and alicyclic petroleum resins.
  • aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, and alicyclic petroleum resins are more preferable from the viewpoints of adhesion, moisture resistance, compatibility, and the like of the resin composition. From the viewpoint of improving transparency, alicyclic petroleum resins are particularly preferred.
  • As the alicyclic petroleum resin a hydrogenated aromatic petroleum resin may be used.
  • the hydrogenation rate of the alicyclic petroleum resin is preferably 30 to 99%, more preferably 40 to 97%, and even more preferably 50 to 90%. If the hydrogenation rate is too low, there is a tendency for transparency to deteriorate 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 1 H-NMR peak intensities of hydrogen in the aromatic ring before hydrogenation and after hydrogenation.
  • a cyclohexane ring-containing hydrogenated petroleum resin and a dicyclopentadiene hydrogenated petroleum resin are particularly preferable. 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, and even more preferably from 500 to 1,000.
  • the hygroscopic filler (hereinafter also abbreviated as “component (c)”) is not particularly limited as long as it is a filler capable of absorbing moisture, but is preferably a hygroscopic metal oxide.
  • the hygroscopic metal oxide means a metal oxide that has the ability to absorb moisture and chemically reacts with the absorbed moisture to become a hydroxide. Specific examples include calcium oxide, magnesium oxide, strontium oxide, aluminum oxide, barium oxide, unfired hydrotalcite, semi-fired hydrotalcite, fired hydrotalcite, and fired dolomite. Of these, semi-calcined hydrotalcite and calcined hydrotalcite are preferable in terms of hygroscopicity.
  • Hydrotalcite can be classified into unfired hydrotalcite, semi-fired hydrotalcite, and fired hydrotalcite.
  • Uncalcined hydrotalcite is 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, It consists of a layer [Mg 1-X Al X (OH) 2 ] X + and a middle layer [(CO 3 ) X / 2 ⁇ mH 2 O] X— which are the basic skeleton.
  • the uncalcined hydrotalcite in the present invention is a concept including a hydrotalcite-like compound such as synthetic hydrotalcite. Examples of the hydrotalcite-like compound include those represented by the following formula (I) and the following formula (II).
  • M 2+ is Mg 2+, a divalent metal ion such as Zn 2+, M 3+ represents a trivalent metal ion such as Al 3+, Fe 3+, A n- is CO 3 2-, Cl Represents an n-valent anion such as ⁇ and NO 3 — , 0 ⁇ x ⁇ 1, 0 ⁇ m ⁇ 1, and n is a positive number.
  • M 2+ is preferably Mg 2+
  • M 3+ is preferably Al 3+
  • a n- is preferably CO 3 2-.
  • 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 ⁇ , NO 3 ⁇
  • x is 2 or more.
  • Z is a positive number of 2 or less
  • m is a positive number
  • n is a positive number.
  • M 2+ is preferably Mg 2+, A n-is preferably CO 3 2-.
  • Semi-fired hydrotalcite refers to a metal hydroxide having a layered crystal structure in which the amount of interlayer water is reduced or eliminated, obtained by firing unfired hydrotalcite.
  • the “interlayer water” refers to “H 2 O” described in the composition formula of the unfired natural hydrotalcite and hydrotalcite-like compound described above using a composition formula.
  • calcined hydrotalcite refers to a metal oxide having an amorphous structure obtained by calcining uncalcined hydrotalcite or semi-calcined hydrotalcite, and not only interlayer water but also hydroxyl groups disappeared by condensation dehydration.
  • Unfired hydrotalcite, semi-fired hydrotalcite and fired hydrotalcite can be distinguished by saturated water absorption.
  • the saturated water absorption of the semi-calcined hydrotalcite is 1% by weight or more and less than 20% by weight.
  • the saturated water absorption of unfired hydrotalcite is less than 1% by weight, and the saturated water absorption of fired hydrotalcite is 20% by weight or more.
  • the saturated water absorption rate of the semi-fired hydrotalcite is preferably 3% by weight or more and less than 20% by weight, more preferably 5% by weight or more and less than 20% by weight.
  • unfired hydrotalcite, semi-fired hydrotalcite and fired hydrotalcite can be distinguished by the thermogravimetric reduction rate measured by thermogravimetric analysis.
  • the thermal weight loss rate at 280 ° C. of the semi-calcined hydrotalcite is less than 15% by mass, and the thermal weight reduction rate at 380 ° C. is 12% by mass or more.
  • the thermal weight reduction rate at 280 ° C. of the unfired hydrotalcite is 15% by mass or more, and the thermal weight reduction rate at 380 ° C. of the sintered hydrotalcite is less than 12% by mass.
  • Thermogravimetric analysis was performed using Hitachi High-Tech Science TG / DTA EXSTAR6300, weighing 5 mg of hydrotalcite into an aluminum sample pan, and without opening the lid, in an atmosphere with a nitrogen flow rate of 200 mL / min.
  • the temperature can be increased from 30 ° C. to 550 ° C. at a temperature increase rate of 10 ° C./min.
  • unfired hydrotalcite, semi-fired hydrotalcite and fired hydrotalcite can be distinguished by the peak and relative intensity ratio measured by powder X-ray diffraction.
  • Semi-calcined hydrotalcite shows a peak that is split into two around 8 to 18 ° by powder X-ray diffraction, or a peak having a shoulder due to the synthesis of two peaks.
  • the uncalcined hydrotalcite has only one peak at around 8 to 18 °, or the relative intensity ratio of the diffraction intensity of the peak or shoulder appearing on the low angle side and the peak or shoulder appearing on the high angle side is in the above range. Get out.
  • the calcined hydrotalcite does not have a characteristic peak in the region of 8 ° to 18 °, but has a characteristic peak at 43 °.
  • Powder X-ray diffraction measurement was performed using a powder X-ray diffractometer (Empyrean, manufactured by PANalytical), counter-cathode CuK ⁇ (1.5405 mm), voltage: 45 V, current: 40 mA, sampling width: 0.0260 °, scanning speed: 0 0.0657 ° / s, diffraction angle range (2 ⁇ ): 5.0131 to 79.9711 °.
  • the peak search uses the peak search function of the software attached to the diffractometer. “Minimum significance: 0.50, minimum peak tip: 0.01 °, maximum peak tip: 1.00 °, peak base width: 2 0.000, method: minimum value of second derivative ”.
  • BET specific surface area of the semi-sintered hydrotalcite is preferably 1 ⁇ 250m 2 / g, more preferably 5 ⁇ 200m 2 / g.
  • the BET specific surface area of semi-calcined hydrotalcite should be calculated using the BET multipoint method by adsorbing nitrogen gas to the sample surface using a specific surface area measuring device (Macsorb HM Model 1210 Mountec) according to the BET method. Can do.
  • the average particle size of the semi-fired hydrotalcite is preferably 1 to 1,000 nm, and more preferably 10 to 800 nm.
  • the average particle size of the semi-calcined hydrotalcite is the median size of the particle size distribution when the particle size distribution is prepared on a volume basis by laser diffraction scattering type particle size distribution measurement (JIS Z 8825).
  • the component surface-treated with a surface treatment agent can be used.
  • a surface treatment agent used for the surface treatment for example, higher fatty acids, alkylsilanes, silane coupling agents and the like can be used, and among these, higher fatty acids and alkylsilanes are preferable.
  • One or more surface treatment agents can be used.
  • higher fatty acid examples include higher fatty acids having 18 or more carbon atoms such as stearic acid, montanic acid, myristic acid, and palmitic acid, among which stearic acid is preferable. You may use these 1 type or in combination of 2 or more types.
  • Alkylsilanes include methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane, octyltriethoxysilane, n-octadecyldimethyl ( And 3- (trimethoxysilyl) propyl) ammonium chloride. You may use these 1 type or in combination of 2 or more types.
  • silane coupling agent examples include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxy.
  • Epoxy silane coupling agents such as silane; mercapto silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane ; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltri Amino-based silane cups such as toxisilane, N-methylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane Ringing agents; Ureido silane coupling agents such
  • the surface treatment of the component (c) can be performed, for example, by adding and spraying the surface treatment agent while stirring and dispersing the untreated component (c) at room temperature with a mixer and stirring for 5 to 60 minutes.
  • a mixer a well-known mixer can be used, for example, blenders, such as V blender, a ribbon blender, and a bubble cone blender, mixers, such as a Henschel mixer and a concrete mixer, a ball mill, a cutter mill, etc. are mentioned.
  • a method of surface treatment by mixing the above-mentioned higher fatty acid, alkylsilanes or silane coupling agent is also possible.
  • the treatment amount of the surface treatment agent varies depending on the type of component (c) or the type of surface treatment agent, but is preferably 1 to 10 parts by mass with respect to 100 parts by mass of 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 a substrate such as glass and the transparency of the resin composition layer, the content is 60 mass per 100 mass% of the total nonvolatile content in the resin composition. % Or less, preferably 55% by mass or less, more preferably 50% by mass or less, and further preferably 45% by mass or less. Further, from the viewpoint of sufficiently obtaining a hygroscopic effect, the content is preferably 10% by mass or more, more preferably 20% by mass or more, and more preferably 30% by mass per 100% by mass of the total nonvolatile content in the resin composition. The above is more preferable.
  • Specific examples of the component (c) in the present invention include the following: DHT-4C (manufactured by Kyowa Chemical Industry Co., Ltd.): Semi-calcined hydrotalcite (average particle size: 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.): calcined hydrotalcite (average particle size: 400 nm, BET specific surface area: 146 m 2 / g) DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.): uncalcined hydrotalcite (average particle size: 400 nm, BET specific surface area: 10 m 2 / g)
  • the resin composition may further contain (d) a curing agent (hereinafter sometimes abbreviated as “component (d)”) from the viewpoint of improving the curing performance of the resin composition.
  • component (d) is not particularly limited, and examples thereof include amine-based curing agents, guanidine-based curing agents, imidazole-based curing agents, phosphonium-based curing agents, and phenol-based curing agents.
  • Component (d) may be used alone or in combination of two or more.
  • the amine curing agent is not particularly limited, but includes quaternary ammonium salts such as tetramethylammonium bromide and tetrabutylammonium bromide; DBU (1,8-diazabicyclo [5.4.0] undecene-7), DBN ( 1,5-diazabicyclo [4.3.0] nonene-5), DBU-phenol salt, DBU-octylate, DBU-p-toluenesulfonate, DBU-formate, DBU-phenol novolac resin salt, etc.
  • quaternary ammonium salts such as tetramethylammonium bromide and tetrabutylammonium bromide
  • DBU 1,8-diazabicyclo [5.4.0] undecene-7
  • DBN 1,5-diazabicyclo [4.3.0] nonene-5
  • DBU-phenol salt DBU-octylate
  • Diazabicyclo compounds such as benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol and their salts, aromatic dimethylurea, aliphatic dimethylurea, aromatic And dimethylurea compounds such as dimethylurea; These may be used alone or in combination of two or more.
  • the guanidine curing agent is not particularly limited, but dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, Trimethyl guanidine, tetramethyl guanidine, pentamethyl guanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4 .0] dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl Biguanide, 1-allyl biguanide, 1-phenyl biguanide 1-(o-to
  • the imidazole curing agent is not particularly limited, but 1H-imidazole, 2-methyl-imidazole, 2-phenyl-4-methylimidazole, 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-methylimidazole, 2-phenyl-imidazole, 2-dodecyl-imidazole, Examples include 2-heptadecylimidazole and 1,2-dimethyl-imidazole. You may use these 1 type or in combination of 2 or more types.
  • the phosphonium curing agent is not particularly limited, but is triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triate.
  • Examples thereof include phenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. You may use these 1 type or in combination of 2 or more types.
  • the type of phenolic curing agent is not particularly limited, but is MEH-7700, MEH-7810, MEH-7851 (Maywa Kasei), NHN, CBN, GPH (Nippon Kayaku), SN170, SN180, SN190. SN475, SN485, SN495, SN375, SN395 (manufactured by Tohto Kasei), TD2090 (manufactured by DIC), and the like.
  • Specific examples of the triazine skeleton-containing phenolic curing agent include LA3018 (manufactured by DIC).
  • Specific examples of the triazine skeleton-containing phenol novolak curing agent include LA7052, LA7054, LA1356 (manufactured by DIC) and the like. You may use these 1 type or in combination of 2 or more types.
  • the content of the component (d) in the resin composition is not particularly limited. However, from the viewpoint of preventing a decrease in moisture permeation resistance, when the component (d) is used, its content is preferably 5% by mass or less per 100% by mass of the total nonvolatile content in the resin composition. The mass% or less is more preferable. On the other hand, from the viewpoint of suppressing tackiness, when the component (d) is used, its content is preferably 0.01% by mass or more per 100% by mass of the total nonvolatile content in the resin composition. The mass% or more is more preferable.
  • ⁇ (E) Resin having a functional group capable of reacting with an epoxy group a functional group capable of reacting with an epoxy group
  • component (e) a functional group capable of reacting with the epoxy group
  • the functional group capable of reacting with the epoxy group include a hydroxyl group, a phenolic hydroxyl group, an amino group, a carboxy group, and an acid anhydride group, and an acid anhydride group is preferable.
  • 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.
  • Examples of the resin include polyolefin resin (excluding the polyolefin resin having an acid anhydride group as component (a)), acrylic resin, melamine resin, phenol resin, urea resin, polyester resin, alkyd resin, polyurethane, polyimide.
  • Examples of the resin include polyolefin resins.
  • the polyolefin resin as the component is the same as the component (a) described above except that it has a hydroxyl group, a phenolic hydroxyl group, an amino group, a carboxy group or the like as a functional group instead of an acid anhydride group.
  • Polyolefin resins are preferred, and polybutene is preferred.
  • the content of the component (e) in the resin composition is not particularly limited. However, from the viewpoint of preventing a decrease in moisture permeation resistance, when the component (e) is used, its content is preferably 30% by mass or less per 100% by mass of the total nonvolatile content in the resin composition. The mass% or less is more preferable. On the other hand, from the viewpoint of suppressing tackiness, when the component (e) is used, the content thereof is preferably 5% by mass or more and preferably 10% by mass or more per 100% by mass of the total nonvolatile content in the resin composition. More preferred.
  • ⁇ (F) Resin having a functional group capable of reacting with an acid anhydride group In the resin composition, when a polyolefin-based resin having an acid anhydride group is used as the component (a), (f) a functional group capable of reacting with the acid anhydride group as a component for forming a crosslinked structure with the component (a). It is desirable to use a resin having a group (hereinafter sometimes abbreviated as “component (f)”).
  • the functional group capable of reacting with the acid anhydride group include a hydroxyl group, a primary or secondary amino group, a thiol group, an epoxy group, and an oxetane group, and an epoxy group is preferable.
  • the resin examples include polyolefin resin (excluding the polyolefin resin having an epoxy group as component (a)), acrylic resin, melamine resin, phenol resin, urea resin, polyester resin, alkyd resin, polyurethane, polyimide resin, etc. And polyolefin resins are preferred.
  • the component (f) is a polyolefin-based resin as described above except that it has a hydroxyl group, a primary or secondary amino group, a thiol group, an epoxy group, an oxetane group, and the like as a functional group instead of an epoxy group (
  • the polyolefin resin similar to a) component is mentioned, A polybutene is preferable.
  • the content of the component (f) in the resin composition is not particularly limited. However, from the viewpoint of preventing a decrease in moisture permeation resistance, when the component (f) is used, its content is preferably 30% by mass or less per 100% by mass of the total nonvolatile content in the resin composition. The mass% or less is more preferable. On the other hand, from the viewpoint of suppressing tackiness, when the component (f) is used, the content thereof is preferably 5% by mass or more, preferably 10% by mass or more, per 100% by mass of the total nonvolatile content in the resin composition. More preferred.
  • the resin composition may further contain (g) a plasticizer (hereinafter sometimes abbreviated as “(g) component”).
  • a plasticizer hereinafter sometimes abbreviated as “(g) component.
  • the flexibility and moldability of the resin composition can be improved.
  • a liquid material is used suitably at room temperature.
  • plasticizers include paraffinic process oil, naphthenic process oil, liquid paraffin, polyethylene wax, polypropylene wax, petroleum jelly and other mineral oils, castor oil, cottonseed oil, rapeseed oil, soybean oil, palm oil, palm oil, olive oil. And other liquid oils such as vegetable oil, liquid polybutene, hydrogenated liquid polybutene, liquid polybutadiene, and hydrogenated liquid polybutadiene.
  • liquid poly ⁇ -olefins are preferable, and liquid polybutadiene is particularly preferable.
  • the liquid poly ⁇ -olefin preferably has a low molecular weight from the viewpoint of adhesiveness, and preferably has a weight average molecular weight in the range of 500 to 5,000, more preferably 1,000 to 3,000.
  • plasticizers may be used alone or in combination of two or more.
  • “liquid” means a state of a plasticizer at room temperature (25 ° C.).
  • the component (g) is used, the content thereof is preferably 50% by mass or less per 100% by mass of the total nonvolatile content in the resin composition from the viewpoint of not exerting an adverse effect on the organic EL element.
  • the resin composition may optionally contain various additives other than the above-described components to the extent that the effects of the present invention are not impaired.
  • additives include resins other than the components (a), (e) and (f) described above (for example, epoxy resins, urethane resins, acrylic resins, polyamide resins, etc.), silica, barium sulfate.
  • Inorganic fillers such as barium oxide and calcium zirconate (excluding hygroscopic fillers); Organic fillers such as rubber particles, silicone powder, nylon powder and fluororesin powder; Thickeners such as Orben and Benton; Silicone , Fluorinated or polymeric antifoaming agent or levelin Agent; triazole compounds, thiazole compounds, triazine compounds, adhesion imparting agents such as porphyrin compounds; and the like.
  • the method for preparing the resin composition is not particularly limited, and examples thereof include a method in which the compounding components are mixed using a kneading roller, a rotary mixer, or the like, if necessary, by adding a solvent or the like.
  • the thickness of the (A) pressure-sensitive adhesive resin composition layer 1 in the sealing sheet of the present invention is not particularly limited, but is preferably 1 ⁇ m or more from the viewpoint of stable sealing performance, handleability, and the like, and is 3 ⁇ m or more. Is more preferable. Further, from the viewpoints of thinning of the sealing structure, embedding property, etc., 100 ⁇ m or less is preferable, and 50 ⁇ m or less is more preferable.
  • the moisture-proof property (water vapor barrier property) of the pressure-sensitive adhesive resin composition layer 1 alone depends on, for example, the constituent material and thickness of the pressure-sensitive adhesive resin composition layer 1, but the thickness is when it is above the preferred range (3 ⁇ 50 ⁇ m), JIS Z 0208: is measured by a method conforming to 1976, temperature 40 ° C., 1 m 2 per water vapor transmission of the measurement conditions of humidity 90% RH, 24 hours The degree is generally from 0.1 to 100 g / (m 2 ⁇ 24 h), preferably from 0.1 to 50 g / (m 2 ⁇ 24 h).
  • the sealing sheet of the present invention has a configuration in which (B) a moisture-proof inorganic coating 2 is directly formed on one surface of the (A) pressure-sensitive adhesive resin composition layer.
  • (B) Moisture-proof inorganic coating (hereinafter also simply referred to as “inorganic coating”) 2 is a moisture-proof coating formed of an inorganic substance, and “inorganic substance” is an organic substance (carbon dioxide when burned). Substances other than those that occur or become black and charcoal.
  • (B1) Silica glass coating comprising heat-treated product of polysilazane-containing coating>
  • the said (B1) silica glass film is obtained by heating the polysilazane containing coating film formed in the single side
  • n represents an arbitrary natural number.
  • Rx and Ry each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted group.
  • Rz is a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group A non-hydrolyzable group such as a group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group or an alkylsilyl group.) (Hereinafter also referred to as “polysilazane compound of formula (1)”) having a repeating unit represented by the formula:
  • alkyl group of the unsubstituted or substituted alkyl group examples include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, Examples thereof include alkyl groups having 1 to 10 carbon atoms such as n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group and n-octyl group.
  • Examples of the unsubstituted or substituted cycloalkyl group include cycloalkyl groups having 3 to 10 carbon atoms such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
  • alkenyl group of the unsubstituted or substituted alkenyl group examples include, for example, a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, and the like. ⁇ 10 alkenyl groups.
  • substituents for the alkyl group, cycloalkyl group and alkenyl group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group
  • halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom
  • hydroxyl group such as hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group
  • An unsubstituted or substituted aryl group such as a phenyl group, a 4-methylphenyl group, and a 4-chlorophenyl group;
  • Examples of the unsubstituted or substituted aryl group include aryl groups having 6 to 10 carbon atoms such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • substituent for the aryl group examples include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkyl groups having 1 to 6 carbon atoms such as methyl group and ethyl group; carbon numbers such as methoxy group and ethoxy group 1-6 alkoxy groups; nitro groups; cyano groups; hydroxyl groups; thiol groups; epoxy groups; glycidoxy groups; (meth) acryloyloxy groups; unsubstituted phenyl groups, 4-methylphenyl groups, 4-chlorophenyl groups, etc.
  • alkylsilyl group examples include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tri-t-butylsilyl group, a methyldiethylsilyl group, a dimethylsilyl group, a diethylsilyl group, a methylsilyl group, and an ethylsilyl group.
  • Rx, Ry, and Rz a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group is preferable.
  • the polysilazane represented by the formula (1) can be produced by a conventionally known method. For example, it can be obtained by reacting ammonia or a primary amine with a reaction product of an unsubstituted or substituted halogenosilane compound represented by the following formula (2) and a secondary amine.
  • R 1 4-m SiX m (2) (In the formula, m represents 2 or 3, X represents a halogen atom, and R 1 represents a substituent of any one of Rx, Ry, and Rz in Formula (1).)
  • Secondary amine, ammonia and primary amine may be appropriately selected according to the structure of the target polysilazane compound.
  • the polysilazane may be a perhydroxypolysilazane in which Rx, Ry, and Rz in the formula (1) are all hydrogen atoms, or an organopolysilazane in which at least one of Rx, Ry, and Rz is not a hydrogen atom.
  • perhydroxypolysilazane is preferable from the viewpoint of stability of conversion to polysiloxane (hydrolysis reaction).
  • the molecular weight of polysilazane is not particularly limited, but usually the number average molecular weight is about 100 to 50,000.
  • the number average molecular weight can be measured by VPO (vapor pressure drop method) using a polymer toluene solution or the like.
  • Polysilazane compounds can be used alone or in combination of two or more.
  • the polysilazane-containing coating film is formed, for example, by applying a coating liquid containing polysilazane and a solvent on (A) the pressure-sensitive adhesive resin composition layer 1 and drying it. Drying may be natural drying or warm drying. In addition, when drying the applied coating liquid by heating and drying in a steam-containing atmosphere, drying of the coating liquid and generation of a silica glass coating by heating (heat treatment) in the steam-containing atmosphere of the coating after drying. Can be done continuously.
  • the solvent is not particularly limited as long as it dissolves polysilazane and is inert to polysilazane, but from the viewpoint of volatility and environmental hygiene, for example, dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, etc.
  • Ether-based organic solvents are preferred.
  • One or more air-based organic solvents can be used.
  • the polysilazane concentration in the coating solution is preferably about 1 to 30% by mass.
  • the coating liquid may contain various additives such as a hydrolysis catalyst.
  • such a polysilazane-containing coating solution is commercially available under names such as “glass coating agent” and “silica coating agent”, and commercially available products can be used as they are.
  • commercially available products include “Olam Z” and “Olam OZ” manufactured by Art Breed Co., Ltd., “NAX110”, “NAX120”, “NL110A”, and “NN110” manufactured by Merck Co., Ltd.
  • a method of applying a coating liquid onto the pressure-sensitive adhesive resin composition layer 1 is a method in which a coating liquid such as spin coating, spray coating, dip coating, bar coating, etc. can be applied to a liquid film having a substantially uniform thickness. If it is, it will not specifically limit.
  • the coating amount of the coating liquid is not particularly limited, but the coating amount is generally 0.01 to 100 g / m 2 , preferably 0.05 to 10 g / m 2 in terms of solid content. When the coating amount is within such a range, it is possible to form a coating film that produces a silica glass coating film that exhibits a sufficiently high moisture-proof property (water vapor barrier property) with a small thickness.
  • the polysilazane-containing coating is heated (heat treatment) in a steam-containing atmosphere.
  • a steam-containing atmosphere examples include air, humidified air, humidified inert gas (for example, nitrogen, argon, helium, etc.) ) And the like.
  • the heating (heat treatment) temperature of the coating film is preferably 200 ° C. or less, more preferably 50 to 150 ° C., from the viewpoint of preventing modification and deterioration of the (A) pressure-sensitive adhesive resin composition layer.
  • the heating time is generally 30 minutes to 5 hours.
  • air having a humidity of 20 to 100% RH or humidified air is a preferable steam-containing atmosphere.
  • composition of the silica glass coating can be changed stepwise by changing the heating temperature, the water vapor concentration in the water vapor-containing atmosphere, and the like.
  • the heating means used for drying the coating liquid applied to the pressure-sensitive adhesive resin composition layer and heating (heat treatment) of the coating film to produce a silica glass coating is not particularly limited.
  • a heat circulation oven, a hot plate, or the like is used.
  • Various ceramic coating agents containing silica (SiO 2 ) as a main component are known. As shown in a comparative example to be described later, (A) a ceramic coating on one side of the pressure-sensitive adhesive resin composition layer. Even if a thermosetting film of the agent coating is formed, (A) the pressure-sensitive adhesive resin composition layer cannot be given moisture resistance, and (A) the pressure-sensitive adhesive resin composition layer is a single layer. Compared to the water vapor transmission amount of the sheet, the water vapor transmission amount of the sheet ((A) pressure-sensitive adhesive resin composition layer / thermosetting film) on which the thermosetting film is formed becomes larger.
  • the inorganic deposition film is formed by depositing an inorganic substance on one side of the (A) pressure-sensitive adhesive resin composition layer 1.
  • inorganic substances include SiC, SiO 2 , Si 3 N 4 , SiCN, SiOC, SiOCN, polysilazane, alkoxysilane, and other silicon compounds, aluminum oxide, indium oxide, tin oxide, gallium oxide, indium tin oxide (ITO), One or more selected from aluminum-added zinc oxide (AZO), zinc-tin composite oxide (ZTO), aluminum nitride, zirconium oxide and the like can be mentioned.
  • a silicon compound is preferable from the viewpoint that (A) a pressure-sensitive adhesive resin composition layer 1 is excellent in adhesiveness and can form a vapor-deposited film having high moisture resistance. That is, (B2) the inorganic deposited film is preferably a silicon compound deposited film.
  • the inorganic vapor deposition film may be a vapor deposition film formed by either chemical vapor deposition or physical vapor deposition.
  • the inorganic vapor deposited film may be a single layer film or a multilayer film.
  • a preferred embodiment includes a SiO 2 —SiCN multilayer vapor-deposited film including one or more SiO 2 vapor-deposited films and one or more SiCN vapor-deposited films.
  • the thickness of each of the one SiO 2 layer and one SiCN layer is preferably 10 to 100 nm.
