WO2017135112A1 - 封止用の熱硬化性樹脂組成物および封止用シート - Google Patents
封止用の熱硬化性樹脂組成物および封止用シート Download PDFInfo
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- WO2017135112A1 WO2017135112A1 PCT/JP2017/002428 JP2017002428W WO2017135112A1 WO 2017135112 A1 WO2017135112 A1 WO 2017135112A1 JP 2017002428 W JP2017002428 W JP 2017002428W WO 2017135112 A1 WO2017135112 A1 WO 2017135112A1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- TXMIUMUSEKVUBH-UHFFFAOYSA-M tetrabutylphosphanium;2,2,2-trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F.CCCC[P+](CCCC)(CCCC)CCCC TXMIUMUSEKVUBH-UHFFFAOYSA-M 0.000 description 1
- GFZMLBWMGBLIDI-UHFFFAOYSA-M tetrabutylphosphanium;acetate Chemical compound CC([O-])=O.CCCC[P+](CCCC)(CCCC)CCCC GFZMLBWMGBLIDI-UHFFFAOYSA-M 0.000 description 1
- WHDWTYUVZOXXKX-UHFFFAOYSA-M tetrabutylphosphanium;formate Chemical compound [O-]C=O.CCCC[P+](CCCC)(CCCC)CCCC WHDWTYUVZOXXKX-UHFFFAOYSA-M 0.000 description 1
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
- H05B33/04—Sealing arrangements, e.g. against humidity
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/841—Self-supporting sealing arrangements
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a thermosetting resin composition for sealing and a sealing sheet, and particularly suitable for sealing light-emitting elements such as organic EL (Electroluminescence) elements and photoelectric conversion elements such as light-receiving elements such as solar cells.
- the present invention relates to a thermosetting resin composition for sealing and a sealing sheet.
- An organic EL 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.
- 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 formed on the substrate to seal the organic EL device. Is done.
- the resin composition used for sealing the organic EL element is required to have a high moisture barrier property.
- hygroscopic metal oxide particles such as calcium oxide, magnesium oxide, strontium oxide, and barium oxide are included in the resin composition in order to achieve high barrier properties and high adhesive strength.
- Has been proposed for example, Patent Document 1).
- An object of the present invention is to provide a thermosetting resin composition for sealing that can form a sealing layer having excellent moisture barrier properties.
- the present inventor has formulated semi-baked hydrotalcite as an inorganic filler in a thermosetting resin composition for sealing containing a thermosetting resin, and thermosetting.
- Set the difference in thermal weight loss rate before and after moisture absorption of the cured resin composition to satisfy a specific numerical range, and set the total content of inorganic filler including semi-fired hydrotalcite to a specific range By doing so, the moisture barrier property of the sealing layer obtained from the sealing resin composition can be maintained for a long time, the deterioration of the sealed element due to moisture can be suppressed, and the element life can be greatly extended.
- the present invention has been completed.
- thermosetting resin composition comprising (A) a thermosetting resin, (B) a curing agent, and (C) semi-baked hydrotalcite as an inorganic filler,
- the thermogravimetric reduction rate at 280 ° C. by thermogravimetric analysis of the cured product of the thermosetting resin composition before moisture absorption is X 1 (%)
- the thermogravimetric reduction rate at 380 ° C. is Y 1 (%).
- the thermogravimetric reduction rate at 280 ° C. by thermogravimetric analysis of the cured product of the thermosetting resin composition is X 2 (%) and the thermogravimetric reduction rate at 380 ° C.
- thermosetting resin composition in which the content of the entire inorganic filler including semi-fired hydrotalcite is 20 to 60% by mass based on the entire nonvolatile content of the thermosetting resin composition.
- thermosetting resin composition according to the above [1] wherein the content of the semi-fired hydrotalcite is 5 to 60% by mass with respect to the entire nonvolatile content of the thermosetting resin composition.
- thermosetting resin composition according to [3] The thermosetting resin composition according to any one of [1] to [4], wherein the thermosetting resin is an epoxy resin.
- thermosetting resin composition according to [5] wherein the content of the epoxy resin is 10 to 79.9% by mass based on the entire nonvolatile content of the thermosetting resin composition.
- Composition. [8] The thermosetting resin composition according to any one of [1] to [7], wherein the content of silica is 0 to 10% by mass based on the entire nonvolatile content of the thermosetting resin composition. [9] The thermosetting resin composition according to any one of [1] to [8], which is used for sealing an organic EL element. [10] A sealing sheet in which a layer of the thermosetting resin composition according to any one of [1] to [8] is formed on a support. [11] The sealing sheet according to [10], which is used for sealing an organic EL element. [12] An organic EL device in which an organic EL element is sealed with a cured product of the thermosetting resin composition according to any one of [1] to [8].
- thermosetting resin composition for sealing From the thermosetting resin composition for sealing according to the present invention, it is possible to obtain a sealing layer in which moisture barrier properties are maintained for a longer time. Therefore, if the thermosetting resin composition for sealing of the present invention is used for forming a sealing layer of an element which is weak against moisture such as an organic EL element, the moisture blocking of the sealing layer for a longer time. Thus, the deterioration of the element due to moisture can be suppressed for a longer time, and the element life can be greatly extended.
- thermogravimetric decrease rate at 280 ° C. by thermogravimetric analysis of the cured product of the thermosetting resin composition before moisture absorption is X 1 (%)
- thermogravimetric decrease rate at 380 ° C. Is Y 1 (%)
- thermogravimetric decrease rate at 280 ° C. by thermogravimetric analysis of the cured product of the thermosetting resin composition after moisture absorption is X 2 (%)
- thermogravimetric decrease rate at 380 ° C. is Y 2. (%)
- One of the characteristics is that the relationship of 2% ⁇ X 2 ⁇ X 1 and Y 2 ⁇ Y 1 ⁇ 10% is satisfied.
- thermogravimetric reduction rate (X 1 and Y 1 ) by thermogravimetric analysis of the cured product before moisture absorption is obtained by heating the cured product obtained by heating the thermosetting resin composition in the air atmosphere.
- the value obtained by starting thermogravimetric analysis within 10 minutes from the end of heating of the curable resin composition is used. Between the end of heating and the start of thermogravimetric analysis, moisture absorption as described later is not performed, and the cured product is placed in an atmosphere at a temperature of 25 ° C. and a relative humidity of 40%.
- thermogravimetric analysis cannot be started within 10 minutes from the end of the heating
- the cured product is put in a moisture-proof bag (for example, a bag having an aluminum layer) to prevent moisture absorption from the atmosphere.
- a moisture-proof bag for example, a bag having an aluminum layer
- the time for placing the cured product in an atmosphere of a temperature of 25 ° C. and a relative humidity of 40% RH is set within 10 minutes.
- thermogravimetric reduction rate (X 2 and Y 2 ) by thermogravimetric analysis of the cured product after moisture absorption is obtained by heating the cured product obtained by heating the thermosetting resin composition in the atmosphere.
- the curable resin composition is allowed to stand for 100 hours in an environment of 85 ° C. and 85% relative humidity to absorb moisture.
- the value obtained by starting the thermogravimetric analysis within is used.
- the cured product is placed in an atmosphere at a temperature of 25 ° C. and a relative humidity of 40%.
- the cured product is placed in a moisture-proof bag (for example, a bag having an aluminum layer) to prevent moisture absorption from the atmosphere, and moisture absorption starts from the end of heating.
- a moisture-proof bag for example, a bag having an aluminum layer
- the time for placing the cured product in an atmosphere having a temperature of 25 ° C. and a relative humidity of 40% RH is set within 10 minutes.
- thermogravimetric analysis cannot be started within 10 minutes from the end of moisture absorption under the above conditions
- the cured product is put in a moisture-proof bag to prevent moisture absorption from the atmosphere, and from the end of moisture absorption to the start of thermogravimetric analysis.
- the time for placing the cured product in an atmosphere of a temperature of 25 ° C. and a relative humidity of 40% RH is set within 10 minutes.
- X 2 -X 1 It is preferable that 2.5% ⁇ X 2 ⁇ X 1 .
- the upper limit of X 2 -X 1 is not particularly limited, but usually X 2 -X 1 ⁇ 30%, and preferably X 2 -X 1 ⁇ 20%.
- the lower limit of Y 2 -Y 1 is not particularly limited, but usually 1.0% ⁇ Y 2 -Y 1 and preferably 2.0% ⁇ Y 2 -Y 1 .
- thermogravimetric reduction rate a cured product of a thermosetting resin composition having a reaction rate exceeding 70% is used.
- this reaction rate is less than 70%, the measurement of the thermal weight reduction rate tends to be affected by the volatilization of unreacted components and the change in the moisture absorption state.
