WO2017057708A1 - 封止用樹脂組成物 - Google Patents
封止用樹脂組成物 Download PDFInfo
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- WO2017057708A1 WO2017057708A1 PCT/JP2016/079084 JP2016079084W WO2017057708A1 WO 2017057708 A1 WO2017057708 A1 WO 2017057708A1 JP 2016079084 W JP2016079084 W JP 2016079084W WO 2017057708 A1 WO2017057708 A1 WO 2017057708A1
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- resin composition
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- polyolefin
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- 150000003918 triazines Chemical class 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- QLNOVKKVHFRGMA-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical group [CH2]CC[Si](OC)(OC)OC QLNOVKKVHFRGMA-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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
- C08K3/18—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
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
- C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09J201/06—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
-
- 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
- H10K50/844—Encapsulations
Definitions
- the present invention relates to a sealing resin composition, and more particularly to a sealing resin composition that can be suitably used for sealing an organic EL element.
- organic EL (Electroluminescence) element is a light-emitting element using an organic substance as a light-emitting material, and has been attracting attention in recent years because it can emit light with high luminance at a low voltage.
- organic EL elements are extremely sensitive to moisture, and the organic material itself is altered by moisture, resulting in a decrease in brightness, no light emission, the interface between the electrode and the organic EL layer being peeled off due to moisture, metal There is a problem that the metal oxide is oxidized to increase the resistance.
- thermosetting resin composition When the thermosetting resin composition is used as a whole-surface sealing material, it is mentioned that the lamination work is easy because the material viscosity before curing is low, and the moisture permeability of the cured product after thermosetting is high as an advantage. It is done. However, on the other hand, there is a problem that the organic EL element deteriorates due to the heating temperature during thermosetting. Further, in the conventional can sealing structure, light is blocked by the getter agent layer incorporated in the sealing space for the purpose of dehydration, so there is a disadvantage that the light extraction efficiency from the sealing surface side is poor, but the resin composition In the structure where the entire surface is sealed with an object, there is an advantage that light emission from the sealing surface side can be taken out efficiently.
- a resin composition containing a polyolefin such as polyisobutylene, a polyolefin-based copolymer, and a tackifier Etc. are known.
- a hygroscopic metal oxide with the sealing resin composition (for example, Patent Documents 1 and 2).
- an object of the present invention is to provide a sealing resin composition having both good moisture permeation resistance and transparency after using a polyolefin resin capable of avoiding the problem of thermal degradation.
- a sealing resin composition comprising (A) a polyolefin-based resin, and (B) a metal hydroxide selected from the group consisting of hydrocalcite and semi-calcined hydrotalcite.
- the molar ratio of the epoxy group of the polyolefin resin having an epoxy group to the acid anhydride group of the polyolefin resin having an acid anhydride group is 100: 10 to 100: 200.
- the molar ratio of the epoxy group of the polyolefin resin having an epoxy group to the acid anhydride group of the polyolefin resin having an acid anhydride group (epoxy group: acid anhydride group) is 100: 50 to 100: 150.
- the molar ratio of the epoxy group of the polyolefin resin having an epoxy group to the acid anhydride group of the polyolefin resin having an acid anhydride group is 100: 90 to 100: 110.
- the content of the (A) polyolefin-based resin is 80% by mass or less per 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [1] to [27] Resin composition.
- the content of the (A) polyolefin resin is 75% by mass or less per 100% by mass of the total nonvolatile content in the resin composition, as described in any one of the above [1] to [27] Resin composition.
- the content of the (A) polyolefin resin is 70% by mass or less per 100% by mass of the total nonvolatile content in the resin composition, according to any one of [1] to [27] Resin composition.
- the content of the (A) polyolefin resin is 60% by mass or less per 100% by mass of the total nonvolatile content in the resin composition, as described in any one of the above [1] to [27] Resin composition.
- the content of the (A) polyolefin-based resin is 55% by mass or less per 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [1] to [27] Resin composition.
- the content of the (A) polyolefin resin is 50% by mass or less per 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [1] to [27] Resin composition.
- the content of the (A) polyolefin resin is 1% by mass or more per 100% by mass of the total nonvolatile content in the resin composition, as described in any one of the above [1] to [33] Resin composition.
- the content of the (A) polyolefin resin is 3% by mass or more per 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [1] to [33] Resin composition.
- the content of the (A) polyolefin resin is 5% by mass or more per 100% by mass of the total nonvolatile content in the resin composition, as described in any one of the above [1] to [33] Resin composition.
- the content of the (A) polyolefin resin is 7% by mass or more per 100% by mass of the total nonvolatile content in the resin composition, as described in any one of the above [1] to [33] Resin composition.
- the content of the (A) polyolefin resin is 10% by mass or more per 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [1] to [33] Resin composition.
- the content of the (A) polyolefin resin is 35% by mass or more per 100% by mass of the total nonvolatile content in the resin composition, as described in any one of the above [1] to [33] Resin composition.
- the content of the (A) polyolefin resin is 40% by mass or more per 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [1] to [33] Resin composition.
- the metal hydroxide selected from the group consisting of (B) hydrotalcite and semi-calcined hydrotalcite, according to any one of the above [1] to [40], comprising semi-calcined hydrotalcite Resin composition.
- the average particle size of the metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite is 1 to 1000 nm.
- the average particle size of the metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite is 10 to 500 nm.
- (B) The content of the metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite is 60% by mass or less per 100% by mass of the total nonvolatile content in the resin composition.
- the content of the metal hydroxide selected from the group consisting of (B) hydrotalcite and semi-calcined hydrotalcite is 55% by mass or less per 100% by mass of the total nonvolatile content in the resin composition.
- the content of the metal hydroxide selected from the group consisting of (B) hydrotalcite and semi-calcined hydrotalcite is 50% by mass or less per 100% by mass of the total nonvolatile content in the resin composition.
- (B) The content of the metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite is 45% by mass or less per 100% by mass of the total nonvolatile content in the resin composition.
- the content of the metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite is 10% by mass or more per 100% by mass of the total nonvolatile content in the resin composition.
- the content of the metal hydroxide selected from the group consisting of hydrotalcite and semi-fired hydrotalcite is 20% by mass or more per 100% by mass of the total nonvolatile content in the resin composition.
- the content of the metal hydroxide selected from the group consisting of (B) hydrotalcite and semi-calcined hydrotalcite is 30% by mass or more per 100% by mass of the total nonvolatile content in the resin composition.
- the resin composition according to any one of [1] to [49].
- the content of the (C) tackifying resin is 80% by mass or less per 100% by mass of the total nonvolatile content in the resin composition, as described in any one of the above [53] to [56] Resin composition.
- the content of the (C) tackifying resin is 60% by mass or less per 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [53] to [56] Resin composition.
- the content of the (C) tackifying resin is 50% by mass or less per 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [53] to [56] Resin composition.
- the content of the tackifying resin (C) is 40% by mass or less per 100% by mass of the total nonvolatile content in the resin composition, according to any one of [53] to [56] Resin composition.
- the content of the (C) tackifying resin is 5% by mass or more per 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [53] to [60] Resin composition.
- the content of the (C) tackifying resin is 10% by mass or more per 100% by mass of the total nonvolatile content in the resin composition, according to any one of the above [53] to [60] Resin composition.
- the content of the (C) tackifying resin is 15% by mass or more per 100% by mass of the total nonvolatile content in the resin composition, as described in any one of the above [53] to [60] Resin composition.
- the content of the (D) curing agent is 0.01% by mass or more per 100% by mass of the total nonvolatile content in the resin composition, as described in any one of the above [64] to [66] Resin composition.
- the content of the (D) curing agent is 0.05% by mass or more per 100% by mass of the total nonvolatile content in the resin composition, as described in any one of the above [64] to [66] Resin composition.
