WO2012176472A1 - 光半導体用の面封止剤、それを用いた有機elデバイスの製造方法、有機elデバイスおよび有機elディスプレイパネル - Google Patents
光半導体用の面封止剤、それを用いた有機elデバイスの製造方法、有機elデバイスおよび有機elディスプレイパネル Download PDFInfo
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- WO2012176472A1 WO2012176472A1 PCT/JP2012/004072 JP2012004072W WO2012176472A1 WO 2012176472 A1 WO2012176472 A1 WO 2012176472A1 JP 2012004072 W JP2012004072 W JP 2012004072W WO 2012176472 A1 WO2012176472 A1 WO 2012176472A1
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- organic
- sealing agent
- surface sealing
- carbon atoms
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- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- JBYYGVMOBTYNOM-UHFFFAOYSA-N trimethoxy-[3-(4-methylpiperazin-1-yl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCN1CCN(C)CC1 JBYYGVMOBTYNOM-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- PKJOUIVGCFHFTK-UHFFFAOYSA-L zinc;hexanoate Chemical compound [Zn+2].CCCCCC([O-])=O.CCCCCC([O-])=O PKJOUIVGCFHFTK-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- 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
- H10K50/842—Containers
- H10K50/8423—Metallic sealing arrangements
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/70—Chelates
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- 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
- H10K50/842—Containers
- H10K50/8426—Peripheral sealing arrangements, e.g. adhesives, sealants
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
Definitions
- the present invention relates to a surface sealant for an optical semiconductor, a method for producing an organic EL device using the same, an organic EL device, and an organic EL display panel.
- the organic EL element is an optical semiconductor device, and is expected as a liquid crystal backlight or a self-luminous thin flat display device.
- organic EL elements are extremely susceptible to deterioration when exposed to moisture and oxygen. In other words, the interface between the metal electrode and the organic EL layer is peeled off due to the influence of moisture, the metal is oxidized to increase the resistance, or the light emitting material contained in the light emitting layer of the organic EL element is altered by moisture. I do. For this reason, there are disadvantages that the organic EL element does not emit light or the luminance is lowered. Further, even in an optical semiconductor such as an inorganic LED, an electrical circuit connected to the optical semiconductor may be deteriorated by contact with moisture or the like.
- an organic EL sealing agent layer containing (A) a compound having a glycidyl group and (B) an acid anhydride curing agent as main components is laminated on an organic EL element (surface sealing). ), And a method of bonding glass or film is known (for example, see Patent Document 1).
- the organic EL element since the organic EL element is easily deteriorated by moisture, oxygen, etc., it is often sealed with a laminated film having a resin layer made of a resin and an inorganic compound layer made of an inorganic compound.
- the sealing of the organic EL element with the laminated film is 1) a method in which the organic EL element is covered with an inorganic compound layer and then further covered with a resin layer; and 2) after the organic EL element is covered with a resin layer and further inorganic.
- There is a method of covering with a compound layer see Patent Document 2.
- an epoxy resin composition containing a compound represented by Zn (C n H 2n + 1 COO) 2 and an imidazole compound as a curing accelerator has been proposed as a sealant for photosensors and LEDs (for example, patents).
- Reference 3 Further, as a powder coding material, a composition containing a metal complex in which an amine compound and a carboxylate are coordinated to metal ions such as zinc has been proposed (for example, Patent Document 4).
- JP 2006-70221 A JP 2009-252364 A Japanese Patent Laid-Open No. 10-45879 International Publication No. 2006/022899
- the optical semiconductor sealing conditions must be adjusted according to the change in the viscosity of the surface sealant, and the manufacturing efficiency of the optical semiconductor device There was a problem that decreased.
- the storage stability of the surface sealing agent is improved, the surface sealing agent tends to be hard to be cured when the optical semiconductor is sealed, and the curing time becomes long. There was a problem that efficiency decreased.
- optical semiconductors particularly optical semiconductors that emit light, such as organic EL devices
- OLEDs are exposed to sunlight for a long time when used as portable electronic devices or lighting fixtures, so that they need weather resistance.
- the cured product of the surface sealing agent for organic EL elements is discolored by exposure to sunlight or the like, in the case of a top emission type organic EL device, the light extraction efficiency is lowered and the design property is deteriorated. There was a problem.
- the back emission type organic EL device has a problem that the design property is deteriorated.
- composition of Patent Document 3 sometimes had insufficient curability.
- composition of patent document 4 can improve comparatively storage stability, since it is thought that a viscosity is high, it is thought that it is not suitable as a sealing agent.
- the present invention has been made in view of the above circumstances, and the first object of the present invention is a resin composition for sealing an optical semiconductor, which has good curability and storage stability. It is to provide a raw material for a sealing resin layer excellent in weatherability; preferably a raw material for a sealing resin layer further excellent in weather resistance.
- the second object of the present invention is to provide a raw material for a sealing resin layer which is a resin composition for sealing an optical semiconductor and has excellent weather resistance.
- the first of the present invention relates to the following surface sealing agent for optical semiconductors.
- a metal complex (b1) comprising a tertiary amine that can form a complex with a metal ion and has no NH bond, and an anionic ligand having a molecular weight of 17 to 200;
- a surface sealant for optical semiconductors having a viscosity of 10 to 10,000 mPa ⁇ s measured at 25 ° C. and 1.0 rpm with a viscometer.
- R 1 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms, a hydroxyl group, an aryl-containing group, or a cyanoethyl group
- R 2 , R 3 , and R 4 are each independently a hydrogen group
- an aliphatic hydrocarbon group having 1 to 17 carbon atoms, a hydroxyl group, an aryl-containing group, or a cyanoethyl group (In the general formula (2), RB1, RB3, RB4, and RB5 are each independently a hydrogen group, an aliphatic hydrocarbon group that may contain a heteroatom having 1 to 17 carbon atoms, a hydroxyl group, an aryl-containing group, or cyanoethyl.
- RB2 represents an aliphatic hydrocarbon group, a hydroxyl group, an aryl-containing group or a cyanoethyl group which may contain a hetero atom having 1 to 17 carbon atoms; and is selected from RB1, RB2, RB3, RB4, and RB5
- a plurality of groups may be connected to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from oxygen, nitrogen, and sulfur)
- RC1, RC3, RC4, and RC5 each independently represent a hydrogen group, an aliphatic hydrocarbon group that may contain a hetero atom having 1 to 17 carbon atoms, a hydroxyl group, an aryl-containing group, or cyanoethyl.
- RC2 represents an aliphatic hydrocarbon group, a hydroxyl group, an aryl-containing group or a cyanoethyl group which may contain a heteroatom having 1 to 17 carbon atoms; selected from RC1, RC2, RC3, RC4 and RC5
- a plurality of groups may be connected to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from oxygen, nitrogen, and sulfur)
- RE1, RE2, RE3, RE4, and RE5 are each independently a hydrogen group, an aliphatic hydrocarbon group that may contain a heteroatom having 1 to 17 carbon atoms, a hydroxyl group, and an aryl-containing group.
- a cyanoethyl group a plurality of groups selected from RE1, RE2, RE3, RE4, and RE5 are connected to each other and contain an alicyclic ring, an aromatic ring, or a heteroatom selected from oxygen, nitrogen, and sulfur A heterocycle may be formed)
- RF1, RF2, RF3, RF4, RF5, RF6, and RF7 are each independently a hydrogen group, an aliphatic hydrocarbon group that may contain 1 to 17 carbon atoms, or a hydroxyl group.
- a heterocycle containing a heteroatom selected from: (In the general formula (6), RG1, RG2, RG3, and RG4 each independently represent a hydrogen group, an aliphatic hydrocarbon group that may contain a hetero atom having 1 to 17 carbon atoms, a hydroxyl group, an aryl-containing group, or cyanoethyl.
- a plurality of groups selected from RG1, RG2, RG3, and RG4 are linked to each other to form an alicyclic ring, an aromatic ring, or a heterocycle containing a heteroatom selected from oxygen, nitrogen, and sulfur You may) [4]
- the anionic ligand is selected from the group consisting of O, S and P, has 2 or more atoms capable of binding to the metal ion, and is coordinated to the metal ion to be 3 to 7 members.