- This reaction rate can be measured by DSC. Specifically, using a DSC EXSTAR7000X manufactured by Hitachi High-Tech Science Co., Ltd., weighed 3 mg each of the thermosetting resin composition sample before and after curing on an aluminum sample pan, and covered the atmosphere with a nitrogen flow rate of 50 mL / min. Under the condition, the temperature was measured from 15 ° C. to 280 ° C.
- Reaction rate (%) 100 ⁇ (reaction heat amount of thermosetting resin composition after curing) / (reaction heat amount of thermosetting resin composition before curing) (i) It can be calculated from
- Moisture absorption of the cured product is performed under the conditions of a temperature of 85 ° C., a relative humidity of 85%, and a time of 100 hours using a cured product that is folded to a thickness of 0.3 mm and weighed 1 g.
- the cured product can be left standing for 100 hours in a small environmental tester (SH-222 manufactured by Espec Corp.) set at 85 ° C. and 85% RH (relative humidity) under atmospheric pressure. .
- thermogravimetric analysis TG / DTA EXSTAR6300 manufactured by Hitachi High-Tech Science Co., Ltd. was used, and 10 mg of each cured product sample before and after moisture absorption was weighed on an aluminum sample pan, and the nitrogen flow rate was 200 mL / min with the lid open. In an atmosphere of 30 ° C. to 550 ° C. under a temperature increase rate of 10 ° C./min.
- thermosetting resin composition in which the cured product satisfies the relationship of the thermogravimetric reduction rate can be easily prepared by appropriately setting the type and blending amount of the hygroscopic component to be blended in the composition, for example.
- the moisture absorption performance of the resulting cured product is increased, but the moisture uptake rate is also increased. Therefore, if the blending amount is too large, Y 2 -Y 1 It becomes difficult to satisfy the relationship of ⁇ 10%, and as a result, the moisture shielding property tends to decrease.
- the content of the calcined hydrotalcite in the thermosetting resin composition is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, based on the entire nonvolatile content of the thermosetting resin composition. 10% by mass is more preferable, and 0 to 5% by mass is most preferable.
- the mass ratio of semi-calcined hydrotalcite: calcined hydrotalcite is preferably 50:50 to 100: 0, more preferably 52:48 to 100: 0, and still more preferably 55:45 to 100: 0. .
- the content of unfired hydrotalcite in the thermosetting resin composition is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, based on the entire nonvolatile content of the thermosetting resin composition. More preferably, it is ⁇ 5% by mass.
- the mass ratio of semi-fired hydrotalcite: unfired hydrotalcite is preferably 50:50 to 100: 0, more preferably 55:45 to 100: 0, and still more preferably 60:40 to 100: 0. More preferably, it is 65:35 to 100: 0, and particularly preferably 70:30 to 100: 0.
- the content of talc in the thermosetting resin composition is preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less, based on the entire nonvolatile content of the thermosetting resin composition. 20% by mass or less is particularly preferable.
- the mass ratio of semi-fired hydrotalcite: talc is preferably 20:80 to 100: 0, more preferably 30:70 to 100: 0, still more preferably 40:60 to 99.5: 0.5. is there.
- the content of silica in the thermosetting resin composition is preferably 0 to 10% by mass, more preferably 0 to 8% by mass, and more preferably 0 to 5% by mass based on the entire nonvolatile content of the thermosetting resin composition. Is more preferable. That is, the thermosetting resin composition of the present invention preferably contains no silica or 10% by mass or less of silica, and the composition contains no silica or 8% by mass or less.
- the composition preferably does not contain silica or more preferably contains 5% by mass or less of silica (note that the content of silica is a thermosetting resin composition). Is the value per non-volatile content of).
- the mass ratio of semi-calcined hydrotalcite: silica is preferably 80:20 to 100: 0, more preferably 85:15 to 100: 0, and still more preferably 90:10 to 100: 0.
- thermosetting resin composition of the present invention contains a thermosetting resin. Although it does not specifically limit as a thermosetting resin, An epoxy resin is used preferably.
- the epoxy resin can be used without limitation as long as it has an average of two or more epoxy groups per molecule.
- the epoxy resin include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, and phosphorus containing Epoxy resin, bisphenol S type epoxy resin, aromatic glycidylamine type epoxy resin (eg, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidyltoluidine, diglycidylaniline, etc.), alicyclic epoxy resin, aliphatic Chain epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, epoxy resin having butadiene structure Diglycidyl etherified products of bisphenol, diglycidyl etherified products of
- the epoxy equivalent of the epoxy resin is preferably 50 to 5,000, more preferably 50 to 3,000, more preferably 80 to 2,000, and more preferably 100 to 1,500 from the viewpoint of reactivity and the like.
- the “epoxy equivalent” is the number of grams (g / eq) of a resin containing 1 gram equivalent of an epoxy group, and is measured according to the method defined in JIS K 7236.
- the weight average molecular weight of the epoxy resin is preferably 5,000 or less.
- Suitable epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, etc. Can be mentioned.
- the epoxy resin may be either liquid or solid, and a liquid epoxy resin and a solid epoxy resin may be used in combination.
- “liquid” and “solid” are states of the epoxy resin at normal temperature (25 ° C.). From the viewpoints of coatability, workability, and adhesiveness, it is preferable that at least 10% by mass or more of the entire epoxy resin used is a liquid epoxy resin. From the viewpoint of kneadability with hydrotalcite and varnish viscosity, it is particularly preferable to use a liquid epoxy resin and a solid epoxy resin in combination.
- the mass ratio of the liquid epoxy resin to the solid epoxy resin is preferably 1: 2 to 1: 0, and more preferably 1: 1.5 to 1: 0.1.
- the content of the thermosetting resin in the thermosetting resin composition is preferably 10 to 79.9% by mass, more preferably 20 to 70% by mass, and more preferably 30 to 30% by mass based on the entire nonvolatile content of the thermosetting resin composition. 65 mass% is more preferable.
- the content of the epoxy resin in the thermosetting resin composition is preferably 10 to 79.9% by mass, more preferably 20 to 70% by mass, and more preferably 30 to 65% by mass with respect to the entire nonvolatile content of the thermosetting resin composition. % Is more preferable.
- thermosetting resin composition of the present invention contains a curing agent. That is, the sealing layer is a cured product obtained by curing the resin composition.
- the curing agent is not particularly limited as long as it has a function of curing the thermosetting resin composition, but a viewpoint of suppressing thermal deterioration of a light emitting element such as an organic EL element during the curing treatment of the thermosetting resin composition. Therefore, those capable of curing the thermosetting resin composition at a temperature of 140 ° C. or lower (preferably 120 ° C. or lower) are preferable. Only one type of curing agent may be used, or two or more types may be used in combination.
- an epoxy resin curing agent particularly preferable as the thermosetting resin will be exemplified.
- the curing agent include primary amine, secondary amine, tertiary amine-based curing agent, polyaminoamide-based curing agent, dicyandiamide, organic acid dihydrazide, and the like.
- amine adduct compounds (Amicure PN-23, Amicure MY-24, Amicure PN-D, Amicure MY-D, Amicure PN-H, Amicure MY-H, Amicure PN-31 from the viewpoint of rapid curing.
- organic acid dihydrazide (Amicure VDH-J, Amicure UDH, Amicure LDH (all manufactured by Ajinomoto Fine Techno Co., Ltd.)) and the like are preferable. .
- the curing agent in the present invention melts in a temperature region of an ionic liquid (that is, 140 ° C. or less (preferably 120 ° C. or less)) that can cure the epoxy resin at a temperature of 140 ° C. or less (preferably 120 ° C. or less).
- a salt having a curing action of an epoxy resin can also be used particularly preferably.
- the ionic liquid is desirably used in a state where it is uniformly dissolved in a thermosetting resin (particularly an epoxy resin).
- the ionic liquid advantageously acts to improve the moisture barrier property of the cured product of the thermosetting resin composition.
- Examples of the cation constituting the ionic liquid include imidazolium ions, piperidinium ions, pyrrolidinium ions, pyrazonium ions, guanidinium ions, pyridinium ions, and other ammonium-based cations; tetraalkylphosphonium cations (for example, tetrabutylphosphonium ions, Phosphonium cations such as tributylhexyl phosphonium ion; and sulfonium cations such as triethylsulfonium ion.
- anion constituting the ionic liquid examples include halide anions such as fluoride ion, chloride ion, bromide ion and iodide ion; alkyl sulfate anions such as methanesulfonate ion; trifluoromethanesulfonate ion, Fluorine-containing compound anions such as hexafluorophosphonate ion, trifluorotris (pentafluoroethyl) phosphonate ion, bis (trifluoromethanesulfonyl) imide ion, trifluoroacetate ion, tetrafluoroborate ion; phenol ion, 2-methoxy Phenolic anions such as phenol ion and 2,6-di-tert-butylphenol ion; acidic amino acid ions such as aspartate ion and glutamate ion; glycine ion, alan
- R is a linear or branched alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted phenyl group, and X represents a side chain of an amino acid.