- the resin composition layer having a thickness of 20 ⁇ m has a total light transmittance (parallel transmittance) at a wavelength of 450 nm of 90% or more, according to any one of the above [1] to [72] Resin composition.
- the resin composition layer having a thickness of 20 ⁇ m has a total light transmittance (parallel transmittance) at a wavelength of 450 nm of 95% or more, according to any one of the above [1] to [72] Resin composition.
- the polyolefin resin includes a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group, and the resin composition layer has a crosslinked structure in which an acid anhydride group and an epoxy group are reacted.
- the sealing sheet according to [75] which has.
- the encapsulating resin composition of the present invention is selected from the group consisting of (A) a polyolefin-based resin (hereinafter sometimes abbreviated as “(A) component”), and (B) hydrotalcite and semi-calcined hydrotalcite. It contains a selected metal hydroxide (hereinafter sometimes abbreviated as “component (B)”).
- a sealing layer (resin composition layer) having good moisture permeability resistance and transparency can be formed from the sealing resin composition of the present invention. This transparency can be judged by the total light transmittance (parallel light transmittance) of the resin composition layer.
- the total light transmittance (parallel light transmittance) at a wavelength of 450 nm of the resin composition layer having a thickness of 20 ⁇ m is preferably 90% or more, and more preferably 95% or more.
- the total light transmittance is calculated by using glass as a reference, as described in Examples described later.
- the polyolefin resin used in the present invention is not particularly limited as long as it has a skeleton derived from an olefin monomer.
- the polyolefin resins described in Patent Documents 1 and 2 are known.
- the polyolefin resin is preferably a polyethylene resin, a polypropylene resin, a polybutene resin, or a polyisobutylene resin. These polyolefin resins may be homopolymers or copolymers such as random copolymers and block copolymers.
- copolymer examples include copolymers of two or more olefins, and copolymers of olefins with monomers other than olefins such as non-conjugated dienes and styrene.
- preferred copolymers include ethylene-nonconjugated diene copolymers, ethylene-propylene copolymers, ethylene-propylene-nonconjugated diene copolymers, ethylene-butene copolymers, propylene-butene copolymers, propylene.
- a polyolefin-based resin is a polyolefin-based resin having an acid anhydride group (that is, a carbonyloxycarbonyl group (—CO—O—CO—)) from the viewpoint of imparting excellent physical properties such as adhesion and heat-and-moisture heat resistance. It is preferable to include a polyolefin-based resin having a resin and / or 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.
- (A) component can use 1 type (s) or 2 or more types, and may use together the polyolefin resin which has an acid anhydride group, and the polyolefin resin which has an epoxy group.
- 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 polyolefin resin preferably contains both a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group, particularly from the viewpoint of imparting excellent physical properties such as moisture permeability.
- a polyolefin-based resin can form a cross-linked structure by reacting an acid anhydride group and an epoxy group by heating to form a sealing layer having excellent moisture resistance and the like.
- Crosslinking structure formation can also be performed after sealing. For example, when a sealing target is weak to heat, such as an organic EL element, sealing is performed using a sealing film, and the sealing film is manufactured. It is desirable to form a crosslinked structure.
- the ratio of the polyolefin resin having an acid anhydride group and the polyolefin resin having an epoxy group is not particularly limited as long as an appropriate crosslinked structure can be formed, but the molar ratio of the epoxy group to the acid anhydride group (epoxy group: acid anhydride).
- the group) is preferably 100: 10 to 100: 200, more preferably 100: 50 to 100: 150, particularly preferably 100: 90 to 100: 110.
- the number average molecular weight of the polyolefin-based resin is not particularly limited, but from the viewpoint of providing good coatability of the varnish of the resin composition and good compatibility with other components in the resin composition. 1,000,000 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, Most preferred is 150,000 or less.
- the number average molecular weight is 1,000 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.
- the number average molecular weight in this invention is measured by the 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.
- the 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 content of the component (A) in the resin composition of the present invention is not particularly limited. 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.
- (A) polyolefin resin a specific example of (A) polyolefin resin
- 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.
- 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) and “Tuffmer A4085” (ethylene-butene copolymer) manufactured by Mitsui Chemicals.
- propylene-butene copolymer examples include “T-YP341” (glycidyl methacrylate-modified propylene-butene random copolymer, a quantity of butene units per 100% by mass in total of propylene units and butene units) manufactured by Starlight PMC.
- T-YP279 maleic anhydride-modified propylene-butene random copolymer, propylene unit and butene, manufactured by Seiko PMC
- T-YP276 glycidyl methacrylate manufactured by Seiko PMC Modified propylene-butene random copolymer, total of propylene units and butene units Amount of butene units per 00% 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 by Seiko PMC
- hydrotalcite Metal hydroxide selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite>
- the “hydrotalcite” in the present invention is a concept including natural hydrotalcite (Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O) that has not been fired and synthetic hydrotalcite (hydrotalcite-like compound). is there. That is, “hydrotalcite” in the present invention means “unfired hydrotalcite”.
- semi-calcined hydrotalcite is preferable. That is, the metal hydroxide is preferably composed of semi-calcined hydrotalcite.
- semi-calcined hydrotalcite means that the amount of interlayer water obtained by calcining hydrotalcite (that is, natural hydrotalcite or synthetic hydrotalcite (hydrotalcite-like compound)) is reduced or eliminated.
- Metal hydroxide refers to “H 2 O” described in the composition formula of the above-mentioned natural hydrotalcite and the synthetic hydrotalcite (hydrotalcite-like compound) described later, when described using a composition formula.
- hydrotalcite ie, natural hydrotalcite or synthetic hydrotalcite (hydrotalcite-like compound)
- semi-calcined hydrotalcite in which not only interlayer water but also hydroxyl groups have disappeared by condensation dehydration.
- Hydrotalcite is a metal oxide and is not included in the component (B) of the present invention which is a metal hydroxide (that is, hydrotalcite and / or semi-calcined hydrotalcite).
- Hydrotalcite and semi-calcined hydrotalcite have peaks observed in their TG-DTA (Thermogravimetry-Differential-Thermal-Analysis) curves, but the calcined hydrotalcite is in an amorphous state due to the disappearance of hydroxyl groups. No peak is observed on the TG-DTA curve. Therefore, hydrotalcite and semi-calcined hydrotalcite and calcined hydrotalcite can be clearly distinguished by TG-DTA.
- TG-DTA Thermogravimetry-Differential-Thermal-Analysis
- hydrotalcite and semi-calcined hydrotalcite and calcined 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 hydrotalcite is 15% by mass or more, and the thermal weight reduction rate at 380 ° C. of calcined hydrotalcite is less than 12% by mass.
- Thermogravimetric analysis was performed using a TG / DTA EXSTAR6300 manufactured by Hitachi High-Tech Science Co., Ltd. Weighed 5 mg of hydrotalcite in a sample pan made of AL, opened without a lid, and 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.
- hydrotalcite, semi-calcined hydrotalcite and calcined 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.
- hydrotalcite has only one peak in the vicinity of 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 outside the above range.
- 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 (manufactured by PANalytical, Empyrean), counter-cathode CuK ⁇ (1.5405 ⁇ ), voltage: 45 V, current: 40 mA, sampling width: 0.0260 °, scanning speed: 0 0.0657 ° / S, measurement 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 ”.
- hydrotalcite “DHT-4A” manufactured by Kyowa Chemical Industry Co., Ltd. has one peak at 11.4 °.
- Semi-calcined hydrotalcite “DHT-4C” manufactured by Kyowa Chemical Industry Co., Ltd. has a main peak at 13.2 ° and a second peak at 11.4 °.