  • the total number of layers is preferably 2 or more, more preferably 6 or more. Moreover, 20 layers or less are preferable and 12 layers or less are more preferable.
  • the SiO 2 —SiCN multilayer deposited film is preferably one in which SiO 2 deposited layers and SiCN deposited layers are alternately laminated from the viewpoint of excellent water vapor barrier properties.
  • the SiO 2 vapor deposition layer and the SiCN vapor deposition layer may be either physical vapor deposition layers or chemical vapor deposition layers, but chemical vapor deposition can form a film at a low temperature, and the property stability of the sealing sheet From the viewpoint of shape stability and the like, it is preferable that the SiO 2 chemical vapor deposition layer and the SiCN chemical vapor deposition layer are alternately laminated.
  • a preferred embodiment in the case of forming a SiO 2 -SiCN multiple vapor deposition film in which SiO 2 chemical vapor deposition layers and SiCN chemical vapor deposition layers are alternately laminated is as follows.
  • SiO 2 is deposited using hexamethyldisilazane and oxygen gas as source gases. After this deposition is performed for about 1 minute, the source gas is switched to hexamethyldisilazane and hydrogen gas, and SiCN is deposited for another 1 minute.
  • the thickness of the (B) moisture-proof inorganic coating ((B1) silica glass coating, (B2) inorganic vapor deposition coating) 2 is preferably 1000 nm or less, more preferably 500 nm or less, from the viewpoint of thinning the sealing structure, etc. More preferably, it is 400 nm or less. Further, from the viewpoint of obtaining sufficiently high moisture resistance, the thickness is preferably 10 nm or more, more preferably 20 nm or more, and even more preferably 30 nm or more.
  • the moisture resistance (water vapor barrier property) by the moisture-proof inorganic coating 2 is composed of the pressure-sensitive adhesive resin composition layer 1 and the moisture-proof inorganic coating 2 when the moisture-proof inorganic coating 2 has a thickness of 1000 nm or less.
  • the water vapor permeability per 1 m 2 measured at a temperature of 40 ° C., a humidity of 90% RH, and a measurement time of 24 hours, measured by a method according to JIS Z 0208: 1976 of a two-layer sheet, is only for the resin composition layer 1.
  • Moisture resistance (water vapor barrier property) that is 70% or less (preferably 65% or less, more preferably 60% or less) of water vapor permeability per 1 m 2 measured by the same method and under the same conditions of a single layer sheet. Is preferred.
  • the moisture-proof property (water vapor barrier property) of the two-layer sheet comprising the resin composition layer 1 and the moisture-proof inorganic coating 2 obtained by peeling the support 3 is JIS Z 0208: 1976. It is preferable that the water vapor transmission rate per 1 m 2 measured at a temperature of 40 ° C., a humidity of 90% RH, and a measurement time of 24 hours is 40 g / (m 2 ⁇ 24 h) or less, measured by a method conforming to (m 2 ⁇ 24h) in more preferably from less, although 20g / (m 2 ⁇ 24h) or less still more preferred.
  • the release-treated support 3 is a support that has been subjected to a release treatment on one side on which the resin composition layer 1 is formed, and the sealing sheet is actually used for forming a sealing structure. A support that is peeled off before. For this reason, the release-supported support 3 does not necessarily need moisture resistance, but prevents moisture from entering the resin composition layer 1 during the storage period until the sealing sheet is used for sealing. From this viewpoint, it is preferable to have moisture resistance.
  • Examples of the moisture-proof support include a moisture-proof plastic film, a metal foil such as a copper foil and an aluminum foil, and the like.
  • Examples of the plastic film having moisture resistance include a plastic film in which an inorganic material such as SiO 2 , Si 3 N 4 , SiCN, and amorphous silicon is deposited on the surface.
  • examples of the plastic film on which an inorganic substance is deposited on the surface include, for example, polyolefin (for example, polyethylene, polypropylene, polyvinyl chloride, etc.), polyester (for example, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”).
  • plastic films such as polycarbonate and polyimide are preferred, and PET films are particularly preferred.
  • PET films are particularly preferred.
  • commercially available moisture-proof plastic films include the Tech Barrier HX, AX, LX, L series (Mitsubishi Resin Co., Ltd.) and the moisture barrier effect even more than the Tech Barrier HX, AX, LX, L series.
  • X-BARRIER manufactured by Mitsubishi Plastics
  • a support having moisture resistance a support having a multilayer structure of two or more layers, for example, a laminate of the above plastic film and the above metal foil with an adhesive may be used. This is inexpensive and advantageous from the viewpoint of handling properties.
  • a support having no moisture resistance for example, a single plastic film on which the inorganic material is not deposited on the surface
  • the thickness of the support is not particularly limited, but is preferably from 10 to 150 ⁇ m, more preferably from 20 to 100 ⁇ m, from the viewpoint of handling properties of the sealing sheet.
  • the release agent for the release treatment include a fluorine-based release agent, a silicone-based release agent, and an alkyd resin-based release agent. Different types of release agents may be mixed and used.
  • a circularly polarizing plate is generally composed of a polarizing plate and a quarter wavelength plate.
  • a quarter wavelength plate is arrange
  • a moisture-proof support body is arrange
  • the moisture-proof support and the circularly polarizing plate can be bonded with an adhesive or the like.
  • the sealing sheet of the present invention is particularly intended for a sealing sheet suitable for sealing an organic EL element.
  • (B) a moisture-proof inorganic coating 2
  • (A) pressure-sensitive adhesive.
  • the sealing sheet 11 of the organic EL element which can form the sealing structure which the circularly-polarizing plate integrated by adhering the (D) circularly-polarizing plate 4 to the surface on the opposite side to the conductive resin composition layer 1 side. It can be.
  • the circularly polarizing plate 4 includes a retardation film 41 that functions as a quarter-wave plate, and a polarizer (polarizing plate) 42 that is directly bonded to the retardation film 41, and (B) the moisture-proof inorganic coating 2 ( A) It is bonded to the surface opposite to the pressure-sensitive adhesive resin composition layer side through an adhesive layer 5.
  • a known one can be used, for example, described in JP-A-2016-105166, International Publication No. 2014/003189, etc. Can be mentioned.
  • the adhesive used for the adhesive layer 5 is not particularly limited as long as it is a highly transparent adhesive, and for example, an acrylic adhesive, a polyvinyl alcohol adhesive, or the like is used.
  • the circularly polarizing plate 4 can be provided with a protective film (not shown) that protects the polarizer (polarizing plate) 42.
  • a protective film known ones can be used, and examples thereof include a protective film described in JP-A-2016-105166 and International Publication No. 2014/003189.
  • a moisture-proof inorganic coating 2 is formed on (A) the pressure-sensitive adhesive resin composition layer 1 formed on the release-treated support 3. That's fine.
  • the pressure-sensitive adhesive resin composition layer 1 may be formed by a method known to those skilled in the art. For example, a varnish in which the resin composition is dissolved in an organic solvent is prepared, and the varnish is applied to the support. It can be formed by drying. The organic solvent can be dried by blowing hot air or the like.
  • the resin composition of this invention contains curable components, such as polyolefin resin which has an epoxy group, you may further heat a resin composition layer and may form the cured resin composition layer.
  • organic solvent examples include acetone, methyl ethyl ketone (hereinafter sometimes abbreviated as “MEK”), cyclohexanone and other ketones; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate and other acetic acid.
  • aromatic mixed solvents examples include “Swazole” (trade name, manufactured by Maruzen Petroleum Corporation) and “Ipsol” (trade name, manufactured by Idemitsu Kosan Co., Ltd.). You may use an organic solvent 1 type or in combination of 2 or more types.
  • Drying conditions are not particularly limited, but preferably 50 to 100 ° C. for 1 to 60 minutes. By setting it as 50 degreeC or more, it becomes easy to reduce the amount of solvent which remains in a resin composition layer.
  • the resin composition may be heated before the sealing step to form a crosslinked structure, and after the sealing step. It may be heated to form a crosslinked structure.
  • the resin composition layer when sealing an element (for example, organic EL element) using the sealing sheet of the present invention, the resin composition layer may be preheated before the sealing step to form a crosslinked structure. Then, after the sealing step, the resin composition layer may be heated to form a crosslinked structure. From the viewpoint of reducing thermal deterioration of an element (for example, an organic EL element), it is preferable to form a crosslinked structure by heating in advance before the sealing step.
  • the heating conditions are not particularly limited, but the temperature is preferably 50 to 200 ° C, more preferably 100 to 180 ° C, 120 to 160 ° C. is more preferable.
  • the heating time is preferably 15 to 120 minutes, more preferably 30 to 100 minutes.
  • the curing temperature is preferably 50 to 150 ° C. from the viewpoint of preventing thermal degradation of the element (for example, organic EL element). 60 to 100 ° C. is more preferable, and 60 to 80 ° C. is more preferable.
  • a moisture-proof inorganic coating 2 ((B1) silica glass coating or (B2) inorganic deposition coating) is formed by the method described above.
  • a moisture-proof inorganic coating 2 ((B1) silica glass coating or (B2) inorganic deposition coating) is formed by the method described above.
  • an adhesive layer or the surface of (B) moisture-proof inorganic coating 2 ((B1) silica glass coating or (B2) inorganic substance vapor deposition coating)
  • the pressure-sensitive adhesive layer 5 may be formed and the circularly polarizing plate 4 may be bonded.
  • the encapsulating sheet of the present invention is used for encapsulating electronic components such as semiconductors, solar cells, high-brightness LEDs, LCDs and EL elements, preferably optical semiconductors such as solar cells and organic EL elements.
  • it is suitably used for sealing organic EL elements.
  • the sealing sheet of the present invention is used in order to protect the light emitting part of the organic EL element from the outside by applying to the upper part and / or the periphery (side part) of the light emitting part of the organic EL element. it can.
  • the present invention also provides an organic EL device in which an organic EL element is sealed with the above-described sealing sheet of the present invention.
  • 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. The sealing operation is performed by peeling the support 3 that has been released from the sealing sheet and laminating the sealing sheet on the substrate so that the pressure-sensitive adhesive resin composition layer 1 is in direct contact with the substrate.
  • the laminating method may be a batch method or a continuous method using a roll.
  • thermosetting is performed.
  • the moisture-proof inorganic coating 2 is thin, and the rigidity is small compared to a sealing substrate (plastic film having a deposit of inorganic deposit, metal foil, etc.). Damage to the organic EL element during the sealing operation can be significantly reduced.
  • the sealing sheet has excellent moisture resistance (water vapor barrier property) due to the moisture-proof inorganic coating 2, and the pressure-sensitive adhesive resin composition layer 1 contains a hygroscopic filler. A low and excellent moisture-permeable sealing structure can be formed. For this reason, thickness reduction and performance enhancement of an organic EL device can be achieved.
  • seat which integrated the circularly-polarizing plate is used an organic electroluminescent device provided with the prevention function etc. of the reflection of external light by which thickness reduction and high performance were achieved can be obtained easily.
  • Hygroscopic filler DHT-4C manufactured by Kyowa Chemical Industry Co., Ltd.: Semi-calcined hydrotalcite (average particle size: 400 nm, BET specific surface area: 15 m 2 / g)
  • Coating agent for inorganic film formation (1) OlamZ (Art Breed Co., Ltd.) Polysilazane glass coating agent (perhydroxypolysilazane) (2) SSG HB21N (Nitto Bo Medical Co., Ltd.) Alkoxysilane glass coating agent (tetraethoxysilane) (3) G401 (Niken Corporation) Alkoxy metal salt ceramic coating agent (main components: SiO 2, ZrO 3 ) (4) SZ-90 (Niken Corporation) Alkoxy metal salt ceramic coating agent (main component: silicone resin, ZrO 3 ) (5) GA1-92-52 (Niken Corporation) Alkoxy metal salt / resin hybrid ceramic coating agent (main components: SiO 2 , Al 2 O 3 , Ag, acrylic resin) (6) GB1-92 (Niken Corporation) Alkoxy metal salt / resin hybrid ceramic coating agent (main components: SiO 2 , Al 2 O 3 , butyral resin) (7) G1-90 (Niken Corporation) Alkoxy metal salt ceramic coating
  • Examples 1 to 9 and Comparative Examples 1 to 6 A resin composition having a formulation shown in Table 1 and Table 2 was prepared, and a sealing sheet (sheet 1) in which only a pressure-sensitive adhesive resin composition layer was formed on a release-treated PET film (support); A pressure-sensitive adhesive resin composition layer is formed on the release-treated PET film (support), and the coating film for forming an inorganic film shown in Table 1 and Table 2 is used to form the pressure-sensitive adhesive resin composition layer.
  • a sealing sheet (sheet 2) having an inorganic coating formed on one side was produced.
  • the amount of components other than the organic solvent is a value converted in terms of nonvolatile content.
  • Example 1 130 parts of cyclohexane ring-containing hydrogenated petroleum resin (Alcon P125, 60% swazole # 1000 solution), 210 parts of ethylene-methyl methacrylate copolymer (CM5022, 20% toluene solution), 94 parts of polybutene (HV-1900), and 100 parts of semi-fired hydrotalcite (DHT-4C) was dispersed with three rolls to obtain a mixture. To the obtained mixture, 0.5 part of an amine curing agent (TAP) and 100 parts of toluene were blended, and the obtained mixture was uniformly dispersed with a high-speed rotary mixer to obtain a varnish of a resin composition.
  • TAP an amine curing agent
  • the obtained varnish is uniformly coated with a die coater on a release treatment surface of a PET film (thickness 38 ⁇ m) treated with a silicone release agent, and heated at 130 ° C. for 60 minutes to obtain a thickness.
  • a sealing sheet (sheet 1) having a 45 ⁇ m pressure-sensitive adhesive resin composition layer was obtained.
  • Sheets 1 and 2 were produced in the same manner as in Example 1 except that ACRYFT CM5022 was changed to a propylene-butene copolymer (X1102).
  • Example 3 ACRYFT CM5022 was changed to 40 parts of propylene-butene copolymer (X1102) and 35 parts of maleic anhydride-modified liquid polybutene (HV-300M), and polybutene (HV-1900) was changed to 60 parts.
  • X1102 propylene-butene copolymer
  • HV-300M maleic anhydride-modified liquid polybutene
  • HV-1900 polybutene
  • Example 4 After SiO 2 was chemically deposited on the sheet 1 obtained in Example 1 by 30 nm, SiCN was chemically deposited by 30 nm. This was repeated to obtain a sheet 2 having a SiO 2 —SiCN multilayer vapor deposition film composed of 6 SiO 2 chemical vapor deposition layers + 6 SiCN chemical vapor deposition layers (total thickness 360 nm).
  • the sheet 1 is the same as that in the first embodiment.
  • Example 5 A sheet 2 was obtained by performing chemical vapor deposition of SiO and SiCN in the same manner as in Example 4 except that it was changed to 3 layers of SiO 2 chemical vapor deposition layer and 3 layers of SiCN chemical vapor deposition layer (total thickness 180 nm).
  • the sheet 1 is the same as that in the first embodiment.
  • Example 6 A sheet 1 was prepared in the same manner as in Example 4 except that the semi-fired hydrotalcite (DHT-4C) was removed, and the same SiO 2 -SiCN multilayered vapor-deposited coating (SiO 2 chemical vapor deposition layer 6 layers) as in Example 4 + SiCN chemical vapor deposition layer 6 layers, total thickness 360 nm) was formed to obtain a sheet 2.
  • DHT-4C semi-fired hydrotalcite
  • SiO 2 chemical vapor deposition layer 6 layers SiO 2 chemical vapor deposition layer 6 layers
  • Example 7 A sheet 2 was obtained in the same manner as in Example 6 except that it was changed to 3 SiO 2 chemical vapor deposition layers + 3 SiCN chemical vapor deposition layers (total thickness 180 nm). Sheet 1 is the same as in Example 6.
  • 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 it was changed to 3 SiO 2 chemical vapor deposition layers + 3 SiCN chemical vapor deposition layers (total thickness 180 nm). Sheet 1 is the same as in Example 8.
  • 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 that in the first embodiment.
  • 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 that in the first embodiment.
  • 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 that in the first embodiment.
  • 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 that in the first embodiment.
  • 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 that in the first embodiment.
  • 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 that in the first embodiment.
  • the moisture permeation resistance (water vapor permeation amount) of the sealing sheets of Examples and Comparative Examples obtained as described above was evaluated as follows. The results are shown in Tables 1 and 2.
  • the number of parts of Alcon P125 and CM5022 in the material composition of the pressure-sensitive adhesive resin composition layer in Tables 1 and 2 is a solid content conversion value.

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

封止用シートSealing sheet
　本発明は封止用シートに関し、詳しくは、それのみで高い防湿性の封止構造を形成し得る封止用シートに関する。 The present invention relates to a sealing sheet, and more particularly to a sealing sheet that can form a highly moisture-proof sealing structure by itself.
　有機ＥＬ（Electroluminescence）素子は発光材料に有機物質を使用した発光素子であり、低電圧で高輝度の発光を得ることができるため近年脚光を浴びている。しかしながら、有機ＥＬ素子は水分に極めて弱く、発光材料（発光層）が水分によって変質して、輝度が低下したり、発光しなくなったり、電極と発光層との界面が水分の影響で剥離したり、金属が酸化して高抵抗化してしまったりする問題がある。このため、素子内部を外気中の水分から遮断するために、例えば、基板上に形成された有機ＥＬ素子の発光層の全面を覆うように、樹脂組成物による封止層を形成して有機ＥＬ素子を封止することが行われる。 An organic EL (Electroluminescence) element is a light-emitting element using an organic substance as a light-emitting material, and has recently attracted attention because it can emit light with high luminance at a low voltage. However, organic EL elements are extremely vulnerable to moisture, and the light emitting material (light emitting layer) is altered by moisture, resulting in a decrease in luminance, no light emission, or peeling of the interface between the electrode and the light emitting layer due to moisture. There is a problem that the metal is oxidized to increase the resistance. For this reason, in order to block the inside of the element from moisture in the outside air, for example, a sealing layer made of a resin composition is formed so as to cover the entire surface of the light emitting layer of the organic EL element formed on the substrate. The element is sealed.
　このような封止用の樹脂組成物として、例えば、特許文献１には、ポリイソブチレン樹脂、エポキシ基と反応し得る官能基を持つポリイソプレン樹脂および／またはポリイソブチレン樹脂、粘着付与樹脂、並びにエポキシ樹脂を含有する樹脂組成物が開示されている。また、特許文献２には、スチレン－イソブチレン変性樹脂および粘着付与樹脂を含有する樹脂組成物が開示されている。また、封止層の耐透湿性を高めるために、吸湿性フィラーを樹脂組成物に配合する場合がある。 As such a sealing resin composition, for example, Patent Document 1 discloses a polyisobutylene resin, a polyisoprene resin having a functional group capable of reacting with an epoxy group and / or a polyisobutylene resin, a tackifying resin, and an epoxy. A resin composition containing a resin is disclosed. Patent Document 2 discloses a resin composition containing a styrene-isobutylene-modified resin and a tackifier resin. Moreover, in order to improve the moisture permeability resistance of a sealing layer, a hygroscopic filler may be mix | blended with a resin composition.
　このような樹脂組成物による有機ＥＬ素子の封止は、生産性、封止作業性等の観点から、支持体上に樹脂組成物層を形成した封止用シートによって行われる場合がある。なお、高い防湿性の封止構造を形成するために、樹脂組成物層の耐透湿性を高めるだけでなく、防湿性支持体や封止基材が使用される場合がある。 Sealing of the organic EL element with such a resin composition may be performed by a sealing sheet in which a resin composition layer is formed on a support from the viewpoints of productivity, sealing workability, and the like. In addition, in order to form a highly moisture-proof sealing structure, not only the moisture permeability of the resin composition layer is increased, but also a moisture-proof support or a sealing substrate may be used.
国際公開第２０１１／６２１６７号International Publication No. 2011/62167 国際公開第２０１３／１０８７３１号International Publication No. 2013/108731
　有機ＥＬ素子の封止を封止用シートで行う場合、封止用シートの支持体が防湿性を有する支持体である場合は、有機ＥＬ素子を有する基板に封止用シートを樹脂組成物層が有機ＥＬ素子を被覆するようにラミネートした後、支持体を剥離せず、そのまま有機ＥＬ素子の封止工程を完了する。封止工程後に熱硬化が必要な場合は、熱硬化を行う。 When sealing an organic EL element with a sealing sheet, if the support of the sealing sheet is a moisture-proof support, the sealing sheet is placed on the substrate having the organic EL element as a resin composition layer. After laminating so as to cover the organic EL element, the support is not peeled off, and the sealing process of the organic EL element is completed as it is. When thermosetting is necessary after the sealing step, thermosetting is performed.
　一方、防湿性を有しない支持体を使用した封止用シートを使用する場合、有機ＥＬ素子を有する基板に封止用シートを樹脂組成物層が有機ＥＬ素子を被覆するようにラミネートした後、支持体を剥離し、露出した樹脂組成物層に封止基材を圧着することで、有機ＥＬ素子の封止工程が完了する。封止基材は、防湿効果を向上させるため、２枚またはそれ以上を貼り合わせて使用することもある。 On the other hand, when using a sealing sheet using a support having no moisture resistance, after laminating the sealing sheet on the substrate having the organic EL element so that the resin composition layer covers the organic EL element, The sealing process of an organic EL element is completed by peeling a support body and crimping | bonding a sealing base material to the exposed resin composition layer. In order to improve the moisture-proof effect, two or more sealing substrates may be used by bonding them together.
　通常、上述の防湿性を有する支持体及び封止基材としては、防湿性を有するプラスチックフィルムや、銅箔、アルミニウム箔などの金属箔等が使用される。防湿性を有するプラスチックフィルムとしては、ＳｉＯ２、ＳｉＮ、ＳｉＣＮ、アモルファスシリコン等の無機物を表面に蒸着させたプラスチックフィルム等が挙げられる。 Usually, as the above-mentioned moisture-proof support and sealing substrate, a moisture-proof plastic film, a metal foil such as a copper foil or an aluminum foil, or the like is used. Examples of the moisture-proof plastic film include a plastic film in which an inorganic material such as SiO 2 , SiN, SiCN, and amorphous silicon is deposited on the surface.
　ところで、近時、有機ＥＬデバイスの需要の拡大に伴い、有機ＥＬデバイスの薄型化が望まれているが、防湿性を有する支持体や封止基材が薄型化の妨げになっている。 By the way, with the recent increase in demand for organic EL devices, it is desired to reduce the thickness of organic EL devices, but moisture-proof supports and sealing substrates have hindered the reduction in thickness.
　本発明は、上記の事情に鑑みて成されたものであり、その解決しようとする課題は、封止基材や防湿性の支持体を含まずに高い防湿性を有する封止構造を形成し得る、封止用シートを提供することにある。 The present invention has been made in view of the above circumstances, and the problem to be solved is to form a sealing structure having high moisture resistance without including a sealing substrate and a moisture-proof support. It is in providing the sheet | seat for sealing obtained.
　上記の課題を解決するための本発明の構成は以下の通りである。 The configuration of the present invention for solving the above problems is as follows.
［１］　（Ａ）感圧接着性樹脂組成物層及び該（Ａ）感圧接着性樹脂組成物層の片面に直接形成された（Ｂ）防湿性無機被膜を含む封止用シート。
［２］　前記（Ｂ）防湿性無機被膜が、（Ｂ１）ポリシラザン含有塗膜の熱処理生成物からなるシリカガラス被膜であるか、或いは、（Ｂ２）無機物蒸着被膜である、上記［１］記載の封止用シート。
［３］　ポリシラザンがパーヒドロキシポリシラザンを含む、上記［２］記載の封止用シート。
［４］　（Ｂ２）無機物蒸着被膜がケイ素化合物蒸着被膜である、上記［２］記載の封止用シート。
［５］　ケイ素化合物蒸着被膜が、ＳｉＯ２蒸着膜とＳｉＣＮ蒸着膜を含むＳｉＯ２－ＳｉＣＮ多層蒸着膜である、上記［４］記載の封止用シート。
［６］　ＳｉＯ２－ＳｉＣＮ多層蒸着膜が、ＳｉＯ２蒸着膜とＳｉＣＮ蒸着膜が交互に形成されたＳｉＯ２－ＳｉＣＮ多層蒸着膜である、上記［５］記載の封止用シート。
［７］　（Ｂ）防湿性無機被膜の厚さが１０００ｎｍ以下である、上記［１］～［６］のいずれか１つに記載の封止用シート。
［８］　（Ａ）感圧接着性樹脂組成物層の厚さが３～５０μｍである、上記［１］～［７］のいずれか１つに記載の封止用シート。
［９］　（Ａ）感圧接着性樹脂組成物層が吸湿性フィラーを含有する、上記［１］～［８］のいずれか１つに記載の封止用シート。
［１０］　（Ａ）感圧接着性樹脂組成物層が粘着付与樹脂を含有する、上記［１］～［９］のいずれか１つに記載の封止用シート。
［１１］　（Ｃ）離型処理された支持体をさらに含み、（Ｃ）離型処理された支持体／（Ａ）感圧接着性樹脂組成物層／（Ｂ）防湿性無機被膜の積層構成を有する、上記［１］～［１０］のいずれか１つに記載の封止用シート。
［１２］　（Ｃ）離型処理された支持体が、防湿性を有する支持体である、上記［１１］記載の封止用シート。
［１３］　有機ＥＬ素子の封止用である、上記［１］～［１２］いずれか１つに記載の封止用シート。
［１４］　（Ｂ）防湿性無機被膜の（Ａ）感圧接着性樹脂組成物層の側とは反対側の表面にさらに（Ｄ）円偏光板が接着されてなり、有機ＥＬ素子の封止用シートである、上記［１］～［１０］のいずれか１つに記載の封止用シート。
［１５］　（Ｂ）防湿性無機被膜の（Ａ）感圧接着性樹脂組成物層の側とは反対側の表面にさらに（Ｄ）円偏光板が接着されてなり、有機ＥＬ素子の封止用シートである、上記［１１］または［１２］記載の封止用シート。
［１６］　上記［１］～［１０］、［１４］のいずれか１つに記載の封止用シートで有機ＥＬ素子が封止されて成る有機ＥＬデバイス。
［１７］　（Ａ）感圧接着性樹脂組成物層の片面にポリシラザン含有塗膜を形成し、該塗膜を水蒸気含有雰囲気下で加熱して（Ｂ１）シリカガラス被膜に転化する工程を含むか、或いは、（Ａ）感圧接着性樹脂組成物層の片面に無機物を蒸着して（Ｂ２）無機物蒸着被膜を形成する工程を含む、封止用シートの製造方法。 [1] A sealing sheet comprising (A) a pressure-sensitive adhesive resin composition layer and (B) a moisture-proof inorganic coating formed directly on one side of the (A) pressure-sensitive adhesive resin composition layer.
[2] The above-mentioned [1], wherein (B) the moisture-proof inorganic coating is a silica glass coating made of a heat-treated product of (B1) a polysilazane-containing coating, or (B2) is an inorganic vapor deposition coating. Sealing sheet.