- amino acid in the formula (1) examples include aspartic acid, glutamic acid, glycine, alanine, and phenylalanine. Among them, glycine is preferable.
- the cation is preferably an ammonium cation or a phosphonium cation, more preferably an imidazolium ion or a phosphonium ion. More specifically, the imidazolium ion is 1-ethyl-3-methylimidazolium ion, 1-butyl-3-methylimidazolium ion, 1-propyl-3-methylimidazolium ion or the like.
- the anion is preferably a phenolic anion, an N-acyl amino acid ion or a carboxylic acid anion represented by the general formula (1), and more preferably an N-acyl amino acid ion or a carboxylic acid anion.
- phenolic anion examples include 2,6-di-tert-butylphenol ion.
- carboxylate anion examples include acetate ion, decanoate ion, 2-pyrrolidone-5-carboxylate ion, formate ion, ⁇ -lipoic acid ion, lactate ion, tartrate ion, hippurate ion, N- Methyl hippurate ion and the like, among which acetate ion, 2-pyrrolidone-5-carboxylate ion, formate ion, lactate ion, tartrate ion, hippurate ion and N-methylhippurate ion are preferable, acetate ion, N -Methyl hippurate ion and formate ion are particularly preferred.
- N-acylamino acid ion represented by the general formula (1) examples include N-benzoylalanine ion, N-acetylphenylalanine ion, aspartate ion, glycine ion, N-acetylglycine ion, and the like.
- N-benzoylalanine ion, N-acetylphenylalanine ion and N-acetylglycine ion are preferable, and N-acetylglycine ion is particularly preferable.
- Specific ionic liquids include, for example, 1-butyl-3-methylimidazolium lactate, tetrabutylphosphonium-2-pyrrolidone-5-carboxylate, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium tri Fluoroacetate, tetrabutylphosphonium ⁇ -lipoate, tetrabutylphosphonium formate, tetrabutylphosphonium lactate, bis (tetrabutylphosphonium) tartrate, tetrabutylphosphonium hippurate, tetrabutylphosphonium N-methylhippurate, benzoyl-DL -Alanine tetrabutylphosphonium salt, N-acetylphenylalanine tetrabutylphosphonium salt, 2,6-di-tert-butylphenoltetrabutylphospho Um salt,
- a precursor composed of a cation moiety such as an alkylimidazolium, alkylpyridinium, alkylammonium and alkylsulfonium ions and an anion moiety containing a halogen is added to NaBF 4 , NaPF 6 , CF 3 SO 3
- the content of the curing agent in the thermosetting resin composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, and still more preferably based on the entire nonvolatile content of the thermosetting resin composition. Is 1 to 30% by mass. When the content is less than 0.1% by mass, sufficient curability may not be obtained. Conversely, when the content is more than 50% by mass, the storage stability of the thermosetting resin composition is increased. It may be damaged.
- the content of the ionic liquid is 100 parts by mass of the epoxy resin (non-volatile component) from the viewpoint of moisture barrier properties of the cured product of the thermosetting resin composition. The amount is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass.
- thermosetting resin composition of the present invention contains semi-calcined hydrotalcite as an inorganic filler. That is, the thermosetting resin composition of the present invention contains an inorganic filler containing semi-calcined hydrotalcite. Hydrotalcite can be classified into unfired hydrotalcite, semi-fired hydrotalcite, and fired hydrotalcite.
- Unfired hydrotalcite is, for example, a metal hydroxide having a layered crystal structure typified by natural hydrotalcite (Mg 6 Al 2 (OH) 16 CO 3 ⁇ 4 H 2 O), for example, And a layer [Mg 1-X Al X (OH) 2 ] X + serving as a basic skeleton and an intermediate layer [(CO 3 ) X / 2 ⁇ mH 2 O] X- .
- unfired hydrotalcite 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 above-mentioned unfired natural hydrotalcite and hydrotalcite-like compound, using the composition formula.
- the present invention is characterized by using this semi-calcined hydrotalcite.
- 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.
- Semi-baked hydrotalcite usually has a saturated water absorption of 1% by mass or more and less than 20% by mass.
- the unsintered hydrotalcite has a saturated water absorption of less than 1% by mass
- the calcined hydrotalcite has a saturated water absorption of 20% by mass or more.
- the saturated water absorption is 1.5 g of uncalcined hydrotalcite, semi-calcined hydrotalcite or calcined hydrotalcite with a balance, and after measuring the initial mass, 60 ° C. and 90% under atmospheric pressure.
- the saturated water absorption rate of the semi-fired hydrotalcite is preferably 3% by mass or more and less than 20% by mass, more preferably 5% by mass or more and less than 20% by mass.
- unfired hydrotalcite, semi-fired hydrotalcite and fired hydrotalcite can be distinguished by the thermogravimetric reduction rate measured by thermogravimetric analysis.
- the semi-calcined hydrotalcite has a thermal weight loss rate at 280 ° C. of less than 15%, and the thermal weight loss rate at 380 ° C. is 12% or more.
- the thermal weight reduction rate at 280 ° C. of the unfired hydrotalcite is 15% or more
- the thermal weight reduction rate at 380 ° C. of the sintered hydrotalcite is less than 12%.
- thermogravimetric analysis TG / DTA ⁇ ⁇ ⁇ ⁇ ⁇ EXSTAR6300 manufactured by Hitachi High-Tech Science Co., Ltd. was used, and 5 mg of hydrotalcite was weighed in an aluminum sample pan, and it was opened without a lid, under an atmosphere with a nitrogen flow rate of 200 mL / min. , From 30 ° C. to 550 ° C. at a rate of temperature increase of 10 ° C./min. From the mass when the predetermined temperature is reached and the mass before heating, the thermal weight loss rate is calculated using the above formula (ii). Can be sought.
- unfired hydrotalcite, semi-fired hydrotalcite and fired hydrotalcite can be distinguished by the peak and relative intensity ratio measured by soot 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 diffraction intensity of the peak or shoulder appearing on the low angle side and the peak or shoulder appearing on the high angle side.
- the intensity ratio falls outside the above range, and calcined hydrotalcite does not have a characteristic peak in the region of 8 ° to 18 °, but has a characteristic peak at 43 °.
- the line diffraction measurement was performed using a powder X-ray diffractometer (manufactured by PANalytical, Empyrean) with an anti-cathode CuK ⁇ (1.5405 mm), voltage: 45 V, current: 40 mA, sampling width: 0.0260 °, scanning speed: 0.0657.
- 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 the semi-calcined hydrotalcite is 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, manufactured by Mountec Co., Ltd.) according to the BET method. be able to.
- 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 diameter of the semi-calcined hydrotalcite is the median diameter of the particle size distribution when the particle size distribution is created on a volume basis by laser diffraction scattering particle size distribution measurement (JIS Z 8825).
- Semi-baked hydrotalcite can be surface-treated with a surface treatment agent.
- 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. These can use 1 type (s) or 2 or more types.
- alkylsilanes include methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane, octyltriethoxysilane, and n-octadecyl. Examples thereof include dimethyl (3- (trimethoxysilyl) propyl) ammonium chloride. These can use 1 type (s) or 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-aminopropylto Amino silanes such as methoxysilane, N-methylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane Coupling agents; Ureido silane coupling agents such as 3-
- the surface treatment of the semi-fired hydrotalcite is performed, for example, by adding and spraying the surface treatment agent and stirring for 5 to 60 minutes while stirring and dispersing the untreated semi-fired hydrotalcite at room temperature with a mixer.
- 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 adding the higher fatty acid, alkylsilanes or silane coupling agent is also possible.
- the amount of the surface treatment agent used varies depending on the type of the semi-fired hydrotalcite or the type of the surface treatment agent, but is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the semi-fired hydrotalcite that has not been surface-treated. .
- the surface-treated semi-calcined hydrotalcite is also included in the “semi-calcined hydrotalcite” in the present invention.
- the content of the semi-fired hydrotalcite in the thermosetting resin composition of the present invention is not particularly limited as long as the effect of the present invention is exhibited, but per whole nonvolatile content of the thermosetting resin composition, 5 to 60% by mass is preferable, 10 to 50% by mass is more preferable, and 25 to 50% by mass is further preferable. Since semi-calcined hydrotalcite is excellent in moisture absorption performance, the sealing performance of the resulting cured product is improved if its content is increased. However, if the content exceeds 60% by mass, the viscosity of the thermosetting resin composition increases, and the adhesion between the substrate to be sealed and the thermosetting resin composition decreases due to a decrease in wettability. However, the strength of the cured product tends to decrease and become brittle.