- the surface sealing agent for optical semiconductors according to any one of [1] to [3], which is capable of forming a ring.
- the tertiary amine is a compound represented by any one of the general formulas (1) to (3), and the anionic ligand is a carboxy represented by the following general formula (7A)
- RD1 is a free or hydrogen atom
- RD2 is a hydrogen group, a hydrocarbon group having 1 to 10 carbon atoms, or a hydroxyl group
- [6] of the surface sealant in CDCl 3, 25 ° C.
- chemical shifts derived from the tertiary amine of the 1 HNMR chemical shift at 270MHz is the tertiary amine alone, in CDCl 3, 25 ° C.
- the surface sealing agent for optical semiconductors according to any one of [1] to [5], which contains a peak that moves 0.1 ppm or more with respect to a 1 HNMR chemical shift at 270 MHz.
- the surface sealant for optical semiconductors according to any one of [1] to [6], wherein the molar ratio of the tertiary amine to the metal ion is 0.5 to 6.0.
- the carboxylate compound is 2-ethylhexanoic acid, formic acid, acetic acid, butanoic acid, 2-ethylbutanoic acid, 2,2-dimethylbutanoic acid, 3-methylbutanoic acid, 2,2-dimethylpropanoic acid, benzoic acid.
- a surface sealant for optical semiconductors according to [5] which is at least one compound selected from the group consisting of naphthenic acid.
- the tertiary amine is 1,8-diazobicyclo [5,4,0] undec-7-ene, 1-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1 -At least one compound selected from the group consisting of isobutyl-2-methylimidazole, 1-butylimidazole and 1,5-diazobicyclo [4,3,0] non-5-ene; 8]
- the surface sealing agent for optical semiconductors in any one of.
- the second of the present invention relates to the following surface sealant for optical semiconductors.
- An E-type viscometer comprising an epoxy resin (a) having two or more epoxy groups in one molecule and a curing accelerator (b2) represented by the following general formula (11) or (12) A surface sealant for optical semiconductors having a viscosity of 10 to 10,000 mPa ⁇ s measured at 25 ° C. and 1.0 rpm.
- R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen group, an aliphatic hydrocarbon group having 1 to 17 carbon atoms, a hydroxyl group, an aryl-containing group or a cyanoethyl group.
- R 1 is a hydrogen group
- R 2 and R 4 are an aryl group
- RA 1 , RA 2 , RA 3 and RA 4 are each independently a hydrogen group, an aliphatic hydrocarbon group having 1 to 17 carbon atoms, a hydroxyl group, an aryl-containing group, or a dimethylaminomethyl group.
- RA 1 , RA 2 , RA 3 and RA 4 is a dimethylaminomethyl group
- R 1 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms, a hydroxyl group, an aryl-containing group, or a cyanoethyl group. Stopper.
- the surface sealing agent for an optical semiconductor includes the metal complex (b1) in a range where the equivalent ratio of active functional group / epoxy group of tertiary amine is 0.008 to 0.3. [1] The surface sealant for optical semiconductors according to any one of [9]. [13] The surface sealing agent for an optical semiconductor contains the curing accelerator (b2) in a range where the equivalent ratio of active functional group / epoxy group of tertiary amine is 0.008 to 0.152. The surface sealing agent for optical semiconductors as described in [10] or [11]. [14] The surface sealing agent for an optical semiconductor further includes an acid anhydride in a range where the equivalent ratio of acid anhydride group / epoxy group is 0.8 to 1.2.
- the surface sealing agent for optical semiconductors in any one of.
- the third of the present invention relates to the following method for producing an organic EL device.
- the process of manufacturing an organic EL device including the process.
- An organic EL device including a cured product layer and a passivation layer in contact with the cured product layer.
- the organic EL element and the organic EL element are sealed, and consist of Zn, Bi, Ca, Al, Cd, La, and Zr in the spectrum measured by X-ray photoelectron spectroscopy (XPS).
- the surface sealant of the first aspect of the present invention has good curability and is excellent in storage stability. Therefore, the sealing conditions of the optical semiconductor such as the organic EL element can be made constant to some extent, and the manufacturing efficiency of the optical semiconductor can be increased. Moreover, the light resistance of the sealing film of an optical semiconductor can be improved by using the surface sealing agent of the 2nd form of this invention, for example, the transparency can be maintained. Therefore, light emitted from an optical semiconductor such as an organic EL element can be extracted with high efficiency, and design properties can be maintained. In addition, light incident on the optical semiconductor can be taken into the optical semiconductor without being greatly attenuated. Therefore, in particular, improvement of the luminance of the organic EL element is realized.
- the epoxy resin composition of the present invention includes an epoxy resin (a) and an amine compound (b); and may further include an acid anhydride (c) and the like.
- the epoxy resin composition of the present invention can be used, for example, as a surface sealant, a transparent fill agent, etc .; preferably as a surface sealant.
- the transparent fill agent refers to a material that requires transparency to fill a space between a substrate such as a touch panel and an image display device such as a liquid crystal panel.
- the surface sealant of the present invention includes the surface sealant of the first or second form described later.
- the epoxy resin (a) contained in the surface sealing agent of the present invention may be an epoxy resin having two or more epoxy groups in one molecule, and the molecular weight is not particularly limited. An epoxy resin having no molecular weight distribution or an epoxy resin having a molecular weight distribution can be used.
- epoxy resins having two epoxy groups in one molecule include hydroquinone diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, dicyclopentadienediol diglycidyl ether, 1,6-naphthalenediol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F di Examples include glycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol F diglycidyl ether.
- Examples of the compound having 3 or more epoxy groups in one molecule include trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, phenol novolac type epoxy, cresol novolac type epoxy and the like.
- the epoxy resin may contain a polymer or oligomer having an epoxy group.
- the polymer or oligomer having an epoxy group is not particularly limited, but can be obtained by polymerizing a vinyl monomer having an epoxy group.
- vinyl monomers having an epoxy group are preferably (meth) acrylate monomers such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and methylglycidyl (meth) acrylate.
- the epoxy resin may be a copolymer or oligomer of a vinyl monomer having an epoxy group and another vinyl monomer.
- examples of other vinyl monomers include (meth) acrylates.
- the ester groups of (meth) acrylates are methyl, ethyl, isopropyl, normal butyl, isobutyl, tertiary butyl, 2-ethylhexyl, cyclohexyl, benzyl, isoboronyl, lauryl, myristyl.
- a non-functional alkyl ester is preferable regardless of a linear structure or a branched structure.
- the epoxy resin may be a copolymer of a vinyl monomer having an epoxy group and styrene, ⁇ -methylstyrene, vinyl acetate or the like.
- Preferred specific examples of the epoxy resin (a) contained in the surface sealant of the present invention include tetrafunctional naphthalene type epoxy resin (aa), triphenylmethane type epoxy resin (ab), and dicyclopentadiene type.
- the heat resistance of the cured resin containing these epoxy resins is likely to be improved.
- the cured resin containing these epoxy resins is likely to increase transparency and adhesion.
- the viscosity of the surface sealant containing these epoxy resins is easily adjusted to a desired range (viscosity measured at 25 ° C. and 1.0 rpm with an E-type viscometer is 10 to 10,000 mPa ⁇ s). Therefore, the surface sealing agent of the present invention is easy to form a film by screen printing or the like.
- a cured resin containing an epoxy resin having such a bulky group is subject to plasma and thus its transparency is lowered and haze is likely to increase.
- the surface sealing agent of this invention which mix
- the surface sealant of the present invention preferably contains at least a low molecular weight epoxy resin (a-1) as the epoxy resin (a) so that the viscosity can be easily adjusted to a range described later. Further, a surface-sealing molded product such as a sheet can be obtained by further adding a high molecular weight epoxy resin (a-2) to the surface sealing agent of the present invention as necessary.
- the low molecular weight epoxy resin (a-1) is an epoxy resin having a weight average molecular weight of 200 to 800; preferably an epoxy resin having a weight average molecular weight of 300 to 700.
- the “weight average molecular weight (Mw)” is measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
- Examples of the epoxy resin (a-1) include bisphenol type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds and the like.
- Examples of the bisphenol type epoxy compound include a compound represented by the general formula (X), and preferable examples include a compound represented by the general formula (X ′).