[3] The sealing sheet according to the above [2], wherein the polysilazane contains perhydroxypolysilazane.
[4] (B2) The sealing sheet according to the above [2], wherein the inorganic deposited film is a silicon compound deposited film.
[5] The silicon compound vapor deposited film is a SiO 2 -SiCN multilayered vapor deposition film comprising SiO 2 deposited film and SiCN deposited film, sheet for sealing the [4], wherein.
[6] SiO 2 -SiCN multilayer deposition film, a SiO 2 -SiCN multilayered vapor deposition film SiO 2 deposited film and SiCN deposited film are alternately formed, the [5] encapsulating sheet according.
[7] The sealing sheet according to any one of [1] to [6], wherein (B) the moisture-proof inorganic coating has a thickness of 1000 nm or less.
[8] The sealing sheet according to any one of [1] to [7], wherein (A) the pressure-sensitive adhesive resin composition layer has a thickness of 3 to 50 μm.
[9] The sealing sheet according to any one of [1] to [8], wherein the (A) pressure-sensitive adhesive resin composition layer contains a hygroscopic filler.
[10] The sealing sheet according to any one of [1] to [9], wherein the (A) pressure-sensitive adhesive resin composition layer contains a tackifying resin.
[11] (C) Further comprising a release-treated support, (C) Release-treated support / (A) Pressure-sensitive adhesive resin composition layer / (B) Moisture-proof inorganic coating laminated structure The sealing sheet according to any one of [1] to [10] above, comprising:
[12] (C) The sealing sheet according to [11], wherein the release-treated support is a moisture-proof support.
[13] The sealing sheet according to any one of [1] to [12], which is used for sealing an organic EL element.
[14] (D) A circularly polarizing plate is further adhered to the surface of the moisture-proof inorganic coating on the side opposite to the side of the (A) pressure-sensitive adhesive resin composition layer, thereby sealing the organic EL device The sealing sheet according to any one of the above [1] to [10], which is a sheet for use.
[15] (D) A circularly polarizing plate is further bonded to the surface of the moisture-proof inorganic coating on the side opposite to the side of the (A) pressure-sensitive adhesive resin composition layer, thereby sealing the organic EL device The sheet for sealing according to the above [11] or [12], which is a sheet for use.
[16] An organic EL device in which an organic EL element is sealed with the sealing sheet according to any one of [1] to [10] and [14].
[17] Does (A) include a step of forming a polysilazane-containing coating film on one side of the pressure-sensitive adhesive resin composition layer and heating the coating film in a steam-containing atmosphere (B1) to convert to a silica glass coating? Or the manufacturing method of the sheet | seat for sealing including the process of vapor-depositing an inorganic substance on the single side | surface of (A) pressure-sensitive-adhesive resin composition layer, and forming an inorganic substance vapor deposition film (B2).
　本発明の封止用シートによれば、封止基材や防湿性の支持体を含まずに高い防湿性を有する封止構造を形成することができるため、封止構造を薄厚にすることができる。従って、例えば、本発明の封止用シートを有機ＥＬ素子の封止に使用することで、薄型の有機ＥＬデバイスを得ることができる。 According to the sealing sheet of the present invention, it is possible to form a sealing structure having high moisture resistance without including a sealing substrate or a moisture-proof support, and therefore, the sealing structure can be made thin. it can. Therefore, for example, a thin organic EL device can be obtained by using the sealing sheet of the present invention for sealing an organic EL element.
本発明の一実施形態による封止用シートの模式断面図である。It is a schematic cross section of the sheet | seat for sealing by one Embodiment of this invention. 本発明の他の実施形態による封止用シートの模式断面図である。It is a schematic cross section of the sheet | seat for sealing by other embodiment of this invention.
　図１は本発明の一実施形態による封止用シートの断面を模式的に示した図である。
　本発明の封止用シートは、かかる一実施形態の封止用シート１０に示されるように、（Ａ）感圧接着性樹脂組成物層１及び該（Ａ）感圧接着性樹脂組成物層の片面に直接形成された（Ｂ）防湿性無機被膜２を少なくとも含む。 FIG. 1 is a diagram schematically showing a cross section of a sealing sheet according to an embodiment of the present invention.
The sealing sheet of the present invention includes (A) the pressure-sensitive adhesive resin composition layer 1 and (A) the pressure-sensitive adhesive resin composition layer, as shown in the sealing sheet 10 of one embodiment. (B) at least the moisture-proof inorganic coating 2 formed directly on one side.
　典型的には、本発明の封止用シートは、図１に示されるような、（Ｃ）離型処理された支持体３をさらに含み、（Ｃ）離型処理された支持体３／（Ａ）感圧接着性樹脂組成物層１／（Ｂ）防湿性無機被膜２の積層構成を有するシートである。 Typically, the sealing sheet of the present invention further includes (C) a release-treated support 3 as shown in FIG. 1, and (C) a release-treated support 3 / ( A) A sheet having a laminated structure of a pressure-sensitive adhesive resin composition layer 1 / (B) a moisture-proof inorganic coating 2.
　なお、（Ｃ）離型処理された支持体３は、（Ａ）感圧接着性樹脂組成物層１を形成する際の支持体であり、実際に封止対象を封止する前は、（Ａ）感圧接着性樹脂組成物層１から剥離される。従って、離型処理された支持体３は、必ずしも防湿性を有していなくてもよいが、封止用シートの製造後、封止作業を行うまでの封止用シートの保管期間での（Ａ）感圧接着性樹脂組成物層１への水分の浸入を防止するという観点から、（Ｃ）離型処理された支持体３として、防湿性を有する支持体を用いることができる。 Note that (C) the release-treated support 3 is a support for forming the (A) pressure-sensitive adhesive resin composition layer 1, and before actually sealing the sealing target, A) It peels from the pressure-sensitive-adhesive resin composition layer 1. Therefore, the release-treated support 3 does not necessarily have moisture resistance, but after the production of the sealing sheet, during the storage period of the sealing sheet until the sealing operation is performed ( A) From the viewpoint of preventing moisture from entering the pressure-sensitive adhesive resin composition layer 1, (C) a support having moisture resistance can be used as the support 3 subjected to the release treatment.
　以下、封止用シートの各構成要素について詳しく説明する。
［（Ａ）感圧接着性樹脂組成物層］
　（Ａ）感圧接着性樹脂組成物層１は封止用シートを有機ＥＬ素子等の封止対象にラミネートすることで封止対象に接着した封止層を形成するための層であり、感圧接着性樹脂組成物によって形成される。 Hereinafter, each component of the sealing sheet will be described in detail.
[(A) Pressure-sensitive adhesive resin composition layer]
(A) The pressure-sensitive adhesive resin composition layer 1 is a layer for forming a sealing layer adhered to a sealing target by laminating a sealing sheet on the sealing target such as an organic EL element. It is formed by a pressure-bonding resin composition.
　（Ａ）感圧接着性樹脂組成物層１を形成する感圧接着性樹脂組成物（以下、単に「樹脂組成物」とも称す。）は、粘着性及び吸湿性を有する樹脂組成物が好ましく、例えば、（ａ）ポリオレフィン系樹脂、（ｂ）粘着付樹脂及び（ｃ）吸湿性フィラーを含む樹脂組成物が挙げられる。当該（Ａ）感圧接着性樹脂組成物層１が吸湿性を有することで、封止対象への水分の到達を効果的に阻止することができる。 (A) The pressure-sensitive adhesive resin composition forming the pressure-sensitive adhesive resin composition layer 1 (hereinafter also simply referred to as “resin composition”) is preferably a resin composition having adhesiveness and hygroscopicity, For example, the resin composition containing (a) polyolefin resin, (b) adhesive resin, and (c) hygroscopic filler is mentioned. Since the (A) pressure-sensitive adhesive resin composition layer 1 has hygroscopicity, it is possible to effectively prevent moisture from reaching the object to be sealed.
＜（ａ）ポリオレフィン系樹脂＞
　（ａ）ポリオレフィン系樹脂（以下、「（ａ）成分」とも略称する。）としては、オレフィンモノマー由来の骨格を有するものであれば特に限定されない。例えば、ポリオレフィン系樹脂としては、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリブテン系樹脂、ポリイソブチレン系樹脂が挙げられる。 <(A) Polyolefin resin>
The (a) polyolefin resin (hereinafter also abbreviated as “component (a)”) is not particularly limited as long as it has a skeleton derived from an olefin monomer. For example, examples of polyolefin resins include polyethylene resins, polypropylene resins, polybutene resins, and polyisobutylene resins.
　ポリオレフィン系樹脂は、ホモポリマー、ランダム共重合体、またはブロック共重合体のいずれであってもよい。また、共重合体としては、（ｉ）２種以上のオレフィンの共重合体、（ｉｉ）オレフィンと非共役ジエンの共重合体、または（ｉｉｉ）オレフィンとメチルメタクリレートやスチレン等のオレフィン以外のモノマー（非共役ジエンを除く）との共重合体が挙げられる。（ｉｉ）の共重合体及び（ｉｉｉ）の共重合体において、オレフィンは１種または２種以上を使用できる。 The polyolefin resin may be a homopolymer, a random copolymer, or a block copolymer. The copolymer includes (i) a copolymer of two or more olefins, (ii) a copolymer of an olefin and a non-conjugated diene, or (iii) a monomer other than an olefin such as an olefin and methyl methacrylate or styrene. And a copolymer thereof (excluding non-conjugated dienes). In the copolymer of (ii) and the copolymer of (iii), the olefin can use 1 type (s) or 2 or more types.
　ホモポリマーの好ましい例として、例えば、ポリブテンが挙げられる。共重合体の好ましい例として、エチレン－非共役ジエン共重合体、エチレン－プロピレン共重合体、エチレン－ブテン－非共役ジエン共重合体、エチレン－プロピレン－非共役ジエン共重合体、エチレン－プロピレン－ブテン共重合体、プロピレン－ブテン共重合体、プロピレン－ブテン－非共役ジエン共重合体、イソブチレン－ブテン共重合体、イソブチレン－ブテン－非共役ジエン共重合体、スチレン－イソブチレン共重合体、スチレン－イソブチレン－スチレン共重合体、エチレン－メチルメタクリレート共重合体等が挙げられる。 A preferred example of a homopolymer is polybutene, for example. Preferred examples of the copolymer include ethylene-nonconjugated diene copolymer, ethylene-propylene copolymer, ethylene-butene-nonconjugated diene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-propylene- Butene copolymer, propylene-butene copolymer, propylene-butene-nonconjugated diene copolymer, isobutylene-butene copolymer, isobutylene-butene-nonconjugated diene copolymer, styrene-isobutylene copolymer, styrene- Examples include isobutylene-styrene copolymer and ethylene-methyl methacrylate copolymer.
　ポリオレフィン系樹脂は、樹脂組成物層の封止対象物への接着性、樹脂組成物層の接着湿熱耐性等の優れた物性を付与する観点から、酸無水物基（即ち、カルボニルオキシカルボニル基（－ＣＯ－Ｏ－ＣＯ－））を有するポリオレフィン系樹脂および／またはエポキシ基を有するポリオレフィン系樹脂を含むことができる。酸無水物基としては、例えば、無水コハク酸に由来する基、無水マレイン酸に由来する基、無水グルタル酸に由来する基等が挙げられる。酸無水物基は１種または２種以上を有することができる。酸無水物基を有するポリオレフィン系樹脂は、例えば、酸無水物基を有する不飽和化合物で、ポリオレフィン系樹脂をラジカル反応条件下にてグラフト変性することで得られる。また、酸無水物基を有する不飽和化合物を、オレフィン等とともにラジカル共重合するようにしてもよい。同様に、エポキシ基を有するポリオレフィン系樹脂は、例えば、グリシジル（メタ）アクリレート、４－ヒドロキシブチルアクリレートグリシジルエーテル、アリルグリシジルエーテル等のエポキシ基を有する不飽和化合物で、ポリオレフィン系樹脂をラジカル反応条件下にてグラフト変性することで得られる。また、エポキシ基を有する不飽和化合物を、オレフィン等とともにラジカル共重合するようにしてもよい。 The polyolefin-based resin has an acid anhydride group (that is, a carbonyloxycarbonyl group (that is, a carbonyloxycarbonyl group) from the viewpoint of imparting excellent physical properties such as adhesion of the resin composition layer to an object to be sealed and adhesion and heat resistance of the resin composition layer. -CO-O-CO-)) and / or polyolefin resins 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 can have one type or two or more types. The polyolefin resin having an acid anhydride group can be obtained, for example, by an unsaturated compound having an acid anhydride group and graft-modifying the polyolefin resin under radical reaction conditions. Moreover, you may make it carry out radical copolymerization of the unsaturated compound which has an acid anhydride group with an olefin. Similarly, the polyolefin resin having an epoxy group is an unsaturated compound having an epoxy group such as glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, allyl glycidyl ether, etc. It can be obtained by graft modification with Moreover, you may make it carry out radical copolymerization of the unsaturated compound which has an epoxy group with an olefin.
　酸無水物基を有するポリオレフィン系樹脂としては、例えば、酸無水物基有する液状ポリブテンが好ましく、無水マレイン酸変性液状ポリブテンがより好ましい。エポキシ基を有するポリオレフィン系樹脂としては、例えば、エポキシ基を有するエポキシ変性ポリエチレン、エポキシ変性ポリプロピレン、エポキシ変性ポリブテンなどが好ましい。 As the polyolefin resin having an acid anhydride group, for example, liquid polybutene having an acid anhydride group is preferable, and maleic anhydride-modified liquid polybutene is more preferable. As the polyolefin-based resin having an epoxy group, for example, an epoxy-modified polyethylene having an epoxy group, an epoxy-modified polypropylene, an epoxy-modified polybutene and the like are preferable.
　酸無水物基を有するポリオレフィン系樹脂中の酸無水物基の濃度は、０．０５～１０ｍｍｏｌ／ｇが好ましく、０．１～５ｍｍｏｌ／ｇがより好ましい。酸無水物基の濃度はＪＩＳ　Ｋ　２５０１の記載に従い、樹脂１ｇ中に存在する酸を中和するのに必要な水酸化カリウムのｍｇ数として定義される酸価の値より得られる。また、（ａ）成分中の酸無水物基を有するポリオレフィン系樹脂の量は、好ましくは０～７０質量％、より好ましくは１０～５０質量％である。 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 is obtained from the value of the acid value defined as the number of mg of potassium hydroxide necessary to neutralize the acid present in 1 g of resin according to the description of JIS K 2501. The amount of the polyolefin resin having an acid anhydride group in the component (a) is preferably 0 to 70% by mass, more preferably 10 to 50% by mass.
　また、エポキシ基を有するポリオレフィン系樹脂中のエポキシ基の濃度は、０．０５～１０ｍｍｏｌ／ｇが好ましく、０．１～５ｍｍｏｌ／ｇがより好ましい。エポキシ基濃度はＪＩＳ　Ｋ　７２３６－１９９５に基づいて得られるエポキシ当量から求められる。また、（ａ）成分中のエポキシ基を有するポリオレフィン系樹脂の量は、好ましくは０～７０質量％、より好ましくは１０～５０質量％である。 The concentration of the epoxy group in the polyolefin 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 based on JIS K 7236-1995. Further, the amount of the polyolefin resin having an epoxy group in the component (a) is preferably 0 to 70% by mass, more preferably 10 to 50% by mass.
　（ａ）成分の数平均分子量は、特に限定はされないが、樹脂組成物のワニスの良好な塗工性と樹脂組成物における他の成分との良好な相溶性をもたらすという観点から、１，０００，０００以下が好ましく、７５０，０００以下がより好ましく、５００，０００以下がより一層好ましく、４００，０００以下がさらに好ましく、３００，０００以下がさらに一層好ましく、２００，０００以下が特に好ましく、１５０，０００以下が最も好ましい。一方、樹脂組成物のワニスの塗工時のハジキを防止し、形成される樹脂組成物層の耐透湿性を発現させ、機械強度を向上させるという観点から、２,０００以上が好ましく、１０，０００以上がより好ましく、３０,０００以上がさら一層好ましく、５０,０００以上が特に好ましい。なお、数平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法（ポリスチレン換算）で測定される。ＧＰＣ法による数平均分子量は、具体的には、測定装置として社島津製作所製ＬＣ－９Ａ／ＲＩＤ－６Ａを、カラムとして昭和電工社製Ｓｈｏｄｅｘ Ｋ－８００Ｐ／Ｋ－８０４Ｌ／Ｋ－８０４Ｌを、移動相としてトルエン等を用いて、カラム温度４０℃にて測定し、標準ポリスチレンの検量線を用いて算出することができる。 The number average molecular weight of the component (a) is not particularly limited, but is 1,000 from the viewpoint of providing good coatability of the varnish of the resin composition and good compatibility with other components in the resin composition. , 000 or less, more preferably 750,000 or less, even more preferably 500,000 or less, still more preferably 400,000 or less, even more preferably 300,000 or less, particularly preferably 200,000 or less, 000 or less is most preferable. On the other hand, it is preferably 2,000 or more from the viewpoint of preventing repelling during coating of the varnish of the resin composition, expressing moisture resistance of the formed resin composition layer, and improving mechanical strength. 000 or more is more preferable, 30,000 or more is even more preferable, and 50,000 or more is particularly preferable. The number average molecular weight is measured by gel permeation chromatography (GPC) method (polystyrene conversion). The number average molecular weight by the GPC method is specifically determined by moving LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex® K-800P / K-804L / K-804L manufactured by Showa Denko KK as a column. Using toluene or the like as a phase, the measurement can be made at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.
　なお、（ａ）成分の好ましい態様の一つとして、数平均分子量が１０００以上、３０００以下の液状ポリオレフィン（好ましくは液状ポリブテン及び／又は無水マレイン酸変性液状ポリブテン）を（ａ）成分全体の１０質量％以上、９０質量％以下の範囲で含有する態様が挙げられる。（ａ）成分がかかる好ましい態様であると、高い接着強度が得られやすい。 As a preferred embodiment of the component (a), a liquid polyolefin (preferably liquid polybutene and / or maleic anhydride-modified liquid polybutene) having a number average molecular weight of 1000 or more and 3000 or less is added in an amount of 10 mass of the component (a). The aspect contained in% or more and 90 mass% or less is mentioned. When the component (a) is such a preferred embodiment, high adhesive strength is easily obtained.
　本発明における（ａ）ポリオレフィン系樹脂は、ワニスの増粘による流動性の低下を抑制する観点から非晶性であるのが好ましい。ここで、非晶性とは、ポリオレフィン系樹脂が明確な融点を有しないことを意味し、例えば、ポリオレフィン系樹脂のＤＳＣ（示差走査熱量測定）で融点を測定した場合に明確なピークが観察されないものを使用することができる。 The (a) polyolefin resin in the present invention is preferably amorphous from the viewpoint of suppressing a decrease in fluidity due to thickening of the varnish. Here, the term “amorphous” means that the polyolefin resin does not have a clear melting point. For example, when the melting point is measured by DSC (differential scanning calorimetry) of the polyolefin resin, no clear peak is observed. Things can be used.
　（ａ）成分は１種または２種以上を組み合わせて使用してもよい。樹脂組成物中の（ａ）成分の含有量は特に制限はない。しかし、良好な塗工性と相溶性をもたらし、良好な湿熱耐性と取り扱い性（タック抑制）を確保できるという観点から、該含有量は、樹脂組成物中の不揮発分の合計１００質量％あたり、８０質量％以下が好ましく、７５質量％以下がより好ましく、７０質量％以下がより一層好ましく、６０質量％以下がさらに好ましく、５５質量％以下がさらに一層好ましく、５０質量％以下が特に好ましい。一方、耐透湿性を向上させ、透明性も向上させるという観点から、該含有量は、樹脂組成物中の不揮発分の合計１００質量％あたり、１質量％以上が好ましく、３質量％以上がより好ましく、５質量％以上がより一層好ましく、７質量％以上がさらに好ましく、１０質量％以上がさらに一層好ましく、３５質量％以上が特に好ましく、４０質量％以上が最も好ましい。 (A) The component may be used alone or in combination of two or more. There is no restriction | limiting in particular in content of (a) component in a resin composition. However, from the viewpoint of providing good coatability and compatibility and ensuring good wet heat resistance and handleability (tack suppression), the content is about 100% by mass in total of the non-volatile content in the resin composition, 80 mass% or less is preferable, 75 mass% or less is more preferable, 70 mass% or less is still more preferable, 60 mass% or less is further more preferable, 55 mass% or less is further more preferable, 50 mass% or less is especially preferable. On the other hand, from the viewpoint of improving moisture permeability resistance and transparency, the content is preferably 1% by mass or more, more preferably 3% by mass or more per 100% by mass of the total nonvolatile content in the resin composition. Preferably, 5% by mass or more is more preferable, 7% by mass or more is more preferable, 10% by mass or more is further more preferable, 35% by mass or more is particularly preferable, and 40% by mass or more is most preferable.
　次に、（ａ）ポリオレフィン系樹脂の具体例を説明する。ポリイソブチレン樹脂の具体例としては、ＢＡＳＦ社製「オパノールＢ１００」（粘度平均分子量：１，１１０，０００）、ＢＡＳＦ社製「Ｂ５０ＳＦ」（粘度平均分子量：４００，０００）が挙げられる。 Next, a specific example of (a) polyolefin resin will be described. Specific examples of the polyisobutylene resin include “OPanol B100” (viscosity average molecular weight: 11,110,000) manufactured by BASF, and “B50SF” (viscosity average molecular weight: 400,000) manufactured by BASF.
　ポリブテン系樹脂の具体例としては、ＪＸエネルギー社製「ＨＶ－１９００」（ポリブテン、数平均分子量：２，９００）、東邦化学工業社製「ＨＶ－３００Ｍ」（無水マレイン酸変性液状ポリブテン（「ＨＶ－３００」（数平均分子量：１，４００）の変性品）、数平均分子量：２，１００、酸無水物基を構成するカルボキシ基の数：３．２個／１分子、酸価：４３．４ｍｇＫＯＨ／ｇ、酸無水物基濃度：０．７７ｍｍｏｌ／ｇ）が挙げられる。 Specific examples of the polybutene resin include “HV-1900” (polybutene, number average molecular weight: 2,900) manufactured by JX Energy, and “HV-300M” (maleic anhydride-modified liquid polybutene (“HV”) manufactured by Toho Chemical Industry Co., Ltd. -300 "(modified product of number average molecular weight: 1,400)), number average molecular weight: 2,100, number of carboxy groups constituting acid anhydride group: 3.2 / 1 molecule, acid value: 43. 4 mg KOH / g, acid anhydride group concentration: 0.77 mmol / g).
　スチレン－イソブチレン共重合体の具体例としては、カネカ社製「ＳＩＢＳＴＡＲ　Ｔ１０２」（スチレン－イソブチレン－スチレンブロック共重合体、数平均分子量：１００，０００、スチレン含量：３０質量％）、星光ＰＭＣ社製「Ｔ－ＹＰ７５７Ｂ」（無水マレイン酸変性スチレン－イソブチレン－スチレンブロック共重合体、酸無水物基濃度：０．４６４ｍｍｏｌ／ｇ、数平均分子量：１００，０００）、星光ＰＭＣ社製「Ｔ－ＹＰ７６６」（グリシジルメタクリレート変性スチレン－イソブチレン－スチレンブロック共重合体、エポキシ基濃度：０．６３８ｍｍｏｌ／ｇ、数平均分子量：１００，０００）、星光ＰＭＣ社製「Ｔ－ＹＰ８９２０」（無水マレイン酸変性スチレン－イソブチレン－スチレン共重合体、酸無水物基濃度：０．４６４ｍｍｏｌ／ｇ、数平均分子量：３５，８００）、星光ＰＭＣ社製「Ｔ－ＹＰ８９３０」（グリシジルメタクリレート変性スチレン－イソブチレン－スチレン共重合体、エポキシ基濃度：０．６３８ｍｍｏｌ／ｇ、数平均分子量：４８，７００）が挙げられる。 Specific examples of the styrene-isobutylene copolymer include “SIBSTAR T102” manufactured by Kaneka (styrene-isobutylene-styrene block copolymer, number average molecular weight: 100,000, styrene content: 30% by mass), manufactured by Starlight 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 Seiko PMC (Glycidyl methacrylate-modified styrene-isobutylene-styrene block copolymer, epoxy group concentration: 0.638 mmol / g, number average molecular weight: 100,000), “T-YP8920” (maleic anhydride modified styrene-isobutylene, manufactured by Seiko PMC) -Styrene copolymer, acid anhydride base concentration : 0.464 mmol / g, number average molecular weight: 35,800), “T-YP8930” (glycidyl methacrylate modified styrene-isobutylene-styrene copolymer, epoxy group concentration, 0.638 mmol / g, number average, manufactured by Seiko PMC) Molecular weight: 48,700).
　ポリエチレン系樹脂またはポリプロピレン系樹脂の具体例としては、三井化学社製「ＥＰＴ　Ｘ－３０１２Ｐ」（エチレン－プロピレン－５－エチリデン－２－ノルボルネン共重合体、三井化学社製「ＥＰＴ１０７０」（エチレン－プロピレン－ジシクロペンタジエン共重合体）、三井化学社製「タフマーＡ４０８５」（エチレン－ブテン共重合体）等が挙げられる。 Specific examples of the polyethylene resin or polypropylene resin include “EPT X-3012P” (ethylene-propylene-5-ethylidene-2-norbornene copolymer manufactured by Mitsui Chemicals, “EPT1070” manufactured by Mitsui Chemicals (ethylene-propylene). -Dicyclopentadiene copolymer), "Tuffmer A4085" (ethylene-butene copolymer) manufactured by Mitsui Chemicals, and the like.