- the amount of water in the sealing layer increases due to the interlayer water of the semi-fired hydrotalcite, for example, in the manufacture of an organic EL device, a light emitting material (light emission) due to moisture in the sealing layer
- a light emitting material due to moisture in the sealing layer
- thermosetting resin composition of the present invention calcined hydrotalcite may be contained, but the content thereof is preferably 0 to 20% by mass, based on the entire nonvolatile content of the thermosetting resin composition, 0 to 15% by mass is more preferable, 0 to 10% by mass is further preferable, and 0 to 5% by mass is most preferable. Since the calcined hydrotalcite has a large saturated water absorption amount, if its content exceeds 20% by mass, the moisture intake rate tends to decrease due to an increase in the rate of water intake into the sealed body.
- the mass ratio of semi-calcined hydrotalcite: calcined hydrotalcite is preferably 50:50 to 100: 0, more preferably 52:48 to 100: 0, and still more preferably 55:45 to 100: 0. .
- uncalcined hydrotalcite may be contained in the thermosetting resin composition of the present invention, its content is preferably 0 to 20% by mass based on the entire nonvolatile content of the thermosetting resin composition. Is more preferably from 10 to 10% by weight, further preferably from 0 to 5% by weight, most preferably 0% by weight. Since the unburned hydrotalcite has a high water content, if it exceeds 20% by mass, there is a concern that the occurrence of dark spots in the initial stage increases as in the case of the semi-fired hydrotalcite.
- the mass ratio of semi-fired hydrotalcite: unfired hydrotalcite is preferably 50:50 to 100: 0, more preferably 55:45 to 100: 0, and still more preferably 60:40 to 100: 0. More preferably, it is 65:35 to 100: 0, and particularly preferably 70:30 to 100: 0.
- examples of the calcined hydrotalcite include “KW-2200” (manufactured by Kyowa Chemical Industry Co., Ltd., average particle size: 400 nm, BET specific surface area: 146 m 2 / g). Examples thereof include “DHT-4A” (manufactured by Kyowa Chemical Industry Co., Ltd., average particle size: 400 nm, BET specific surface area: 10 m 2 / g).
- the thermosetting resin composition of the present invention may contain a curing accelerator for the purpose of adjusting the curing time.
- the curing accelerator include an organic phosphine compound, an imidazole compound, an amine adduct compound (for example, an epoxy adduct compound obtained by stopping the addition reaction of a tertiary amine to an epoxy resin, etc.), and a tertiary amine compound.
- Etc Specific examples of the organic phosphine compound include TPP, TPP-K, TPP-S, and TPTP-S (manufactured by Hokuko Chemical Co., Ltd.).
- imidazole compound examples include Curazole 2MZ, 2E4MZ, C11Z, C11Z-CN, C11Z-CNS, C11Z-A, 2MZOK, 2MA-OK, and 2PHZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.).
- Specific examples of amine adduct compounds include Fuji Cure (Fuji Kasei Kogyo Co., Ltd.).
- tertiary amine compounds include DBU (1,8-diazabicyelo [5.4.0] undec-7-ene), DBU 2-ethylhexanoate, octylate and other DBU-organic acid salts, U And aromatic dimethylurea such as U-3503T (manufactured by San Apro), and the like.
- urea compounds are preferable from the viewpoint of moisture resistance, and aromatic dimethylurea is particularly preferably used.
- the content thereof is preferably 0.05 to 5% by mass, more preferably 0.1 to 5% by mass, based on the entire nonvolatile content of the thermosetting resin composition. If this content is less than 0.05% by mass, curing tends to be slow, and a long thermosetting time tends to be required. If it exceeds 5% by mass, the storage stability of the thermosetting resin composition is lowered. Tend to.
- the thermosetting resin composition of the present invention may contain a silane coupling agent.
- 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 agent; Ureido silane coupling agent such
- a silane coupling agent When a silane coupling agent is used, its content is preferably 0.5 to 10% by mass, more preferably 0.5 to 5% by mass, based on the entire nonvolatile content of the thermosetting resin composition.
- thermosetting resin composition of the present invention is provided with flexibility to a sealing layer obtained by curing the thermosetting resin composition, and a thermosetting resin composition when preparing a sealing sheet.
- a thermoplastic resin can be contained.
- the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyethersulfone resin, polysulfone resin, polyester resin, (meth) acrylic polymer, and the like. These thermoplastic resins may use only 1 type and may use 2 or more types together.
- the weight average molecular weight of the thermoplastic resin is preferably 15,000 or more, and more preferably 20,000 or more.
- this weight average molecular weight is preferably 1,000,000 or less, and more preferably 800,000 or less.
- the weight average molecular weight in the present invention is measured by gel permeation chromatography (GPC) method (polystyrene conversion).
- GPC gel permeation chromatography
- the weight average molecular weight measured by the GPC method is 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.
- chloroform or the like as a phase the measurement can be performed at a column temperature of 40 ° C., and a standard polystyrene calibration curve can be used.
- thermoplastic resin a phenoxy resin is particularly preferable.
- the phenoxy resin has good compatibility with a thermosetting resin (particularly an epoxy resin), and advantageously acts on the moisture barrier property of a cured product obtained from the thermosetting resin composition.
- the weight average molecular weight of the phenoxy resin is preferably 15,000 or more, more preferably 20,000 or more, preferably 1,000,000 or less, more preferably 800,000 or less.
- Suitable phenoxy resins include one or more skeletons selected from bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, and norbornene skeleton. The thing which has. One or more phenoxy resins can be used.
- phenoxy resins examples include YX7200B35 (biphenyl skeleton-containing phenoxy resin), 1256 (bisphenol A skeleton-containing phenoxy resin), and YX6954BH35 (bisphenolacetophenone skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical Corporation.
- thermosetting resin composition of the present invention contains a thermoplastic resin (particularly a phenoxy resin), the content is preferably 1 to 40% by mass based on the entire nonvolatile content of the thermosetting resin composition. More preferable is 30% by mass.
- thermosetting resin composition of the present invention the moisture blocking property of the cured product of the thermosetting resin composition, the coating property of the thermosetting resin composition varnish when preparing a sealing sheet (prevention of repelling).
- the thermosetting resin composition of the present invention can further contain an inorganic filler other than the semi-fired hydrotalcite.
- inorganic fillers include, for example, talc, silica, alumina, barium sulfate, clay, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate in addition to the above-mentioned uncalcined hydrotalcite and calcined hydrotalcite.
- One or more inorganic fillers can be used.
- the content of the entire inorganic filler including the semi-fired hydrotalcite needs to be 20 to 60% by mass with respect to the entire nonvolatile content of the thermosetting resin composition.
- the total content of the inorganic filler including semi-baked hydrotalcite is preferably 57% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less, preferably 22% by mass or more, more preferably Is 25% by mass or more. If the content of the entire inorganic filler is too large, the viscosity of the thermosetting resin composition will increase and the wettability to the adherend will decrease. The strength tends to decrease and become brittle.
- the primary particle size of the inorganic filler is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less.
- a primary particle having a particle size of 0.001 to 3 ⁇ m, more preferably 0.005 to 2 ⁇ m can be used.
- the particle form of the inorganic filler is not particularly limited, and those having a substantially spherical shape, a rectangular parallelepiped shape, a plate shape, a linear shape such as a fiber, or a branched shape can be used.
- talc, silica, zeolite, titanium oxide, alumina, zirconium oxide, silicate, mica, magnesium hydroxide, aluminum hydroxide and the like are preferable, talc and silica are more preferable, and talc is particularly preferable.
- silica amorphous silica, fused silica, crystalline silica, synthetic silica wet silica, dry silica, colloidal silica (water dispersion type, organic solvent dispersion type, gas phase silica, etc.) is preferable, and it is difficult to precipitate and settle. From the standpoint of easy compounding, organic solvent-dispersed colloidal silica (organosilica sol) is particularly preferred.
- talc As examples of talc, “FG-15” (average particle size: 1.4 ⁇ m), “D-1000” (average particle size: 1.0 ⁇ m), “D-600” (average particle size: 0.6 ⁇ m) manufactured by Nippon Talc Co., Ltd. Etc.
- the content of silica is preferably 0 to 10% by mass, more preferably 0 to 8% by mass, and further preferably 0 to 5% by mass based on the entire nonvolatile content of the thermosetting resin composition. That is, the thermosetting resin composition of the present invention preferably contains no silica or 10% by mass or less of silica, and the composition contains no silica or 8% by mass or less. It is more preferable to contain silica, and the composition preferably does not contain silica or more preferably contains 5% by mass or less of silica (note that the content of silica is a thermosetting resin composition). Is the value per non-volatile content of). When there is too much content of silica, it will become the tendency for adhesiveness to fall.
- thermosetting resin composition contains talc, the content thereof is preferably 0.5 to 40% by mass, more preferably 0.5 to 30% by mass, based on the entire nonvolatile content of the thermosetting resin composition. 0.5 to 25% by mass is more preferable, and 0.5 to 20% by mass is particularly preferable.