- hydrotalcite and semi-calcined hydrotalcite and calcined 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 rate of hydrotalcite is less than 1% by weight, and the saturated water absorption rate of calcined hydrotalcite is 20% by weight or more.
- “Saturated water absorption” in the present invention means that hydrotalcite, semi-calcined hydrotalcite or calcined hydrotalcite is weighed by 1.5 g using a balance, and the initial mass is measured.
- hydrotalcite-like compound for example, the formula (I): [M 2+ 1-x M 3+ x (OH) 2 ] x + ⁇ [(A n ⁇ ) x / n ⁇ mH 2 O] x ⁇ (I)
- 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 - , An NO 3- and the like, and 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-.
- hydrotalcite-like compound for example, formula (II): M 2+ x Al 2 (OH) 2x + 6-nz (A n ⁇ ) z ⁇ mH 2 O (II)
- 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+
- BET specific surface area of the component is preferably 1 ⁇ 200m 2 / g, more preferably 5 ⁇ 150m 2 / g.
- the BET specific surface area of the component (B) is determined 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, and using the BET multipoint method. It is obtained by calculating.
- the average particle size of the component (B) is preferably 1 to 1000 nm, more preferably 10 to 500 nm.
- the average particle diameter of the component (B) is obtained by the median diameter of the particle size distribution when the particle size distribution is created on a volume basis by laser diffraction scattering type particle size distribution measurement (JIS Z 8825).
- the component surface-treated with the surface treatment agent can be used.
- 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.
- 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 (B) can be performed, for example, by adding and spraying the surface treatment agent and stirring for 5 to 60 minutes while stirring and dispersing the untreated component (B) 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 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 (B) 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 (B).
- the content of the component (B) in the resin composition of the present invention 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.
- component (B) 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: 10 m 2 / g) DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.): hydrotalcite (average particle size: 400 nm, BET specific surface area: 10 m 2 / g)
- the resin composition of the present invention does not substantially contain a hygroscopic metal oxide.
- the content of the hygroscopic metal oxide is, for example, desirably in a range where the transmittance value of the resin composition layer described below is preferably 90% or more, more preferably 95% or more.
- the content of the hygroscopic metal oxide is preferably 1% by mass or less (that is, 0 to 1% by mass) and preferably 0.5% by mass or less (that is, 0% to 1% by mass) per 100% by mass of the nonvolatile content in the resin composition. 0 to 0.5% by mass) is more preferable.
- the hygroscopic metal oxide include calcium oxide, magnesium oxide, strontium oxide, aluminum oxide, barium oxide, calcined dolomite (a mixture containing calcium oxide and magnesium oxide), and calcined hydrotalcite.
- the resin composition of the present invention may further contain (C) a tackifier resin (hereinafter sometimes abbreviated as “component (C)”).
- component (C) a tackifier resin
- the tackifying resin is also called a tackifier and is a resin that is added to a plastic polymer to impart tackiness.
- the component (C) is not particularly limited, and includes terpene resins, modified terpene resins (hydrogenated terpene resins, terpene phenol copolymer resins, aromatic modified terpene resins, etc.), coumarone resins, indene resins, petroleum resins ( 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.
- terpene resins modified terpene resins (hydrogenated terpene resins, terpene phenol copolymer resins, aromatic modified terpene resins, etc.), coumarone resins, indene resins, petroleum resins ( Aliphatic petroleum resins, hydrogenated alicyclic petroleum resins, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, alicyclic petroleum resins,
- Examples of commercially available products that can be used as the component (C) 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 (C) is preferably from 50 to 200 ° C., more preferably from 90 to 180 ° 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.
- (C) Component may be used alone or in combination of two or more. There is no restriction
- 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.
- the content thereof 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 resin composition of the present invention may further contain (D) a curing agent (hereinafter sometimes abbreviated as “(D) component”) 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.
- 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; You may use these 1 type or in combination of 2 or more types.
- 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.
- ком ⁇ онент (E) ⁇ (E) Resin having a functional group capable of reacting with an epoxy group
- component (E) a resin having the following (hereinafter sometimes abbreviated as “component (E)”).
- 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.
- the acid anhydride group examples include a group derived from succinic anhydride, a group derived from maleic anhydride, a group derived from glutaric anhydride, and the like.
- the resin 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
- the resin include polyolefin resins.
- the (E) component polyolefin-based resin is the same as the above-described component (A) except that it has a hydroxyl group, a phenolic hydroxyl group, an amino group, a carboxy group, etc. 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, its content 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.
- ⁇ (F) Resin having a functional group capable of reacting with an acid anhydride group when a polyolefin resin having an acid anhydride group is used as the component (A), the component (A) reacts 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 functional group that can be used (hereinafter sometimes referred to 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.
- resins examples include polyolefin resins (excluding polyolefin resins having an epoxy group as component (A)), acrylic resins, melamine resins, phenol resins, urea resins, polyester resins, alkyd resins, polyurethanes, polyimide resins, etc. And polyolefin resins are preferred.
- the polyolefin resin as the component (F) is 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, etc. as a functional group instead of an epoxy group (
- a polyolefin resin similar to the component A) is exemplified, and 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, the content thereof 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, its content 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.
- the resin composition of the present invention may further contain (G) a plasticizer (hereinafter sometimes abbreviated as “(G) component”).
- a plasticizer hereinafter sometimes abbreviated as “(G) component.
- (G) component a plasticizer
- a liquid material is used suitably at room temperature.
- plasticizers include paraffinic process oil, naphthenic process oil, liquid paraffin, polyethylene wax, polypropylene wax, mineral oil such as petroleum jelly, castor oil, cottonseed oil, rapeseed oil, soybean oil, palm oil, palm oil, olive oil.
- 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 adversely affecting the organic EL element.
- the resin composition of the present invention 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, and barium sulfate.
- Inorganic fillers such as barium acid and calcium zirconate (excluding hygroscopic metal oxides); Organic fillers such as rubber particles, silicone powder, nylon powder and fluororesin powder; Thickeners such as Orben and Benton; Silicone, fluorine and polymer antifoaming agents or leveling Grayed agent; triazole compounds, thiazole compounds, triazine compounds, adhesion imparting agents such as porphyrin compounds; and the like.
- the sealing resin composition of the present invention is preferably a pressure sensitive adhesive.
- the pressure-sensitive adhesive means an adhesive that adheres by simply applying pressure at a normal temperature for a relatively short time, and is well known to those skilled in the art.
- the resin composition for sealing of the present invention is a pressure-sensitive adhesive that includes (C) a tackifying resin and has tackiness.
- the method for producing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which the compounding components are mixed with a kneading roller, a rotary mixer, or the like, if necessary, by adding a solvent or the like.
- the resin composition 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.
- the resin composition of this invention is used suitably for sealing of an organic EL element.
- the resin composition of the present invention can be used 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. .
- the transparency of the sealing layer (resin composition layer) formed by the resin composition can be measured with a spectrophotometer. .
- the total light transmittance (parallel transmittance) at a wavelength of 450 nm of the sealing layer is preferably 90% or more, and 95% or more. It is particularly preferred.
- the value of the total light transmittance at 450 nm described above is a measured value in a sealing layer (resin composition layer) having a thickness of 20 ⁇ m, but the thickness of the sealing layer is generally 3 to It is set in the range of 200 ⁇ m.
- This invention also provides the sheet
- Specific examples include a support and a sealing sheet having a resin composition layer formed from the resin composition of the present invention on the support.
- the resin composition layer may be formed by a method known to those skilled in the art. For example, a varnish in which the resin composition of the present invention is dissolved in an organic solvent is prepared, and the varnish is applied and dried on a support. Can be formed. 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.