　エチレン－メチルメタクリレート共重合体の具体例としては、住友化学社製「ＡＣＲＹＦＴ　ＣＭ５０２２」（エチレン－メチルメタクリレート共重合体、エチレン単位とメチルメタクリレート単位の合計１００質量％あたりのメチルメタクリレート単位の量：３３質量％）、星光ＰＭＣ社製「Ｔ－ＹＰ４２９」（無水マレイン酸変性エチレン－メチルメタクリレート共重合体、エチレン単位とメチルメタクリレート単位の合計１００質量％あたりのメチルメタクリレート単位の量：３２質量％、酸無水物基濃度：０．４６ｍｍｏｌ／ｇ、数平均分子量：２，３００）、星光ＰＭＣ社製「Ｔ－ＹＰ４３０」（無水マレイン酸変性エチレン－メチルメタクリレート共重合体、エチレン単位とメチルメタクリレート単位の合計１００質量％あたりのメチルメタクリレート単位の量：３２質量％、酸無水物基濃度：１．１８ｍｍｏｌ／ｇ、数平均分子量：４，５００）、星光ＰＭＣ社製「Ｔ－ＹＰ４３１」（グリシジルメタクリレート変性エチレン－メチルメタクリレート共重合体、エポキシ基濃度：０．６４ｍｍｏｌ／ｇ、数平均分子量：２，４００）、星光ＰＭＣ社製「Ｔ－ＹＰ４３２」（グリシジルメタクリレート変性エチレン－メチルメタクリレート共重合体、エポキシ基濃度：１．６３ｍｍｏｌ／ｇ、数平均分子量：３，１００）が挙げられる。また、プロピレン－ブテン系共重合体の具体例としては、星光ＰＭＣ社製「Ｔ－ＹＰ３４１」（グリシジルメタクリレート変性プロピレン－ブテンランダム共重合体、プロピレン単位とブテン単位の合計１００質量％あたりのブテン単位の量：２９質量％、エポキシ基濃度：０．６３８ｍｍｏｌ／ｇ、数平均分子量：１５５，０００）、星光ＰＭＣ社製「Ｔ－ＹＰ２７９」（無水マレイン酸変性プロピレン－ブテンランダム共重合体、プロピレン単位とブテン単位の合計１００質量％あたりのブテン単位の量：３６質量％、酸無水物基濃度：０．４６４ｍｍｏｌ／ｇ、数平均分子量：３５，０００）、星光ＰＭＣ社製「Ｔ－ＹＰ２７６」（グリシジルメタクリレート変性プロピレン－ブテンランダム共重合体、プロピレン単位とブテン単位の合計１００質量％あたりのブテン単位の量：３６質量％、エポキシ基濃度：０．６３８ｍｍｏｌ／ｇ、数平均分子量：５７，０００）、星光ＰＭＣ社製「Ｔ－ＹＰ３１２」（無水マレイン酸変性プロピレン－ブテンランダム共共重合体、プロピレン単位とブテン単位の合計１００質量％あたりのブテン単位の量：２９質量％、酸無水物基濃度：０．４６４ｍｍｏｌ／ｇ、数平均分子量：６０，９００）、星光ＰＭＣ社製「Ｔ－ＹＰ３１３」（グリシジルメタクリレート変性プロピレン－ブテンランダム共重合体、プロピレン単位とブテン単位の合計１００質量％あたりのブテン単位の量：２９質量％、エポキシ基濃度：０．６３８ｍｍｏｌ／ｇ、数平均分子量：１５５，０００）が挙げられる。 Specific examples of the ethylene-methyl methacrylate copolymer include “ACRYFT CM5022” manufactured by Sumitomo Chemical Co., Ltd. (ethylene-methyl methacrylate copolymer, the amount of methyl methacrylate units per 100% by mass in total of ethylene units and methyl methacrylate units: 33 % By mass), “T-YP429” (maleic anhydride-modified ethylene-methyl methacrylate copolymer, amount of methyl methacrylate units per 100% by mass in total of ethylene units and methyl methacrylate units: 32% by mass, acid Anhydride group concentration: 0.46 mmol / g, number average molecular weight: 2,300), “T-YP430” (maleic anhydride modified ethylene-methyl methacrylate copolymer, total of ethylene units and methyl methacrylate units) manufactured by Seiko PMC 100% by weight Of methyl methacrylate unit: 32% by mass, acid anhydride group concentration: 1.18 mmol / g, number average molecular weight: 4,500), “T-YP431” (glycidyl methacrylate modified ethylene-methyl methacrylate co-produced by Starlight PMC) Polymer, epoxy group concentration: 0.64 mmol / g, number average molecular weight: 2,400), “T-YP432” (glycidyl methacrylate-modified ethylene-methyl methacrylate copolymer, epoxy group concentration: 1.63 mmol, manufactured by Seiko PMC) / G, number average molecular weight: 3,100). Specific examples of the propylene-butene copolymer include “T-YP341” (glycidyl methacrylate-modified propylene-butene random copolymer manufactured by Seiko PMC Co., Ltd., butene units per 100% by mass in total of propylene units and butene units). 29 mass%, epoxy group concentration: 0.638 mmol / g, number average molecular weight: 155,000), “T-YP279” (maleic anhydride modified propylene-butene random copolymer, propylene unit, manufactured by Seiko PMC) The amount of butene units per 100% by mass of total butene units: 36% by mass, acid anhydride group concentration: 0.464 mmol / g, number average molecular weight: 35,000), “T-YP276” (manufactured by Seiko PMC) Glycidyl methacrylate modified propylene-butene random copolymer, containing propylene units and butene units Total amount of butene units per 100% by mass: 36% by mass, epoxy group concentration: 0.638 mmol / g, number average molecular weight: 57,000), “T-YP312” (maleic anhydride modified propylene- Butene random copolymer, amount of butene units per 100% by mass of propylene units and butene units: 29% by mass, acid anhydride group concentration: 0.464 mmol / g, number average molecular weight: 60,900), starlight “T-YP313” (glycidyl methacrylate-modified propylene-butene random copolymer, amount of butene units per total 100% by mass of propylene units and butene units: 29% by mass, epoxy group concentration: 0.638 mmol / g, manufactured by PMC , Number average molecular weight: 155,000).
＜（ｂ）粘着付与樹脂＞
　（ｂ）粘着付与樹脂（以下、「（ｂ）成分」とも略称する。）は、タッキファイヤーとも呼ばれ、可塑性高分子に配合して粘着性を付与させる樹脂である。（ｂ）成分としては、特に限定されるものではなく、テルペン樹脂、変性テルペン樹脂（水素添加テルペン樹脂、テルペンフェノール共重合樹脂、芳香族変性テルペン樹脂等）、クマロン樹脂、インデン樹脂、石油樹脂（脂肪族系石油樹脂、水添脂環式石油樹脂、芳香族系石油樹脂、脂肪族芳香族共重合系石油樹脂、脂環族系石油樹脂、ジシクロペンタジエン系石油樹脂およびその水素化物等）が好ましく使用される。 <(B) Tackifying resin>
(B) Tackifying resin (hereinafter also abbreviated as “component (b)”) is also called a tackifier and is a resin that is added to a plastic polymer to impart tackiness. The component (b) is not particularly limited, and is not limited to terpene resin, modified terpene resin (hydrogenated terpene resin, terpene phenol copolymer resin, aromatic modified terpene resin, etc.), coumarone resin, indene resin, petroleum resin ( Aliphatic petroleum resins, hydrogenated alicyclic petroleum resins, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, alicyclic petroleum resins, dicyclopentadiene petroleum resins and their hydrides) Preferably used.
　（ｂ）成分として使用できる市販品としては、例えば、以下のものが挙げられる。テルペン樹脂として、ＹＳレジンＰＸ、ＹＳレジンＰＸＮ（いずれもヤスハラケミカル社製）等が挙げられ、芳香族変性テルペン樹脂として、ＹＳレジンＴＯ、ＴＲシリーズ（いずれもヤスハラケミカル社製）等が挙げられ、水素添加テルペン樹脂として、クリアロンＰ、クリアロンＭ、クリアロンＫシリーズ（いずれもヤスハラケミカル社製）等が挙げられ、テルペンフェノール共重合樹脂として、ＹＳポリスター２０００、ポリスターＵ、ポリスターＴ、ポリスターＳ、マイティエースＧ（いずれもヤスハラケミカル社製）等が挙げられ、水添脂環式石油樹脂として、Ｅｓｃｏｒｅｚ５３００シリーズ、５６００シリーズ（いずれもエクソンモービル社製）等が挙げられ、芳香族系石油樹脂としてＥＮＤＥＸ１５５（イーストマン社製）等が挙げられ、脂肪族芳香族共重合系石油樹脂としてＱｕｉｎｔｏｎｅＤ１００（日本ゼオン社製）等が挙げられ、脂環族系石油樹脂としてＱｕｉｎｔｏｎｅ１３２５、Ｑｕｉｎｔｏｎｅ１３４５（いずれも日本ゼオン社製）等が挙げられ、シクロヘキサン環含有水素化石油樹脂としてアルコンＰ１００、アルコンＰ１２５、アルコンＰ１４０（いずれも荒川化学社製）等が挙げられ、シクロヘキサン環含有飽和炭化水素樹脂としてＴＦＳ１３－０３０（荒川化学社製）等が挙げられる。 Examples of commercially available products that can be used as the component (b) include the following. Examples of terpene resins include YS resin PX and YS resin PXN (both manufactured by Yasuhara Chemical Co.), and examples of aromatic modified terpene resins include YS resin TO and TR series (both manufactured by Yasuhara Chemical Co., Ltd.). Examples of terpene resins include Clearon P, Clearon M, and Clearon K series (all manufactured by Yashara Chemical Co., Ltd.). Examples of terpene phenol copolymer resins include YS Polystar 2000, Polyster U, Polyster T, Polyster S, and Mighty Ace (any) And the like. Examples of hydrogenated alicyclic petroleum resins include Escorez 5300 series and 5600 series (both manufactured by ExxonMobil). ENDEX155 (manufactured by Eastman) is an aromatic petroleum resin. Quintone D100 (manufactured by Nippon Zeon Co., Ltd.) and the like as an aliphatic aromatic copolymer petroleum resin, and Quintone 1325 and Quintone 1345 (both manufactured by Nippon Zeon Co., Ltd.) as an alicyclic petroleum resin, cyclohexane Examples of the ring-containing hydrogenated petroleum resin include Alcon P100, Alcon P125, and Alcon P140 (all manufactured by Arakawa Chemical Co.), and examples of the cyclohexane ring-containing saturated hydrocarbon resin include TFS13-030 (manufactured by Arakawa Chemical Co., Ltd.).
　（ｂ）成分の軟化点は、樹脂組成物シートの積層工程でシートが軟化し、かつ所望の耐熱性を持つという観点から、５０～２００℃が好ましく、９０～１８０℃がより好ましく、１００～１５０℃がさらに好ましい。なお、軟化点の測定は、ＪＩＳ Ｋ２２０７に従い環球法により測定される。 The softening point of the component (b) is preferably 50 to 200 ° C., more preferably 90 to 180 ° C., more preferably 100 to 100 ° C. from the viewpoint that the sheet softens in the resin composition sheet lamination step and has the desired heat resistance. 150 ° C. is more preferable. The softening point is measured by the ring and ball method according to JIS K2207.
　（ｂ）成分は１種または２種以上を組み合わせて使用してもよい。樹脂組成物中の（ｂ）成分の含有量は特に制限はない。しかし、樹脂組成物の良好な耐透湿性を維持するという観点から、（ｂ）成分を使用する場合、その含有量は、樹脂組成物中の不揮発分の合計１００質量％あたり、８０質量％以下が好ましく、６０質量％以下がより好ましく、５０質量％以下がさらに好ましく、４０質量％以下が特に好ましい。一方、十分な接着性を有するという観点から、（ｂ）成分を使用する場合、その含有量は、樹脂組成物中の不揮発分の合計１００質量％あたり、５質量％以上が好ましく、１０質量％以上がより好ましく、１５質量％以上がさらに好ましい。 (B) Component may be used alone or in combination of two or more. The content of component (b) in the resin composition is not particularly limited. However, from the viewpoint of maintaining good moisture resistance of the resin composition, when the component (b) is used, its content is 80% by mass or less per 100% by mass of the total nonvolatile content in the resin composition. Is preferable, 60 mass% or less is more preferable, 50 mass% or less is more preferable, and 40 mass% or less is particularly preferable. On the other hand, from the viewpoint of having sufficient adhesiveness, when the component (b) is used, its content is preferably 5% by mass or more per 100% by mass of the total nonvolatile content in the resin composition, and is preferably 10% by mass. The above is more preferable, and 15% by mass or more is more preferable.
　なかでも、樹脂組成物の接着性、耐透湿性、透明性等の観点から、石油樹脂が好ましい。石油樹脂としては、脂肪族系石油樹脂、芳香族系石油樹脂、脂肪族芳香族共重合系石油樹脂、脂環族系石油樹脂等が挙げられる。なかでも、樹脂組成物の接着性、耐透湿性、相溶性等の観点から、芳香族系石油樹脂、脂肪族芳香族共重合系石油樹脂、脂環族系石油樹脂がより好ましい。また透明性を良好にする観点から、脂環族系石油樹脂が特に好ましい。脂環族系石油樹脂は芳香族系石油樹脂を水素添加処理したものを用いることもできる。この場合、脂環族系石油樹脂の水素化率は３０～９９％が好ましく、４０～９７％がより好ましく、５０～９０％がさらに好ましい。水素化率が低すぎると、着色により透明性が低下する問題が生じる傾向にあり、水素化率が高すぎると生産コストが上昇する傾向となる。水素化率は水添前と水素添加後の芳香環の水素の１Ｈ－ＮＭＲのピーク強度の比から求めることができる。脂環族系石油樹脂としては、特にシクロヘキサン環含有水素化石油樹脂、ジシクロペンタジエン系水素化石油樹脂が好ましい。石油樹脂は１種または２種以上を組み合わせて使用してもよい。石油樹脂の数平均分子量Ｍｎは１００～２，０００が好ましく、７００～１，５００がより好ましく、５００～１，０００がさらに好ましい。 Of these, petroleum resins are preferred from the viewpoints of the adhesiveness, moisture permeability resistance, transparency and the like of the resin composition. Examples of petroleum resins include aliphatic petroleum resins, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, and alicyclic petroleum resins. Of these, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, and alicyclic petroleum resins are more preferable from the viewpoints of adhesion, moisture resistance, compatibility, and the like of the resin composition. From the viewpoint of improving transparency, alicyclic petroleum resins are particularly preferred. As the alicyclic petroleum resin, a hydrogenated aromatic petroleum resin may be used. In this case, the hydrogenation rate of the alicyclic petroleum resin is preferably 30 to 99%, more preferably 40 to 97%, and even more preferably 50 to 90%. If the hydrogenation rate is too low, there is a tendency for transparency to deteriorate 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 1 H-NMR peak intensities of hydrogen in the aromatic ring before hydrogenation and after hydrogenation. As the alicyclic petroleum resin, a cyclohexane ring-containing hydrogenated petroleum resin and a dicyclopentadiene hydrogenated petroleum resin are particularly preferable. 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, and even more preferably from 500 to 1,000.
＜（ｃ）吸湿性フィラー＞
　（ｃ）吸湿性フィラー（以下、「（ｃ）成分」とも略称する。）は、水分を吸収する能力を有するフィラーであれば特に限定はされないが、好ましくは吸湿性金属酸化物である。吸湿性金属酸化物は、水分を吸収する能力をもち、吸湿した水分と化学反応して水酸化物になる金属酸化物を意味する。具体的には、酸化カルシウム、酸化マグネシウム、酸化ストロンチウム、酸化アルミニウム、酸化バリウム、未焼成ハイドロタルサイト、半焼成ハイドロタルサイト、焼成ハイドロタルサイト、焼成ドロマイト等が挙げられる。中でも、吸湿性の点から、半焼成ハイドロタルサイト、焼成ハイドロタルサイトが好ましい。 <(C) Hygroscopic filler>
(C) The hygroscopic filler (hereinafter also abbreviated as “component (c)”) is not particularly limited as long as it is a filler capable of absorbing moisture, but is preferably a hygroscopic metal oxide. The hygroscopic metal oxide means a metal oxide that has the ability to absorb moisture and chemically reacts with the absorbed moisture to become a hydroxide. Specific examples include calcium oxide, magnesium oxide, strontium oxide, aluminum oxide, barium oxide, unfired hydrotalcite, semi-fired hydrotalcite, fired hydrotalcite, and fired dolomite. Of these, semi-calcined hydrotalcite and calcined hydrotalcite are preferable in terms of hygroscopicity.
　ハイドロタルサイトは、未焼成ハイドロタルサイト、半焼成ハイドロタルサイト、および焼成ハイドロタルサイトに分類することができる。 Hydrotalcite can be classified into unfired hydrotalcite, semi-fired hydrotalcite, and fired hydrotalcite.
　未焼成ハイドロタルサイトは、例えば、天然ハイドロタルサイト（Ｍｇ６Ａｌ２（ＯＨ）１６ＣＯ３・４Ｈ２Ｏ）に代表されるような層状の結晶構造を有する金属水酸化物であり、例えば、基本骨格となる層［Ｍｇ１－ＸＡｌＸ（ＯＨ）２］Ｘ＋と中間層［（ＣＯ３）Ｘ／２・ｍＨ２Ｏ］Ｘ－からなる。本発明における未焼成ハイドロタルサイトは、合成ハイドロタルサイト等のハイドロタルサイト様化合物を含む概念である。ハイドロタルサイト様化合物としては、例えば、下記式（Ｉ）および下記式（ＩＩ）で表されるものが挙げられる。 Uncalcined hydrotalcite is 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, It consists of a layer [Mg 1-X Al X (OH) 2 ] X + and a middle layer [(CO 3 ) X / 2 · mH 2 O] X— which are the basic skeleton. The uncalcined hydrotalcite in the present invention is a concept including a hydrotalcite-like compound such as synthetic hydrotalcite. Examples of the hydrotalcite-like compound include those represented by the following formula (I) and the following formula (II).
　［Ｍ２＋ １－ｘＭ３＋ｘ（ＯＨ）２］ｘ＋・［（Ａｎ－）ｘ／ｎ・ｍＨ２Ｏ］ｘ－　　
　（Ｉ）
（式中、Ｍ２＋はＭｇ２＋、Ｚｎ２＋などの２価の金属イオンを表し、Ｍ３＋はＡｌ３＋、Ｆｅ３＋などの３価の金属イオンを表し、Ａｎ－はＣＯ３ ２－、Ｃｌ－、ＮＯ３ －などのｎ価のアニオンを表し、０＜ｘ＜１であり、０≦ｍ＜１であり、ｎは正の数である。）
　式（Ｉ）中、Ｍ２＋は、好ましくはＭｇ２＋であり、Ｍ３＋は、好ましくはＡｌ３＋であり、Ａｎ－は、好ましくはＣＯ３ ２－である。 [M 2+ 1-x M 3+ x (OH) 2 ] x + · [(A n− ) x / n · mH 2 O] x−
(I)
(Wherein, M 2+ is Mg 2+, a divalent metal ion such as Zn 2+, M 3+ represents a trivalent metal ion such as Al 3+, Fe 3+, A n- is CO 3 2-, Cl Represents an n-valent anion such as − and NO 3 — , 0 <x <1, 0 ≦ m <1, and n is a positive number.)
Wherein (I), M 2+ is preferably Mg 2+, M 3+ is preferably Al 3+, A n-is preferably CO 3 2-.
　Ｍ２＋ ｘＡｌ２（ＯＨ）２ｘ＋６－ｎｚ（Ａｎ－）ｚ・ｍＨ２Ｏ　　　（ＩＩ）
（式中、Ｍ２＋はＭｇ２＋、Ｚｎ２＋などの２価の金属イオンを表し、Ａｎ－はＣＯ３ ２－、Ｃｌ－、ＮＯ３－などのｎ価のアニオンを表し、ｘは２以上の正の数であり、ｚは２以下の正の数であり、ｍは正の数であり、ｎは正の数である。）
　式（ＩＩ）中、Ｍ２＋は、好ましくはＭｇ２＋であり、Ａｎ－は、好ましくはＣＯ３ ２－である。 M 2+ x Al 2 (OH) 2x + 6-nz (A n− ) z · mH 2 O (II)
(In the formula, 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 − , NO 3− , and x is 2 or more. Z is a positive number of 2 or less, m is a positive number, and n is a positive number.)
Wherein (II), M 2+ is preferably Mg 2+, A n-is preferably CO 3 2-.
　半焼成ハイドロタルサイトは、未焼成ハイドロタルサイトを焼成して得られる、層間水の量が減少または消失した層状の結晶構造を有する金属水酸化物をいう。「層間水」とは、組成式を用いて説明すれば、上述した未焼成の天然ハイドロタルサイトおよびハイドロタルサイト様化合物の組成式に記載の「Ｈ２Ｏ」を指す。　 Semi-fired hydrotalcite refers to a metal hydroxide having a layered crystal structure in which the amount of interlayer water is reduced or eliminated, obtained by firing unfired hydrotalcite. The “interlayer water” refers to “H 2 O” described in the composition formula of the unfired natural hydrotalcite and hydrotalcite-like compound described above using a composition formula.
　一方、焼成ハイドロタルサイトは、未焼成ハイドロタルサイトまたは半焼成ハイドロタルサイトを焼成して得られ、層間水だけでなく、水酸基も縮合脱水によって消失した、アモルファス構造を有する金属酸化物をいう。 On the other hand, calcined hydrotalcite refers to a metal oxide having an amorphous structure obtained by calcining uncalcined hydrotalcite or semi-calcined hydrotalcite, and not only interlayer water but also hydroxyl groups disappeared by condensation dehydration.
　未焼成ハイドロタルサイト、半焼成ハイドロタルサイトおよび焼成ハイドロタルサイトは、飽和吸水率により区別することができる。半焼成ハイドロタルサイトの飽和吸水率は、１重量％以上２０重量％未満である。一方、未焼成ハイドロタルサイトの飽和吸水率は、１重量％未満であり、焼成ハイドロタルサイトの飽和吸水率は、２０重量％以上である。 Unfired hydrotalcite, semi-fired hydrotalcite and fired hydrotalcite can be distinguished by saturated water absorption. The saturated water absorption of the semi-calcined hydrotalcite is 1% by weight or more and less than 20% by weight. On the other hand, the saturated water absorption of unfired hydrotalcite is less than 1% by weight, and the saturated water absorption of fired hydrotalcite is 20% by weight or more.
　本発明における「飽和吸水率」とは、未焼成ハイドロタルサイト、半焼成ハイドロタルサイトまたは焼成ハイドロタルサイトを天秤にて１．５ｇ量り取り、初期質量を測定した後、大気圧下、６０℃、９０％ＲＨ（相対湿度）に設定した小型環境試験器（エスペック社製ＳＨ－２２２）に２００時間静置した場合の、初期質量に対する質量増加率を言い、下記式（ｉ）：
　飽和吸水率（質量％）＝１００×（吸湿後の質量－初期質量）／初期質量　　　（ｉ）
で求めることができる。 “Saturated water absorption” in the present invention means that uncalcined hydrotalcite, semi-calcined hydrotalcite or calcined hydrotalcite is weighed by 1.5 g using a balance, and the initial mass is measured. , The mass increase rate with respect to the initial mass when left in a small environmental tester (Espec SH-222) set to 90% RH (relative humidity) for 200 hours, the following formula (i):
Saturated water absorption (mass%) = 100 × (mass after moisture absorption−initial mass) / initial mass (i)
Can be obtained.
　半焼成ハイドロタルサイトの飽和吸水率は、好ましくは３重量％以上２０質量％未満、より好ましくは５重量％以上２０質量％未満である。 The saturated water absorption rate of the semi-fired hydrotalcite is preferably 3% by weight or more and less than 20% by weight, more preferably 5% by weight or more and less than 20% by weight.
　また、未焼成ハイドロタルサイト、半焼成ハイドロタルサイトおよび焼成ハイドロタルサイトは、熱重量分析で測定される熱重量減少率により区別することができる。半焼成ハイドロタルサイトの２８０℃における熱重量減少率は１５質量％未満であり、かつその３８０℃における熱重量減少率は１２質量％以上である。一方、未焼成ハイドロタルサイトの２８０℃における熱重量減少率は、１５質量％以上であり、焼成ハイドロタルサイトの３８０℃における熱重量減少率は、１２質量％未満である。 Further, unfired hydrotalcite, semi-fired hydrotalcite and fired hydrotalcite can be distinguished by the thermogravimetric reduction rate measured by thermogravimetric analysis. The thermal weight loss rate at 280 ° C. of the semi-calcined hydrotalcite is less than 15% by mass, and the thermal weight reduction rate at 380 ° C. is 12% by mass or more. On the other hand, the thermal weight reduction rate at 280 ° C. of the unfired hydrotalcite is 15% by mass or more, and the thermal weight reduction rate at 380 ° C. of the sintered hydrotalcite is less than 12% by mass.
　熱重量分析は、日立ハイテクサイエンス社製ＴＧ／ＤＴＡ ＥＸＳＴＡＲ６３００を用いて、アルミニウム製のサンプルパンにハイドロタルサイトを５ｍｇ秤量し、蓋をせずオープンの状態で、窒素流量２００ｍＬ／分の雰囲気下、３０℃から５５０℃まで昇温速度１０℃／分の条件で行うことができる。熱重量減少率は、下記式（ｉｉ）：
　熱重量減少率（質量％）
＝１００×（加熱前の質量－所定温度に達した時の質量）／加熱前の質量　　　（ｉｉ）で求めることができる。 Thermogravimetric analysis was performed using Hitachi High-Tech Science TG / DTA EXSTAR6300, weighing 5 mg of hydrotalcite into an aluminum sample pan, and without opening the lid, in an atmosphere with a nitrogen flow rate of 200 mL / min. The temperature can be increased from 30 ° C. to 550 ° C. at a temperature increase rate of 10 ° C./min. The thermal weight loss rate is expressed by the following formula (ii):
Thermal weight loss rate (mass%)
= 100 × (mass before heating−mass when reaching a predetermined temperature) / mass before heating (ii).
　また、未焼成ハイドロタルサイト、半焼成ハイドロタルサイトおよび焼成ハイドロタルサイトは、粉末Ｘ線回折で測定されるピークおよび相対強度比により区別することができる。半焼成ハイドロタルサイトは、粉末Ｘ線回折により２θが８～１８°付近に二つにスプリットしたピーク、または二つのピークの合成によりショルダーを有するピークを示し、低角側に現れるピークまたはショルダーの回折強度（＝低角側回折強度）と、高角側に現れるピークまたはショルダーの回折強度（＝高角側回折強度）の相対強度比（低角側回折強度／高角側回折強度）は、０．００１～１，０００である。一方、未焼成ハイドロタルサイトは８～１８°付近で一つのピークしか有しないか、または低角側に現れるピークまたはショルダーと高角側に現れるピークまたはショルダーの回折強度の相対強度比が前述の範囲外となる。焼成ハイドロタルサイトは８°～１８°の領域に特徴的ピークを有さず、４３°に特徴的なピークを有する。粉末Ｘ線回折測定は、粉末Ｘ線回折装置（PANalytical社製、Empyrean）により、対陰極ＣｕＫα（１．５４０５Å）、電圧：４５Ｖ、電流：４０ｍＡ、サンプリング幅：０．０２６０°、走査速度：０．０６５７°／ｓ、測定回折角範囲（２θ）：５．０１３１～７９．９７１１°の条件で行った。ピークサーチは、回折装置付属のソフトウエアのピークサーチ機能を利用し、「最小有意度：０．５０、最小ピークチップ：０．０１°、最大ピークチップ：１．００°、ピークベース幅：２．００°、方法：２次微分の最小値」の条件で行うことができる。 Further, unfired hydrotalcite, semi-fired hydrotalcite and fired hydrotalcite can be distinguished by the peak and relative intensity ratio measured by powder X-ray diffraction. Semi-calcined hydrotalcite shows a peak that is split into two around 8 to 18 ° by powder X-ray diffraction, or a peak having a shoulder due to the synthesis of two peaks. The relative intensity ratio (low angle side diffraction intensity / high angle side diffraction intensity) of the diffraction intensity (= low angle side diffraction intensity) and the peak or shoulder diffraction intensity appearing on the high angle side (= high angle side diffraction intensity) is 0.001. ~ 1,000. On the other hand, the uncalcined hydrotalcite has only one peak at around 8 to 18 °, or the relative intensity ratio of the diffraction intensity of the peak or shoulder appearing on the low angle side and the peak or shoulder appearing on the high angle side is in the above range. Get out. The calcined hydrotalcite does not have a characteristic peak in the region of 8 ° to 18 °, but has a characteristic peak at 43 °. Powder X-ray diffraction measurement was performed using a powder X-ray diffractometer (Empyrean, manufactured by PANalytical), counter-cathode CuKα (1.5405 mm), voltage: 45 V, current: 40 mA, sampling width: 0.0260 °, scanning speed: 0 0.0657 ° / s, diffraction angle range (2θ): 5.0131 to 79.9711 °. The peak search uses the peak search function of the software attached to the diffractometer. “Minimum significance: 0.50, minimum peak tip: 0.01 °, maximum peak tip: 1.00 °, peak base width: 2 0.000, method: minimum value of second derivative ”.