- the ratio of a thermosetting resin and a semi-baking hydrotalcite component will decrease too much, and it will become the tendency for the sealing performance of the hardened
- the content of the semi-calcined hydrotalcite in the thermosetting resin composition containing talc is preferably 5 to 59.5% by mass, more preferably 10 to 50% by mass, based on the entire nonvolatile content of the curable resin composition. Preferably, it is 25 to 50% by mass.
- the inorganic filler in the thermosetting resin composition of the present invention is preferably composed of only semi-calcined hydrotalcite or semi-calcined hydrotalcite and talc, more preferably semi-calcined hydrotalcite and talc.
- the content of the semi-calcined hydrotalcite with respect to 100 parts by mass of the whole inorganic filler is preferably 20 to 100 parts by mass, more preferably 25 to 100 parts by mass, and further preferably 30 to 99.5 parts by mass. is there.
- thermosetting resin composition of the present invention may further contain other additives different from the above components.
- additives include organic fillers such as rubber particles, silicone powder, nylon powder, and fluororesin powder; thickeners such as olben and benton; silicone-based, fluorine-based, and polymer-based antifoaming agents. Or a leveling agent; Adhesion imparting agents, such as a triazole compound, a thiazole compound, a triazine compound, and a porphyrin compound;
- thermosetting resin composition of the present invention can be produced by mixing the above-described components and, if necessary, a solvent or the like using a kneading roller or a rotary mixer.
- thermosetting resin composition of the present invention and the sealing sheet described later are, for example, electronic components such as semiconductors, solar cells, high-brightness LEDs, LCDs, and EL elements, preferably optical semiconductors such as organic EL elements and solar cells. Used for sealing.
- the thermosetting resin composition and the sealing sheet of the present invention are particularly suitably used for sealing organic EL elements. Specifically, in order to protect the light emitting part of the organic EL element from the outside by applying it to the upper part and / or the periphery (side part) of the light emitting part of the organic EL element, A stop sheet can be used.
- the sealing layer can be formed by directly applying the thermosetting resin composition of the present invention to an object to be sealed and curing the coating film. Further, a sealing sheet in which a layer of the thermosetting resin composition of the present invention is formed on a support is prepared, and the sealing sheet is laminated on a necessary portion of the sealing target to thermoset the resin composition. You may form a sealing layer by transcribe
- the sealing sheet in which the layer of the thermosetting resin composition of the present invention is formed on a support is a method known to those skilled in the art, for example, thermosetting in which the thermosetting resin composition is dissolved in an organic solvent.
- thermosetting in which the thermosetting resin composition is dissolved in an organic solvent.
- the support used for the sealing sheet examples include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes referred to as “PET”), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and the like.
- PET polyethylene terephthalate
- the plastic film is mentioned.
- PET is particularly preferable.
- the support may be a metal foil such as an aluminum foil, a stainless steel foil, or a copper foil.
- the support may be subjected to a release treatment in addition to a mat treatment and a corona treatment. Examples of the release treatment include a release treatment with a release agent such as a silicone resin release agent, an alkyd resin release agent, and a fluororesin release agent.
- a plastic film having a barrier layer may be used as a support.
- the barrier layer include nitrides such as silicon nitride, oxides such as aluminum oxide, stainless steel foil, and metal foil of aluminum foil.
- the plastic film include the above-described plastic film.
- a commercial product may be used as the plastic film having the barrier layer.
- the film which compound-laminated metal foil and the plastic film may be sufficient.
- commercially available products of polyethylene terephthalate film with aluminum foil include “PET Tsuki AL1N30” manufactured by Tokai Toyo Aluminum Sales Co., “PET Tsuki AL3025” manufactured by Fukuda Metals.
- the support may be subjected to a release treatment using a silicone resin release agent, an alkyd resin release agent, a fluororesin release agent, a mat treatment, a corona treatment, or the like.
- a release treatment using a silicone resin release agent, an alkyd resin release agent, a fluororesin release agent, a mat treatment, a corona treatment, or the like.
- the release layer is also regarded as a part of the support.
- the thickness of the support is not particularly limited, but is preferably 20 to 200 ⁇ m, more preferably 20 to 125 ⁇ m, from the viewpoint of handleability and the like.
- organic solvent examples include ketones such as acetone, methyl ethyl ketone (hereinafter abbreviated as “MEK”), cyclohexanone, and acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate.
- ketones such as acetone, methyl ethyl ketone (hereinafter abbreviated as “MEK”), cyclohexanone, and acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate.
- Carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.
- Drying conditions are not particularly limited, but usually about 50 to 100 ° C. and about 3 to 15 minutes are preferable.
- the thickness of the thermosetting resin composition layer after drying is usually 3 ⁇ m to 200 ⁇ m, preferably 5 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 50 ⁇ m.
- the layer of the thermosetting resin composition may be protected with a protective film.
- a protective film By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches.
- the protective film is preferably a plastic film similar to the support. Further, the protective film may be subjected to a release treatment in addition to the mat treatment and the corona treatment.
- the thickness of the protective film is not particularly limited, but is usually 1 to 150 ⁇ m, preferably 10 to 100 ⁇ m.
- the sealing sheet has a moisture-proof and high-permeability support for the support, the sealing sheet is laminated on the necessary portion of the object to be sealed, and the thermosetting resin is left as it is.
- a sealing structure having high moisture resistance can be formed.
- a substrate having moisture resistance and high transmittance include a plastic film in which an inorganic substance such as silicon oxide (silica), silicon nitride, SiCN, and amorphous silicon is deposited on the surface.
- the plastic film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate, and polyimide.
- PET is particularly preferable.
- examples of commercially available moisture-proof plastic films include Tech Barrier HX, AX, LX, L series (Mitsubishi Plastics) and X-BARRIER (Mitsubishi Plastics) with improved moisture resistance. It is done.
- a support having a multilayer structure of two or more layers may be used.
- the resin composition layer is usually cured by thermal curing.
- the means include a hot air circulation oven, an infrared heater, a heat gun, a high frequency induction heating device, and heating by pressure bonding of a heat tool.
- the lower limit of each of the curing temperature and the curing time is 50 ° C. from the viewpoint of bonding the cured thermosetting resin composition layer (sealing layer) to the object to be sealed with sufficient adhesive strength.
- the above is preferable, 55 ° C. or higher is more preferable, and the curing time is preferably 10 minutes or longer, more preferably 20 minutes or longer.
- % and “part” other than the reaction rate and thermal weight loss rate of the cured product mean “% by mass” and “part by mass”, respectively.
- hydrotalcite all commercially available hydrotalcite was used after measuring the saturated water absorption rate, thermal weight loss rate, and X-ray diffraction peak value.
- N-acetylglycine tetrabutylphosphonium salt was synthesized by the following procedure. 3.50 g of N-acetylglycine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at 0 ° C. to 20.0 g of a 41.4% tetrabutylphosphonium hydroxide aqueous solution (manufactured by Hokuko Chemical Co., Ltd.) and stirred for 10 minutes. . The reaction solution was concentrated using an evaporator at a pressure of 40 to 50 mmHg at 60 to 80 ° C. for 2 hours and at 90 ° C. for 5 hours.
- the obtained concentrate was dissolved in 14.2 ml of ethyl acetate (manufactured by Junsei Chemical Co., Ltd.) at room temperature to prepare a solution, and the obtained solution was 70 to 90 at a pressure of 40 to 50 mmHg using an evaporator. Concentration at 3 ° C. for 3 hours gave 11.7 g (purity: 96.9%) of N-acetylglycine tetrabutylphosphonium salt as an oily compound.
- N-acetylglycine tetrabutylphosphonium salt is described as “TBP ⁇ N-Ac-Gly”.
- Example 1 57 parts of liquid bisphenol A type epoxy resin (Mitsubishi Chemical "jER828EL", epoxy equivalent of about 190), 1.5 parts of silane coupling agent (Shin-Etsu Chemical "KBM-403"), talc powder (Japan) 16 parts of “FG-15” manufactured by Talc Co., Ltd. and 22 parts of commercially available hydrotalcite A (BET specific surface area 13 m 2 / g) were kneaded and dispersed by a three-roll mill to obtain a mixture.
- silane coupling agent Shin-Etsu Chemical "KBM-403
- talc powder Japan 16 parts of “FG-15” manufactured by Talc Co., Ltd.
- 22 parts of commercially available hydrotalcite A BET specific surface area 13 m 2 / g
- thermosetting resin composition varnish is dried on a support (polyethylene terephthalate film treated with an alkyd release agent, thickness 38 ⁇ m, hereinafter abbreviated as “release PET film”).
- release PET film polyethylene terephthalate film treated with an alkyd release agent, thickness 38 ⁇ m, hereinafter abbreviated as “release PET film”.
- thermosetting resin composition varnish was produced in the same manner as in Example 1 except that hydrotalcite B (BET specific surface area 15 m 2 / g, 15 parts) was used instead of hydrotalcite A (22 parts). A sealing sheet was obtained.