- component (A) uses both a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group
- component (E) that is, a resin having a functional group capable of reacting with the curing agent epoxy group
- component (F) that is, a resin having a functional group capable of reacting with an acid anhydride group
- the resin composition is heated and crosslinked before the sealing step.
- a structure may be formed, or a crosslinked structure may be formed by heating after the sealing step.
- 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, and further preferably 120 to 160 ° C.
- the heating time is preferably 15 to 120 minutes, more preferably 30 to 100 minutes.
- the curing temperature is preferably 50 to 150 ° C., more preferably 60 to 100 ° C. from the viewpoint of preventing thermal degradation of the element (for example, organic EL element). 60 to 80 ° C. is more preferable.
- the thickness of the resin composition layer in the sealing sheet is preferably 3 to 200 ⁇ m, more preferably 5 to 100 ⁇ m, and even more preferably 5 to 50 ⁇ m.
- the final sealing structure of interest is a structure in which a sealing substrate is laminated on the resin composition layer
- only the side part of the resin composition layer can be penetrated by moisture. Therefore, by reducing the thickness of the resin composition layer, the area in contact with the outside air on the side portion is reduced. Therefore, it is desirable to reduce the thickness of the resin composition layer in order to block moisture.
- the thickness of the resin composition layer is too small, the element may be damaged when the sealing substrate is bonded, and the workability when the sealing substrate is bonded tends to be reduced. is there.
- setting the thickness of the resin composition layer to the above-mentioned preferable range means that the resin composition layer after the resin composition layer is transferred to a sealing target (for example, a substrate on which an element such as an organic EL element is formed). This is also effective in maintaining the uniformity of the layer thickness.
- the support used for the sealing sheet a support having moisture resistance is preferable.
- 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.
- the plastic film having moisture resistance include a plastic film in which an inorganic substance such as silicon oxide (silica), silicon nitride, SiCN, amorphous silicon or the like 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), etc.
- 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.
- the support body which does not have moisture resistance (For example, the single body of the plastic film in which the inorganic substance is not vapor-deposited on the said surface) can also be used for the support body of a resin composition sheet.
- 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 the handleability of the sealing sheet.
- the surface of the resin composition layer is a protective film in order to prevent the adhesion and scratches of dust and the like to the surface of the resin composition layer until the sealing sheet of the present invention is actually used for forming a sealing structure.
- the protective film is preferably a plastic film exemplified by the above support.
- the protective film may be subjected to a mold release treatment in addition to a mat treatment and a corona treatment.
- Specific examples of the release agent include a fluorine-based release agent, a silicon-based release agent, and an alkyd resin-based release agent. Different types of release agents may be mixed and used.
- the thickness of the protective film is not particularly limited, but is preferably 1 to 40 ⁇ m, and more preferably 10 to 30 ⁇ m.
- the sealing sheet of the present invention is used by being laminated on a sealing target.
- laminate refers to a state in which the object to be sealed is covered with a sealing sheet with a support, and the object to be sealed is covered with a resin composition layer transferred from the sheet for sealing. Including the state.
- a sealing sheet that is a support that does not have moisture resistance for example, a single plastic film with no inorganic material deposited on the surface
- the sealing sheet is laminated to the object to be sealed. Thereafter, the support is peeled off (that is, the resin composition layer is transferred), and then a sealing substrate is preferably separately laminated on the resin composition layer.
- a substrate on which an organic EL element is formed (hereinafter, also referred to as “organic EL element formation substrate”) is an object to be sealed, an embodiment in which such a sealing substrate is laminated is preferable.
- the "sealing base material" as used in this invention uses the support body which has the moisture resistance used for the sheet
- a “sealing substrate” also includes a highly moisture-proof plate that does not have flexibility such as a glass plate, a metal plate, and a steel plate, which is unsuitable for use as a support for a sealing sheet.
- the sealing resin composition of the present invention can be easily made into a sealing resin composition excellent in moisture permeability resistance by appropriately adopting the preferable conditions described above.
- the moisture permeation resistance is preferably less than 15 g / m 2 ⁇ 24 hr when the water vapor transmission amount is measured under the following conditions regardless of the thickness of the resin composition layer (sealing layer). More preferably, it is less than 10 g / m 2 ⁇ 24 hr.
- the amount of water vapor transmission is the amount of water vapor transmission per 1 m 2 of the resin composition layer (thickness can be arbitrary) according to JIS Z0208 under the conditions of temperature 40 ° C., humidity 90% RH and 24 hours. taking measurement.
- the thickness of the sealing layer is not particularly limited, and the thickness may be adjusted preferably so that the moisture permeation resistance is the above value.
- the thickness of the sealing layer is generally set in the range of 3 to 200 ⁇ m.
- the total light transmittance at 450 nm of the resin composition layer having a thickness of 20 ⁇ m is preferably 90% or more.
- a resin composition layer can be recognized visually as being transparent.
- the resin composition for sealing of the present invention can easily form a resin composition layer (sealing layer) excellent in total light transmittance by appropriately adopting the preferable conditions described above.
- the total light transmittance at 450 nm of the resin composition layer having a thickness of 20 ⁇ m is preferably 90% or more, and more preferably 95% or more.
- the total light transmittance at 450 nm of the resin composition layer was formed by laminating the resin composition layer on a glass plate as described in the examples described later (see examples below for lamination conditions).
- the value of the total light transmittance at 450 nm described above is a measured value of the resin composition layer having a thickness of 20 ⁇ m, but the thickness of the resin composition layer is generally in the range of 3 to 200 ⁇ m. .
- the present invention also provides an organic EL device having an organic EL element sealed with the above-described resin composition 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. When the sealing sheet is protected by a protective film, after peeling it off, the sealing sheet is laminated on the substrate so that the resin composition layer 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.
- a sealing material for an organic EL element needs to be dried before sealing work to remove the absorbed water, and the work is complicated, but the support has moisture resistance. Since the sealing sheet of the present invention using a high moisture permeation resistance, the water absorption rate during storage and device manufacturing operations is also low. Moreover, the damage given to the organic EL element at the time of sealing work is also remarkably reduced.
- the support When using a sealing sheet using a support that does not have moisture resistance, after laminating the sealing sheet on a substrate having an organic EL element, the support is peeled off and the exposed resin composition layer is sealed with a sealing group.
- the sealing process of the organic EL element is completed by pressure bonding the material.
- Two or more sealing substrates may be used by bonding them from the viewpoint of improving the moisture-proof effect.
- the thickness of the sealing substrate is preferably 5 mm or less, more preferably 1 mm or less, and even more preferably 100 ⁇ m or less from the viewpoint of making the organic EL device itself thin and light.
- the pressure at the time of press-bonding the sealing substrate is preferably about 0.3 to 10 kgf / cm 2 , and 25 to 130 ° C. is preferable when the pressure is applied under heating.
- the organic EL element is a substrate having an organic EL element formed on a transparent substrate
- the transparent substrate side is a display surface of a display or a light emitting surface of a lighting fixture
- the support for the sheet for sealing is used. It is not always necessary to use a transparent material, and a metal plate, metal foil, opaque plastic film, or plate may be used.
- the substrate having the organic EL element is an organic EL element formed on a substrate made of an opaque or low-transparency material
- the sealing substrate side is used as the display surface of the display or the light emitting surface of the lighting fixture. Therefore, a transparent plastic film, a glass plate, a transparent plastic plate or the like is used as the sealing substrate.