　半焼成ハイドロタルサイトのＢＥＴ比表面積は、１～２５０ｍ２／ｇが好ましく、５～２００ｍ２／ｇがより好ましい。半焼成ハイドロタルサイトのＢＥＴ比表面積は、ＢＥＴ法に従って、比表面積測定装置（Ｍａｃｓｏｒｂ ＨＭ Ｍｏｄｅｌ １２１０　マウンテック社製）を用いて試料表面に窒素ガスを吸着させ、ＢＥＴ多点法を用いて算出することができる。 BET specific surface area of the semi-sintered hydrotalcite is preferably 1 ~ 250m 2 / g, more preferably 5 ~ 200m 2 / g. The BET specific surface area of semi-calcined hydrotalcite should be calculated using the BET multipoint method by adsorbing nitrogen gas to the sample surface using a specific surface area measuring device (Macsorb HM Model 1210 Mountec) according to the BET method. Can do.
　半焼成ハイドロタルサイトの平均粒子径は、１～１，０００ｎｍが好ましく、１０～８００ｎｍがより好ましい。半焼成ハイドロタルサイトの平均粒子径は、レーザー回折散乱式粒度分布測定（ＪＩＳ Ｚ ８８２５）により粒度分布を体積基準で作成したときの該粒度分布のメディアン径である。 The average particle size of the semi-fired hydrotalcite is preferably 1 to 1,000 nm, and more preferably 10 to 800 nm. The average particle size of the semi-calcined hydrotalcite is the median size of the particle size distribution when the particle size distribution is prepared on a volume basis by laser diffraction scattering type particle size distribution measurement (JIS Z 8825).
　（ｃ）成分は、表面処理剤で表面処理したものを用いることができる。表面処理に使用する表面処理剤としては、例えば、高級脂肪酸、アルキルシラン類、シランカップリング剤等を使用することができ、なかでも、高級脂肪酸、アルキルシラン類が好適である。表面処理剤は、１種または２種以上を使用できる。 (C) The component surface-treated with a surface treatment agent can be used. As the surface treatment agent used for the surface treatment, for example, higher fatty acids, alkylsilanes, silane coupling agents and the like can be used, and among these, higher fatty acids and alkylsilanes are preferable. One or more surface treatment agents can be used.
　高級脂肪酸としては、例えば、ステアリン酸、モンタン酸、ミリスチン酸、パルミチン酸などの炭素数１８以上の高級脂肪酸が挙げられ、中でも、ステアリン酸が好ましい。これらは１種または２種以上組み合わせて使用してもよい。アルキルシラン類としては、メチルトリメトキシシラン、エチルトリメトキシシラン、ヘキシルトリメトキシシラン、オクチルトリメトキシシラン、デシルトリメトキシシラン、オクタデシルトリメトキシシラン、ジメチルジメトキシシラン、オクチルトリエトキシシラン、ｎ－オクタデシルジメチル（３－（トリメトキシシリル）プロピル）アンモニウムクロライド等が挙げられる。これらは１種または２種以上組み合わせて使用してもよい。シランカップリング剤としては、例えば、３－グリシジルオキシプロピルトリメトキシシラン、３－グリシジルオキシプロピルトリエトキシシラン、３－グリシジルオキシプロピル（ジメトキシ）メチルシランおよび２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシランなどのエポキシ系シランカップリング剤；３－メルカプトプロピルトリメトキシシラン、３－メルカプトプロピルトリエトキシシラン、３－メルカプトプロピルメチルジメトキシシランおよび１１－メルカプトウンデシルトリメトキシシランなどのメルカプト系シランカップリング剤；３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－アミノプロピルジメトキシメチルシラン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、Ｎ－メチルアミノプロピルトリメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシランおよびＮ－（２－アミノエチル）－３－アミノプロピルジメトキシメチルシランなどのアミノ系シランカップリング剤；３－ウレイドプロピルトリエトキシシランなどのウレイド系シランカップリング剤、ビニルトリメトキシシラン、ビニルトリエトキシシランおよびビニルメチルジエトキシシランなどのビニル系シランカップリング剤；ｐ－スチリルトリメトキシシランなどのスチリル系シランカップリング剤；３－アクリルオキシプロピルトリメトキシシランおよび３－メタクリルオキシプロピルトリメトキシシランなどのアクリレート系シランカップリング剤；３－イソシアネートプロピルトリメトキシシランなどのイソシアネート系シランカップリング剤、ビス（トリエトキシシリルプロピル）ジスルフィド、ビス（トリエトキシシリルプロピル）テトラスルフィドなどのスルフィド系シランカップリング剤；フェニルトリメトキシシラン、メタクリロキシプロピルトリメトキシシラン、イミダゾールシラン、トリアジンシラン等を挙げることができる。これらは１種または２種以上組み合わせて使用してもよい。 Examples of the higher fatty acid include higher fatty acids having 18 or more carbon atoms such as stearic acid, montanic acid, myristic acid, and palmitic acid, among which stearic acid is preferable. You may use these 1 type or in combination of 2 or more types. Alkylsilanes include methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane, octyltriethoxysilane, n-octadecyldimethyl ( And 3- (trimethoxysilyl) propyl) ammonium chloride. You may use these 1 type or in combination of 2 or more types. Examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxy. Epoxy silane coupling agents such as silane; mercapto silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane ; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltri Amino-based silane cups such as toxisilane, N-methylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane Ringing agents; Ureido silane coupling agents such as 3-ureidopropyltriethoxysilane, vinyl silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldiethoxysilane; p-styryltrimethoxysilane Styryl-based silane coupling agents; acrylate-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; 3-isocyanatopropyltrimeth Isocyanate silane coupling agents such as silane, sulfide silane coupling agents such as bis (triethoxysilylpropyl) disulfide and bis (triethoxysilylpropyl) tetrasulfide; phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazole Examples thereof include silane and triazine silane. You may use these 1 type or in combination of 2 or more types.
　（ｃ）成分の表面処理は、例えば、未処理の（ｃ）成分を混合機で常温にて攪拌分散させながら、表面処理剤を添加噴霧して５～６０分間攪拌することによって行なうことができる。混合機としては、公知の混合機を使用することができ、例えば、Ｖブレンダー、リボンブレンダー、バブルコーンブレンダー等のブレンダー、ヘンシェルミキサーおよびコンクリートミキサー等のミキサー、ボールミル、カッターミル等が挙げられる。又、ボールミルなどで吸湿材を粉砕する際に、前記の高級脂肪酸、アルキルシラン類またはシランカップリング剤を混合し、表面処理する方法も可能である。表面処理剤の処理量は（ｃ）成分の種類または表面処理剤の種類等によっても異なるが、（ｃ）成分１００質量部に対して１～１０質量部が好ましい。 The surface treatment of the component (c) can be performed, for example, by adding and spraying the surface treatment agent while stirring and dispersing the untreated component (c) at room temperature with a mixer and stirring for 5 to 60 minutes. . As a mixer, a well-known mixer can be used, For example, blenders, such as V blender, a ribbon blender, and a bubble cone blender, mixers, such as a Henschel mixer and a concrete mixer, a ball mill, a cutter mill, etc. are mentioned. Further, when the hygroscopic material is pulverized with a ball mill or the like, a method of surface treatment by mixing the above-mentioned higher fatty acid, alkylsilanes or silane coupling agent is also possible. The treatment amount of the surface treatment agent varies depending on the type of component (c) or the type of surface treatment agent, but is preferably 1 to 10 parts by mass with respect to 100 parts by mass of component (c).
　樹脂組成物における（ｃ）成分の含有量は特に限定されるものではない。しかし、樹脂組成物層とガラス等の基板との密着性および樹脂組成物層の透明性を維持する観点から、該含有量は、樹脂組成物中の不揮発分の合計１００質量％あたり、６０質量％以下が好ましく、５５質量％以下が好ましく、５０質量％以下がより好ましく、４５質量％以下がさらに好ましい。また、吸湿性の効果を十分得るという観点から、該含有量は、樹脂組成物中の不揮発分の合計１００質量％あたり、１０質量％以上が好ましく、２０質量％以上がより好ましく、３０質量％以上がさらに好ましい。 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 a substrate such as glass and the transparency of the resin composition layer, the content is 60 mass per 100 mass% of the total nonvolatile content in the resin composition. % Or less, preferably 55% by mass or less, more preferably 50% by mass or less, and further preferably 45% by mass or less. Further, from the viewpoint of sufficiently obtaining a hygroscopic effect, the content is preferably 10% by mass or more, more preferably 20% by mass or more, and more preferably 30% by mass per 100% by mass of the total nonvolatile content in the resin composition. The above is more preferable.
　本発明における（ｃ）成分の具体例としては、以下のものが挙げられる：
・ＤＨＴ－４Ｃ（協和化学工業社製）：半焼成ハイドロタルサイト（平均粒子径：４００ｎｍ、ＢＥＴ比表面積：１５ｍ２/ｇ）
・ＤＨＴ－４Ａ－２（協和化学工業社製）：半焼成ハイドロタルサイト（平均粒子径：４００ｎｍ、ＢＥＴ比表面積：１３ｍ２/ｇ）
・ＫＷ－２２００（協和化学工業社製）：焼成ハイドロタルサイト（平均粒子径：４００ｎｍ、ＢＥＴ比表面積：１４６ｍ２／ｇ）
・ＤＨＴ－４Ａ（協和化学工業社製）：未焼成ハイドロタルサイト（平均粒子径：４００ｎｍ、ＢＥＴ比表面積：１０ｍ２/ｇ） Specific examples of the component (c) in the present invention include the following:
DHT-4C (manufactured by Kyowa Chemical Industry Co., Ltd.): Semi-calcined hydrotalcite (average particle size: 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.): calcined hydrotalcite (average particle size: 400 nm, BET specific surface area: 146 m 2 / g)
DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.): uncalcined hydrotalcite (average particle size: 400 nm, BET specific surface area: 10 m 2 / g)
＜（ｄ）硬化剤＞
　樹脂組成物は、樹脂組成物の硬化性能を向上させる観点から、さらに（ｄ）硬化剤（以下「（ｄ）成分」と略称することがある。）を含んでいてもよい。（ｄ）成分としては、特に限定はされないが、アミン系硬化剤、グアニジン系硬化剤、イミダゾール系硬化剤、ホスホニウム系硬化剤、フェノール系硬化剤などが挙げられる。（ｄ）成分は１種または２種以上組み合わせて使用してもよい。 <(D) Curing agent>
The resin composition may further contain (d) a curing agent (hereinafter sometimes abbreviated as “component (d)”) from the viewpoint of improving the curing performance of the resin composition. The component (d) is not particularly limited, and examples thereof include amine-based curing agents, guanidine-based curing agents, imidazole-based curing agents, phosphonium-based curing agents, and phenol-based curing agents. Component (d) may be used alone or in combination of two or more.
　アミン系硬化剤としては、特に制限はないが、テトラメチルアンモニウムブロマイド、テトラブチルアンモニウムブロマイド等の４級アンモニウム塩；ＤＢＵ（１，８－ジアザビシクロ［５．４．０］ウンデセン－７）、ＤＢＮ（１，５－ジアザビシクロ［４．３．０］ノネン－５）、ＤＢＵ－フェノール塩、ＤＢＵ－オクチル酸塩、ＤＢＵ－ｐ－トルエンスルホン酸塩、ＤＢＵ－ギ酸塩、ＤＢＵ－フェノールノボラック樹脂塩等のジアザビシクロ化合物；ベンジルジメチルアミン、２－（ジメチルアミノメチル）フェノール、２，４，６－トリス（ジアミノメチル）フェノール等の３級アミンおよびそれらの塩、芳香族ジメチルウレア、脂肪族ジメチルウレア、芳香族ジメチルウレア等のジメチルウレア化合物；等が挙げられる。これらは１種または２種以上を組み合わせて使用してもよい。 The amine curing agent is not particularly limited, but includes quaternary ammonium salts such as tetramethylammonium bromide and tetrabutylammonium bromide; DBU (1,8-diazabicyclo [5.4.0] undecene-7), DBN ( 1,5-diazabicyclo [4.3.0] nonene-5), DBU-phenol salt, DBU-octylate, DBU-p-toluenesulfonate, DBU-formate, DBU-phenol novolac resin salt, etc. Diazabicyclo compounds; tertiary amines such as benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol and their salts, aromatic dimethylurea, aliphatic dimethylurea, aromatic And dimethylurea compounds such as dimethylurea; These may be used alone or in combination of two or more.
　グアニジン系硬化剤としては、特に制限はないが、ジシアンジアミド、１－メチルグアニジン、１－エチルグアニジン、１－シクロヘキシルグアニジン、１－フェニルグアニジン、１－（ｏ－トリル）グアニジン、ジメチルグアニジン、ジフェニルグアニジン、トリメチルグアニジン、テトラメチルグアニジン、ペンタメチルグアニジン、１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン、７－メチル－１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン、１－メチルビグアニド、１－エチルビグアニド、１－ｎ－ブチルビグアニド、１－ｎ－オクタデシルビグアニド、１，１－ジメチルビグアニド、１，１－ジエチルビグアニド、１－シクロヘキシルビグアニド、１－アリルビグアニド、１－フェニルビグアニド、１－（ｏ－トリル）ビグアニド等が挙げられる。これらは１種または２種以上組み合わせて使用してもよい。 The guanidine curing agent is not particularly limited, but dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, Trimethyl guanidine, tetramethyl guanidine, pentamethyl guanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4 .0] dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl Biguanide, 1-allyl biguanide, 1-phenyl biguanide 1-(o-tolyl) biguanide, and the like. You may use these 1 type or in combination of 2 or more types.
　イミダゾール系硬化剤としては、特に制限はないが、１Ｈ－イミダゾール、２－メチル－イミダゾール、２－フェニル－４－メチルイミダゾール、１－シアノエチルー２－エチル－４－メチル－イミダゾール、２－フェニル－４，５－ビス（ヒドロキシメチル）－イミダゾール、１－ベンジル－２－メチルイミダゾール、１－ベンジル－２－フェニルイミダゾール、２－エチル－４－メチルイミダゾール、２－フェニル－イミダゾール、２－ドデシル－イミダゾール、２－ヘプタデシルイミダゾール、１，２－ジメチル－イミダゾール等が挙げられる。これらは１種または２種以上組み合わせて使用してもよい。 The imidazole curing agent is not particularly limited, but 1H-imidazole, 2-methyl-imidazole, 2-phenyl-4-methylimidazole, 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-methylimidazole, 2-phenyl-imidazole, 2-dodecyl-imidazole, Examples include 2-heptadecylimidazole and 1,2-dimethyl-imidazole. You may use these 1 type or in combination of 2 or more types.
　ホスホニウム系硬化剤としては、特に制限はないが、トリフェニルホスフィン、ホスホニウムボレート化合物、テトラフェニルホスホニウムテトラフェニルボレート、ｎ－ブチルホスホニウムテトラフェニルボレート、テトラブチルホスホニウムデカン酸塩、（４－メチルフェニル）トリフェニルホスホニウムチオシアネート、テトラフェニルホスホニウムチオシアネート、ブチルトリフェニルホスホニウムチオシアネート等が挙げられる。これらは１種または２種以上組み合わせて使用してもよい。 The phosphonium curing agent is not particularly limited, but is triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triate. Examples thereof include phenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. You may use these 1 type or in combination of 2 or more types.
　フェノール系硬化剤の種類は、特に制限はないが、ＭＥＨ－７７００、ＭＥＨ－７８１０、ＭＥＨ－７８５１（明和化成社製）、ＮＨＮ、ＣＢＮ、ＧＰＨ（日本化薬社製）、ＳＮ１７０、ＳＮ１８０、ＳＮ１９０、ＳＮ４７５、ＳＮ４８５、ＳＮ４９５、ＳＮ３７５、ＳＮ３９５（東都化成社製）、ＴＤ２０９０（ＤＩＣ社製）等が挙げられる。トリアジン骨格含有フェノール系硬化剤の具体例としては、ＬＡ３０１８（ＤＩＣ社製）等が挙げられる。トリアジン骨格含有フェノールノボラック硬化剤の具体例としては、ＬＡ７０５２、ＬＡ７０５４、ＬＡ１３５６（ＤＩＣ社製）等が挙げられる。これらは１種または２種以上組み合わせて使用してもよい。 The type of phenolic curing agent is not particularly limited, but is MEH-7700, MEH-7810, MEH-7851 (Maywa Kasei), NHN, CBN, GPH (Nippon Kayaku), SN170, SN180, SN190. SN475, SN485, SN495, SN375, SN395 (manufactured by Tohto Kasei), TD2090 (manufactured by DIC), and the like. Specific examples of the triazine skeleton-containing phenolic curing agent include LA3018 (manufactured by DIC). Specific examples of the triazine skeleton-containing phenol novolak curing agent include LA7052, LA7054, LA1356 (manufactured by DIC) and the like. You may use these 1 type or in combination of 2 or more types.
　樹脂組成物中の（ｄ）成分の含有量は特に制限はない。しかし、耐透湿性の低下を防止するという観点から、（ｄ）成分を使用する場合、その含有量は、樹脂組成物中の不揮発分の合計１００質量％あたり、５質量％以下が好ましく、１質量％以下がより好ましい。一方、タックを抑制させるという観点から、（ｄ）成分を使用する場合、その含有量は、樹脂組成物中の不揮発分の合計１００質量％あたり、０．０１質量％以上が好ましく、０．０５質量％以上がより好ましい。 The content of the component (d) in the resin composition is not particularly limited. However, from the viewpoint of preventing a decrease in moisture permeation resistance, when the component (d) is used, its content is preferably 5% by mass or less per 100% by mass of the total nonvolatile content in the resin composition. The mass% or less is more preferable. On the other hand, from the viewpoint of suppressing tackiness, when the component (d) is used, its content is preferably 0.01% by mass or more per 100% by mass of the total nonvolatile content in the resin composition. The mass% or more is more preferable.
＜（ｅ）エポキシ基と反応し得る官能基を有する樹脂＞
　本発明の樹脂組成物において、（ａ）成分としてエポキシ基を有するポリオレフィン系樹脂を用いる場合、（ａ）成分と架橋構造を形成するための成分として、（ｅ）エポキシ基と反応し得る官能基を有する樹脂（以下「（ｅ）成分」と略称することがある。）を使用するのが望ましい。エポキシ基と反応し得る官能基としては、水酸基、フェノール性水酸基、アミノ基、カルボキシ基および酸無水物基等が挙げられ、酸無水物基が好ましい。酸無水物基としては、例えば、無水コハク酸に由来する基、無水マレイン酸に由来する基、無水グルタル酸に由来する基等が挙げられる。樹脂としては、ポリオレフィン系樹脂（但し、（ａ）成分である酸無水物基を有するポリオレフィン系樹脂を除く）、アクリル樹脂、メラミン樹脂、フェノール樹脂、ユリア樹脂、ポリエステル樹脂、アルキド樹脂、ポリウレタン、ポリイミド樹脂などが挙げられ、ポリオレフィン系樹脂が好ましい。（ｅ）成分であるポリオレフィン系樹脂としては、官能基として、酸無水物基ではなく、水酸基、フェノール性水酸基、アミノ基、カルボキシ基等を有すること以外は、上述した（ａ）成分と同様のポリオレフィン系樹脂が挙げられ、ポリブテンが好ましい。 <(E) Resin having a functional group capable of reacting with an epoxy group>
In the resin composition of the present invention, when a polyolefin-based resin having an epoxy group is used as the component (a), as a component for forming a crosslinked structure with the component (a), (e) a functional group capable of reacting with the epoxy group It is desirable to use a resin having the following (sometimes abbreviated as “component (e)”). Examples of the functional group capable of reacting with the epoxy group include a hydroxyl group, a phenolic hydroxyl group, an amino group, a carboxy group, and an acid anhydride group, and an acid anhydride group is preferable. 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. Examples of the resin include polyolefin resin (excluding the polyolefin resin having an acid anhydride group as component (a)), acrylic resin, melamine resin, phenol resin, urea resin, polyester resin, alkyd resin, polyurethane, polyimide. Examples of the resin include polyolefin resins. (E) The polyolefin resin as the component is the same as the component (a) described above except that it has a hydroxyl group, a phenolic hydroxyl group, an amino group, a carboxy group or the like as a functional group instead of an acid anhydride group. Polyolefin resins are preferred, and polybutene is preferred.
　樹脂組成物中の（ｅ）成分の含有量は特に制限はない。しかし、耐透湿性の低下を防止するという観点から、（ｅ）成分を使用する場合、その含有量は、樹脂組成物中の不揮発分の合計１００質量％あたり、３０質量％以下が好ましく、２０質量％以下がより好ましい。一方、タックを抑制させるという観点から、（ｅ）成分を使用する場合、その含有量は、樹脂組成物中の不揮発分の合計１００質量％あたり、５質量％以上が好ましく、１０質量％以上がより好ましい。 The content of the component (e) in the resin composition is not particularly limited. However, from the viewpoint of preventing a decrease in moisture permeation resistance, when the component (e) is used, its content is preferably 30% by mass or less per 100% by mass of the total nonvolatile content in the resin composition. The mass% or less is more preferable. On the other hand, from the viewpoint of suppressing tackiness, when the component (e) is used, the content thereof is preferably 5% by mass or more and preferably 10% by mass or more per 100% by mass of the total nonvolatile content in the resin composition. More preferred.
＜（ｆ）酸無水物基と反応し得る官能基を有する樹脂＞
　樹脂組成物において、（ａ）成分として酸無水物基を有するポリオレフィン系樹脂を用いる場合、（ａ）成分と架橋構造を形成するための成分として、（ｆ）酸無水物基と反応し得る官能基を有する樹脂（以下「（ｆ）成分」と略称することがある。）を使用するのが望ましい。酸無水物基と反応し得る官能基としては、水酸基、１級または２級のアミノ基、チオール基、エポキシ基、オキセタン基等が挙げられ、エポキシ基が好ましい。樹脂としては、ポリオレフィン系樹脂（但し、（ａ）成分であるエポキシ基を有するポリオレフィン系樹脂を除く）、アクリル樹脂、メラミン樹脂、フェノール樹脂、ユリア樹脂、ポリエステル樹脂、アルキド樹脂、ポリウレタン、ポリイミド樹脂などが挙げられ、ポリオレフィン系樹脂が好ましい。（ｆ）成分であるポリオレフィン系樹脂としては、官能基として、エポキシ基ではなく、水酸基、１級または２級のアミノ基、チオール基、エポキシ基、オキセタン基等を有すること以外は、上述した（ａ）成分と同様のポリオレフィン系樹脂が挙げられ、ポリブテンが好ましい。 <(F) Resin having a functional group capable of reacting with an acid anhydride group>
In the resin composition, when a polyolefin-based resin having an acid anhydride group is used as the component (a), (f) a functional group capable of reacting with the acid anhydride group as a component for forming a crosslinked structure with the component (a). It is desirable to use a resin having a group (hereinafter sometimes abbreviated as “component (f)”). Examples of the functional group capable of reacting with the acid anhydride group include a hydroxyl group, a primary or secondary amino group, a thiol group, an epoxy group, and an oxetane group, and an epoxy group is preferable. Examples of the resin include polyolefin resin (excluding the polyolefin resin having an epoxy group as component (a)), acrylic resin, melamine resin, phenol resin, urea resin, polyester resin, alkyd resin, polyurethane, polyimide resin, etc. And polyolefin resins are preferred. The component (f) is a polyolefin-based resin as described above except that it has a hydroxyl group, a primary or secondary amino group, a thiol group, an epoxy group, an oxetane group, and the like as a functional group instead of an epoxy group ( The polyolefin resin similar to a) component is mentioned, A polybutene is preferable.
　樹脂組成物中の（ｆ）成分の含有量は特に制限はない。しかし、耐透湿性の低下を防止するという観点から、（ｆ）成分を使用する場合、その含有量は、樹脂組成物中の不揮発分の合計１００質量％あたり、３０質量％以下が好ましく、２０質量％以下がより好ましい。一方、タックを抑制させるという観点から、（ｆ）成分を使用する場合、その含有量は、樹脂組成物中の不揮発分の合計１００質量％あたり、５質量％以上が好ましく、１０質量％以上がより好ましい。 The content of the component (f) in the resin composition is not particularly limited. However, from the viewpoint of preventing a decrease in moisture permeation resistance, when the component (f) is used, its content is preferably 30% by mass or less per 100% by mass of the total nonvolatile content in the resin composition. The mass% or less is more preferable. On the other hand, from the viewpoint of suppressing tackiness, when the component (f) is used, the content thereof is preferably 5% by mass or more, preferably 10% by mass or more, per 100% by mass of the total nonvolatile content in the resin composition. More preferred.
＜（ｇ）可塑剤＞
　樹脂組成物は、さらに（ｇ）可塑剤（以下「（ｇ）成分」と略称することがある。）を含んでいてもよい。（ｇ）成分を使用することにより、樹脂組成物の柔軟性や成形性を向上させることができる。（ｇ）成分としては、特に限定はされないが、室温で液状の材料が好適に用いられる。可塑剤の具体例としては、パラフィン系プロセスオイル、ナフテン系プロセスオイル、流動パラフィン、ポリエチレンワックス、ポリプロピレンワックス、ワセリン等の鉱物油、ヒマシ油、綿実油、菜種油、大豆油、パーム油、ヤシ油、オリーブ油等の植物油、液状ポリブテン、水添液状ポリブテン、液状ポリブタジエン、水添液状ポリブタジエン等の液状ポリαオレフィン類等が挙げられる。本発明に使用する可塑剤としては、液状ポリαオレフィン類が好ましく、特に液状ポリブタジエンが好ましい。また液状ポリαオレフィンとしては接着性の観点から分子量が低いものが好ましく、重量平均分子量で５００～５，０００、さらには１，０００～３，０００の範囲のものが好ましい。これら可塑剤は１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。なお、ここで「液状」とは、室温（２５℃）での可塑剤の状態である。（ｇ）成分を使用する場合、有機ＥＬ素子への悪影響を及ぼさないという観点から、その含有量は、樹脂組成物中の不揮発分の合計１００質量％あたり、５０質量％以下が好ましい。 <(G) Plasticizer>
The resin composition may further contain (g) a plasticizer (hereinafter sometimes abbreviated as “(g) component”). By using the component (g), the flexibility and moldability of the resin composition can be improved. (G) Although it does not specifically limit as a component, A liquid material is used suitably at room temperature. Specific examples of plasticizers include paraffinic process oil, naphthenic process oil, liquid paraffin, polyethylene wax, polypropylene wax, petroleum jelly and other mineral oils, castor oil, cottonseed oil, rapeseed oil, soybean oil, palm oil, palm oil, olive oil. And other liquid oils such as vegetable oil, liquid polybutene, hydrogenated liquid polybutene, liquid polybutadiene, and hydrogenated liquid polybutadiene. As the plasticizer used in the present invention, liquid polyα-olefins are preferable, and liquid polybutadiene is particularly preferable. The liquid polyα-olefin preferably has a low molecular weight from the viewpoint of adhesiveness, and preferably has a weight average molecular weight in the range of 500 to 5,000, more preferably 1,000 to 3,000. These plasticizers may be used alone or in combination of two or more. Here, “liquid” means a state of a plasticizer at room temperature (25 ° C.). When the component (g) is used, the content thereof is preferably 50% by mass or less per 100% by mass of the total nonvolatile content in the resin composition from the viewpoint of not exerting an adverse effect on the organic EL element.