- hydrotalcite B BET specific surface area 15 m 2 / g, 15 parts
- Example 3 Hydrotalcite A (14 parts) and hydrotalcite C (BET specific surface area 146 m 2 / g, 5 parts) mixed hydrotalcite (BET specific surface area 48 m 2 / g) instead of hydrotalcite A (22 parts)
- a thermosetting resin composition varnish was produced in the same manner as in Example 1 except that a sealing sheet was obtained.
- Example 4 Thermosetting resin as in Example 1 except that hydrotalcite A (49 parts) was used instead of hydrotalcite A (22 parts) and talc FG-15 (16 parts) was not used. A composition varnish was produced to obtain a sealing sheet.
- thermosetting resin composition varnish was produced in the same manner as in Example 1 except that hydrotalcite E (BET specific surface area 9 m 2 / g, 22 parts) was used instead of hydrotalcite A (22 parts). A sealing sheet was obtained.
- hydrotalcite E BET specific surface area 9 m 2 / g, 22 parts
- Example 6 Example 1 except that hydrotalcite F (BET specific surface area 9 m 2 / g, 43 parts) was used instead of hydrotalcite A (22 parts) and talc FG-15 (16 parts) was not used. In the same manner as above, a thermosetting resin composition varnish was produced to obtain a sealing sheet.
- hydrotalcite F BET specific surface area 9 m 2 / g, 43 parts
- talc FG-15 (16 parts) was not used.
- thermosetting resin composition varnish was produced in the same manner as in Example 1 except that hydrotalcite D (BET specific surface area 10 m 2 / g, 22 parts) was used instead of hydrotalcite A (22 parts). A sealing sheet was obtained.
- hydrotalcite D BET specific surface area 10 m 2 / g, 22 parts
- thermosetting resin composition varnish was produced in the same manner as in Example 1 to obtain a sealing sheet.
- thermosetting resin composition varnish was produced in the same manner as in Example 1 except that hydrotalcite A (22 parts) was not used and the amount of talc FG-15 was changed to 29 parts. A sheet was obtained.
- thermosetting resin composition varnish was produced in the same manner as in Example 1 except that hydrotalcite C (15 parts) was used instead of hydrotalcite A (22 parts) to obtain a sealing sheet. .
- thermosetting resin composition varnish was produced in the same manner as in Example 1 except that hydrotalcite C (24 parts) was used instead of hydrotalcite A (22 parts) and talc FG-15 (16 parts). And the sheet
- thermosetting resin composition varnish was produced to obtain a sealing sheet.
- Powder X-ray diffraction measurement was performed using a powder X-ray diffractometer (manufactured by PANalytical, Empyrean), 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.
- hydrotalcite A, B, E and F are “semi-calcined hydrotalcite” and hydrotalcite C is “calcined hydrotalcite”. Yes, hydrotalcite D is “unfired hydrotalcite”.
- the types of these hydrotalcites A to F are also shown in Table 1.
- the sample for evaluation containing a calcium film was used as a model of an organic EL device containing an organic EL element.
- the distance from the end of the sample for evaluation to the calcium membrane was measured with a Measuring Microscope MF-U manufactured by Mitutoyo Corporation, and this value was designated as X2.
- an evaluation sample was put into a constant temperature and humidity chamber set at a temperature of 85 ° C. and a humidity of 85% RH.
- the sealing distance X1 (mm) from the end of the sample for evaluation after introduction into the thermostatic chamber to the calcium membrane is the seal from the end of the sample for evaluation before introduction into the thermostatic chamber to the calcium membrane.
- the sample for evaluation was taken out from the constant temperature and humidity chamber at a time increased by 0.1 mm from the stopping distance X2 (mm), and the time was defined as a decrease start time t (hour).
- thermosetting resin composition layer having a thickness of 20 ⁇ m was folded on a hot plate at 50 ° C., and a resin composition layer having a thickness of 0.3 mm was taken out.
- the removed thermosetting resin composition layer was heat-cured at 110 ° C. for 30 minutes to 1 hour.
- a DSC EXSTAR7000X manufactured by Hitachi High-Tech Science Co., Ltd. weighed 3 mg each of the thermosetting resin composition sample before and after curing in an aluminum sample pan, and in a state of covering with a nitrogen flow rate of 50 mL / min, Measurement was performed from 15 ° C. to 280 ° C.
- thermogravimetric analysis measurement before and after moisture absorption was performed under the above-described conditions described in this specification.
- thermosetting resin composition layer having a thickness of 0.3 mm, which was confirmed to have a DSC reaction rate of 70% or more, was used as a sample before moisture absorption. Furthermore, 1 g of the cured product of the thermosetting resin composition layer was allowed to stand for 100 hours in a small environmental tester (SH-222 manufactured by Espec Corp.) set at 85 ° C. and 85% RH (relative humidity) under atmospheric pressure. A cured product of the thermosetting resin composition layer after moisture absorption was prepared and used as a sample after moisture absorption.
- SH-222 manufactured by Espec Corp. set at 85 ° C. and 85% RH (relative humidity) under atmospheric pressure.
- Thermogravimetric analysis was performed using Hitachi High-Tech Science TG / DTA EXSTAR6300, and weighed 10 mg of each sample before and after moisture absorption into an aluminum sample pan. An atmosphere with a nitrogen flow rate of 200 mL / min was opened without a lid. The temperature was increased from 30 ° C. to 550 ° C. at a temperature increase rate of 10 ° C./min. Using the above formula (ii), the thermal weight reduction rate at 280 ° C. and 380 ° C. is obtained, the thermal weight reduction rate at 280 ° C. of the cured product before moisture absorption is X 1 (%), and the thermal weight reduction rate at 380 ° C.
- thermogravimetric decrease rate at 280 ° C. of the cured product after moisture absorption is X 2 (%)
- thermogravimetric decrease rate at 380 ° C. is Y 2 (%)
- Table 2 The results are shown in Table 2.
- thermosetting resin composition for sealing From the thermosetting resin composition for sealing according to the present invention, it is possible to obtain a sealing layer in which moisture barrier properties are maintained for a longer time. Therefore, by using the thermosetting resin composition for sealing of the present invention for sealing an element that is sensitive to moisture such as an organic EL element, a device such as an organic EL device having a greatly extended element lifetime is provided. be able to.