- X represents a single bond, a methylene group, an isopropylidene group, —S—, or —SO 2 —; each R 1 independently represents an alkyl group having 1 to 5 carbon atoms.
- N represents an integer of 2 or more, and P represents an integer of 0 to 4.
- oligomeric phenol derivatives containing phenol derivatives and epichlorohydrin as monomer components examples include bisphenol, hydrogenated bisphenol, phenol novolac, cresol novolac, and the like.
- the low molecular weight epoxy resin (a-1) include a bisphenol type epoxy compound or an oligomer having bisphenol and epichlorohydrin as monomer components, and more preferably in the general formula (X), An oligomer having a repeating number n of 2 to 4. This is because the affinity for the high molecular weight epoxy resin (a-2), which can be arbitrarily blended with the surface sealing agent of the present invention, is high when obtaining the surface sealing molded product described later.
- the repeating structural unit contained in the low molecular weight epoxy resin (a-1) may be the same as or different from the repeating structural unit contained in the high molecular weight epoxy resin (a-2).
- the epoxy equivalent of the low molecular weight epoxy resin (a-1) is preferably 100 to 800 g / eq.
- the low molecular weight epoxy resin (a-1) contained in the encapsulating composition of the present invention mainly improves the fluidity of the encapsulating sheet when thermocompression-bonded to the element and improves the adhesion to the element. It has a function.
- a surface-sealed molded product such as a sheet can be obtained by using the surface-sealing agent of the present invention.
- the surface sealing molded product may contain either one or both of a high molecular weight epoxy resin (a-2) and a low molecular weight epoxy resin (a-1).
- Examples of the high molecular weight epoxy resin (a-2) include a resin or an oligomer containing a phenol resin and epichlorohydrin as monomer components, and preferably an oligomer.
- the phenol resin includes a hydroxyaryl resin such as a naphthol resin.
- the weight average molecular weight (Mw) of the high molecular weight phenol type epoxy resin (a-2) is 3 ⁇ 10 3 to 2 ⁇ 10 4 , preferably 3 ⁇ 10 3 to 7 ⁇ 10 3 .
- the “weight average molecular weight (Mw)” is measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
- the weight average molecular weight (Mw) of the epoxy resin (a-2) By setting the weight average molecular weight (Mw) of the epoxy resin (a-2) within the above numerical range, it is possible to obtain a surface-sealed molded product that produces a sealing film having strong adhesion and low moisture permeability. Moreover, the surface sealing agent containing the epoxy resin (a-2) whose weight average molecular weight (Mw) is in the above numerical range is easy to apply and form a film in a sheet shape.
- the weight average molecular weight (Mw) of the epoxy resin (a-2) is not excessively high and is appropriately controlled. For this reason, the hardened
- the epoxy resin (a-2) is preferably an oligomer having a phenol resin and epichlorohydrin as monomer components. All of the monomer components of the epoxy resin (a-2) may be a phenol resin and epichlorohydrin, or a part of the monomer component may be a compound (comonomer component) other than the phenol resin and epichlorohydrin. By using a part of the monomer component as the comonomer component, the weight average molecular weight (Mw) of the resulting epoxy resin (a-2) can be easily controlled to a desired value. By appropriately selecting the monomer component of the epoxy resin (a-2), the smoothness of the coating film surface of the sealing composition can be improved.
- the epoxy equivalent of the epoxy resin (a-2) is preferably 500 to 10,000 g / eq.
- the ratio of the high molecular weight epoxy resin (a-2) and the low molecular weight epoxy resin (a-1) in the epoxy resin contained in the surface-sealed molded product of the present invention is not particularly limited, and a desired viscosity is realized. It is preferable to adjust the composition so that it is possible. If the content of the high molecular weight epoxy resin (a-2) is too large, the moisture permeability of the cured product (seal member) tends to increase. Moreover, the fluidity
- Amine compound (b) The amine compound (b) contained in the surface sealing agent of the present invention may be a tertiary amine metal complex (b1) or a specific amine compound (b2). These amine compounds (b) can function as curing accelerators.
- the surface sealing agent of the first embodiment of the present invention contains a tertiary amine metal complex (b1).
- the tertiary amine metal complex (b1) includes a metal ion, a tertiary amine that coordinates to the metal ion, and an anionic ligand that coordinates or ionically bonds to the metal ion.
- the metal ion in the metal complex (b1) may be a metal ion selected from the group consisting of Zn, Bi, Ca, Al, Cd, La, and Zr. Zn is preferable from the viewpoint of improving the transparency of the surface sealing agent.
- the metal complex (b1) contains two or more metal ions, at least one of the metal ions may be a metal ion selected from Zn, Bi, Ca, Al, Cd, La, and Zr.
- the tertiary amine in the metal complex (b1) is preferably capable of forming a complex with a metal ion and not having an N—H bond in order to reduce the reactivity of the tertiary amine under storage conditions.
- the molecular weight of the tertiary amine in the metal complex (b1) is preferably 65 to 300. This is because if the molecular weight of the tertiary amine is too large, the solubility of the metal complex (b1) in the surface sealing agent may be decreased, and the catalytic activity may be decreased.
- the tertiary amine in the metal complex (b1) is preferably a compound represented by any one of the following general formulas (1) to (6).
- a conjugated electron cloud gathers on the nitrogen atoms constituting the ring, and a complex is easily formed with a metal ion.
- the cured product layer of the surface sealing agent containing these compounds is considered to have good plasma resistance and weather resistance with little decrease in transparency and increase in haze even if plasma treatment is performed.
- R 2 , R 3 , and R 4 are each independently a hydrogen group, an aliphatic hydrocarbon group having 1 to 17 carbon atoms, a hydroxyl group, an aryl-containing group, or a cyanoethyl group.
- the aliphatic hydrocarbon group having 1 to 17 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms.
- the aryl-containing group include an aryl group such as a phenyl group and a naphthyl group, and an arylalkyl group such as a benzyl group.
- the number of carbon atoms constituting the aryl-containing group is preferably in the range of 6 to 11.
- R 1 is a substituent other than a hydrogen atom (an aliphatic hydrocarbon group, an aryl group, a hydroxyl group, or a cyanoethyl group). Compared with the case where R 1 is another substituent, when R 1 is a hydrogen atom, the sealing layer made of a cured product of the surface sealing agent is exposed to plasma or the like, thereby reducing transparency. Because there are things to do.
- amine compound represented by the general formula (1) examples include the following 1-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, -Butylimidazole, 1-benzyl-2-phenylimidazole, 2-phenyl-4-methylimidazole and the like.
- RB1, RB3, RB4, and RB5 are each independently a hydrogen group, an aliphatic hydrocarbon group that may contain a heteroatom having 1 to 17 carbon atoms, a hydroxyl group, an aryl-containing group, or a cyanoethyl group.
- RB2 represents an aliphatic hydrocarbon group, a hydroxyl group, an aryl-containing group or a cyanoethyl group that may contain a hetero atom having 1 to 17 carbon atoms.
- a plurality of groups appropriately selected from RB1, RB2, RB3, RB4, and RB5 are connected to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from oxygen, nitrogen, and sulfur. May be.
- the aliphatic hydrocarbon group having 1 to 17 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms.
- Examples of the aryl-containing group include an aryl group such as a phenyl group and a naphthyl group, and an arylalkyl group such as a benzyl group.
- the number of carbon atoms constituting the aryl-containing group is preferably in the range of 6 to 11.
- amine compound represented by the general formula (2) include the following 1,8-diazobicyclo [5,4,0] undec-7-ene.
- RC1, RC3, RC4, and RC5 each independently represent a hydrogen group, an aliphatic hydrocarbon group that may contain a hetero atom having 1 to 17 carbon atoms, a hydroxyl group, an aryl-containing group, or a cyanoethyl group.
- RC2 represents an aliphatic hydrocarbon group, a hydroxyl group, an aryl-containing group or a cyanoethyl group which may contain a hetero atom having 1 to 17 carbon atoms.
- a plurality of groups appropriately selected from RC1, RC2, RC3, RC4, and RC5 are connected to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from oxygen, nitrogen, and sulfur. May be.
- the aliphatic hydrocarbon group having 1 to 17 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms.