＜その他の添加剤＞
　樹脂組成物には、本発明の効果を阻害しない程度に、上述した成分以外の各種添加剤を任意で含有させてもよい。このような添加剤としては、例えば、上述した（ａ）成分、（ｅ）成分および（ｆ）成分以外の樹脂（例えば、エポキシ樹脂、ウレタン樹脂、アクリル樹脂、ポリアミド樹脂等）、シリカ、硫酸バリウム、タルク、クレー、雲母粉、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、窒化ホウ素、ホウ酸アルミニウム、チタン酸バリウム、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸マグネシウム、チタン酸ビスマス、ジルコン酸バリウム、ジルコン酸カルシウム等の無機充填材（但し、吸湿性フィラーを除く）；ゴム粒子、シリコーンパウダー、ナイロンパウダー、フッ素樹脂パウダー等の有機充填剤；オルベン、ベントン等の増粘剤；シリコン系、フッ素系、高分子系の消泡剤またはレベリング剤；トリアゾール化合物、チアゾール化合物、トリアジン化合物、ポルフィリン化合物等の密着性付与剤；等を挙げることができる。 <Other additives>
The resin composition may optionally contain various additives other than the above-described components to the extent that the effects of the present invention are not impaired. Examples of such additives include resins other than the components (a), (e) and (f) described above (for example, epoxy resins, urethane resins, acrylic resins, polyamide resins, etc.), silica, barium sulfate. , Talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, zircon Inorganic fillers such as barium oxide and calcium zirconate (excluding hygroscopic fillers); Organic fillers such as rubber particles, silicone powder, nylon powder and fluororesin powder; Thickeners such as Orben and Benton; Silicone , Fluorinated or polymeric antifoaming agent or levelin Agent; triazole compounds, thiazole compounds, triazine compounds, adhesion imparting agents such as porphyrin compounds; and the like.
＜樹脂組成物の調製＞
　樹脂組成物の調製方法は、特に限定されるものではなく、配合成分を、必要により溶媒等を添加し、混練ローラーや回転ミキサーなどを用いて混合する方法などが挙げられる。 <Preparation of resin composition>
The method for preparing the resin composition is not particularly limited, and examples thereof include a method in which the compounding components are mixed using a kneading roller, a rotary mixer, or the like, if necessary, by adding a solvent or the like.
　本発明の封止用シートにおける（Ａ）感圧接着性樹脂組成物層１の厚さは特に限定はされないが、安定した封止性能、取扱い性等の観点から、１μｍ以上が好ましく、３μｍ以上がより好ましい。また、封止構造の薄厚化、埋め込み性等の観点から、１００μｍ以下が好ましく、５０μｍ以下がより好ましい。 The thickness of the (A) pressure-sensitive adhesive resin composition layer 1 in the sealing sheet of the present invention is not particularly limited, but is preferably 1 μm or more from the viewpoint of stable sealing performance, handleability, and the like, and is 3 μm or more. Is more preferable. Further, from the viewpoints of thinning of the sealing structure, embedding property, etc., 100 μm or less is preferable, and 50 μm or less is more preferable.
　なお、（Ａ）感圧接着性樹脂組成物層１単体における防湿性（水蒸気バリア性）は、例えば、感圧接着性樹脂組成物層１の構成材料や厚さによっても異なるが、厚さが上記の好適範囲（３～５０μｍ）であるときに、ＪＩＳ　Ｚ　０２０８：１９７６に準拠する方法で測定される、温度４０℃、湿度９０％ＲＨ、２４時間の測定条件での１ｍ２当たりの水蒸気透過度が、一般的には０．１～１００ｇ／（ｍ２・２４ｈ）であり、好ましくは０．１～５０ｇ／（ｍ２・２４ｈ）である。 Note that (A) the moisture-proof property (water vapor barrier property) of the pressure-sensitive adhesive resin composition layer 1 alone depends on, for example, the constituent material and thickness of the pressure-sensitive adhesive resin composition layer 1, but the thickness is when it is above the preferred range (3 ~ 50μm), JIS Z 0208: is measured by a method conforming to 1976, temperature 40 ° C., 1 m 2 per water vapor transmission of the measurement conditions of humidity 90% RH, 24 hours The degree is generally from 0.1 to 100 g / (m 2 · 24 h), preferably from 0.1 to 50 g / (m 2 · 24 h).
［（Ｂ）防湿性無機被膜］
　本発明の封止用シートは、上記（Ａ）感圧接着性樹脂組成物層の片面に（Ｂ）防湿性無機被膜２が直接形成された構成を有する。
　（Ｂ）防湿性無機被膜（以下、単に「無機被膜」ともいう。）２とは、無機物によって形成された防湿性を有する被膜のことであり、「無機物」は、有機物（燃やすと二酸化炭素を発生したり、黒くこげて炭になる物質）以外の物質を指す。 [(B) Moisture-proof inorganic coating]
The sealing sheet of the present invention has a configuration in which (B) a moisture-proof inorganic coating 2 is directly formed on one surface of the (A) pressure-sensitive adhesive resin composition layer.
(B) Moisture-proof inorganic coating (hereinafter also simply referred to as “inorganic coating”) 2 is a moisture-proof coating formed of an inorganic substance, and “inorganic substance” is an organic substance (carbon dioxide when burned). Substances other than those that occur or become black and charcoal.
　（Ｂ）防湿性無機被膜２には、薄厚でも封止用シートに優れた防湿性を付与することができることから、（Ｂ１）ポリシラザン含有塗膜の熱処理生成物からなるシリカガラス被膜（以下、「（Ｂ１）シリカガラスフィルム」とも略称する。）か、或いは、（Ｂ２）無機物蒸着被膜が好適に使用される。 (B) Since the moisture-proof inorganic coating 2 can impart excellent moisture-proof properties to the sealing sheet even when it is thin, (B1) a silica glass coating (hereinafter referred to as “a heat-treated product of a polysilazane-containing coating”). (B1) also abbreviated as “silica glass film”) or (B2) an inorganic deposited film is preferably used.
＜（Ｂ１）ポリシラザン含有塗膜の熱処理生成物からなるシリカガラス被膜＞
　当該（Ｂ１）シリカガラス被膜は、（Ａ）感圧接着性樹脂組成物層１の片面に形成したポリシラザン含有塗膜を水蒸気含有雰囲気下で加熱することで得られる。 <(B1) Silica glass coating comprising heat-treated product of polysilazane-containing coating>
The said (B1) silica glass film is obtained by heating the polysilazane containing coating film formed in the single side | surface of (A) pressure sensitive adhesive resin composition layer 1 in water vapor | steam containing atmosphere.
　ポリシラザンとしては、例えば、式（１） As polysilazane, for example, formula (1)
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　（式中、ｎは任意の自然数を表す。Ｒｘ、Ｒｙは、それぞれ独立して、水素原子、無置換若しくは置換基を有するアルキル基、無置換若しくは置換基を有するシクロアルキル基、無置換若しくは置換基を有するアルケニル基、無置換若しくは置換基を有するアリール基等の非加水分解性基を表す。Ｒｚは、水素原子、無置換若しくは置換基を有するアルキル基、無置換若しくは置換基を有するシクロアルキル基、無置換若しくは置換基を有するアルケニル基、無置換若しくは置換基を有するアリール基又はアルキルシリル基等の非加水分解性基を表す。）
で表される繰り返し単位を有する化合物（以下、「式（１）のポリシラザン化合物」とも称す。）が使用される。 (In the formula, n represents an arbitrary natural number. Rx and Ry each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted group. Represents a non-hydrolyzable group such as an alkenyl group having a group, an unsubstituted or substituted aryl group, etc. Rz is a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group A non-hydrolyzable group such as a group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group or an alkylsilyl group.)
(Hereinafter also referred to as “polysilazane compound of formula (1)”) having a repeating unit represented by the formula:
　上記無置換若しくは置換基を有するアルキル基のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｎ－へキシル基、ｎ－ヘプチル基、ｎ－オクチル基等の炭素数１～１０のアルキル基が挙げられる。 Examples of the alkyl group of the unsubstituted or substituted alkyl group include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, Examples thereof include alkyl groups having 1 to 10 carbon atoms such as n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group and n-octyl group.
　上記無置換若しくは置換基を有するシクロアルキル基のシクロアルキル基としては、シクロブチル基、シクロペンチル基、シクロへキシル基、シクロへプチル基等の炭素数３～１０のシクロアルキル基が挙げられる。 Examples of the unsubstituted or substituted cycloalkyl group include cycloalkyl groups having 3 to 10 carbon atoms such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
　上記無置換若しくは置換基を有するアルケニル基のアルケニル基としては、例えば、ビニル基、１－プロペニル基、２－プロペニル基、１－ブテニル基、２－ブテニル基、３－ブテニル基等の炭素数２～１０のアルケニル基が挙げられる。 Examples of the alkenyl group of the unsubstituted or substituted alkenyl group include, for example, a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, and the like. ˜10 alkenyl groups.
　上記アルキル基、シクロアルキル基及びアルケニル基の置換基としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；ヒドロキシル基；チオール基；エポキシ基；グリシドキシ基；（メタ）アクリロイルオキシ基；フェニル基、４－メチルフェニル基、４－クロロフェニル基等の無置換若しくは置換基を有するアリール基；等が挙げられる。 Examples of the substituent for the alkyl group, cycloalkyl group and alkenyl group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group An unsubstituted or substituted aryl group such as a phenyl group, a 4-methylphenyl group, and a 4-chlorophenyl group;
　上記無置換又は置換基を有するアリール基のアリール基としては、例えば、フェニル基、１－ナフチル基、２－ナフチル基等の炭素数６～１０のアリール基が挙げられる。 Examples of the unsubstituted or substituted aryl group include aryl groups having 6 to 10 carbon atoms such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
　上記アリール基の置換基としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；メチル基、エチル基等の炭素数１～６のアルキル基；メトキシ基、エトキシ基等の炭素数１～６のアルコキシ基；ニトロ基；シアノ基；ヒドロキシル基；チオール基；エポキシ基；グリシドキシ基；（メタ）アクリロイルオキシ基；フェニル基、４－メチルフェニル基、４－クロロフェニル基等の無置換若しくは置換基を有するアリール基；等が挙げられる。 Examples of the substituent for the aryl group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkyl groups having 1 to 6 carbon atoms such as methyl group and ethyl group; carbon numbers such as methoxy group and ethoxy group 1-6 alkoxy groups; nitro groups; cyano groups; hydroxyl groups; thiol groups; epoxy groups; glycidoxy groups; (meth) acryloyloxy groups; unsubstituted phenyl groups, 4-methylphenyl groups, 4-chlorophenyl groups, etc. An aryl group having a substituent; and the like.
　アルキルシリル基としては、トリメチルシリル基、トリエチルシリル基、トリイソプロピルシリル基、トリｔ－ブチルシリル基、メチルジエチルシリル基、ジメチルシリル基、ジエチルシリル基、メチルシリル基、エチルシリル基等が挙げられる。 Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tri-t-butylsilyl group, a methyldiethylsilyl group, a dimethylsilyl group, a diethylsilyl group, a methylsilyl group, and an ethylsilyl group.
　これらの中でも、Ｒｘ、Ｒｙ、Ｒｚとしては、水素原子、炭素数１～６のアルキル基、又はフェニル基が好ましい。 Among these, as Rx, Ry, and Rz, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group is preferable.
　式（１）のポリシラザンは、従来公知の方法により製造することができる。例えば、下記式（２）で表される無置換若しくは置換基を有するハロゲノシラン化合物と２級アミンとの反応生成物に、アンモニア又は１級アミンを反応させることにより得ることができる。 The polysilazane represented by the formula (1) can be produced by a conventionally known method. For example, it can be obtained by reacting ammonia or a primary amine with a reaction product of an unsubstituted or substituted halogenosilane compound represented by the following formula (2) and a secondary amine.
　Ｒ１ ４-ｍＳｉＸｍ　　　（２）
　（式中、ｍは２又は３を表し、Ｘはハロゲン原子を表し、Ｒ１は、式（１）における、Ｒｘ、Ｒｙ、Ｒｚのいずれかの置換基を表す。） R 1 4-m SiX m (2)
(In the formula, m represents 2 or 3, X represents a halogen atom, and R 1 represents a substituent of any one of Rx, Ry, and Rz in Formula (1).)
　２級アミン、アンモニア及び１級アミンは、目的とするポリシラザン化合物の構造に応じて、適宜選択すればよい。 Secondary amine, ammonia and primary amine may be appropriately selected according to the structure of the target polysilazane compound.
　ポリシラザンは、式（１）中の、Ｒｘ、Ｒｙ、Ｒｚが全て水素原子であるパーヒドロキシポリシラザンであっても、Ｒｘ、Ｒｙ、Ｒｚの少なくとも１つが水素原子ではないオルガノポリシラザンのいずれであってもよいが、ポリシロキサンへの転化（加水分解反応）の安定性の観点から、パーヒドロキシポリシラザンが好ましい。 The polysilazane may be a perhydroxypolysilazane in which Rx, Ry, and Rz in the formula (1) are all hydrogen atoms, or an organopolysilazane in which at least one of Rx, Ry, and Rz is not a hydrogen atom. However, perhydroxypolysilazane is preferable from the viewpoint of stability of conversion to polysiloxane (hydrolysis reaction).
　また、ポリシラザンの分子量は特に限定はされないが、通常、数平均分子量が約１００～５０，０００である。なお、数平均分子量は、重合体のトルエン溶液等を用いたＶＰＯ（蒸気圧降下法）により測定することができる。 The molecular weight of polysilazane is not particularly limited, but usually the number average molecular weight is about 100 to 50,000. The number average molecular weight can be measured by VPO (vapor pressure drop method) using a polymer toluene solution or the like.
　ポリシラザン化合物は１種または２種以上を使用することができる。 Polysilazane compounds can be used alone or in combination of two or more.
　ポリシラザン含有塗膜は、例えば、ポリシラザン及び溶剤を含む塗液を、（Ａ）感圧接着性樹脂組成物層１上に塗布し、乾燥することで形成される。乾燥は自然乾燥でも加温乾燥でもよい。なお、塗布した塗液を加熱乾燥する場合、水蒸気含有雰囲気下で加熱乾燥することで、塗液の乾燥と乾燥後塗膜の水蒸気含有雰囲気下で加熱（熱処理）によるシリカガラス被膜の生成とを連続的に行うことができる。 The polysilazane-containing coating film is formed, for example, by applying a coating liquid containing polysilazane and a solvent on (A) the pressure-sensitive adhesive resin composition layer 1 and drying it. Drying may be natural drying or warm drying. In addition, when drying the applied coating liquid by heating and drying in a steam-containing atmosphere, drying of the coating liquid and generation of a silica glass coating by heating (heat treatment) in the steam-containing atmosphere of the coating after drying. Can be done continuously.
　上記溶剤としては、ポリシラザンを溶解し、ポリシラザンに不活性な有機溶剤であれば特に限定されないが、揮発性、環境衛生上の観点から、例えば、ジメチルエーテル、ジエチルエーテル、ジプロピルエーテル、ジブチルエーテル等のエーテル系有機溶剤が好ましい。エーエル系有機溶剤は１種または２種以上を使用することができる。また、エーテル系有機溶剤に対して１０質量％以下の範囲でアニソール等の芳香族炭化水素系溶剤を混合してもよい。塗液におけるポリシラザン濃度は１～３０質量％程度であることが好ましい。また、塗液には加水分解触媒等の各種添加剤を含んでもよい。 The solvent is not particularly limited as long as it dissolves polysilazane and is inert to polysilazane, but from the viewpoint of volatility and environmental hygiene, for example, dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, etc. Ether-based organic solvents are preferred. One or more air-based organic solvents can be used. Moreover, you may mix aromatic hydrocarbon solvents, such as anisole, in the range of 10 mass% or less with respect to an ether type organic solvent. The polysilazane concentration in the coating solution is preferably about 1 to 30% by mass. The coating liquid may contain various additives such as a hydrolysis catalyst.
　なお、このようなポリシラザン含有塗液は、「ガラスコート剤」や「シリカコート剤」等の呼び名で市販されており、市販品をそのまま使用することができる。市販品としては、例えば、アートブリード株式会社製の「Ｏｌａｍ Ｚ」、「Ｏｌａｍ ＯＺ」、メルク株式会社製の「ＮＡＸ１１０」、「ＮＡＸ１２０」、「ＮＬ１１０Ａ」、「ＮＮ１１０」等が挙げられる。 In addition, such a polysilazane-containing coating solution is commercially available under names such as “glass coating agent” and “silica coating agent”, and commercially available products can be used as they are. Examples of commercially available products include “Olam Z” and “Olam OZ” manufactured by Art Breed Co., Ltd., “NAX110”, “NAX120”, “NL110A”, and “NN110” manufactured by Merck Co., Ltd.
　（Ａ）感圧接着性樹脂組成物層１上への塗液の塗布方法は、スピンコート、スプレーコート、ディップコート、バーコート等の塗液をほぼ均一な厚さの液膜に塗布できる方法であれば特に限定されない。また、塗液の塗布量も特に限定はされないが、塗布量は一般的には固形分換算で０．０１～１００ｇ／ｍ2、好ましくは０．０５～１０ｇ／ｍ2である。塗布量がかかる範囲にあることで、薄い厚さで、十分に高い防湿性（水蒸気バリア性）を示すシリカガラス被膜を生成する塗膜を形成することができる。 (A) A method of applying a coating liquid onto the pressure-sensitive adhesive resin composition layer 1 is a method in which a coating liquid such as spin coating, spray coating, dip coating, bar coating, etc. can be applied to a liquid film having a substantially uniform thickness. If it is, it will not specifically limit. The coating amount of the coating liquid is not particularly limited, but the coating amount is generally 0.01 to 100 g / m 2 , preferably 0.05 to 10 g / m 2 in terms of solid content. When the coating amount is within such a range, it is possible to form a coating film that produces a silica glass coating film that exhibits a sufficiently high moisture-proof property (water vapor barrier property) with a small thickness.
　シリカガラス被膜を生成するために、ポリシラザン含有塗膜を水蒸気含有雰囲気下で加熱（熱処理）するが、水蒸気含有雰囲気としては、空気、加湿空気、加湿不活性ガス（例えば、窒素、アルゴン、ヘリウム等）等が挙げられる。 In order to produce a silica glass coating, the polysilazane-containing coating is heated (heat treatment) in a steam-containing atmosphere. Examples of the steam-containing atmosphere include air, humidified air, humidified inert gas (for example, nitrogen, argon, helium, etc.) ) And the like.
　塗膜の加熱（熱処理）温度は、（Ａ）感圧接着性樹脂組成物層の変性や劣化を防止する観点から２００℃以下が好ましく、より好ましくは５０～１５０℃である。加熱時間は一般的には３０分～５時間である。例えば、湿度が２０～１００％ＲＨの空気又は加湿空気は好ましい水蒸気含有雰囲気である。 The heating (heat treatment) temperature of the coating film is preferably 200 ° C. or less, more preferably 50 to 150 ° C., from the viewpoint of preventing modification and deterioration of the (A) 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 preferable steam-containing atmosphere.
　なお、加熱温度や水蒸気含有雰囲気中の水蒸気濃度等を変化させることにより、シリカガラス被膜の組成を段階的に変化させることもできる。 It should be noted that the composition of the silica glass coating can be changed stepwise by changing the heating temperature, the water vapor concentration in the water vapor-containing atmosphere, and the like.
　（Ａ）感圧接着性樹脂組成物層に塗布した塗液の乾燥、シリカガラス被膜を生成するための塗膜の加熱（熱処理）に使用する加熱手段としては、特に制限はされず、例えば、熱循環式オーブン、ホットプレート等が使用される。 (A) The heating means used for drying the coating liquid applied to the pressure-sensitive adhesive resin composition layer and heating (heat treatment) of the coating film to produce a silica glass coating is not particularly limited. A heat circulation oven, a hot plate, or the like is used.
　なお、シリカ（ＳｉＯ２）を主成分とする、種々のセラミックコーティング剤が知られているが、後述の比較例に示すように、（Ａ）感圧接着性樹脂組成物層の片面にセラミックコーティング剤の塗膜の熱硬化被膜を形成しても、（Ａ）感圧接着性樹脂組成物層に防湿性を付与することができず、（Ａ）感圧接着性樹脂組成物層の単層シートの水蒸気透過量に比べて、熱硬化被膜を形成したシート（（Ａ）感圧接着性樹脂組成物層／熱硬化被膜）の水蒸気透過量は却って大きくなってしまう。 Various ceramic coating agents containing silica (SiO 2 ) as a main component are known. As shown in a comparative example to be described later, (A) a ceramic coating on one side of the pressure-sensitive adhesive resin composition layer. Even if a thermosetting film of the agent coating is formed, (A) the pressure-sensitive adhesive resin composition layer cannot be given moisture resistance, and (A) the pressure-sensitive adhesive resin composition layer is a single layer. Compared to the water vapor transmission amount of the sheet, the water vapor transmission amount of the sheet ((A) pressure-sensitive adhesive resin composition layer / thermosetting film) on which the thermosetting film is formed becomes larger.
＜（Ｂ２）無機物蒸着被膜＞
　（Ｂ２）無機物蒸着被膜は、（Ａ）感圧接着性樹脂組成物層１の片面に無機物を蒸着して形成される。無機物としては、例えば、ＳｉＣ、ＳｉＯ２、Ｓｉ３Ｎ４、ＳｉＣＮ、ＳｉＯＣ、ＳｉＯＣＮ、ポリシラザン、アルコキシシラン等のケイ素化合物、酸化アルミニウム、酸化インジウム、酸化スズ、酸化ガリウム、酸化インジウムスズ（ＩＴＯ）、アルミニウム添加亜鉛酸化物（ＡＺＯ）、亜鉛スズ複合酸化物（ＺＴＯ）、窒化アルミニウム、酸化ジルコニウム等の選択される１種または２種以上を挙げることができる。中でも、（Ａ）感圧接着性樹脂組成物層１との接着性に優れ、かつ、防湿性の高い蒸着膜を形成できる観点から、ケイ素化合物が好ましい。すなわち、（Ｂ２）無機物蒸着被膜はケイ素化合物蒸着被膜であることが好ましい。 <(B2) Inorganic deposited film>
(B2) The inorganic deposition film is formed by depositing an inorganic substance on one side of the (A) pressure-sensitive adhesive resin composition layer 1. Examples of inorganic substances include SiC, SiO 2 , Si 3 N 4 , SiCN, SiOC, SiOCN, polysilazane, alkoxysilane, and other silicon compounds, aluminum oxide, indium oxide, tin oxide, gallium oxide, indium tin oxide (ITO), One or more selected from aluminum-added zinc oxide (AZO), zinc-tin composite oxide (ZTO), aluminum nitride, zirconium oxide and the like can be mentioned. Among these, a silicon compound is preferable from the viewpoint that (A) a pressure-sensitive adhesive resin composition layer 1 is excellent in adhesiveness and can form a vapor-deposited film having high moisture resistance. That is, (B2) the inorganic deposited film is preferably a silicon compound deposited film.
　（Ｂ２）無機物蒸着被膜は化学蒸着法及び物理蒸着法のいずれの方法で形成された蒸着膜であってもよい。 (B2) The inorganic vapor deposition film may be a vapor deposition film formed by either chemical vapor deposition or physical vapor deposition.
　また、（Ｂ２）無機物蒸着被膜は単層膜でも多層膜であってもよい。（Ｂ２）無機物蒸着被膜がケイ素化合物蒸着被膜である場合、好適態様として、一層以上のＳｉＯ２蒸着膜と一層以上のＳｉＣＮ蒸着膜を含むＳｉＯ２－ＳｉＣＮ多層蒸着膜が挙げられる。かかるＳｉＯ２－ＳｉＣＮ多層蒸着膜における一層のＳｉＯ２層及び一層のＳｉＣＮ層のそれぞれの厚さは１０～１００ｎｍが好ましい。また、全体の層数は２層以上が好ましく、６層以上がより好ましい。また、２０層以下が好ましく、１２層以下がより好ましい。また、ＳｉＯ２－ＳｉＣＮ多層蒸着膜は、優れた水蒸気バリア性の点から、ＳｉＯ２蒸着層とＳｉＣＮ蒸着層が交互に積層されたものが好ましい。また、ＳｉＯ２蒸着層及びＳｉＣＮ蒸着層はそれぞれ物理蒸着層であっても化学蒸着層であってもよいが、化学蒸着は低温での膜形成が可能であり、封止用シートの性状安定性及び形状安定性等の観点から、ＳｉＯ２化学蒸着層とＳｉＣＮ化学蒸着層が交互に積層されたものであることが好ましい。 Further, (B2) the inorganic vapor deposited film may be a single layer film or a multilayer film. (B2) When the inorganic vapor-deposited film is a silicon compound vapor-deposited film, a preferred embodiment includes a SiO 2 —SiCN multilayer vapor-deposited film including one or more SiO 2 vapor-deposited films and one or more SiCN vapor-deposited films. In the SiO 2 —SiCN multilayer deposited film, the thickness of each of the one SiO 2 layer and one SiCN layer is preferably 10 to 100 nm. The total number of layers is preferably 2 or more, more preferably 6 or more. Moreover, 20 layers or less are preferable and 12 layers or less are more preferable. In addition, the SiO 2 —SiCN multilayer deposited film is preferably one in which SiO 2 deposited layers and SiCN deposited layers are alternately laminated from the viewpoint of excellent water vapor barrier properties. In addition, the SiO 2 vapor deposition layer and the SiCN vapor deposition layer may be either physical vapor deposition layers or chemical vapor deposition layers, but chemical vapor deposition can form a film at a low temperature, and the property stability of the sealing sheet From the viewpoint of shape stability and the like, it is preferable that the SiO 2 chemical vapor deposition layer and the SiCN chemical vapor deposition layer are alternately laminated.