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Abstract
Description
[1] (A)熱硬化性樹脂、(B)硬化剤、および無機充填剤として(C)半焼成ハイドロタルサイトを含む封止用の熱硬化性樹脂組成物であって、
吸湿前の該熱硬化性樹脂組成物の硬化物の熱重量分析による280℃における熱重量減少率をX1(%)、380℃における熱重量減少率をY1(%)とし、吸湿後の該熱硬化性樹脂組成物の硬化物の熱重量分析による280℃における熱重量減少率をX2(%)、380℃における熱重量減少率をY2(%)としたとき、2%≦X2-X1、且つY2-Y1≦10%の関係を満たし、
半焼成ハイドロタルサイトを含む無機充填剤全体の含有量が、熱硬化性樹脂組成物の不揮発分全体当たり20~60質量%である熱硬化性樹脂組成物。
[2] 半焼成ハイドロタルサイトの含有量が、熱硬化性樹脂組成物の不揮発分全体当たり5~60質量%である前記[1]に記載の熱硬化性樹脂組成物。
[3] 無機充填剤としてタルクをさらに含む前記[1]に記載の熱硬化性樹脂組成物。
[4] 硬化性樹脂組成物の不揮発分全体当たり、半焼成ハイドロタルサイトの含有量が5~59.5質量%であり、且つタルクの含有量が0.5~40質量%である前記[3]に記載の熱硬化性樹脂組成物。
[5] 熱硬化性樹脂が、エポキシ樹脂である前記[1]~[4]のいずれか一つに記載の熱硬化性樹脂組成物。
[6] エポキシ樹脂の含有量が、熱硬化性樹脂組成物の不揮発分全体当たり10~79.9質量%である前記[5]に記載の熱硬化性樹脂組成物。
[7] 硬化剤の含有量が、熱硬化性樹脂組成物の不揮発分全体当たり0.1~50質量%である前記[1]~[6]のいずれか一つに記載の熱硬化性樹脂組成物。
[8] シリカの含有量が、熱硬化性樹脂組成物の不揮発分全体当たり0~10質量%である前記[1]~[7]のいずれか一つに記載の熱硬化性樹脂組成物。
[9] 有機EL素子の封止用である前記[1]~[8]のいずれか一つに記載の熱硬化性樹脂組成物。
[10] 前記[1]~[8]のいずれか一つに記載の熱硬化性樹脂組成物の層が支持体上に形成されている封止用シート。
[11] 有機EL素子の封止用である前記[10]に記載の封止用シート。
[12] 前記[1]~[8]のいずれか一つに記載の熱硬化性樹脂組成物の硬化物で有機EL素子が封止されている有機ELデバイス。
本発明の熱硬化性樹脂組成物は、吸湿前の該熱硬化性樹脂組成物の硬化物の熱重量分析による280℃における熱重量減少率をX1(%)、380℃における熱重量減少率をY1(%)とし、吸湿後の該熱硬化性樹脂組成物の硬化物の熱重量分析による280℃における熱重量減少率をX2(%)、380℃における熱重量減少率をY2(%)としたとき、2%≦X2-X1、且つY2-Y1≦10%の関係を満たすことを特徴の一つとする。X2-X1が2%未満であると、硬化物の吸湿性能が低くなる傾向となり、水分遮蔽性に劣ることとなる。またY2-Y1が10%を超えると、硬化物の水分取り込み速度が高くなる傾向となり、水分遮蔽性に劣ることとなる。
反応率(%)=100×(硬化後の熱硬化性樹脂組成物の反応熱量)/(硬化前の熱硬化性樹脂組成物の反応熱量) (i)
から算出することができる。
熱重量減少率(%)
=100×(加熱前の質量(μg)-所定温度に達した時の質量(μg))/加熱前の質量(μg) (ii)
から算出することができる。
本発明の熱硬化性樹脂組成物は、熱硬化性樹脂を含む。熱硬化性樹脂としては、特に限定されないが、エポキシ樹脂が好ましく用いられる。
本発明の熱硬化性樹脂組成物は、硬化剤を含有する。すなわち、封止層は、樹脂組成物を硬化させて得られる硬化物である。硬化剤は、熱硬化性樹脂組成物を硬化する機能を有するものであれば特に限定されないが、熱硬化性樹脂組成物の硬化処理時における有機EL素子等の発光素子の熱劣化を抑制する観点から、140℃以下(好ましくは120℃以下)の温度下で、熱硬化性樹脂組成物を硬化し得るものが好ましい。硬化剤は、1種のみを使用してもよく、2種以上を併用してもよい。
本発明の熱硬化性樹脂組成物は、無機充填剤として半焼成ハイドロタルサイトを含む。即ち、本発明の熱硬化性樹脂組成物は、半焼成ハイドロタルサイトを含む無機充填剤を含有する。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。
(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。
(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。
飽和吸水率(質量%)
=100×(吸湿後の質量-初期質量)/初期質量 (iii)
で求めることができる。
本発明の熱硬化性樹脂組成物は、硬化時間を調整する等の目的で硬化促進剤を含有してもよい。硬化促進剤としては、例えば、有機ホスフィン化合物、イミダゾール化合物、アミンアダクト化合物(例えば、エポキシ樹脂への3級アミンの付加反応を、途中で止めることによって得られるエポキシアダクト化合物等)、3級アミン化合物などが挙げられる。有機ホスフィン化合物の具体例としては、TPP、TPP-K、TPP-S、TPTP-S(北興化学工業社製)などが挙げられる。イミダゾール化合物の具体例としては、キュアゾール2MZ、2E4MZ、C11Z、C11Z-CN、C11Z-CNS、C11Z-A、2MZOK、2MA-OK、2PHZ(四国化成工業社製)などが挙げられる。アミンアダクト化合物の具体例としては、フジキュア(富士化成工業社製)などが挙げられる。3級アミン化合物の具体例としては、DBU(1,8-diazabicyelo[5.4.0]undec-7-ene)、DBUの2-エチルヘキサン酸塩、オクチル酸塩などのDBU-有機酸塩、U-3512T(サンアプロ社製)等の芳香族ジメチルウレア、U-3503N(サンアプロ社製)等の脂肪族ジメチルウレアなどが挙げられる。中でも耐湿性の点からウレア化合物が好ましく、芳香族ジメチルウレアが特に好ましく用いられる。硬化促進剤を使用する場合、その含有量は、熱硬化性樹脂組成物の不揮発分全体当たり、好ましくは0.05~5質量%、より好ましくは0.1~5質量%である。この含有量が0.05質量%未満であると、硬化が遅くなり、熱硬化時間が長く必要となる傾向にあり、5質量%を超えると、熱硬化性樹脂組成物の保存安定性が低下する傾向となる。
本発明の熱硬化樹脂組成物はシランカップリング剤を含有していてもよい。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。これらの中でも、ビニル系シランカップリング剤、エポキシ系シランカップリング剤が好ましく、エポキシ系シランカップリング剤が特に好ましい。シランカップリング剤は、1種または2種以上を使用することができる。
本発明の熱硬化性樹脂組成物には、熱硬化性樹脂組成物を硬化して得られる封止層への可撓性の付与、封止用シートを調製する際の熱硬化性樹脂組成物ワニスの塗工性(はじき防止)等の観点から、熱可塑性樹脂を含有させることができる。熱可塑性樹脂としては、例えば、フェノキシ樹脂、ポリビニルアセタール樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリエーテルスルホン樹脂、ポリスルホン樹脂、ポリエステル樹脂、(メタ)アクリル系ポリマー等を挙げることができる。これらの熱可塑性樹脂は、1種のみを使用してもよく、2種以上を併用してもよい。
本発明の熱硬化性樹脂組成物には、熱硬化性樹脂組成物の硬化物の水分遮断性、封止用シートを調製する際の熱硬化性樹脂組成物ワニスの塗工性(はじき防止)等の観点から、本発明の熱硬化性樹脂組成物に、半焼成ハイドロタルサイト以外の無機充填剤をさらに含有させることができる。そのような無機充填剤としては、上述した未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の他に、例えば、タルク、シリカ、アルミナ、硫酸バリウム、クレー、マイカ、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、酸化チタン、酸化ジルコニウム、ジルコン酸バリウム、ジルコン酸カルシウム、ケイ酸塩などが挙げられる。無機充填剤は1種または2種以上を使用できる。
本発明の熱硬化性樹脂組成物は、上述の成分とは異なるその他の添加剤をさらに含有していてもよい。このような添加剤としては、例えば、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;シリコーン系、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。
本発明の熱硬化性樹脂組成物は、上述の成分、および必要により溶媒等を、混練ローラーや回転ミキサーなどを用いて混合することによって製造することができる。
本発明の熱硬化性樹脂組成物および後述する封止用シートは、例えば、半導体、太陽電池、高輝度LED、LCD、EL素子等の電子部品、好ましくは有機EL素子、太陽電池等の光学半導体の封止に使用される。本発明の熱硬化性樹脂組成物および封止用シートは、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、本発明の熱硬化性樹脂組成物および封止用シートを用いることができる。
本発明の熱硬化性樹脂組成物の層が支持体上に形成されている封止用シートは、当業者に公知の方法、例えば、熱硬化性樹脂組成物が有機溶剤に溶解した熱硬化性樹脂組成物ワニスを調製し、該ワニスを支持体上に塗布し、さらに加熱、あるいは熱風吹きつけ等によって塗布された該ワニスを乾燥させて熱硬化性樹脂組成物の層を形成させることによって製造することができる。
本発明の熱硬化性樹脂組成物の硬化物で有機EL素子が封止されている有機ELデバイス等を製造する場合は、上記封止用シートを用いて封止を行うのが好適である。すなわち、封止用シートは樹脂組成物層が保護フィルムで保護されている場合はこれを剥離した後、封止用シートをその樹脂組成物層が封止対象物(例えば、有機EL素子形成基板上の有機EL素子等)に直接接するようにラミネートする。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。ラミネート後、支持体を剥離し、後述の樹脂組成物層の熱硬化作業を行なう。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、封止用シートをラミネートした後、支持体を剥離せず、そのまま後述の樹脂組成物層の熱硬化作業を行なう。