- Examples of the aryl-containing group include an aryl group such as a phenyl group and a naphthyl group, and an arylalkyl group such as a benzyl group.
- the number of carbon atoms constituting the aryl-containing group is preferably in the range of 6 to 11.
- amine compound represented by the general formula (3) include the following 1,5-diazobicyclo [4,3,0] non-5-ene.
- RE1, RE2, RE3, RE4, and RE5 each independently represent a hydrogen group, an aliphatic hydrocarbon group that may contain a heteroatom having 1 to 17 carbon atoms, a hydroxyl group, an aryl-containing group, or A cyanoethyl group is shown.
- a plurality of groups selected from RE1, RE2, RE3, RE4, and RE5 are connected to each other to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from oxygen, nitrogen, and sulfur. May be.
- the aliphatic hydrocarbon group having 1 to 17 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms.
- Examples of the aryl-containing group include an aryl group such as a phenyl group and a naphthyl group, and an arylalkyl group such as a benzyl group.
- the number of carbon atoms constituting the aryl-containing group is preferably in the range of 6 to 11.
- amine compound represented by the general formula (4) examples include a compound represented by the following formula (4-1).
- RF1, RF2, RF3, RF4, RF5, RF6, and RF7 are each independently a hydrogen group, an aliphatic hydrocarbon group that may contain a heteroatom having 1 to 17 carbon atoms, a hydroxyl group, An aryl-containing group or a cyanoethyl group is shown.
- a plurality of groups selected from RF1, RF2, RF3, RF4, RF5, RF6, and RF7 are connected to each other, and an alicyclic ring, an aromatic ring, or a heterocycle containing a heteroatom selected from oxygen, nitrogen, and sulfur May be formed.
- the aliphatic hydrocarbon group having 1 to 17 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms.
- Examples of the aryl-containing group include an aryl group such as a phenyl group and a naphthyl group, and an arylalkyl group such as a benzyl group.
- the number of carbon atoms constituting the aryl-containing group is preferably in the range of 6 to 11.
- amine compound represented by the general formula (5) examples include a compound represented by the following formula (5-1).
- RG1, RG2, RG3, and RG4 each independently represent a hydrogen group, an aliphatic hydrocarbon group that may contain a heteroatom having 1 to 17 carbon atoms, a hydroxyl group, an aryl-containing group, or a cyanoethyl group. Indicates. A plurality of groups selected from RG1, RG2, RG3, and RG4 may be connected to each other to form an alicyclic ring, an aromatic ring, or a heterocycle containing a heteroatom selected from oxygen, nitrogen, and sulfur. .
- the aliphatic hydrocarbon group having 1 to 17 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms.
- Examples of the aryl-containing group include an aryl group such as a phenyl group and a naphthyl group, and an arylalkyl group such as a benzyl group.
- the number of carbon atoms constituting the aryl-containing group is preferably in the range of 6 to 11.
- amine compound represented by the general formula (6) examples include a compound represented by the following formula (6-1).
- the pKa of the compound represented by the formula (4) is around 5, whereas the pKa of the compound represented by the formula (1) is around 7, and the formula (2)
- the tertiary amine in the metal complex (b1) is a compound represented by any one of the general formulas (1) to (3) because of its high basicity and good curing activity with respect to the epoxy resin. It is preferable.
- the tertiary amine that forms a complex with the metal ion may be one type or two or more types. That is, the metal complex (b1) may be a binuclear complex having a plurality of metal ions as a central metal.
- the molar ratio of the tertiary amine to the metal ion in the metal complex (b1) is preferably 0.5 to 6.0, more preferably 0.6 to 2.0.
- the molar ratio is 0.5 or more, there are many tertiary amines coordinated to the metal complex (b1), and the curability of the surface sealing agent tends to be good.
- the molar ratio is 6.0 or less, there are few tertiary amines coordinated to the metal complex (b1), so that the storage stability of the surface sealing agent becomes good.
- the molar ratio is within the above range, the balance between curability and storage stability is good.
- the anionic ligand in the metal complex (b1) is a compound that has an acidic group having an atom selected from the group consisting of O, S, P, and halogen and coordinates or ionically bonds to a metal ion.
- the valence of the anionic ligand is preferably smaller than the valence of the metal ion. This is because an anionic ligand having a valence smaller than that of a metal ion can bind two or more to one metal ion and can stabilize the metal complex (b1).
- the molecular weight of the anionic ligand is preferably 17 to 200.
- the molecular weight of the anionic ligand is 17 or more, as will be described later, the coordination bond distance between the metal ion and the tertiary amine tends to be small, so that the curability of the metal complex (b1) is hardly impaired. Conceivable.
- the molecular weight of the anionic ligand is 200 or less, since the anionic ligand is not too large, the steric hindrance does not significantly interfere with the coordination of the tertiary amine to the metal ion. It is done. As a result, it is considered that the stability of the metal complex (b1) under storage conditions is not easily impaired.
- the radius of the anionic ligand is preferably 2.0 mm or more, and more preferably 2.4 mm or more. This is for improving the curability of the metal complex (b1). For example, when two anionic ligands are coordinated to a metal ion, when a tertiary amine is further coordinated to the metal ion, the bond between one anionic ligand and the metal ion and the other It is thought that the angle formed by the bond between the anionic ligand and the metal ion is narrowed and stabilized. If the radius of the anionic ligand is 2.0 mm or more, the angle formed by these bonds is difficult to narrow, so the coordination bond distance between the metal ion and the tertiary amine is likely to be small.
- the curability of the metal complex (b1) is hardly impaired. If the curability of the metal complex (b1) is difficult to be impaired, the degree of curing of the surface of the cured product tends to increase. When the degree of cure of the surface of the cured product is high, the smoothness of the surface of the cured product is unlikely to be impaired when a passivation layer or the like is formed on the surface of the cured product. Therefore, it is considered that the external haze of the cured product is unlikely to increase and the transparency is not easily impaired.
- the upper limit of the radius of the anionic ligand can be about 200 mm.
- the radius of the anionic ligand is 200 mm or less, it is considered that the size of the anionic ligand does not significantly prevent the tertiary amine from coordinating to the metal ion due to its steric hindrance. As a result, it is considered that the stability of the metal complex (b1) under storage conditions is not easily impaired.
- the radius of the anionic ligand can be calculated after determining the connolly volume of the anionic ligand; the radius when the connolly volume is assumed to be a true sphere volume.
- the connolly volume of the anionic ligand can be calculated using, for example, Material Studio 6.0 Dmol3 after optimizing the structure of the anionic ligand. Optimization of the structure of the anionic ligand can be performed by MM2 (molecular mechanics calculation method) or PBE / DNP 4.4. Thus, after optimizing the structure of the anionic ligand, connolly volume is obtained by setting connolly radius to 1.0 ⁇ .
- the radius of acetate ions For example, the case of calculating the radius of acetate ions will be described.
- the connelly volume of acetate ions is obtained by the method described above, it is 54.8 kg.
- the radius of the true sphere is determined to be about 2.36 cm, which can be used as the radius of acetate ions (ligands).
- the radii of chloride ions, sulfate ions, etc. can be the ionic radii (calculated values by Shannon and Prewitt) described in the Chemical Handbook, Basic Edition, Revised edition 2, edited by the Chemical Society of Japan.
- the valence of the anionic ligand is smaller than that of the metal ion, and the radius of the anionic ligand is 2.0 mm or more (preferably 2.4 mm or more).
- Anionic ligands include carboxylate compounds, 1,3-dicarbonyl compounds, dithiocarboxylic acids and their carboxylate anions, thiocarboxylic acids and their carboxylate anions, thionocarboxylic acids and their carboxylate anions, 1,3-dithiocarbonyl It can be a compound, a nitrate ion, a halogen ion or the like.
- the carboxylate compound is preferably a compound represented by the following formula (7A).
- RD1 is free or represents a hydrogen group.
- RD2 represents a hydrogen group, a hydrocarbon group having 1 to 10 carbon atoms, or a hydroxyl group.
- the hydrocarbon group having 1 to 10 carbon atoms may be an alkyl group having 1 to 10 carbon atoms or an aryl-containing group having 6 to 10 carbon atoms, and may be a linear or branched alkyl group having 1 to 7 carbon atoms. Is preferred.