　ＳｉＯ２化学蒸着層とＳｉＣＮ化学蒸着層が交互に積層されたＳｉＯ２－ＳｉＣＮ多重蒸着膜を形成する場合の好適な実施形態は以下の通りである。 A preferred embodiment in the case of forming a SiO 2 -SiCN multiple vapor deposition film in which SiO 2 chemical vapor deposition layers and SiCN chemical vapor deposition layers are alternately laminated is as follows.
　蒸着チャンバー内の圧力を１Ｐａ程度、温度を１００℃程度に保った上でヘキサメチルジシラザンおよび酸素ガスを原料ガスとしてＳｉＯ２の蒸着を行う。この蒸着を１分間程度行った後、原料ガスをヘキサメチルジシラザンおよび水素ガスに切り替え、さらに１分間程度ＳｉＣＮを蒸着する。所望の層構成になるまで、上記プロセスを繰り返すことでＳｉＯ２化学蒸着層とＳｉＣＮ化学蒸着層が交互に積層されたＳｉＯ２－ＳｉＣＮ多重蒸着膜を形成する。 After maintaining the pressure in the deposition chamber at about 1 Pa and the temperature at about 100 ° C., SiO 2 is deposited using hexamethyldisilazane and oxygen gas as source gases. After this deposition is performed for about 1 minute, the source gas is switched to hexamethyldisilazane and hydrogen gas, and SiCN is deposited for another 1 minute. By repeating the above process until a desired layer configuration is obtained, a SiO 2 —SiCN multiple vapor deposition film in which SiO 2 chemical vapor deposition layers and SiCN chemical vapor deposition layers are alternately stacked is formed.
　（Ｂ）防湿性無機被膜（（Ｂ１）シリカガラス被膜、（Ｂ２）無機物蒸着被膜）２の厚さは、封止構造の薄厚化等の観点から、１０００ｎｍ以下が好ましく、５００ｎｍ以下がより好ましく、４００ｎｍ以下がさらに一層好ましい。また、十分に高い防湿性を得る観点から、１０ｎｍ以上が好ましく、２０ｎｍ以上がより好ましく、３０ｎｍ以上がさらに一層好ましい。 The thickness of the (B) moisture-proof inorganic coating ((B1) silica glass coating, (B2) inorganic vapor deposition coating) 2 is preferably 1000 nm or less, more preferably 500 nm or less, from the viewpoint of thinning the sealing structure, etc. More preferably, it is 400 nm or less. Further, from the viewpoint of obtaining sufficiently high moisture resistance, the thickness is preferably 10 nm or more, more preferably 20 nm or more, and even more preferably 30 nm or more.
　なお、防湿性無機被膜２による防湿性（水蒸気バリア性）は、防湿性無機被膜２が１０００ｎｍ以下の厚さであるときに、感圧接着性樹脂組成物層１及び防湿性無機被膜２からなる二層シートのＪＩＳ　Ｚ　０２０８：１９７６に準拠する方法で測定される、温度４０℃、湿度９０％ＲＨ、２４時間の測定条件での１ｍ２当たりの水蒸気透過度が、樹脂組成物層１のみの単層シートの同法及び同条件で測定される１ｍ２当たりの水蒸気透過度の７０％以下（好ましくは６５％以下、より好ましくは６０％以下）となる防湿性（水蒸気バリア性）であることが好ましい。 The moisture resistance (water vapor barrier property) by the moisture-proof inorganic coating 2 is composed of the pressure-sensitive adhesive resin composition layer 1 and the moisture-proof inorganic coating 2 when the moisture-proof inorganic coating 2 has a thickness of 1000 nm or less. The water vapor permeability per 1 m 2 measured at a temperature of 40 ° C., a humidity of 90% RH, and a measurement time of 24 hours, measured by a method according to JIS Z 0208: 1976 of a two-layer sheet, is only for the resin composition layer 1. Moisture resistance (water vapor barrier property) that is 70% or less (preferably 65% or less, more preferably 60% or less) of water vapor permeability per 1 m 2 measured by the same method and under the same conditions of a single layer sheet. Is preferred.
　本発明の封止用シートにおいて、支持体３を剥離して得られる、樹脂組成物層１及び防湿性無機被膜２からなる二層シートの防湿性（水蒸気バリア性）は、ＪＩＳ　Ｚ　０２０８：１９７６に準拠する方法で測定される、温度４０℃、湿度９０％ＲＨ、２４時間の測定条件での１ｍ２当たりの水蒸気透過度が４０ｇ／（ｍ２・２４ｈ）以下であるのが好ましく、３０ｇ／（ｍ２・２４ｈ）以下であるのがより好ましく、２０ｇ／（ｍ２・２４ｈ）以下であるがさらに一層好ましい。 In the sealing sheet of the present invention, the moisture-proof property (water vapor barrier property) of the two-layer sheet comprising the resin composition layer 1 and the moisture-proof inorganic coating 2 obtained by peeling the support 3 is JIS Z 0208: 1976. It is preferable that the water vapor transmission rate per 1 m 2 measured at a temperature of 40 ° C., a humidity of 90% RH, and a measurement time of 24 hours is 40 g / (m 2 · 24 h) or less, measured by a method conforming to (m 2 · 24h) in more preferably from less, although 20g / (m 2 · 24h) or less still more preferred.
［（Ｃ）離型処理された支持体］
　離型処理された支持体３は、樹脂組成物層１が形成される側の片面に離型処理が施された支持体であり、封止用シートを実際に封止構造の形成に使用する前に剥離される支持体である。このため、離型処理された支持体３には必ずしも防湿性は必要ではないが、封止用シートが封止に供されるまでの保管期間の樹脂組成物層１への水分の侵入を防止する観点からは、防湿性を有することが好ましい。 [(C) Release-treated support]
The release-treated support 3 is a support that has been subjected to a release treatment on one side on which the resin composition layer 1 is formed, and the sealing sheet is actually used for forming a sealing structure. A support that is peeled off before. For this reason, the release-supported support 3 does not necessarily need moisture resistance, but prevents moisture from entering the resin composition layer 1 during the storage period until the sealing sheet is used for sealing. From this viewpoint, it is preferable to have moisture resistance.
　防湿性を有する支持体としては、防湿性を有するプラスチックフィルムや、銅箔、アルミニウム箔などの金属箔等が挙げられる。防湿性を有するプラスチックフィルムとしてはＳｉＯ２、Ｓｉ３Ｎ４、ＳｉＣＮ、アモルファスシリコン等の無機物を表面に蒸着させたプラスチックフィルム等が挙げられる。ここで、表面に無機物が蒸着されるプラスチックフィルムとしては、例えば、ポリオレフィン（例えば、ポリエチレン、ポリプロピレン、ポリ塩化ビニル等）、ポリエステル（例えば、ポリエチレンテレフタレート（以下「ＰＥＴ」と略称することがある。）、ポリエチレンナフタレート等）、ポリカーボネート、ポリイミド等のプラスチックフィルムが好適であり、ＰＥＴフィルムが特に好ましい。市販されている防湿性を有するプラスチックフィルムの例としては、テックバリアＨＸ、ＡＸ、ＬＸ、Ｌシリーズ（三菱樹脂社製）や、該テックバリアＨＸ、ＡＸ、ＬＸ、Ｌシリーズよりもさらに防湿効果を高めたＸ－ＢＡＲＲＩＥＲ（三菱樹脂社製）等が挙げられる。また、防湿性を有する支持体として、２層以上の複層構造を有するもの、例えば、上記のプラスチックフィルムと上記の金属箔とを接着剤を介して張り合わせたものも使用できる。このものは安価であり、ハンドリング性の観点からも有利である。 Examples of the moisture-proof support include a moisture-proof plastic film, a metal foil such as a copper foil and an aluminum foil, and the like. Examples of the plastic film having moisture resistance include a plastic film in which an inorganic material such as SiO 2 , Si 3 N 4 , SiCN, and amorphous silicon is deposited on the surface. Here, examples of the plastic film on which an inorganic substance is deposited on the surface include, for example, polyolefin (for example, polyethylene, polypropylene, polyvinyl chloride, etc.), polyester (for example, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”). , Polyethylene naphthalate, etc.), plastic films such as polycarbonate and polyimide are preferred, and PET films are particularly preferred. Examples of commercially available moisture-proof plastic films include the Tech Barrier HX, AX, LX, L series (Mitsubishi Resin Co., Ltd.) and the moisture barrier effect even more than the Tech Barrier HX, AX, LX, L series. X-BARRIER (manufactured by Mitsubishi Plastics), etc. In addition, as the support having moisture resistance, a support having a multilayer structure of two or more layers, for example, a laminate of the above plastic film and the above metal foil with an adhesive may be used. This is inexpensive and advantageous from the viewpoint of handling properties.
　なお、離型処理された支持体３には、防湿性を有しない支持体（例えば、上記の表面に無機物が蒸着されていないプラスチックフィルムの単体）も使用できる。支持体の厚さは特に限定されないが、封止用シートの取り扱い性等の観点から、１０～１５０μｍが好ましく、２０～１００μｍがより好ましい。 In addition, as the support 3 that has been subjected to the mold release treatment, a support having no moisture resistance (for example, a single plastic film on which the inorganic material is not deposited on the surface) can be used. The thickness of the support is not particularly limited, but is preferably from 10 to 150 μm, more preferably from 20 to 100 μm, from the viewpoint of handling properties of the sealing sheet.
　離型処理のための離型剤としては、具体的には、フッ素系離型剤、シリコーン系離型剤、アルキッド樹脂系離型剤等が挙げられる。離型剤は異なる種類のものを混合して用いてもよい。 Specific examples of the release agent for the release treatment include a fluorine-based release agent, a silicone-based release agent, and an alkyd resin-based release agent. Different types of release agents may be mixed and used.
［（Ｄ）円偏光板］
　円偏光板は、一般に偏光板と１／４波長板により構成される。円偏光板を支持体として使用する場合は、一般に１／４波長板が封止用樹脂組成物層側に配置される。また円偏光板と防湿性支持体の双方を含む支持体を用いる場合、好ましくは防湿性支持体が封止用樹脂組成物層側に配置され、円偏光板の１／４波長板が防湿性支持体側に配置される。防湿性支持体と円偏光板は、接着剤等により接着することができる。本発明の封止用シートは特に有機ＥＬ素子の封止に好適な封止用シートを意図しており、図２に示すように、（Ｂ）防湿性無機被膜２の（Ａ）感圧接着性樹脂組成物層１の側とは反対側の表面に（Ｄ）円偏光板４を接着することで、円偏光板が一体化した封止構造を形成できる有機ＥＬ素子の封止用シート１１とすることができる。 [(D) Circularly polarizing plate]
A circularly polarizing plate is generally composed of a polarizing plate and a quarter wavelength plate. When using a circularly-polarizing plate as a support body, generally a quarter wavelength plate is arrange | positioned at the resin composition layer side for sealing. Moreover, when using the support body containing both a circularly-polarizing plate and a moisture-proof support body, Preferably a moisture-proof support body is arrange | positioned at the resin composition layer side for sealing, and the quarter wavelength plate of a circularly-polarizing plate is moisture-proof. Arranged on the support side. The moisture-proof support and the circularly polarizing plate can be bonded with an adhesive or the like. The sealing sheet of the present invention is particularly intended for a sealing sheet suitable for sealing an organic EL element. As shown in FIG. 2, (B) a moisture-proof inorganic coating 2 (A) pressure-sensitive adhesive. The sealing sheet 11 of the organic EL element which can form the sealing structure which the circularly-polarizing plate integrated by adhering the (D) circularly-polarizing plate 4 to the surface on the opposite side to the conductive resin composition layer 1 side. It can be.
　図２において、図１と同一符号は同一または相当する部分を示し、４は円偏光板である。円偏光板４は、１／４波長板として機能する位相差フィルム４１と該位相差フィルム４１に直接接着した偏光子（偏光板）４２とを有し、（Ｂ）防湿性無機被膜２の（Ａ）感圧接着性樹脂組成物層側とは反対側の表面に接着剤層５を介して接着されている。位相差フィルム４１と偏光子（偏光板）４２からなる円偏光板４には公知のものを使用することができ、例えば、特開２０１６－１０５１６６号公報、国際公開２０１４／００３１８９号パンフレット等に記載の円偏光板を挙げることができる。 2, the same reference numerals as those in FIG. 1 denote the same or corresponding parts, and 4 denotes a circularly polarizing plate. The circularly polarizing plate 4 includes a retardation film 41 that functions as a quarter-wave plate, and a polarizer (polarizing plate) 42 that is directly bonded to the retardation film 41, and (B) the moisture-proof inorganic coating 2 ( A) It is bonded to the surface opposite to the pressure-sensitive adhesive resin composition layer side through an adhesive layer 5. As the circularly polarizing plate 4 composed of the retardation film 41 and the polarizer (polarizing plate) 42, a known one can be used, for example, described in JP-A-2016-105166, International Publication No. 2014/003189, etc. Can be mentioned.
　接着剤層５に用いる接着剤は、透明性の高い接着剤であれば特に限定されず、例えば、アクリル系接着剤、ポリビニルアルコール系接着剤等が使用される。 The adhesive used for the adhesive layer 5 is not particularly limited as long as it is a highly transparent adhesive, and for example, an acrylic adhesive, a polyvinyl alcohol adhesive, or the like is used.
　なお、円偏光板４には、偏光子（偏光板）４２の保護する保護フィルム（図示せず）を設けることができる。この保護フィルムも公知のものを使用することができ、例えば、特開２０１６－１０５１６６号公報や国際公開２０１４／００３１８９号パンフレット等に記載の保護フィルムを挙げることができる。 The circularly polarizing plate 4 can be provided with a protective film (not shown) that protects the polarizer (polarizing plate) 42. As this protective film, known ones can be used, and examples thereof include a protective film described in JP-A-2016-105166 and International Publication No. 2014/003189.
［封止用シートの製造］
　本発明の封止用シートは、（Ｃ）離型処理された支持体３上に形成された（Ａ）感圧接着性樹脂組成物層１上に（Ｂ）防湿性無機被膜２を形成すればよい。 [Manufacture of sealing sheet]
In the sealing sheet of the present invention, (B) a moisture-proof inorganic coating 2 is formed on (A) the pressure-sensitive adhesive resin composition layer 1 formed on the release-treated support 3. That's fine.
　（Ａ）感圧接着性樹脂組成物層１は当業者に公知の方法で形成すればよく、例えば、有機溶剤に樹脂組成物を溶解したワニスを調製し、支持体上に、ワニスを塗布および乾燥することで形成することができる。有機溶剤の乾燥は熱風吹きつけ等によって行うことができる。なお、本発明の樹脂組成物が、エポキシ基を有するポリオレフィン系樹脂等の硬化性成分を含む場合、樹脂組成物層をさらに加熱して、硬化した樹脂組成物層を形成してもよい。 (A) The pressure-sensitive adhesive resin composition layer 1 may be formed by a method known to those skilled in the art. For example, a varnish in which the resin composition is dissolved in an organic solvent is prepared, and the varnish is applied to the support. It can be formed by drying. The organic solvent can be dried by blowing hot air or the like. In addition, when the resin composition of this invention contains curable components, such as polyolefin resin which has an epoxy group, you may further heat a resin composition layer and may form the cured resin composition layer.
　有機溶剤としては、例えば、アセトン、メチルエチルケトン（以下「ＭＥＫ」と略称することがある）、シクロヘキサノン等のケトン類；酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、カルビトールアセテート等の酢酸エステル類；セロソルブ、ブチルカルビトール等のカルビトール類；トルエン、キシレン等の芳香族炭化水素類；ジメチルホルムアミド、ジメチルアセトアミド、Ｎ－メチルピロリドン等；ソルベントナフサ等の芳香族系混合溶剤を挙げることができる。芳香族系混合溶剤として「スワゾール」（丸善石油社製、商品名）、「イプゾール」（出光興産社製、商品名）が挙げられる。有機溶剤は１種または２種以上組み合わせて使用してもよい。 Examples of the organic solvent include acetone, methyl ethyl ketone (hereinafter sometimes abbreviated as “MEK”), cyclohexanone and other ketones; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate and other acetic acid. Esters; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc .; aromatic mixed solvents such as solvent naphtha it can. Examples of aromatic mixed solvents include “Swazole” (trade name, manufactured by Maruzen Petroleum Corporation) and “Ipsol” (trade name, manufactured by Idemitsu Kosan Co., Ltd.). You may use an organic solvent 1 type or in combination of 2 or more types.
　乾燥条件は特に制限はないが、５０～１００℃で１～６０分が好ましい。５０℃以上とすることで、樹脂組成物層中に残存する溶剤量を低下させ易くなる。 Drying conditions are not particularly limited, but preferably 50 to 100 ° C. for 1 to 60 minutes. By setting it as 50 degreeC or more, it becomes easy to reduce the amount of solvent which remains in a resin composition layer.
　（１）（ａ）成分として酸無水物基を有するポリオレフィン系樹脂およびエポキシ基を有するポリオレフィン系樹脂の両方を使用する、（２）（ａ）成分としてエポキシ基を有するポリオレフィン系樹脂を使用し、且つ（ｅ）成分（即ち、エポキシ基と反応し得る官能基を有する樹脂）を使用する、または（３）（ａ）成分として酸無水物基を有するポリオレフィン系樹脂を使用し、且つ（ｆ）成分（即ち、酸無水物基と反応し得る官能基を有する樹脂）を使用することによって、封止工程前に樹脂組成物を加熱して架橋構造を形成してもよく、また封止工程後に加熱して架橋構造を形成してもよい。例えば、本発明の封止用シートを用いて、素子（例えば、有機ＥＬ素子）の封止を行う場合、封止工程前に樹脂組成物層を予め加熱して架橋構造を形成してもよいし、封止工程後に樹脂組成物層を加熱して架橋構造を形成してもよい。素子（例えば、有機ＥＬ素子）の熱劣化を低減させるという観点から、封止工程前に予め加熱して架橋構造を形成することが好ましい。 (1) (a) using both a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group as the component (2) (a) using a polyolefin resin having an epoxy group as the component; And (e) component (that is, a resin having a functional group capable of reacting with an epoxy group) is used, or (3) (a) a polyolefin-based resin having an acid anhydride group is used as component, and (f) By using a component (that is, a resin having a functional group capable of reacting with an acid anhydride group), the resin composition may be heated before the sealing step to form a crosslinked structure, and after the sealing step. It may be heated to form a crosslinked structure. For example, when sealing an element (for example, organic EL element) using the sealing sheet of the present invention, the resin composition layer may be preheated before the sealing step to form a crosslinked structure. Then, after the sealing step, the resin composition layer may be heated to form a crosslinked structure. From the viewpoint of reducing thermal deterioration of an element (for example, an organic EL element), it is preferable to form a crosslinked structure by heating in advance before the sealing step.
　封止工程前に（Ａ）感圧接着性樹脂組成物層１を加熱する場合は、加熱条件は特に制限はないが、温度は、５０～２００℃が好ましく、１００～１８０℃がより好ましく、１２０～１６０℃がさらに好ましい。加熱時間は、１５～１２０分が好ましく、３０～１００分がより好ましい。 When (A) the pressure-sensitive adhesive resin composition layer 1 is heated before the sealing step, the heating conditions are not particularly limited, but the temperature is preferably 50 to 200 ° C, more preferably 100 to 180 ° C, 120 to 160 ° C. is more preferable. The heating time is preferably 15 to 120 minutes, more preferably 30 to 100 minutes.
　封止工程後に（Ａ）感圧接着性樹脂組成物層１を熱硬化する場合は、素子（例えば、有機ＥＬ素子）の熱劣化を防止する観点から、硬化温度は、５０～１５０℃が好ましく、６０～１００℃がより好ましく、６０～８０℃がさらに好ましい。 When (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 degradation of the element (for example, organic EL element). 60 to 100 ° C. is more preferable, and 60 to 80 ° C. is more preferable.
　（Ａ）感圧接着性樹脂組成物層１の形成後、前述の方法により、（Ｂ）防湿性無機被膜２（（Ｂ１）シリカガラス被膜又は（Ｂ２）無機物蒸着被膜）を形成する。なお、（Ｄ）円偏光板４を有する封止シートを製造する場合、（Ｂ）防湿性無機被膜２（（Ｂ１）シリカガラス被膜又は（Ｂ２）無機物蒸着被膜）の表面に、接着剤層又は粘着剤層５を形成し、円偏光板４を接着すればよい。 (A) After forming the pressure-sensitive adhesive resin composition layer 1, (B) a moisture-proof inorganic coating 2 ((B1) silica glass coating or (B2) inorganic deposition coating) is formed by the method described above. In addition, when manufacturing the sealing sheet which has (D) circularly-polarizing plate 4, an adhesive layer or the surface of (B) moisture-proof inorganic coating 2 ((B1) silica glass coating or (B2) inorganic substance vapor deposition coating) The pressure-sensitive adhesive layer 5 may be formed and the circularly polarizing plate 4 may be bonded.
＜封止用シートの用途＞
　本発明の封止用シートは、半導体、太陽電池、高輝度ＬＥＤ、ＬＣＤ、ＥＬ素子等の電子部品、好ましくは太陽電池、有機ＥＬ素子等の光学半導体の封止に使用される。特に有機ＥＬ素子の封止に好適に使用される。具体的には、有機ＥＬ素子の発光部の上部および／または周囲（側部）に適用して有機ＥＬ素子の発光部を外部から保護するために、本発明の封止用シートを用いることができる。 <Use of sealing sheet>
The encapsulating sheet of the present invention is used for encapsulating electronic components such as semiconductors, solar cells, high-brightness LEDs, LCDs and EL elements, preferably optical semiconductors such as solar cells and organic EL elements. In particular, it is suitably used for sealing organic EL elements. Specifically, the sealing sheet of the present invention is used in order to protect the light emitting part of the organic EL element from the outside by applying to the upper part and / or the periphery (side part) of the light emitting part of the organic EL element. it can.
＜有機ＥＬデバイス＞
　本発明は、上述した本発明の封止用シートで有機ＥＬ素子が封止された有機ＥＬデバイスも提供する。例えば、有機ＥＬ素子を有する基板に本発明の封止用シートをラミネートすることで、本発明の有機ＥＬデバイスが得られる。封止作業は、封止用シートから離型処理された支持体３を剥離し、感圧接着性樹脂組成物層１が該基板に直接接するように、封止用シートを該基板上にラミネートする。ラミネートの方法はバッチ式であってもロールでの連続式であってもよい。なお、封止に熱硬化が必要な場合は、熱硬化を行う。 <Organic EL device>
The present invention also provides an organic EL device in which an organic EL element is sealed with the above-described sealing sheet 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. The sealing operation is performed by peeling the support 3 that has been released from the sealing sheet and laminating the sealing sheet on the substrate so that the pressure-sensitive adhesive resin composition layer 1 is in direct contact with the substrate. To do. The laminating method may be a batch method or a continuous method using a roll. In addition, when thermosetting is required for sealing, thermosetting is performed.
　本発明の封止用シートにより有機ＥＬ素子を封止すると、防湿性無機被膜２は薄厚で、封止基材（無機物蒸着被膜を有するプラスチックフィルム、金属箔等）に比べて剛性が小さいので、封止作業時の有機ＥＬ素子に与えるダメージを著しく軽減できる。しかも、封止用シートは防湿性無機被膜２によって優れた防湿性（水蒸気バリア性）を有するとともに、感圧接着性樹脂組成物層１が吸湿性フィラーを含有することから、薄厚で吸水率が低く、しかも、優れた耐透湿性の封止構造を形成することができる。このため、有機ＥＬデバイスの薄型化と高性能化を図ることができる。また、円偏光板を一体化させた封止用シートを使用すれば、薄型化及び高性能化が図られた外光反射の防止機能等を備える有機ＥＬデバイスを簡単に得ることができる。 When the organic EL element is sealed with the sealing sheet of the present invention, the moisture-proof inorganic coating 2 is thin, and the rigidity is small compared to a sealing substrate (plastic film having a deposit of inorganic deposit, metal foil, etc.). Damage to the organic EL element during the sealing operation can be significantly reduced. In addition, the sealing sheet has excellent moisture resistance (water vapor barrier property) due to the moisture-proof inorganic coating 2, and the pressure-sensitive adhesive resin composition layer 1 contains a hygroscopic filler. A low and excellent moisture-permeable sealing structure can be formed. For this reason, thickness reduction and performance enhancement of an organic EL device can be achieved. Moreover, if the sealing sheet | seat which integrated the circularly-polarizing plate is used, an organic electroluminescent device provided with the prevention function etc. of the reflection of external light by which thickness reduction and high performance were achieved can be obtained easily.
　以下に実施例を示して本発明をより詳しく説明するが、本発明はこれらの実施例に限定されるものではない。なお、以下の記載において、成分および共重合単位の量における「部」および「％」は、特に断りがない限り、それぞれ、「質量部」および「質量％」を意味する。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. In the following description, “parts” and “%” in the amounts of components and copolymerized units mean “parts by mass” and “% by mass”, respectively, unless otherwise specified.
　実施例および比較例に用いた原料は以下の通りである。
１．感圧接着性樹脂組成物層形成用材料
（ａ）ポリオレフィン系樹脂
　・ＡＣＲＹＦＴ　ＣＭ５０２２（住友化学（株）製）：エチレン－メチルメタクリレート共重合体、エチレン単位とメチルメタクリレート単位の合計１００％当たりのメチルメタクリレート単位の量（３３％）、数平均分子量７１,０００）
　・タフセレン　Ｘ１１０２（住友化学（株）製）：プロピレン－ブテン共重合体、プロピレン単位とブテン単位の合計１００質量％当たりのブテン単位の量（２９％）、数平均分子量６５８,０００）
　・ＨＶ－３００Ｍ（東邦化学工業社製）：無水マレイン酸変性液状ポリブテン（酸無水物基濃度：０．７７ｍｍｏｌ／ｇ、数平均分子量２，１００）
　・ＨＶ－１９００（ＪＸエネルギー社製）：ポリブテン（数平均分子量２，９００） The raw materials used in Examples and Comparative Examples are as follows.
1. Material for forming pressure-sensitive adhesive resin composition layer (a) Polyolefin resin ACRYFT CM5022 (manufactured by Sumitomo Chemical Co., Ltd.): ethylene-methyl methacrylate copolymer, methyl per 100% in total of ethylene units and methyl methacrylate units Amount of methacrylate units (33%), number average molecular weight 71,000)
Tough selenium X1102 (manufactured by Sumitomo Chemical Co., Ltd.): propylene-butene copolymer, amount of butene units per 29% total of propylene units and butene units (29%), number average molecular weight 658,000)
HV-300M (manufactured by Toho Chemical Co., Ltd.): maleic anhydride-modified liquid polybutene (acid anhydride group concentration: 0.77 mmol / g, number average molecular weight 2,100)
HV-1900 (manufactured by JX Energy): polybutene (number average molecular weight 2,900)
（ｂ）粘着付与樹脂
　・アルコンＰ１２５（荒川化学社製）：シクロヘキサン環含有水素化石油樹脂（軟化点１２５℃） (B) Tackifying resin Alcon P125 (Arakawa Chemical Co., Ltd.): Hydrogenated petroleum resin containing cyclohexane ring (softening point 125 ° C.)