- T-YP431 (manufactured by Seiko PMC): glycidyl methacrylate-modified ethylene-methyl methacrylate copolymer (epoxy group concentration: 0.64 mmol / g, number average molecular weight: 2,400)
- T-YP432 (manufactured by Seiko PMC): glycidyl methacrylate-modified ethylene-methyl methacrylate copolymer (epoxy group concentration: 1.63 mmol / g, number average molecular weight: 3,100)
- T-YP8920 (manufactured by Seiko PMC): g
- TAP Curing agent / amine curing agent (2,4,6-tris (diaminomethyl) phenol, hereinafter abbreviated as “TAP”)
- Aromatic mixed solvent toluene, swazole # 1000 (manufactured by Maruzen Petroleum Co., Ltd.): Aromatic mixed solvent
- compositions of Examples and Comparative Examples were prepared by the following procedure. The blending was carried out in the amounts shown in Tables 1 and 2. In addition, the quantity of components other than the organic solvent of Table 1 and 2 is the value converted in the non volatile matter.
- Example 1 130 parts of hydrogenated petroleum resin containing cyclohexane ring (Alcon P125, 60% Swazole # 1000 solution), 120 parts of maleic anhydride-modified ethylene-methyl methacrylate copolymer (T-YP429, 20% toluene solution), polybutene (HV- 1900) 60 parts and semi-calcined hydrotalcite (DHT-4C) 100 parts were dispersed with three rolls to obtain a mixture.
- Alcon P125 60% Swazole # 1000 solution
- T-YP429 maleic anhydride-modified ethylene-methyl methacrylate copolymer
- HV- 1900 polybutene
- DHT-4C semi-calcined hydrotalcite
- T-YP431, 20% toluene solution a glycidyl methacrylate-modified ethylene-methyl methacrylate copolymer
- TAP an amine curing agent
- 170 parts of toluene were obtained.
- the obtained mixture was uniformly dispersed with a high-speed rotary mixer to obtain a resin composition varnish.
- 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 having a resin composition layer of 20 ⁇ m was obtained.
- Example 2 A resin composition varnish and a sealing sheet were prepared in the same manner as in Example 1, except that the amount of semi-fired hydrotalcite (DHT-4C) was changed from 100 parts to 80 parts.
- DHT-4C semi-fired hydrotalcite
- Example 3 In the same manner as in Example 1, except that the same amount of semi-calcined hydrotalcite (DHT-4A-2) was used instead of semi-calcined hydrotalcite (DHT-4C), the varnish of the resin composition and A sealing sheet was produced.
- DHT-4A-2 semi-calcined hydrotalcite
- DHT-4C semi-calcined hydrotalcite
- Example 4 Resin composition varnish and sealing sheet in the same manner as in Example 1 except that the same amount of hydrotalcite (DHT-4A) was used instead of semi-fired hydrotalcite (DHT-4C) was made.
- DHT-4A hydrotalcite
- DHT-4C semi-fired hydrotalcite
- Example 5> instead of maleic anhydride-modified ethylene-methyl methacrylate copolymer (T-YP429, 20% toluene solution), the same amount of maleic anhydride-modified ethylene-methyl methacrylate copolymer (T-YP430, 20% toluene solution) was used. The same amount of glycidyl methacrylate-modified ethylene-methyl methacrylate copolymer (T-YP432, 20% toluene) was used instead of the glycidyl methacrylate-modified ethylene-methyl methacrylate copolymer (T-YP431, 20% toluene solution). A resin composition varnish and a sealing sheet were prepared in the same manner as in Example 1 except that the (solution) was used.
- Example 6> instead of maleic anhydride-modified ethylene-methyl methacrylate copolymer (T-YP429, 20% toluene solution), the same amount of maleic anhydride-modified styrene-isobutylene-styrene copolymer (T-YP8920, 20% toluene solution) And the same amount of glycidyl methacrylate-modified styrene-isobutylene-styrene copolymer (T-YP8930, 20) instead of glycidyl methacrylate-modified ethylene-methyl methacrylate copolymer (T-YP431, 20% toluene solution). % Toluene solution) was used in the same manner as in Example 1 to prepare a resin composition varnish and a sealing sheet.
- Example 7 Instead of maleic anhydride modified ethylene-methyl methacrylate copolymer (T-YP429, 20% toluene solution), the same amount of maleic anhydride modified propylene-polybutene copolymer (T-YP312, 20% toluene solution) was used. The same amount of glycidyl methacrylate modified propylene-butene copolymer (T-YP313, 20% toluene solution) instead of glycidyl methacrylate modified ethylene-methyl methacrylate copolymer (T-YP431, 20% toluene solution) A resin composition varnish and a sealing sheet were produced in the same manner as in Example 1 except that was used.
- Example 8> Instead of 120 parts of maleic anhydride-modified ethylene-methyl methacrylate copolymer (T-YP429, 20% toluene solution), 200 parts of glycidyl methacrylate-modified propylene-butene copolymer (T-YP341, 20% toluene solution) are used. And 35 parts of maleic anhydride-modified liquid polybutene (HV-300M) were used in place of 90 parts of glycidyl methacrylate-modified ethylene-methyl methacrylate copolymer (T-YP431, 20% toluene solution). In the same manner as in Example 1, a varnish of the resin composition and a sealing sheet were produced.
- Example 1 A resin composition varnish and a sealing sheet were prepared in the same manner as in Example 1 except that calcined hydrotalcite (KW2200) was used instead of semi-calcined hydrotalcite (DHT-4C).
- the sheet for sealing (thickness of the resin composition layer: 20 ⁇ m) prepared in Examples and Comparative Examples was cut to a length of 50 mm and a width of 20 mm, and the cut sealing sheet was a glass plate ( Batch type vacuum laminator (manufactured by Nichigo Morton, V-160) was used for micro slide glass of length 76mm, width 26mm and thickness 1.2mm, white slide glass S1112 by Marinami Glass Industry Co., Ltd. No.2) And laminated. Lamination conditions were a temperature of 80 ° C., a pressure reduction time of 30 seconds, and a pressure of 0.3 MPa for 30 seconds.
- the light transmittance spectrum of the obtained laminate was a fiber spectrophotometer (MCPD-7700, type 311C, manufactured by Otsuka Electronics Co., Ltd.) equipped with a ⁇ 80 mm integrating sphere (model name SRS-99-010, reflectance 99%). Measurement was performed using an external light source unit: halogen lamp MC-2564 (24 V, 150 W specification), and the total light transmittance at a wavelength of 450 nm was calculated and evaluated according to the following criteria. The distance between the integrating sphere and the sample (laminated body) was 0 mm, and glass was used as a reference. Good ( ⁇ ): 95% or more Possible ( ⁇ ): 90% or more, less than 95% Poor ( ⁇ ): less than 90%
- Example 1 using a metal hydroxide (DHT-4C, DHT-4A-2 or DHT-4A) selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite as shown in Tables 1 and 2
- DHT-4C, DHT-4A-2 or DHT-4A selected from the group consisting of hydrotalcite and semi-calcined hydrotalcite as shown in Tables 1 and 2
- the results of ⁇ 8 are better in transparency (total light transmittance) than Comparative Examples 1 to 4 using a hygroscopic metal oxide (KW2200, N41S, Moistop # 10 or FNM-G).
- the sealing resin composition of the present invention can form a highly transparent sealing layer (resin composition layer). Therefore, the sealing resin composition of the present invention can be suitably used for sealing electronic components (particularly organic EL elements).