イオン液体硬化剤であるN-アセチルグリシンテトラブチルホスホニウム塩を以下の手順にて合成した。41.4%のテトラブチルホスホニウムハイドロキサイド水溶液(北興化学工業社製)20.0gに対し、0℃にてN-アセチルグリシン(東京化成工業社製)3.54gを加え、10分間攪拌した。エバポレーターを用いて40~50mmHgの圧力で、60~80℃にて2時間、90℃にて5時間、反応溶液を濃縮した。得られた濃縮物を、室温にて酢酸エチル(純正化学社製)14.2mlに溶解して溶液を調製し、得られた溶液を、エバポレーターを用いて40~50mmHgの圧力で、70~90℃にて3時間濃縮して、N-アセチルグリシンテトラブチルホスホニウム塩11.7g(純度:96.9%)をオイル状化合物として得た。なお、下記表2では、N-アセチルグリシンテトラブチルホスホニウム塩を「TBP・N-Ac-Gly」と記載する。
液状ビスフェノールA型エポキシ樹脂(三菱化学社製「jER828EL」、エポキシ当量約190)57部と、シランカップリング剤(信越化学工業社製「KBM-403」)1.5部と、タルク粉末(日本タルク社製「FG-15」)16部、および市販のハイドロタルサイトA(BET比表面積13m2/g)22部を混練後、3本ロールミルにて分散を行い、混合物を得た。硬化促進剤(サンアプロ社製「U-3512T」)1.5部をフェノキシ樹脂(三菱化学社製「YX7200B35」、MEK溶液、不揮発分35%))82.9部に溶解させた混合物に、先に調製した3本ロールミルにより分散した混合物と、固形ビスフェノールA型エポキシ樹脂(三菱化学社製「jER1001」、エポキシ当量約475)のMEK溶液(不揮発分80%、下記表2で「jER1001B80」と記載する)17.5部と、イオン液体硬化剤(N-アセチルグリシンテトラブチルホスホニウム塩)3部とを配合し、高速回転ミキサーで均一に分散してワニス状の熱硬化性樹脂組成物を得た。
ハイドロタルサイトA(22部)の代わりにハイドロタルサイトB(BET比表面積15m2/g、15部)を使用したこと以外は実施例1と同様にして熱硬化性樹脂組成物ワニスを製造し、封止用シートを得た。
ハイドロタルサイトA(22部)の代わりにハイドロタルサイトA(14部)とハイドロタルサイトC(BET比表面積146m2/g、5部)との混合ハイドロタルサイト(BET比表面積48m2/g)を使用したこと以外は実施例1と同様にして熱硬化性樹脂組成物ワニスを製造し、封止用シートを得た。
ハイドロタルサイトA(22部)の代わりにハイドロタルサイトA(49部)を使用し、タルクFG-15(16部)を使用しなかったこと以外は実施例1と同様にして熱硬化性樹脂組成物ワニスを製造し、封止用シートを得た。
ハイドロタルサイトA(22部)の代わりにハイドロタルサイトE(BET比表面積9m2/g、22部)を使用したこと以外は実施例1と同様にして熱硬化性樹脂組成物ワニスを製造し、封止用シートを得た。
ハイドロタルサイトA(22部)の代わりにハイドロタルサイトF(BET比表面積9m2/g、43部)を使用し、タルクFG-15(16部)を使用しなかったこと以外は実施例1と同様にして熱硬化性樹脂組成物ワニスを製造し、封止用シートを得た。
ハイドロタルサイトA(22部)の代わりにハイドロタルサイトD(BET比表面積10m2/g、22部)を使用したこと以外は実施例1と同様にして熱硬化性樹脂組成物ワニスを製造し、封止用シートを得た。
ハイドロタルサイトA(22部)の代わりにハイドロタルサイトC(10部)とハイドロタルサイトD(7部)との混合ハイドロタルサイト(BET比表面積90m2/g)を使用したこと以外は実施例1と同様にして熱硬化性樹脂組成物ワニスを製造し、封止用シートを得た。
ハイドロタルサイトA(22部)を使用せず、タルクFG-15の配合量を29部と変更したこと以外は実施例1と同様にして熱硬化性樹脂組成物ワニスを製造し、封止用シートを得た。
ハイドロタルサイトA(22部)の代わりにハイドロタルサイトC(15部)を使用したこと以外は実施例1と同様にして熱硬化性樹脂組成物ワニスを製造し、封止用シートを得た。
ハイドロタルサイトA(22部)およびタルクFG-15(16部)の代わりにハイドロタルサイトC(24部)を使用したこと以外は実施例1と同様にして熱硬化性樹脂組成物ワニスを製造し、封止用シートを得た。
ハイドロタルサイトAの配合量を22部から7部に変更し、タルクFG-15(16部)を使用せず、シリカSC2500-SQ(61部)を使用したこと以外は実施例1と同様にして熱硬化性樹脂組成物ワニスを製造し、封止用シートを得た。
各ハイドロタルサイトを天秤にて1.5g量りとり、初期質量を測定した。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時間静置して、吸湿後の質量を測定し、上記式(iii)を用いて飽和吸水率を求めた。結果を表1に示す。
日立ハイテクサイエンス社製TG/DTA EXSTAR6300を用いて、各ハイドロタルサイトの熱重量分析測定を行った。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10mg秤量し、蓋をせずオープンの状態で、窒素流量200mL/分の雰囲気下で、30℃から550℃まで10℃/分で昇温した。上記式(ii)を用いて、280℃と380℃における熱重量減少率を求めた。結果を表1に示す。
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」の条件で行った。2θが8~18°の範囲内で現れたスプリットした2つのピーク、または2つのピークの合成によりショルダーを有するピークを検出し、低角側に現れた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)を測定し、相対強度比(=低角側回折強度/高角側回折強度)を算出した。結果を表1に示す。
支持体としてアルミ箔/PET複合フィルム「PETツキAL1N30」(アルミ箔:30μm、PET:25μm、:東海東洋アルミ販売社製商品名)を用いたこと以外は各実施例および比較例と同様にして、各実施例および比較例と同じ樹脂組成物層を有する封止用シート得た。
X1=K√t
(式中、X1は、恒温恒湿槽への投入後の評価用サンプルの端部からカルシウム膜までの封止距離(mm)であり、tは、X1=X2+0.1となる減少開始時間(時間)であり、X2は恒温恒湿槽への投入前の評価用サンプルの端部からカルシウム膜までの封止距離(mm)である。)
に基づき、定数Kを算出した。
厚さ20μmの熱硬化性樹脂組成物層を50℃のホットプレート上で折り畳み、厚さ0.3mmの樹脂組成物層を取り出した。取り出した熱硬化性樹脂組成物層を110℃30分~1時間で加熱硬化させた。日立ハイテクサイエンス社製DSC EXSTAR7000Xを用いて、アルミニウム製のサンプルパンに硬化前後の熱硬化性樹脂組成物のサンプルをそれぞれ3mg秤量し、蓋をした状態で、窒素流量50mL/分の雰囲気下で、15℃から280℃まで昇温速度5℃/分の条件で測定を行い、得られた曲線から反応熱量(mJ/mg)を解析し、上記式(i)から反応率を算出した。結果を表2に示す。反応率が70%以上である硬化物を用いて、本明細書に記載した上述の条件で吸湿前後の熱重量分析測定を行った。
DSCでの反応率が70%以上となることを確認した厚さ0.3mmの熱硬化性樹脂組成物層の硬化物を、吸湿前のサンプルとして用いた。さらにその熱硬化性樹脂組成物層の硬化物1gを大気圧下、85℃、85%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100時間静置し、吸湿後の熱硬化性樹脂組成物層の硬化物を調製し、これを吸湿後のサンプルとして用いた。
Claims (12)
- (A)熱硬化性樹脂、(B)硬化剤、および無機充填剤として(C)半焼成ハイドロタルサイトを含む封止用の熱硬化性樹脂組成物であって、
吸湿前の該熱硬化性樹脂組成物の硬化物の熱重量分析による280℃における熱重量減少率をX1(%)、380℃における熱重量減少率をY1(%)とし、吸湿後の該熱硬化性樹脂組成物の硬化物の熱重量分析による280℃における熱重量減少率をX2(%)、380℃における熱重量減少率をY2(%)としたとき、2%≦X2-X1、且つY2-Y1≦10%の関係を満たし、
半焼成ハイドロタルサイトを含む無機充填剤全体の含有量が、熱硬化性樹脂組成物の不揮発分全体当たり20~60質量%である熱硬化性樹脂組成物。 - 半焼成ハイドロタルサイトの含有量が、熱硬化性樹脂組成物の不揮発分全体当たり5~60質量%である請求項1に記載の熱硬化性樹脂組成物。
- 無機充填剤としてタルクをさらに含む請求項1に記載の熱硬化性樹脂組成物。
- 硬化性樹脂組成物の不揮発分全体当たり、半焼成ハイドロタルサイトの含有量が5~59.5質量%であり、且つタルクの含有量が0.5~40質量%である請求項3に記載の熱硬化性樹脂組成物。
- 熱硬化性樹脂が、エポキシ樹脂である請求項1~4のいずれか一項に記載の熱硬化性樹脂組成物。
- エポキシ樹脂の含有量が、熱硬化性樹脂組成物の不揮発分全体当たり10~79.9質量%である請求項5に記載の熱硬化性樹脂組成物。
- 硬化剤の含有量が、熱硬化性樹脂組成物の不揮発分全体当たり0.1~50質量%である請求項1~6のいずれか一項に記載の熱硬化性樹脂組成物。
- シリカの含有量が、熱硬化性樹脂組成物の不揮発分全体当たり0~10質量%である請求項1~7のいずれか一項に記載の熱硬化性樹脂組成物。
- 有機EL素子の封止用である請求項1~8のいずれか一項に記載の熱硬化性樹脂組成物。
- 請求項1~8のいずれか一項に記載の熱硬化性樹脂組成物の層が支持体上に形成されている封止用シート。
- 有機EL素子の封止用である請求項10に記載の封止用シート。
- 請求項1~8のいずれか一項に記載の熱硬化性樹脂組成物の硬化物で有機EL素子が封止されている有機ELデバイス。
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