- “RD1 is free” means that the carboxylate compound is an anion as shown in the following formula (7B).
- the hydroxyl group is coordinated to the metal ion; when RD1 is free, O ⁇ is often coordinated to the metal ion.
- Examples of the carboxylate compound represented by the formula (7A) include alkyl carboxylic acids having 2 to 10 carbon atoms and carboxylate anions thereof, aryl carboxylic acids having 7 to 10 carbon atoms and carboxylate anions thereof.
- alkyl carboxylic acids having 1 to 10 carbon atoms examples include formic acid, acetic acid, butanoic acid, 2-ethylbutanoic acid, 2,2-dimethylbutanoic acid, 2-ethylhexanoic acid, 3-methylbutanoic acid, 2,2-dimethyl Propanic acid and the like are included, and formic acid, acetic acid and 2-ethylhexanoic acid are particularly preferable.
- aryl carboxylic acids having 7 to 10 carbon atoms include benzoic acid and naphthenic acid.
- the 1,3-dicarbonyl compound is preferably a compound represented by the formula (8).
- R1 and R2 are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.
- the alkyl group having 1 to 10 carbon atoms may be a methyl group, an ethyl group, or the like.
- the aryl group having 6 to 10 carbon atoms may be a phenyl group, a naphthyl group, or the like. Examples of 1,3-dicarbonyl compounds include acetylacetonate and the like.
- dithiocarboxylic acid and its carboxylate anion examples include an alkyl dithiocarboxylic acid having 1 to 10 carbon atoms and its dithiocarboxylate anion, an aryl dithiocarboxylic acid having 7 to 15 carbon atoms and its dithiocarboxylate anion.
- alkyl dithiocarboxylic acid having 1 to 10 carbon atoms examples include dithioformic acid, dithioacetic acid, dithiopropanoic acid, dithio-2-ethylhexanoic acid and the like.
- Examples of the thiocarboxylic acid and its carboxylate anion include an alkylthiocarboxylic acid having 1 to 10 carbon atoms and its alkylthiocarboxylate anion, an arylthiocarboxylic acid having 7 to 15 carbon atoms and its arylthiocarboxylate anion.
- alkylthiocarboxylic acid having 1 to 10 carbon atoms examples include thioacetic acid and thio-2-ethylhexanoic acid.
- thionocarboxylic acid and its carboxylate anion examples include alkylthionocarboxylic acid having 1 to 10 carbon atoms and alkylthionocarboxylate anion thereof, arylthionocarboxylic acid having 7 to 15 carbon atoms and arylthionocarboxylate anion thereof. Is included.
- alkylthionocarboxylic acid having 1 to 10 carbon atoms examples include thionoacetic acid and thiono-2-ethylhexanoic acid.
- the 1,3-dithiocarbonyl compound is preferably a compound represented by the formula (9).
- R3 and R4 are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.
- the alkyl group having 1 to 10 carbon atoms may be a methyl group, an ethyl group, or the like.
- the aryl group having 6 to 10 carbon atoms may be a phenyl group, a naphthyl group, or the like.
- nitrates ions NO 3 - are included.
- halogen ions include Br 2- and the like.
- the number of atoms (atoms capable of binding to metal ions) selected from O, S, P and halogen contained in the anionic ligand may be one or two or more.
- An anionic ligand containing two or more atoms that can be bonded to a metal ion may be bonded to the metal ion through one atom; or may be bonded through each of two or more atoms.
- the metal ion contained in the anionic ligand The number of atoms that can be bonded to is preferably 2 or more.
- an anionic ligand containing two or more atoms capable of binding to a metal ion can form a 3- to 7-membered ring with the metal ion.
- anionic ligands include the carboxylate compound represented by the above formula (7A).
- the carboxylate compound represented by the formula (7A) can be bonded to a metal ion through either an oxygen atom constituting a carbonyl group or an oxygen atom adjacent to the carbonyl group.
- the metal complex (b1) includes a tertiary amine represented by any one of the above general formulas (1) to (3) and a carboxylate compound represented by the above general formula (7A). And are each a coordinated compound.
- the tertiary amine coordinated to the metal ion may be any one of the general formulas (1) to (3), or may be two or more.
- the metal complex (b1) is represented by the general formulas (1) to (3). It is preferable that the two amine compounds and the two carboxylate compounds represented by the general formula (7A) be a complex coordinated to a metal ion.
- a metal complex represented by the following general formula (10) is preferable.
- the metal complex (b1) has a polarity close to that of the epoxy resin (a) or an arbitrary acid anhydride (c) so as to be easily dissolved. Moreover, it is preferable that the tertiary amine in the metal complex (b1) is close in polarity so as to be easily dissolved in the epoxy resin (a) or any acid anhydride (c).
- a tertiary amine forms a complex with a metal ion should be confirmed by comparing the 1 H NMR chemical shift of the tertiary amine in the metal complex (b1) with the 1 H NMR chemical shift of the tertiary amine alone. Can do. That is, the chemical shift of 1 HNMR (25 ° C., 270 MHz in CDCl 3 ) of the tertiary amine in the metal complex (b1) is changed to the chemical shift of 1 HNMR (25 ° C., 270 MHz in CDCl 3 ) of the tertiary amine alone.
- the tertiary amine forms a complex with the metal ion by including a peak moving 0.05 ppm or more, preferably 0.1 ppm or more, more preferably 0.4 ppm or more.
- the upper limit of the amount of peak movement is not particularly limited, but is usually about 1 ppm, and more generally 0.7 ppm in many cases.
- Whether the tertiary amine in the surface sealing agent forms a complex with a metal ion is a chemical shift of 1 HNMR of the surface sealing agent. It can also be confirmed by comparing the chemical shift derived from the tertiary amine with the 1 HNMR chemical shift of the tertiary amine alone.
- the chemical shift derived from the tertiary amine out of the chemical shift of 1 HNMR (CDCl 3 , 25 ° C., 270 MHz) of the surface sealing agent is 1 HNMR (CDCl 3 in a surface sealant by including a peak that is moving 0.05 ppm or more, preferably 0.1 ppm or more, more preferably 0.4 ppm or more with respect to a chemical shift of 25 ° C., 270 MHz). It can be confirmed that the secondary amine forms a complex with the metal ion.
- the upper limit of the peak moving amount may be about 1 ppm, preferably about 0.7 ppm, as described above.
- whether or not the tertiary amine in the surface sealing agent forms a complex with a metal ion is a chemical shift of 1 HNMR of the surface sealing agent. And 1 HNMR chemical shift of the metal complex (b1) alone can be confirmed. For example, if there is a chemical shift similar to the 1 HNMR chemical shift of the metal complex (b1) alone during the 1 HNMR chemical shift of the surface sealant, the surface sealant contains the metal complex (b1). It can be judged.
- the peak moving in 1 HNMR originates from a hydrogen atom whose electronic state changes due to coordination of a tertiary amine to a metal ion.
- a hydrogen atom is generally considered to be a hydrogen atom existing around a conjugated system containing a nitrogen atom.
- the tertiary amine is an imidazole compound represented by the formula (1)
- the peak moving in 1 HNMR is often attributed to the hydrogen atom at the 4th or 5th position.
- Tertiary amines that do not have bulky groups around hydrogen atoms that exist around conjugated systems containing nitrogen atoms coordinate with metal ions because the nitrogen atoms contained in the conjugated system tend to approach metal ions. It is expected to be easy.
- the content of the metal complex (b1) in the surface sealing agent is such that the equivalent ratio of “active functional group (tertiary amino group) of the metal complex (b1) / epoxy group contained in the surface sealing agent” is 0.008 to It is preferable that it is 0.3. In order to increase the curability of the surface sealing agent, it is preferably from 0.01 to 0.2, and more preferably from 0.03 to 0.152.
- the metal complex (b1) may be composed of only one kind of metal complex or a combination of two or more kinds of metal complexes.
- the surface sealing agent of the 2nd form of this invention contains a specific amine compound (b2).
- the specific amine compound (b2) is represented by the general formula (11) or (12).
- R 1 to R 4 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 17 carbon atoms, an aryl-containing group, a hydroxyl group, or a cyanoethyl group.
- the aliphatic hydrocarbon group having 1 to 17 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms.