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Abstract
Description
[3] (A)ポリオレフィン系樹脂中の酸無水物基を有するポリオレフィン系樹脂の量が、0~70質量%である前記[2]に記載の樹脂組成物。
[4] (A)ポリオレフィン系樹脂中のエポキシ基を有するポリオレフィン系樹脂の量は、0~70質量%である前記[2]または[3]に記載の樹脂組成物。
[6] (A)ポリオレフィン系樹脂中の酸無水物基を有するポリオレフィン系樹脂の量が、10~50質量%である前記[5]に記載の樹脂組成物。
[7] (A)ポリオレフィン系樹脂中のエポキシ基を有するポリオレフィン系樹脂の量は、10~50質量%である前記[5]または[6]に記載の樹脂組成物。
[9] エポキシ基を有するポリオレフィン系樹脂のエポキシ基と、酸無水物基を有するポリオレフィン系樹脂の酸無水物基とのモル比(エポキシ基:酸無水物基)が、100:50~100:150である前記[5]~[7]のいずれか一つに記載の樹脂組成物。
[10] エポキシ基を有するポリオレフィン系樹脂のエポキシ基と、酸無水物基を有するポリオレフィン系樹脂の酸無水物基とのモル比(エポキシ基:酸無水物基)が、100:90~100:110である前記[5]~[7]のいずれか一つに記載の樹脂組成物。
[12] 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が、0.1~5mmol/gである前記[2]~[10]のいずれか一つに記載の樹脂組成物。
[14] 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が、0.1~5mmol/gである前記[2]~[12]のいずれか一つに記載の樹脂組成物。
[16] (A)ポリオレフィン系樹脂の数平均分子量が、750,000以下である前記[1]~[14]のいずれか一つに記載の樹脂組成物。
[17] (A)ポリオレフィン系樹脂の数平均分子量が、500,000以下である前記[1]~[14]のいずれか一つに記載の樹脂組成物。
[18] (A)ポリオレフィン系樹脂の数平均分子量が、400,000以下である前記[1]~[14]のいずれか一つに記載の樹脂組成物。
[19] (A)ポリオレフィン系樹脂の数平均分子量が、300,000以下である前記[1]~[14]のいずれか一つに記載の樹脂組成物。
[20] (A)ポリオレフィン系樹脂の数平均分子量が、200,000以下である前記[1]~[14]のいずれか一つに記載の樹脂組成物。
[21] (A)ポリオレフィン系樹脂の数平均分子量が、150,000以下である前記[1]~[14]のいずれか一つに記載の樹脂組成物。
[23] (A)ポリオレフィン系樹脂の数平均分子量が、3,000以上である前記[1]~[21]のいずれか一つに記載の樹脂組成物。
[24] (A)ポリオレフィン系樹脂の数平均分子量が、5,000以上である前記[1]~[21]のいずれか一つに記載の樹脂組成物。
[25] (A)ポリオレフィン系樹脂の数平均分子量が、10,000以上である前記[1]~[21]のいずれか一つに記載の樹脂組成物。
[26] (A)ポリオレフィン系樹脂の数平均分子量が、30,000以上である前記[1]~[21]のいずれか一つに記載の樹脂組成物。
[27] (A)ポリオレフィン系樹脂の数平均分子量が、50,000以上である前記[1]~[21]のいずれか一つに記載の樹脂組成物。
[29] (A)ポリオレフィン系樹脂の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、75質量%以下である前記[1]~[27]のいずれか一つに記載の樹脂組成物。
[30] (A)ポリオレフィン系樹脂の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、70質量%以下である前記[1]~[27]のいずれか一つに記載の樹脂組成物。
[31] (A)ポリオレフィン系樹脂の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、60質量%以下である前記[1]~[27]のいずれか一つに記載の樹脂組成物。
[32] (A)ポリオレフィン系樹脂の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、55質量%以下である前記[1]~[27]のいずれか一つに記載の樹脂組成物。
[33] (A)ポリオレフィン系樹脂の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、50質量%以下である前記[1]~[27]のいずれか一つに記載の樹脂組成物。
[35] (A)ポリオレフィン系樹脂の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、3質量%以上である前記[1]~[33]のいずれか一つに記載の樹脂組成物。
[36] (A)ポリオレフィン系樹脂の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、5質量%以上である前記[1]~[33]のいずれか一つに記載の樹脂組成物。
[37] (A)ポリオレフィン系樹脂の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、7質量%以上である前記[1]~[33]のいずれか一つに記載の樹脂組成物。
[38] (A)ポリオレフィン系樹脂の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、10質量%以上である前記[1]~[33]のいずれか一つに記載の樹脂組成物。
[39] (A)ポリオレフィン系樹脂の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、35質量%以上である前記[1]~[33]のいずれか一つに記載の樹脂組成物。
[40] (A)ポリオレフィン系樹脂の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、40質量%以上である前記[1]~[33]のいずれか一つに記載の樹脂組成物。
[43] (B)ハイドロタルサイトおよび半焼成ハイドロタルサイトからなる群から選ばれる金属水酸化物のBET比表面積が、5~150m2/gである前記[1]~[41]のいずれか一つに記載の樹脂組成物。
[45] (B)ハイドロタルサイトおよび半焼成ハイドロタルサイトからなる群から選ばれる金属水酸化物の平均粒子径が、10~500nmである前記[1]~[43]のいずれか一つに記載の樹脂組成物。
[47] (B)ハイドロタルサイトおよび半焼成ハイドロタルサイトからなる群から選ばれる金属水酸化物の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、55質量%以下である前記[1]~[45]のいずれか一つに記載の樹脂組成物。
[48] (B)ハイドロタルサイトおよび半焼成ハイドロタルサイトからなる群から選ばれる金属水酸化物の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、50質量%以下である前記[1]~[45]のいずれか一つに記載の樹脂組成物。
[49] (B)ハイドロタルサイトおよび半焼成ハイドロタルサイトからなる群から選ばれる金属水酸化物の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、45質量%以下である前記[1]~[45]のいずれか一つに記載の樹脂組成物。
[51] (B)ハイドロタルサイトおよび半焼成ハイドロタルサイトからなる群から選ばれる金属水酸化物の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、20質量%以上である前記[1]~[49]のいずれか一つに記載の樹脂組成物。
[52] (B)ハイドロタルサイトおよび半焼成ハイドロタルサイトからなる群から選ばれる金属水酸化物の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、30質量%以上である前記[1]~[49]のいずれか一つに記載の樹脂組成物。
[55] (C)粘着付与樹脂の軟化点が、90~180℃である前記[53]に記載の樹脂組成物。
[56] (C)粘着付与樹脂の軟化点が、100~150℃である前記[53]に記載の樹脂組成物。
[58] (C)粘着付与樹脂の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、60質量%以下である前記[53]~[56]のいずれか一つに記載の樹脂組成物。
[59] (C)粘着付与樹脂の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、50質量%以下である前記[53]~[56]のいずれか一つに記載の樹脂組成物。
[60] (C)粘着付与樹脂の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、40質量%以下である前記[53]~[56]のいずれか一つに記載の樹脂組成物。
[62] (C)粘着付与樹脂の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、10質量%以上である前記[53]~[60]のいずれか一つに記載の樹脂組成物。
[63] (C)粘着付与樹脂の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、15質量%以上である前記[53]~[60]のいずれか一つに記載の樹脂組成物。
[66] (D)硬化剤の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、1質量%以下である前記[64]に記載の樹脂組成物。
[68] (D)硬化剤の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、0.05質量%以上である前記[64]~[66]のいずれか一つに記載の樹脂組成物。
[70] 吸湿性金属酸化物の含有量が、樹脂組成物中の不揮発分の合計100質量%あたり、0.5質量%以下である前記[1]~[68]のいずれか一つに記載の樹脂組成物。
[72] 有機EL素子の封止用である前記[1]~[71]のいずれか一つに記載の樹脂組成物。
[74] 厚さが20μmである樹脂組成物層の波長450nmでの全光線透過率(平行線透過率)が、95%以上である前記[1]~[72]のいずれか一つに記載の樹脂組成物。
[76] (A)ポリオレフィン系樹脂が、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を含み、樹脂組成物層が、酸無水物基とエポキシ基が反応した架橋構造を有する、前記[75]に記載の封止用シート。
[77] 有機EL素子の封止用である前記[75]または[76]に記載の封止用シート。
[79] 前記[75]~[77]のいずれか一つに記載の封止用シートで封止された有機EL素子を有する有機ELデバイス。