（ｃ）吸湿性フィラー
　・ＤＨＴ－４Ｃ（協和化学工業社製）：半焼成ハイドロタルサイト（平均粒子径：４００ｎｍ、ＢＥＴ比表面積：１５ｍ２／ｇ） (C) Hygroscopic filler DHT-4C (manufactured by Kyowa Chemical Industry Co., Ltd.): Semi-calcined hydrotalcite (average particle size: 400 nm, BET specific surface area: 15 m 2 / g)
（ｄ）硬化剤
　・アミン系硬化剤（２，４，６－トリス（ジアミノメチル）フェノール、以下「ＴＡＰ」と略記する。） (D) Curing agent Amine curing agent (2,4,6-tris (diaminomethyl) phenol, hereinafter abbreviated as “TAP”)
　有機溶剤
　・トルエン
　・スワゾール＃１０００（丸善石油社製）：芳香族系混合溶剤 Organic solvent ・ Toluene ・ Swazole # 1000 (Maruzen Oil Co., Ltd.): Aromatic mixed solvent
２．無機被膜形成用コーティング剤
（１）ＯｌａｍＺ（アートブリード株式会社）
　ポリシラザン系ガラスコート剤（パーヒドロキシポリシラザン）
（２）ＳＳＧ　ＨＢ２１Ｎ（ニットーボーメディカル株式会社）
　アルコキシシラン系ガラスコート剤（テトラエトキシシラン）
（３）Ｇ４０１（日研株式会社）
　アルコキシ金属塩系セラミックコーティング剤（主成分：ＳｉＯ２、ＺｒＯ３）
（４）ＳＺ－９０（日研株式会社）
　アルコキシ金属塩系セラミックコーティング剤（主成分：シリコーン樹脂、ＺｒＯ３）（５）ＧＡ１－９２－５２（日研株式会社）
　アルコキシ金属塩・樹脂ハイブリッド系セラミックコーティング剤（主成分：ＳｉＯ２、Ａｌ２Ｏ３、Ａｇ、アクリル樹脂）
（６）ＧＢ１－９２（日研株式会社）
　アルコキシ金属塩・樹脂ハイブリッド系セラミックコーティング剤（主成分：ＳｉＯ２、Ａｌ２Ｏ３、ブチラール樹脂）
（７）Ｇ１－９０（日研株式会社）
　アルコキシ金属塩系セラミックコーティング剤（主成分：ＳｉＯ２、アルキルアルコキシシラン） 2. Coating agent for inorganic film formation (1) OlamZ (Art Breed Co., Ltd.)
Polysilazane glass coating agent (perhydroxypolysilazane)
(2) SSG HB21N (Nitto Bo Medical Co., Ltd.)
Alkoxysilane glass coating agent (tetraethoxysilane)
(3) G401 (Niken Corporation)
Alkoxy metal salt ceramic coating agent (main components: SiO 2, ZrO 3 )
(4) SZ-90 (Niken Corporation)
Alkoxy metal salt ceramic coating agent (main component: silicone resin, ZrO 3 ) (5) GA1-92-52 (Niken Corporation)
Alkoxy metal salt / resin hybrid ceramic coating agent (main components: SiO 2 , Al 2 O 3 , Ag, acrylic resin)
(6) GB1-92 (Niken Corporation)
Alkoxy metal salt / resin hybrid ceramic coating agent (main components: SiO 2 , Al 2 O 3 , butyral resin)
(7) G1-90 (Niken Corporation)
Alkoxy metal salt ceramic coating agent (main components: SiO 2 , alkylalkoxysilane)
［実施例１～９および比較例１～６］
　表１及び表２に示す処方の樹脂組成物を調製し、離型処理したＰＥＴフィルム（支持体）上に感圧接着性樹脂組成物層のみを形成した封止用シート（シート１）と、離型処理したＰＥＴフィルム（支持体）上に感圧接着性樹脂組成物層を形成し、さらに表１および表２に示す無機被膜形成用コーティング剤にて、感圧接着性樹脂組成物層の片面に無機被膜を形成した封止用シート（シート２）を作製した。
　なお、表１および表２に記載の樹脂組成物の処方のうち、有機溶剤以外の成分の量は不揮発分で換算した値である。 [Examples 1 to 9 and Comparative Examples 1 to 6]
A resin composition having a formulation shown in Table 1 and Table 2 was prepared, and a sealing sheet (sheet 1) in which only a pressure-sensitive adhesive resin composition layer was formed on a release-treated PET film (support); A pressure-sensitive adhesive resin composition layer is formed on the release-treated PET film (support), and the coating film for forming an inorganic film shown in Table 1 and Table 2 is used to form the pressure-sensitive adhesive resin composition layer. A sealing sheet (sheet 2) having an inorganic coating formed on one side was produced.
In addition, among the prescriptions of the resin compositions described in Tables 1 and 2, the amount of components other than the organic solvent is a value converted in terms of nonvolatile content.
＜実施例１＞
　シクロヘキサン環含有水素化石油樹脂（アルコンＰ１２５、６０％スワゾール＃１０００溶液）１３０部に、エチレン－メチルメタクリレート共重合体（ＣＭ５０２２、２０％トルエン溶液）２１０部、ポリブテン（ＨＶ－１９００）９４部、および半焼成ハイドロタルサイト（ＤＨＴ－４Ｃ）１００部を３本ロールで分散させて、混合物を得た。得られた混合物に、アミン系硬化剤（ＴＡＰ）０．５部およびトルエン１００部を配合し、得られた混合物を高速回転ミキサーで均一に分散して、樹脂組成物のワニスを得た。得られたワニスをシリコーン系離型剤で処理されたＰＥＴフィルム（厚さ３８μｍ）の離型処理面上に、ダイコーターにて均一に塗布し、１３０℃で６０分間加熱することにより、厚さ４５μｍの感圧接着性樹脂組成物層を有する封止用シート（シート１）を得た。 <Example 1>
130 parts of cyclohexane ring-containing hydrogenated petroleum resin (Alcon P125, 60% swazole # 1000 solution), 210 parts of ethylene-methyl methacrylate copolymer (CM5022, 20% toluene solution), 94 parts of polybutene (HV-1900), and 100 parts of semi-fired hydrotalcite (DHT-4C) was dispersed with three rolls to obtain a mixture. To the obtained mixture, 0.5 part of an amine curing agent (TAP) and 100 parts of toluene were blended, and the obtained mixture was uniformly dispersed with a high-speed rotary mixer to obtain a varnish of a resin composition. The obtained varnish is uniformly coated with a die coater on a release treatment surface of a PET film (thickness 38 μm) treated with a silicone release agent, and heated at 130 ° C. for 60 minutes to obtain a thickness. A sealing sheet (sheet 1) having a 45 μm pressure-sensitive adhesive resin composition layer was obtained.
　上記と同様にして得られた封止用シートの感圧接着性樹脂組成物層上にポリシラザン系ガラスコート剤（「ＯｌａｍＺ」、アートブリード株式会社）１０ｇを塗布した。その後、スピンコーターにて２０００ｒｐｍで１分間かけて成膜を実施した（塗布量：１ｇ／ｍ２（固形分換算））。こうして得られたシートを６０℃で３０分加熱した後、１３０℃で６０分加熱することにより、感圧接着性樹脂組成物層の片面がポリシラザン含有塗膜の熱処理生成物（シリカガラス被膜）で被覆された封止用シート（シート２）を得た。 10 g of a polysilazane glass coating agent (“OlamZ”, Art Breed Co., Ltd.) was applied on the pressure-sensitive adhesive resin composition layer of the sealing sheet obtained in the same manner as described above. Thereafter, film formation was performed with a spin coater at 2000 rpm for 1 minute (coating amount: 1 g / m 2 (in terms of solid content)). The sheet thus obtained is heated at 60 ° C. for 30 minutes, and then heated at 130 ° C. for 60 minutes, so that one side of the pressure-sensitive adhesive resin composition layer is a heat-treated product (silica glass coating) of a polysilazane-containing coating film. A coated sealing sheet (sheet 2) was obtained.
＜実施例２＞
　ＡＣＲＹＦＴ　ＣＭ５０２２をプロピレン－ブテン共重合体（Ｘ１１０２）に変えたこと以外は実施例１と同様にして、シート１、２を作製した。 <Example 2>
Sheets 1 and 2 were produced in the same manner as in Example 1 except that ACRYFT CM5022 was changed to a propylene-butene copolymer (X1102).
＜実施例３＞
　ＡＣＲＹＦＴ　ＣＭ５０２２を、プロピレン－ブテン共重合体（Ｘ１１０２）４０部と無水マレイン酸変性液状ポリブテン（ＨＶ－３００Ｍ）３５部に変えたこと、および、ポリブテン（ＨＶ－１９００）を６０部に変えたこと以外は実施例１と同様にして、シート１、２を作製した。 <Example 3>
ACRYFT CM5022 was changed to 40 parts of propylene-butene copolymer (X1102) and 35 parts of maleic anhydride-modified liquid polybutene (HV-300M), and polybutene (HV-1900) was changed to 60 parts. Were produced in the same manner as in Example 1.
＜実施例４＞
　実施例１で得たシート１の上にＳｉＯ２を３０ｎｍ化学蒸着させたのち、ＳｉＣＮを３０ｎｍ化学蒸着させた。これを繰り返し、ＳｉＯ２化学蒸着層６層＋ＳｉＣＮ化学蒸着層６層（総厚さ３６０ｎｍ）からなるＳｉＯ２－ＳｉＣＮ多層蒸着被膜を有するシート２を得た。シート１は実施例１と同じである。 <Example 4>
After SiO 2 was chemically deposited on the sheet 1 obtained in Example 1 by 30 nm, SiCN was chemically deposited by 30 nm. This was repeated to obtain a sheet 2 having a SiO 2 —SiCN multilayer vapor deposition film composed of 6 SiO 2 chemical vapor deposition layers + 6 SiCN chemical vapor deposition layers (total thickness 360 nm). The sheet 1 is the same as that in the first embodiment.
＜実施例５＞
　ＳｉＯ２化学蒸着層３層＋ＳｉＣＮ化学蒸着層３層（総厚さ１８０ｎｍ）に変えたこと以外は実施例４と同様にＳｉＯとＳｉＣＮの化学蒸着を行ってシート２を得た。シート１は実施例１と同じである。 <Example 5>
A sheet 2 was obtained by performing chemical vapor deposition of SiO and SiCN in the same manner as in Example 4 except that it was changed to 3 layers of SiO 2 chemical vapor deposition layer and 3 layers of SiCN chemical vapor deposition layer (total thickness 180 nm). The sheet 1 is the same as that in the first embodiment.
＜実施例６＞
　半焼成ハイドロタルサイト（ＤＨＴ－４Ｃ）を除いたこと以外は実施例４と同様にしてシート１を作製し、実施例４と同様のＳｉＯ２－ＳｉＣＮ多層蒸着被膜（ＳｉＯ２化学蒸着層６層＋ＳｉＣＮ化学蒸着層６層、総厚さ３６０ｎｍ）を形成してシート２を得た。 <Example 6>
A sheet 1 was prepared in the same manner as in Example 4 except that the semi-fired hydrotalcite (DHT-4C) was removed, and the same SiO 2 -SiCN multilayered vapor-deposited coating (SiO 2 chemical vapor deposition layer 6 layers) as in Example 4 + SiCN chemical vapor deposition layer 6 layers, total thickness 360 nm) was formed to obtain a sheet 2.
＜実施例７＞
　ＳｉＯ２化学蒸着層３層＋ＳｉＣＮ化学蒸着層３層（総厚さ１８０ｎｍ）に変えたこと以外は実施例６と同様にしてシート２を得た。シート１は実施例６と同じである。 <Example 7>
A sheet 2 was obtained in the same manner as in Example 6 except that it was changed to 3 SiO 2 chemical vapor deposition layers + 3 SiCN chemical vapor deposition layers (total thickness 180 nm). Sheet 1 is the same as in Example 6.
＜実施例８＞
　エチレン－メチルメタクリレート共重合体（ＣＭ５０２２）をプロピレン－ブテン共重合体（Ｘ１１０２）に変えたこと以外は実施例４と同様にしてシート１、２を作製した。 <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).
＜実施例９＞
　ＳｉＯ２化学蒸着層３層＋ＳｉＣＮ化学蒸着層３層（総厚さ１８０ｎｍ）に変えたこと以外は実施例８と同様にしてシート２を得た。シート１は実施例８と同じである。 <Example 9>
A sheet 2 was obtained in the same manner as in Example 8 except that it was changed to 3 SiO 2 chemical vapor deposition layers + 3 SiCN chemical vapor deposition layers (total thickness 180 nm). Sheet 1 is the same as in Example 8.
＜比較例１＞
　コーティング剤をＯｌａｍＺからＳＳＧ　ＨＢ２１Ｎに変えたこと以外は実施例１と同様にしてシート２を得た。シート１は実施例１と同じである。 <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 that in the first embodiment.
＜比較例２＞
　コーティング剤をＯｌａｍＺからＧ４０１に変えたこと以外は実施例１と同様にしてシート２を得た。シート１は実施例１と同じである。 <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 that in the first embodiment.
＜比較例３＞
　コーティング剤をＯｌａｍＺからＳＺ－９０に変えたこと以外は実施例１と同様にしてシート２を得た。シート１は実施例１と同じである。 <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 that in the first embodiment.
＜比較例４＞
　コーティング剤をＯｌａｍＺからＳＡ１－９２－５２に変えたこと以外は実施例１と同様にしてシート２を得た。シート１は実施例１と同じである。 <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 that in the first embodiment.
＜比較例５＞
　コーティング剤をＯｌａｍＺからＧＢ１―９２に変えたこと以外は実施例１と同様にしてシート２を得た。シート１は実施例１と同じである。 <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 that in the first embodiment.
＜比較例６＞
　コーティング剤をＯｌａｍＺからＧ１－９０に変えたこと以外は実施例１と同様にしてシート２を得た。シート１は実施例１と同じである。 <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 that in the first embodiment.
　上述のようにして得られた実施例および比較例の封止用シートの耐透湿性（水蒸気透過量）を以下のようにして評価した。結果を表１および２に示す。なお、表１、２中の感圧接着性樹脂組成物層の材料組成におけるアルコンＰ１２５、ＣＭ５０２２の部数は固形分換算値である。 The moisture permeation resistance (water vapor permeation amount) of the sealing sheets of Examples and Comparative Examples obtained as described above was evaluated as follows. The results are shown in Tables 1 and 2. In addition, the number of parts of Alcon P125 and CM5022 in the material composition of the pressure-sensitive adhesive resin composition layer in Tables 1 and 2 is a solid content conversion value.
［封止用シートの耐透湿性（水蒸気透過量）の評価］
（１）シート１の支持体（ＰＥＴフィルム）から剥離した、無機被膜を有しない感圧接着性樹脂組成物層（厚さ：４５μｍ）の１ｍ２あたりの水蒸気透過量を、ＪＩＳ　Ｚ　０２０８：１９７６に準拠する方法にて、温度４０℃、湿度９０％ＲＨおよび２４時間の条件で測定した。この水蒸気透過量を水蒸気透過量Ｉとする。
（２）シート２の支持体（ＰＥＴフィルム）から剥離した、無機被膜を有する感圧接着性樹脂組成物層（厚さ：４５μｍ）の１ｍ２あたりの水蒸気透過量を、ＪＩＳ　Ｚ　０２０８：１９７６に準拠する方法にて、温度４０℃、湿度９０％ＲＨおよび２４時間の条件で測定した。この水蒸気透過量を水蒸気透過量ＩＩとする。 [Evaluation of moisture permeation resistance (water vapor transmission amount) of sealing sheet]
(1) The water vapor permeation amount per 1 m 2 of the pressure-sensitive adhesive resin composition layer (thickness: 45 μm) peeled off from the support (PET film) of the sheet 1 is JIS Z 0208: 1976. Was measured under the conditions of a temperature of 40 ° C., a humidity of 90% RH and 24 hours. This water vapor transmission amount is defined as water vapor transmission amount I.
(2) The water vapor permeation amount per 1 m 2 of the pressure-sensitive adhesive resin composition layer (thickness: 45 μm) having an inorganic coating film peeled from the support (PET film) of the sheet 2 is JIS Z 0208: 1976. The measurement was performed under the conditions of a temperature of 40 ° C., a humidity of 90% RH, and 24 hours by a compliant method. This water vapor transmission amount is defined as water vapor transmission amount II.
（評価）
　シート１の水蒸気透過量（水蒸気透過量Ｉ）とシート２の水蒸気透過量（水蒸気透過量ＩＩ）との対比から以下の基準で評価した。
　極めて良好（◎）：水蒸気透過量Ｉを１としたときの水蒸気透過量ＩＩが０．７未満（水蒸気透過量ＩＩ／水蒸気透過量Ｉ＜０．７）
　良好（○）：水蒸気透過量Ｉを１としたときの水蒸気透過量ＩＩが０．７以上１未満（０．７≦水蒸気透過量ＩＩ／水蒸気透過量Ｉ＜１）
　不良（×）：水蒸気透過量Ｉを１としたときの水蒸気透過量ＩＩが１以上（１≦水蒸気透過量ＩＩ／水蒸気透過量Ｉ） (Evaluation)
From the comparison of the water vapor transmission amount of the sheet 1 (water vapor transmission amount I) and the water vapor transmission amount of the sheet 2 (water vapor transmission amount II), the following criteria were used.
Extremely good (）): Water vapor transmission amount II is less than 0.7 when water vapor transmission amount I is 1 (water vapor transmission amount II / water vapor transmission amount I <0.7).
Good (O): Water vapor transmission amount II when water vapor transmission amount I is 1 is 0.7 or more and less than 1 (0.7 ≦ water vapor transmission amount II / water vapor transmission amount I <1)
Poor (x): Water vapor transmission amount II is 1 or more when water vapor transmission amount I is 1 (1 ≦ water vapor transmission amount II / water vapor transmission amount I)
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表１および２に示されるように、実施例１～９と比較例１～６の対比から、感圧接着性樹脂組成物層の片面にポリシラザン含有塗膜の熱処理生成物からなるシリカガラス被膜か、或いは、ケイ素化合物の蒸着被膜を形成することで、封止用シートの耐透湿性が著しく向上することが分かった。 As shown in Tables 1 and 2, from the comparison between Examples 1 to 9 and Comparative Examples 1 to 6, a silica glass coating comprising a heat-treated product of a polysilazane-containing coating on one side of the pressure-sensitive adhesive resin composition layer Alternatively, it was found that the moisture permeation resistance of the sealing sheet is remarkably improved by forming a vapor deposition film of a silicon compound.
　１　感圧接着性樹脂組成物層
　２　防湿性無機被膜
　３　離型処理された支持体
　４　円偏光板
　５　接着剤層
　４１　位相差フィルム
　４２　偏光子
　１０、１１　封止用シート DESCRIPTION OF SYMBOLS 1 Pressure-sensitive-adhesive resin composition layer 2 Moisture-proof inorganic coating 3 Release-supported body 4 Circularly polarizing plate 5 Adhesive layer 41 Retardation film 42 Polarizer 10, 11 Sealing sheet
　本出願は日本で出願された特願２０１７－０５８０７３を基礎としており、その内容は本明細書に全て包含される。 This application is based on Japanese Patent Application No. 2017-058073 filed in Japan, the contents of which are incorporated in full herein.

Claims (16)

  1. 　（Ａ）感圧接着性樹脂組成物層及び該（Ａ）感圧接着性樹脂組成物層の片面に直接形成された（Ｂ）防湿性無機被膜を含む封止用シート。 (A) A pressure-sensitive adhesive resin composition layer and a sealing sheet comprising (B) a moisture-proof inorganic coating formed directly on one side of the (A) pressure-sensitive adhesive resin composition layer.
  2. 　前記（Ｂ）防湿性無機被膜が、（Ｂ１）ポリシラザン含有塗膜の熱処理生成物からなるシリカガラス被膜であるか、或いは、（Ｂ２）無機物蒸着被膜である、請求項１記載の封止用シート。 The sealing sheet according to claim 1, wherein (B) the moisture-proof inorganic coating is a silica glass coating made of a heat-treated product of (B1) a polysilazane-containing coating, or (B2) an inorganic deposition coating. .
  3. 　ポリシラザンがパーヒドロキシポリシラザンを含む、請求項２に記載の封止用シート。 The sealing sheet according to claim 2, wherein the polysilazane comprises perhydroxypolysilazane.
  4. 　（Ｂ２）無機物蒸着被膜がケイ素化合物蒸着被膜である、請求項２記載の封止用シート。 (B2) The sealing sheet according to claim 2, wherein the inorganic deposition film is a silicon compound deposition film.
  5. 　ケイ素化合物蒸着被膜が、ＳｉＯ２蒸着膜とＳｉＣＮ蒸着膜を含むＳｉＯ２－ＳｉＣＮ多層蒸着膜である、請求項４記載の封止用シート。 Silicon compound vapor deposited film is a SiO 2 -SiCN multilayered vapor deposition film comprising SiO 2 deposited film and SiCN deposited film, sheet for sealing according to claim 4, wherein.
  6. 　ＳｉＯ２－ＳｉＣＮ多層蒸着膜が、ＳｉＯ２蒸着膜とＳｉＣＮ蒸着膜が交互に形成されたＳｉＯ２－ＳｉＣＮ多層蒸着膜である、請求項５記載の封止用シート。 SiO 2 -SiCN multilayer deposition film, a SiO 2 -SiCN multilayered vapor deposition film SiO 2 deposited film and SiCN deposited film are alternately formed, the sheet for sealing according to claim 5, wherein.
  7. 　（Ｂ）防湿性無機被膜の厚さが１０００ｎｍ以下である、請求項１～６のいずれか１項記載の封止用シート。 (B) The sealing sheet according to any one of claims 1 to 6, wherein the moisture-proof inorganic coating has a thickness of 1000 nm or less.
  8. 　（Ａ）感圧接着性樹脂組成物層の厚さが３～５０μｍである、請求項１～７のいずれか１項記載の封止用シート。 The sealing sheet according to any one of claims 1 to 7, wherein (A) the pressure-sensitive adhesive resin composition layer has a thickness of 3 to 50 µm.
  9. 　（Ａ）感圧接着性樹脂組成物層が吸湿性フィラーを含有する、請求項１～８のいずれか１項記載の封止用シート。 (A) The sealing sheet according to any one of claims 1 to 8, wherein the pressure-sensitive adhesive resin composition layer contains a hygroscopic filler.
  10. 　（Ａ）感圧接着性樹脂組成物層が粘着付与樹脂を含有する、請求項１～９のいずれか１項記載の封止用シート。 (A) The sealing sheet according to any one of claims 1 to 9, wherein the pressure-sensitive adhesive resin composition layer contains a tackifying resin.
  11. 　（Ｃ）離型処理された支持体をさらに含み、（Ｃ）離型処理された支持体／（Ａ）感圧接着性樹脂組成物層／（Ｂ）防湿性無機被膜の積層構成を有する、請求項１～１０のいずれか１項記載の封止用シート。 (C) further including a release-treated support, and (C) a release-treated support / (A) a pressure-sensitive adhesive resin composition layer / (B) a moisture-proof inorganic coating. The sealing sheet according to any one of claims 1 to 10.
  12. 　（Ｃ）離型処理された支持体が、防湿性を有する支持体である、請求項１１記載の封止用シート。 (C) The sealing sheet according to claim 11, wherein the release-treated support is a moisture-proof support.
  13. 　有機ＥＬ素子の封止用である、請求項１～１２のいずれか１項記載の封止用シート。 The sealing sheet according to any one of claims 1 to 12, which is used for sealing an organic EL element.
  14. 　（Ｂ）防湿性無機被膜の（Ａ）感圧接着性樹脂組成物層の側とは反対側の表面にさらに（Ｄ）円偏光板が接着されてなり、有機ＥＬ素子の封止用シートである、請求項１～１０のいずれか１項記載の封止用シート。 (B) A (D) circularly polarizing plate is further bonded to the surface of the moisture-proof inorganic coating on the side opposite to the (A) pressure-sensitive adhesive resin composition layer side. The sealing sheet according to any one of claims 1 to 10, wherein:
  15. 　（Ｂ）防湿性無機被膜の（Ａ）感圧接着性樹脂組成物層の側とは反対側の表面にさらに（Ｄ）円偏光板が接着されてなり、有機ＥＬ素子の封止用シートである、請求項１１または１２記載の封止用シート。 (B) A (D) circularly polarizing plate is further bonded to the surface of the moisture-proof inorganic coating on the side opposite to the (A) pressure-sensitive adhesive resin composition layer side. The sheet | seat for sealing of Claim 11 or 12 which exists.
  16. 　請求項１～１０、１４のいずれか１項記載の封止用シートで有機ＥＬ素子が封止されて成る有機ＥＬデバイス。 15. An organic EL device comprising an organic EL element sealed with the sealing sheet according to any one of claims 1 to 10 and 14.
PCT/JP2018/011245 2017-03-23 2018-03-22 Sheet for sealing WO2018174116A1 (en)

Priority Applications (1)

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JP2019507726A JP7099441B2 (en) 2017-03-23 2018-03-22 Sealing sheet

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JP2017-058073 2017-03-23
JP2017058073 2017-03-23

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WO2018174116A1 true WO2018174116A1 (en) 2018-09-27

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012057065A (en) * 2010-09-09 2012-03-22 Lintec Corp Adhesive sheet for sealing, electronic device and organic device
JP2014149961A (en) * 2013-01-31 2014-08-21 Lintec Corp Film-like sealing material for electronic device, sealing sheet for electronic device, and electronic device
WO2015199164A1 (en) * 2014-06-27 2015-12-30 富士フイルム株式会社 Organic electronic device sealing member
WO2016084791A1 (en) * 2014-11-25 2016-06-02 コニカミノルタ株式会社 Sealing film, function element and method for producing sealing film
WO2016139981A1 (en) * 2015-03-02 2016-09-09 富士フイルム株式会社 Adhesive sheet, adhesive film, organic light-emission device, and adhesive agent composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012057065A (en) * 2010-09-09 2012-03-22 Lintec Corp Adhesive sheet for sealing, electronic device and organic device
JP2014149961A (en) * 2013-01-31 2014-08-21 Lintec Corp Film-like sealing material for electronic device, sealing sheet for electronic device, and electronic device
WO2015199164A1 (en) * 2014-06-27 2015-12-30 富士フイルム株式会社 Organic electronic device sealing member
WO2016084791A1 (en) * 2014-11-25 2016-06-02 コニカミノルタ株式会社 Sealing film, function element and method for producing sealing film
WO2016139981A1 (en) * 2015-03-02 2016-09-09 富士フイルム株式会社 Adhesive sheet, adhesive film, organic light-emission device, and adhesive agent composition

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JPWO2018174116A1 (en) 2020-01-30
TW201900832A (en) 2019-01-01

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