- the aryl-containing group include an aryl group such as a phenyl group and a naphthyl group, and an arylalkyl group such as a benzyl group.
- the number of carbon atoms constituting the aryl-containing group is preferably in the range of 6 to 11.
- R 1 is preferably a substituent other than a hydrogen atom (an aliphatic hydrocarbon group, an aryl group, a hydroxyl group or a cyanoethyl group). Compared with the case where R 1 is another substituent, when R 1 is a hydrogen atom, the sealing layer made of a cured product of the surface sealing agent is exposed to plasma or the like, thereby reducing transparency. Because there are things to do.
- R 1 when one or both of R 2 and R 4 are an aryl group, R 1 may be a hydrogen atom. This is because R 2 and R 4 which are aryl groups can lower the reactivity of R 1 which is a hydrogen atom.
- the compound represented by the general formula (11) may be a salt.
- the salt include hydrochloride, isocyanurate, triazine isocyanurate and the like.
- amine compound represented by the general formula (11) include the following compounds.
- RA 1 , RA 2 , RA 3 and RA 4 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 17 carbon atoms, an aryl-containing group, a hydroxyl group, or a dimethylaminomethyl group. Indicates.
- the aliphatic hydrocarbon group having 1 to 17 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms.
- Examples of the aryl-containing group include an aryl group such as a phenyl group and a naphthyl group, and an arylalkyl group such as a benzyl group.
- the number of carbon atoms constituting the aryl-containing group is preferably in the range of 6 to 11.
- one of RA 1, RA 2, RA 3 , RA 4 is a dimethylamino group.
- two of RA 2 , RA 3 and RA 4 are preferably dimethylamino groups, and more preferably all of RA 2 , RA 3 and RA 4 are dimethylamino groups.
- the dimethylaminomethyl group represented by RA 1 , RA 2 , RA 3 or RA 4 in the general formula (2) has moderate reactivity (nucleophilic reactivity).
- the storage stability here means that the curing reaction is difficult to proceed under storage conditions and the viscosity is difficult to increase.
- the compound represented by the general formula (12) may be a salt.
- the salt include hydrochloride, 2-ethylhexanoate and the like.
- amine compound represented by the general formula (12) include the following compounds.
- the polarity of the amine compound (b2) is preferably close to that of the amine compound (b2) so as to be easily dissolved in the epoxy resin (a) or an arbitrary acid anhydride (c).
- the content of the amine compound (b2) in the surface sealing agent is such that the equivalent ratio of “active functional group (tertiary amino group) of the amine compound (b2) / epoxy group contained in the surface sealing agent” is 0.008 to It is preferably 0.152, more preferably 0.02 to 0.15.
- the amine compound (b2) may be composed of only one kind of compound or a combination of two or more kinds of compounds.
- the surface sealing agent of the present invention may contain an acid anhydride (c).
- a highly transparent cured product may be obtained from a surface sealant containing an epoxy resin that is a curable resin and an acid anhydride. Since many aromatic acid anhydrides are colored, aliphatic (aromatic hydrogenated) acid anhydrides are preferred.
- acid anhydrides contained in the sealant include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, hexachloroendomethylenetetrahydrophthalic anhydride, benzophenone tetracarboxylic anhydride, etc. It is.
- An aliphatic acid anhydride having high transparency is hexahydrophthalic anhydride or methylhexahydrophthalic anhydride.
- the surface sealing agent of the present invention preferably contains an acid anhydride (c) so that the equivalent ratio of “acid anhydride group / epoxy group” is 0.8 to 1.2. If the equivalent ratio is too small, the viscosity stability under storage conditions such as room temperature may be reduced. On the other hand, if the equivalent ratio is too large, the amount of unreacted acid anhydride increases and moisture permeability increases, which may cause deterioration of the organic EL element.
- the surface sealing agent of the present invention may contain a coupling agent such as a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, and an aluminum coupling agent.
- a coupling agent such as a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, and an aluminum coupling agent.
- the surface sealant containing the coupling agent increases the adhesion with the glass substrate.
- silane coupling agents include 1) a silane coupling agent having an epoxy group, 2) a silane coupling agent having a functional group capable of reacting with an epoxy group, and 3) other silane coupling agents.
- 1) a silane coupling agent having an epoxy group, and 2) an epoxy group it is preferable to use a silane coupling agent having a reactive functional group. Reacting with an epoxy group means an addition reaction with an epoxy group.
- a silane coupling agent having an epoxy group is a silane coupling agent having an epoxy group such as a glycidyl group; examples thereof include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4- Epoxycyclohexyl) ethyltrimethoxysilane and the like.
- Functional groups capable of reacting with epoxy groups include amino groups such as primary amino groups and secondary amino groups; carboxyl groups and the like, and groups that can be converted into functional groups capable of reacting with epoxy groups (for example, Methacryloyl group, isocyanate group, etc.).
- Examples of such a silane coupling agent having a functional group capable of reacting with an epoxy group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3- Aminopropylmethyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- ( 1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane or 3- (4-methylpiperazino) propyltrimethoxysilane, trimethoxysilylbenzoic acid, ⁇ -methacryloxypropyltrimethoxysilane, And ⁇ -isocyanato
- silane coupling agents examples include vinyltriacetoxysilane and vinyltrimethoxysilane. These silane coupling agents may be used alone or in combination of two or more.
- the molecular weight of the silane coupling agent contained in the surface sealing agent of the present invention is preferably 80 to 800. When the molecular weight of the silane coupling agent exceeds 800, the adhesion may decrease.
- the content of the silane coupling agent in the surface sealing agent of the present invention is preferably 0.05 to 30 parts by mass, and 0.1 to 20 parts by mass with respect to 100 parts by mass of the surface sealing agent. More preferred is 0.3 to 10 parts by mass.
- the surface sealing agent of the present invention can contain other optional component (e) as long as the effects of the present invention are not impaired.
- the other optional component (e) include a resin component, a filler, a modifier, an antioxidant, and a stabilizer.
- the resin component include polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene-styrene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer. And silicon oligomers and polysulfide oligomers.
- resin components can be used individually by 1 type or in combination of 2 or more types.
- an inorganic filler or an organic filler having a difference in refractive index with a material of 0.1 or more and a diameter of 0.1 ⁇ m or more is substantially not included.
- filler examples include glass beads, styrene polymer particles, methacrylate polymer particles, ethylene polymer particles, and propylene polymer particles. These fillers can be used individually by 1 type or in combination of 2 or more types.
- modifiers include polymerization initiation assistants, anti-aging agents, leveling agents, wettability improvers, surfactants, plasticizers, and the like. These modifiers can be used individually by 1 type or in combination of 2 or more types.
- stabilizer include ultraviolet absorbers, preservatives, and antibacterial agents. These stabilizers can be used individually by 1 type or in combination of 2 or more types.
- Antioxidants are those that deactivate radicals generated by plasma irradiation or sunlight irradiation (Hindered Amine Light Stabilizer, ⁇ HALS) and those that decompose peroxides.
- the antioxidant can prevent discoloration of the cured product of the sealant.
- hindered amines include bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4′-hexamethylene Bis (amino-2,2,6,6-tetramethylpihelidine) polycondensation product, bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine -4-Il] sebacate.
- phenolic antioxidants examples include monophenols such as 2,6-di-t-butyl-p-cresol, and bisphenols such as 2,2′-methylenebis (4-methyl-6-t-butylphenol). Polymeric phenols such as 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane are included.
- an antioxidant selected from phosphites and a colorant selected from oxaphosphaphenanthrene oxides are preferably used.
- Tinuvin123 bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacic acid
- Tinuvin765 bis (1,2,2, 6,6-pentamethyl-4-piperidyl) sebacic acid and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacic acid
- Hostavin® PR25 dimethyl® 4-methoxybenzyl® Idenemalonate
- Tinuvin® 312® or Hostavin vsu ethanediamide N- (2-ethoxyphenyl) -N '-(2-ethylphenyl)
- CHIMASSORB 119 FL N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N- Butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-tria
- Solvent (f) The surface sealing agent of the present invention may contain a solvent (f).
- the solvent (f) has a function of uniformly dispersing or dissolving each component.