本発明で使用するポリオレフィン系樹脂としては、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、特許文献1および2に記載されているポリオレフィン系樹脂が、公知のものとして挙げられる。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好ましい。これらポリオレフィン系樹脂は、単独重合体でもよく、ランダム共重合体、ブロック共重合体等の共重合体でもよい。共重合体としては、2種以上のオレフィンの共重合体、およびオレフィンと非共役ジエン、スチレン等のオレフィン以外のモノマーとの共重合体が挙げられる。好ましい共重合体の例として、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-プロピレン-非共役ジエン共重合体、エチレン-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、スチレン-イソブチレン共重合体、スチレン-イソブチレン-スチレン共重合体等が挙げられる。ポリオレフィン系樹脂としては、例えば、特許文献1に記載のイソブチレン変性樹脂、特許文献2に記載のスチレン-イソブチレン変性樹脂等が好ましく用いられる。
本発明における「ハイドロタルサイト」は、焼成されていない天然ハイドロタルサイト(Mg6Al2(OH)16CO3・4H2O)および合成ハイドロタルサイト(ハイドロタルサイト様化合物)を含む概念である。即ち、本発明における「ハイドロタルサイト」とは、「未焼成ハイドロタルサイト」を意味する。
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
で求めることができる。
飽和吸水率(質量%)
=100×(吸湿後の質量-初期質量)/初期質量
で求めることができる。
[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。)で表されるものが挙げられる。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。
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。)
で表されるものが挙げられる。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。
・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:10m2/g)
・DHT-4A(協和化学工業社製):ハイドロタルサイト(平均粒子径:400nm、BET比表面積:10m2/g)
ポリオレフィン系樹脂を含む樹脂組成物に吸湿性金属酸化物を添加すると、その透明性が低下する傾向にある。そのため、透明性を向上させる観点からは、本発明の樹脂組成物では、実質的に吸湿性金属酸化物を含まないことが好ましい。吸湿性金属酸化物の含有量は、例えば、後掲する樹脂組成物層の透過率の値が、好ましくは90%以上、より好ましくは95%以上となるような範囲であるのが望ましい。例えば、吸湿性金属酸化物の含有量は、樹脂組成物中の不揮発分の合計100質量%あたり、1質量%以下(即ち、0~1質量%)が好ましく、0.5質量%以下(即ち、0~0.5質量%)がより好ましい。吸湿性金属酸化物としては、例えば、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、焼成ドロマイト(酸化カルシウムおよび酸化マグネシウムを含む混合物)、焼成ハイドロタルサイトが挙げられる。
本発明の樹脂組成物は、さらに(C)粘着付与樹脂(以下「(C)成分」と略称することがある)を含んでいてもよい。粘着付与樹脂は、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。(C)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。
本発明の樹脂組成物は、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。
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。
本発明の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。
本発明の樹脂組成物は、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。
本発明の樹脂組成物には、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、吸湿性金属酸化物を除く);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。
本発明の封止用樹脂組成物は、感圧性接着剤であることが好ましい。感圧性接着剤とは、常温で比較的短時間圧力を加えるだけで接着する接着剤を意味し、当業者によく知られている。また、本発明の封止用樹脂組成物は、(C)粘着付与樹脂を含み、粘着性を有する感圧性接着剤であることがより好ましい。
本発明の樹脂組成物の製造方法は、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。
本発明の樹脂組成物は、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。本発明の樹脂組成物は、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、本発明の樹脂組成物を用いることができる。
本発明は、上述した本発明の樹脂組成物を含む封止用シートも提供する。具体的な態様としては、支持体、および前記支持体上に本発明の樹脂組成物から形成された樹脂組成物層を有する封止用シートが挙げられる。樹脂組成物層は、当業者に公知の方法で形成すればよく、例えば、有機溶剤に本発明の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。
本発明は、上述した本発明の樹脂組成物で封止された有機EL素子を有する有機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。封止用シート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、樹脂組成物層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。
(A)ポリオレフィン系樹脂
・T-YP429(星光PMC社製):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/メチルメタクリレート単位=68%/32%、酸無水物基濃度:0.46mmol/g、数平均分子量:2,300)
・T-YP431(星光PMC社製):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)
・T-YP430(星光PMC社製):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/メチルメタクリレート単位=68%/32%、酸無水物基濃度:1.18mmol/g、数平均分子量:4,500)
・T-YP432(星光PMC社製):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)
・T-YP8920(星光PMC社製):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(スチレン単位/イソブチレン単位=20%/80%、酸無水物基濃度:0.464mmol/g、数平均分子量:35,800)
・T-YP8930(星光PMC社製):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(スチレン単位/イソブチレン単位=20%/80%、エポキシ基濃度:0.638mmol/g、数平均分子量:48,700)
・T-YP312(星光PMC社製):無水マレイン酸変性プロピレン-ブテン共重合体(プロピレン単位/ブテン単位=71%/29%、酸無水物基濃度:0.464mmol/g、数平均分子量:60,900)
・T-YP313(星光PMC社製):グリシジルメタクリレート変性プロピレン-ブテン共重合体(プロピレン単位/ブテン単位=71%/29%、エポキシ基濃度:0.638mmol/g、数平均分子量:155,000)
・T-YP341(星光PMC社製):グリシジルメタクリレート変性プロピレン-ブテン共重合体(プロピレン単位/ブテン単位:71%/29%、エポキシ基濃度:0.638mmol/g、数平均分子量:155,000)
・HV-300M(東邦化学工業社):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)
・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:10m2/g)
・DHT-4A(協和化学工業社製):ハイドロタルサイト(平均粒子径:400nm、BET比表面積:10m2/g)
・KW2200(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:129m2/g)
・N41S:焼成ハイドロタルサイト(戸田工業社製)(平均粒径:40nm、BET比表面積:133m2/g)
・モイストップ#10(三共製粉社製):酸化カルシウム(平均粒子径:4μm、BET比表面積:5m2/g)
・FNM-G(タテホ化学工業社製):酸化マグネシウム(平均粒子径:400nm、BET比表面積:74m2/g)
・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℃)
・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。)
・トルエン
・スワゾール#1000(丸善石油社製):芳香族系混合溶剤
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、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(T-YP429、20%トルエン溶液)120部、ポリブテン(HV-1900)60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、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(T-YP431、20%トルエン溶液)90部、アミン系硬化剤(TAP)0.5部およびトルエン170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20μmの樹脂組成物層を有する封止用シートを得た。
半焼成ハイドロタルサイト(DHT-4C)の使用量を100部から80部に変えたこと以外は実施例1と同様の方法にて、樹脂組成物のワニスおよび封止用シートを作製した。
半焼成ハイドロタルサイト(DHT-4C)の代わりに同量の半焼成ハイドロタルサイト(DHT-4A-2)を使用したこと以外は実施例1と同様の方法にて、樹脂組成物のワニスおよび封止用シートを作製した。