- Solvent (f) may be various organic solvents, aromatic solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ether, dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol mono Ethers such as alkyl ethers; aprotic polar solvents such as N-methylpyrrolidone; esters such as ethyl acetate and butyl acetate are included.
- a surface-sealing molded product is obtained by adding a high molecular weight epoxy resin (a-2) as an optional component to the surface sealing agent of the present invention
- a high molecular weight epoxy resin (a-2) from the point of being easy to dissolve, a ketone solvent (a solvent having a keto group) such as methyl ethyl ketone is more preferable.
- the viscosity of the surface sealant of the present invention measured by an E-type viscometer at 25 ° C. and 1.0 rpm is preferably 10 to 10,000 mPa ⁇ s, more preferably 200 to 10,000 mPa ⁇ s.
- the viscosity of the surface sealant is measured with an E-type viscometer (RC-500 manufactured by Toki Sangyo Co., Ltd.) at a measurement temperature of 25 ° C.
- the rate of increase in viscosity of the surface sealing agent of the first embodiment of the present invention after storage at 25 ° C. for 24 hours is preferably less than 100%, more preferably 70% or less, and 50% or less. More preferably.
- the water content of the surface sealing agent of the present invention is preferably 0.1% by mass or less, and more preferably 0.06% by mass or less. Since an electric circuit in which an optical semiconductor such as an organic EL element is disposed is easily deteriorated by moisture, it is preferable to reduce the water content of the surface sealing agent as much as possible.
- the moisture content of the surface sealant can be obtained by weighing about 0.1 g of a sample sample, heating to 150 ° C. using a Karl Fischer moisture meter, and measuring the amount of water generated at that time (solid) Vaporization method).
- the surface sealant of the present invention can be preferably used as a surface sealant for optical semiconductors.
- An optical semiconductor is an element that emits light by converting electricity into light, for example.
- Specific examples of the optical semiconductor include inorganic LED elements, organic EL elements, and the like, and preferably organic EL elements. Since an optical semiconductor is easily deteriorated by moisture or the like, the surface needs to be sealed.
- the light transmittance of the cured product of the surface sealing agent of the present invention is preferably 30% or more, more preferably 50% or more, and further preferably 80% or more. If the light transmittance of the cured product is too low, when used as a surface sealant for an organic EL device or the like, the light extraction efficiency from the device is likely to be lowered, and the design is also deteriorated. Generally, the upper limit of the light transmittance of the cured product of the surface sealing agent can be about 99%.
- the light transmittance of the cured product can be adjusted by the type and amount of the amine compound (b) contained in the surface sealing agent.
- cured material can be performed in the following procedures. 1) A surface sealing agent is applied on a substrate and dried, and then cured to obtain a cured product having a thickness of 100 ⁇ m. 2) The light transmittance at a wavelength of 450 nm of the obtained cured product is measured using an ultraviolet / visible light photometer (MULTISPEC-1500 manufactured by Shimadzu Corporation).
- MULTISPEC-1500 ultraviolet / visible light photometer
- the surface sealing agent of the present invention may be used as a liquid sealing agent, but by adding the above-described high molecular weight epoxy resin (a-2) or the like, It may be used as part.
- a-2 high molecular weight epoxy resin
- it can be applied on an optical semiconductor such as an organic EL element by screen printing, dispenser application, etc., and the coated layer is cured to seal the optical semiconductor such as an organic EL element.
- a sealing product such as a film
- an optical semiconductor such as an organic EL element is surface-sealed by laminating and curing a film-like sealing agent on the optical semiconductor such as an organic EL element. Just stop.
- the surface sealant of the present invention can be produced by any method as long as the effects of the present invention are not impaired. For example, 1) a step of preparing an epoxy resin (a), a curing accelerator (b), and other optional components, and 2) a step of mixing each component at 30 ° C. or lower in an inert gas environment. It is manufactured by the method including. Mixing includes a method in which these components are charged into a flask and agitated, and a method in which the components are kneaded with three rolls.
- a liquid surface sealing agent may be applied to a release substrate, the coating film may be dried, and then peeled off.
- the surface sealant may be applied using a method such as screen printing or dispenser application.
- the tertiary amine contained in the surface sealant of the first aspect of the present invention can form a complex with a metal ion coordinated with an electron-donating anionic ligand (preferably a carboxylate compound), It is appropriately fixed as a metal complex. Accordingly, under normal storage conditions of the surface sealing agent of the present invention such as at room temperature, the tertiary amine is less likely to be detached from the metal complex, and the reaction of the epoxy resin or the like in the surface sealing agent is suppressed, and the surface sealing agent is The storage stability of the stopper can be improved.
- the surface sealing agent of the first embodiment of the present invention seals the organic EL device as described later, the coordination bond between the tertiary amine and the metal ion is relaxed when heated or irradiated with light.
- the tertiary amine can advance the curing reaction of the epoxy resin.
- the storage stability here means that the curing reaction is difficult to proceed under storage conditions and the viscosity is difficult to increase.
- the surface sealing agent of the first embodiment of the present invention has high storage stability while having good curability, the sealing step when used as a surface sealing agent for optical semiconductors Work efficiency can be increased.
- the tertiary amine in the metal complex (b1) is a compound represented by the above general formulas (1) to (6), so that the tertiary amine under storage conditions is not deteriorated so as not to impair the curability. It is thought that the reactivity of can be reduced. Thereby, as will be described later, it is considered that haze increase of the cured product layer upon plasma treatment can be suppressed, that is, weather resistance can be improved.
- the specific amine compound (b2) contained in the surface sealing agent of the second aspect of the present invention has a structure represented by the above general formula (11) or (12). Therefore, it is considered that the reactivity of the amine compound (b2) under storage conditions can be reduced to such an extent that the curability is not impaired. Thereby, it is thought that the haze rise of the hardened
- epoxy resin composition of the present invention is used as a surface sealant, it is not limited thereto.
- the epoxy resin composition of the present invention can also be used for various applications.
- the organic EL device of the present invention includes an organic EL element disposed on a substrate, a cured resin layer in contact with the organic EL element and covering (surface-sealing) the organic EL element, and And a sealing substrate that covers the cured resin layer.
- the organic EL device can be used as an organic EL display panel including the organic EL device.
- the organic EL device of the present invention 1) an organic EL element disposed on a substrate, and 2) a cured resin layer that is in contact with the organic EL element and covers (surface seals) the organic EL element And 3) a passivation layer that contacts the cured resin layer and covers the cured resin layer, and 4) a sealing substrate that covers the passivation layer (see FIG. 1A).
- the resin cured product layer is a cured product of the aforementioned surface sealant.
- the organic EL device of the present invention 1) an organic EL element disposed on the substrate, and 2) a contact with the organic EL element and covering (sealing) the organic EL element.
- the resin cured product layer is a cured product of the aforementioned surface sealant.
- FIG. 1A is a cross-sectional view schematically showing a surface-sealing type organic EL device.
- the organic EL panel 20 includes a substrate 22, an organic EL element 24, and a sealing substrate 26 stacked in this order.
- a surface sealing layer 28 is disposed between the substrate 22 and the sealing substrate 26, and the surface sealing layer 28 covers the periphery of the organic EL element 24. In this manner, the surface sealing layer 28 seals the organic EL element 24.
- the surface sealing layer 28 includes a cured product layer 28-1 made of a cured product of the surface sealing agent of the present invention, and a passivation layer 28- covering the cured product layer 28-1. 2 and a second cured resin layer 28-3 covering the passivation layer 28-2.
- the substrate 22 and the sealing substrate 26 are usually a glass substrate or a resin film, and at least one of the substrate 22 and the sealing substrate 26 is a transparent glass substrate or a transparent resin film.
- transparent resin films include aromatic polyester resins such as polyethylene terephthalate.
- the reflective pixel electrode layer 30 (made of aluminum, silver, etc.), the organic EL layer 32, and the transparent counter electrode layer 34 (from ITO, IZO, etc.) Included).
- the reflective pixel electrode layer 30, the organic EL layer 32, and the transparent counter electrode layer 34 may be formed by vacuum deposition, sputtering, or the like.
- the surface sealing layer 28 includes a cured product layer 28-1, made of a cured product of the surface sealing agent of the present invention, a passivation layer 28-2, and a second cured resin layer 28-3.
- the cured product layer 28-1 is preferably in contact with the organic EL element.