半焼成ハイドロタルサイト(DHT-4C)の代わりに同量のハイドロタルサイト(DHT-4A)を使用したこと以外は実施例1と同様の方法にて、樹脂組成物のワニスおよび封止用シートを作製した。
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(T-YP429、20%トルエン溶液)の代わりに、同量の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(T-YP430、20%トルエン溶液)を使用したこと、および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(T-YP431、20%トルエン溶液)の代わりに、同量の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(T-YP432、20%トルエン溶液)を使用したこと以外は実施例1と同様の方法にて、樹脂組成物のワニスおよび封止用シートを作製した。
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(T-YP429、20%トルエン溶液)の代わりに、同量の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(T-YP8920、20%トルエン溶液)を使用したこと、および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(T-YP431、20%トルエン溶液)の代わりに、同量の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(T-YP8930、20%トルエン溶液)を使用したこと以外は実施例1と同様の方法にて、樹脂組成物のワニスおよび封止用シートを作製した。
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(T-YP429、20%トルエン溶液)の代わりに、同量の無水マレイン酸変性プロピレン-ポリブテン共重合体(T-YP312、20%トルエン溶液)を使用したこと、および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(T-YP431、20%トルエン溶液)の代わりに、同量のグリシジルメタクリレート変性プロピレン-ブテン共重合体(T-YP313、20%トルエン溶液)を使用したこと以外は実施例1と同様の方法にて、樹脂組成物のワニスおよび封止用シートを作製した。
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(T-YP429、20%トルエン溶液)120部の代わりに、グリシジルメタクリレート変性プロピレンーブテン共重合体(T-YP341、20%トルエン溶液)200部を使用したこと、および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(T-YP431、20%トルエン溶液)90部の代わりに、無水マレイン酸変性液状ポリブテン(HV-300M)35部を使用したこと以外は実施例1と同様の方法にて、樹脂組成物のワニスおよび封止用シートを作製した。
半焼成ハイドロタルサイト(DHT-4C)の代わりに焼成ハイドロタルサイト(KW2200)を使用したこと以外は実施例1と同様の方法にて、樹脂組成物のワニスおよび封止用シートを作製した。
半焼成ハイドロタルサイト(DHT-4C)の代わりに焼成ハイドロタルサイト(N41S)を使用したこと以外は実施例1と同様の方法にて、樹脂組成物のワニスおよび封止用シートを作製した。
半焼成ハイドロタルサイト(DHT-4C)の代わりに酸化カルシウム(モイストップ#10)を使用したこと以外は実施例1と同様の方法にて、樹脂組成物のワニスおよび封止用シートを作製した。
半焼成ハイドロタルサイト(DHT-4C)の代わりに酸化マグネシウム(FNM-G)を使用したこと以外は実施例1と同様の方法にて、樹脂組成物のワニスおよび封止用シートを作製した。
実施例および比較例で作製した封止用シートの支持体(PETフィルム)から剥離した樹脂組成物層(厚さ:45μm)の1m2あたりの水蒸気透過量を、JIS Z0208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、以下の基準で評価した。結果を表1に示す。
良好(○):水蒸気透過量が10g/m2・24hr未満
可(△):水蒸気透過量が10g/m2・24hr以上、20g/m2・24hr未満
不良(×):水蒸気透過量が20g/m2・24hr以上
実施例および比較例で作製した封止用シート(樹脂組成物層の厚さ:20μm)を長さ50mmおよび幅20mmにカットし、カットした封止用シートをガラス板(長さ76mm、幅26mmおよび厚さ1.2mmのマイクロスライドガラス、松浪ガラス工業社製白スライドグラスS1112 縁磨No.2)にバッチ式真空ラミネーター(ニチゴー・モートン社製、V-160)を用いてラミネートした。ラミネート条件は、温度80℃、減圧時間30秒の後、圧力0.3MPaにて30秒加圧であった。その後、封止用シートのPETフィルムを剥離し、露出した硬化した樹脂組成物層にさらに上記と同じガラス板をラミネートして、積層体を作製した。得られた積層体の光透過率スペクトルを、φ80mm積分球(型名SRS-99-010、反射率99%)を装着したファイバー式分光光度計(MCPD-7700、形式311C、大塚電子社製、外部光源ユニット:ハロゲンランプMC-2564(24V、150W仕様))を用いて測定し、波長450nmでの全光線透過率を算出し、以下の基準で評価した。なお、積分球とサンプル(積層体)の距離を0mmとし、リファレンスとしてはガラスを用いた。
良好(○):95%以上
可(△):90%以上、95%未満
不良(×):90%未満
Claims (13)
- (A)ポリオレフィン系樹脂、並びに(B)ハイドロタルサイトおよび半焼成ハイドロタルサイトからなる群から選ばれる金属水酸化物を含む封止用樹脂組成物。
- (A)ポリオレフィン系樹脂が、酸無水物基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請求項1に記載の樹脂組成物。
- (A)ポリオレフィン系樹脂が、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を含む請求項1に記載の樹脂組成物。
- さらに(C)粘着付与樹脂を含む請求項1~3のいずれか一項に記載の樹脂組成物。
- さらに(D)硬化剤を含む請求項1~4のいずれか一項に記載の樹脂組成物。
- 感圧性接着剤である請求項1~5のいずれか一項に記載の樹脂組成物。
- 有機EL素子の封止用である請求項1~6のいずれか一項に記載の樹脂組成物。
- 厚さが20μmである樹脂組成物層の波長450nmでの全光線透過率(平行線透過率)が、90%以上である請求項1~7のいずれか一項に記載の樹脂組成物
- 請求項1~8のいずれか一項に記載の樹脂組成物からなる樹脂組成物層が支持体の片面または両面に形成されている封止用シート。
- (A)ポリオレフィン系樹脂が、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を含み、樹脂組成物層が、酸無水物基とエポキシ基が反応した架橋構造を有する、請求項9に記載の封止用シート。
- 有機EL素子の封止用である請求項9または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樹脂組成物で封止された有機EL素子を有する有機ELデバイス。
- 請求項9~11のいずれか一項に記載の封止用シートで封止された有機EL素子を有する有機ELデバイス。
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KR20220012200A (ko) | 2020-07-22 | 2022-02-03 | 아지노모토 가부시키가이샤 | 밀봉용 시트 및 점착 조성물 층 |
JP7528605B2 (ja) | 2020-07-22 | 2024-08-06 | 味の素株式会社 | 封止用シートおよびポリマー組成物層 |
DE112021005948T5 (de) | 2020-11-13 | 2023-09-21 | Ajinomoto Co., Inc. | Dichtungsbahn |
KR20230104692A (ko) | 2020-11-13 | 2023-07-10 | 아지노모토 가부시키가이샤 | 밀봉용 시트 |
DE102022116314A1 (de) | 2021-07-01 | 2023-01-05 | Ajinomoto Co., Inc. | Dichtungsfolie |
KR20230005775A (ko) | 2021-07-01 | 2023-01-10 | 아지노모토 가부시키가이샤 | 밀봉용 시트 |
KR20230005780A (ko) | 2021-07-01 | 2023-01-10 | 아지노모토 가부시키가이샤 | 밀봉용 조성물 |
DE102022116437A1 (de) | 2021-07-01 | 2023-01-05 | Ajinomoto Co., Inc. | Dichtungszusammensetzung |
KR20230113169A (ko) | 2022-01-21 | 2023-07-28 | 아지노모토 가부시키가이샤 | 밀봉용 조성물 및 그 제조 방법, 및 밀봉용 시트 |
DE102023101267A1 (de) | 2022-01-21 | 2023-07-27 | Ajinomoto Co., Inc. | Dichtungszusammensetzung und verfahren zu ihrer herstellung, und dichtungsfolie |
KR20230136066A (ko) | 2022-03-17 | 2023-09-26 | 아지노모토 가부시키가이샤 | 밀봉용 조성물 및 밀봉용 시트 |
WO2024135630A1 (ja) * | 2022-12-22 | 2024-06-27 | 株式会社レゾナック | 樹脂組成物 |
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KR20180061335A (ko) | 2018-06-07 |
CN108026430A (zh) | 2018-05-11 |
TW201730316A (zh) | 2017-09-01 |
KR102612145B1 (ko) | 2023-12-12 |
TWI716467B (zh) | 2021-01-21 |
JPWO2017057708A1 (ja) | 2018-07-26 |
CN108026430B (zh) | 2020-09-01 |
JP6683204B2 (ja) | 2020-04-15 |
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