- the thickness of the cured product layer 28-1 is preferably 0.1 to 20 ⁇ m.
- the cured product layer 28-1 made of a cured product of the surface sealant has a Zn content in a spectrum measured by X-ray photoelectron spectroscopy (XPS).
- XPS X-ray photoelectron spectroscopy
- a peak derived from one or more kinds of metal atoms selected from the group consisting of Bi, Ca, Al, Cd, La, and Zr and a peak derived from a nitrogen atom are detected, and the detected metal atom and nitrogen atom
- the molar ratio of nitrogen atom to 1 mol of metal atom may depend on the content of tertiary amine to metal ion in metal complex (b1).
- the metal atom is preferably Zn, and the content thereof is preferably 0.5 to 15% by mass in the cured product.
- XPS measurement can be performed using AXIS-NOVA (manufactured by KRATOS).
- the light source can be monochromatic A1 K ⁇ ; the diameter of the measurement area can be 100 ⁇ m.
- the light transmittance of the cured product layer 28-1 made of the cured product of the surface sealing agent of the present invention is preferably 30% or more, more preferably 50% or more, and further preferably 80% or more. This is because if the light transmittance is too low, the light extraction efficiency from the element and the light absorption efficiency to the element are likely to decrease.
- the upper limit of the light transmittance of the cured product layer 28-1 can be, for example, about 99%.
- the passivation layer 28-2 constituting the surface sealing layer 28 is preferably an inorganic compound layer formed in a plasma environment.
- Forming a film in a plasma environment means, for example, forming a film by a plasma CVD method, but is not particularly limited, and may be formed by a sputtering method or an evaporation method.
- the material of the passivation layer 28-2 is preferably a transparent inorganic compound, and examples thereof include silicon nitride, silicon oxide, SiONF, and SiON, but are not particularly limited.
- the thickness of the passivation layer 28-2 is preferably 0.1 to 5 ⁇ m.
- the passivation layer 28-2 may be formed in contact with the cured product layer 28-1. This is because the cured product layer 28-1 made of the cured product of the surface sealing agent of the present invention can maintain its transparency even when exposed to a plasma environment.
- the passivation layer 28-2 is formed not in direct contact with the organic EL element 24 but in direct contact with the cured product layer 28-1. If an attempt is made to form a film by bringing the passivation layer 28 into direct contact with the organic EL element 24, the edge of the organic EL element 24 is acute, and the coverage by the passivation layer 28 may be reduced.
- the organic EL element 24 is surface-sealed with the hardened material layer 28-1 of the surface sealant of the present invention, and then on the hardened material layer 28-1.
- a passivation layer 28-2 is formed. By sealing the surface with the cured product layer 28-1, the deposition surface of the passivation layer 28-2 can be smoothed, and the coverage is improved.
- the second resin cured product layer 28-3 constituting the surface sealing layer 28 may be the same material (surface sealing agent of the present invention) as the cured product layer 28-1, or a different material. .
- the moisture content of the second resin cured product layer 28-3 may be higher than the moisture content of the cured product layer 28-1. This is because the second cured resin layer 28-3 is not in direct contact with the organic EL element.
- the light transmittance of the second cured resin layer 28-3 is As with the resin cured product layer 28-1, it needs to be high.
- FIG. 1B is a cross-sectional view schematically showing another surface-sealing type organic EL device.
- the organic EL panel 20 has a substrate 22, an organic EL element 24, and a sealing substrate 26 laminated in this order.
- a surface sealing layer 28 is disposed between the substrate 22 and the sealing substrate 26, and the surface sealing layer 28 covers the periphery of the organic EL element 24. In this manner, the surface sealing layer 28 seals the organic EL element 24.
- the surface sealing layer 28 includes a cured product layer 28-1 made of a cured product of the surface sealing agent of the present invention and a passivation covering the end surface of the cured product layer 28-1.
- Layer 28-2 Other components of the organic EL device 20 ′ shown in FIG. 1B are the same as the constituent members of the organic EL device 20 shown in FIG. 1A.
- the organic EL device of the present invention can be produced by an arbitrary method as long as the effects of the present invention are not impaired, but 1) a step of preparing an organic EL element disposed on a substrate, and 2) an organic EL element, A step of covering with a surface sealing agent and curing the surface sealing agent to form a surface sealing layer, and 3) a step of sealing with a sealing substrate.
- a step of preparing an organic EL element disposed on a substrate and 2) an organic EL element
- a step of covering with a surface sealing agent and curing the surface sealing agent to form a surface sealing layer A step of covering with a surface sealing agent and curing the surface sealing agent to form a surface sealing layer
- 3) a step of sealing with a sealing substrate a step of sealing with a sealing substrate.
- Examples of the step of exposing the surface sealing layer to plasma include a step of forming a passivation film on the surface sealing layer by a plasma CVD method, and a step of changing the surface characteristics by irradiating the surface sealing layer with plasma. Etc. are included.
- the surface characteristics for example, increasing wettability
- the adhesion with other members can be improved.
- the sealing layer made of the surface sealing agent of the second aspect of the present invention has excellent plasma resistance, and even after these steps, the surface sealing layer is hardly deteriorated, for example, high transparency is maintained. .
- FIG. 2 schematically shows the manufacturing process of the organic EL device of the present invention.
- a substrate 22 on which an organic EL element 24 is laminated is prepared (FIG. 2A).
- the organic EL element includes a reflective pixel electrode layer 30, an organic EL layer 32, and a transparent counter electrode layer 34, but may further have other functional layers.
- the liquid surface sealing agent of the present invention is applied on the organic EL element 24 laminated on the substrate 22 (so as to cover the transparent counter electrode layer 34), or a film-like surface sealing agent is applied.
- curing is performed to form a cured product layer 28-1 (FIG. 2B).
- a passivation layer 28-2 is formed on the cured product layer 28-1 (FIG. 2C).
- the passivation layer (transparent inorganic compound layer) 28-2 can be formed by any method, for example, a plasma CVD method, a sputtering method, a vapor deposition method, or the like. Especially, when the film is formed by the plasma CVD method, the effect of the present invention is remarkably exhibited. That is, when the passivation layer 28-2 is formed by the plasma CVD method, the hardened material layer 28-1 is exposed to the plasma more significantly than the sputtering method or the like. Transparency is maintained.
- the surface sealing agent of the present invention can be particularly preferably used in a manufacturing process including a step of forming a passivation layer by a plasma CVD method.
- the passivation layer 28-2 is covered with a resin layer (FIG. 2D), and the sealing substrate 26 is further overlapped, and the resin layer is cured in this state to form a second cured resin layer 28-3. Then, the sealing substrate 26 is bonded (FIG. 2E). In this way, the organic EL device 20 of the present invention is obtained.
- FIG. 2 shows a flow of forming one organic EL element 24 on the substrate 22 and sealing it; the plurality of organic EL elements 24 formed on the substrate 22 are processed once in the same procedure. It can be sealed with a flow.
- the surface sealant according to the first embodiment of the present invention tends not to cause deterioration of an optical semiconductor such as an organic EL element.
- an optical semiconductor such as an organic EL element.
- the reason for this is not necessarily clear, but is presumed as follows. That is, when the tertiary amine contained in the surface sealing agent is in a state of being easily moved, the tertiary amine and the metal constituting the charge transport layer and the light emitting layer of the organic EL element interact with each other, and the organic EL element It is considered that the state is easily changed and the element is likely to be deteriorated.
- the tertiary amine contained in the surface sealing agent of the first embodiment of the present invention has previously formed a complex with a metal ion, the periphery of the tertiary amine is bulky. Therefore, it is presumed that the interaction between the tertiary amine and the charge transport layer or the light emitting layer of the organic EL element is unlikely to occur, and deterioration of the organic EL element or the like can be suppressed.
- an organic EL element is produced by a vapor deposition method.
- a surface sealant is applied onto the manufactured element, and then thermally cured to seal the element, whereby Sample 1 is obtained.
- the periphery of the manufactured element is similarly sealed (hollow sealed) with a surface sealant so as not to contact the element, and sample 2 is obtained.
- the initial light emission characteristics, life, and reliability of sample 1 and sample 2 are measured, and both are compared. If there is no difference between the two evaluation results, it can be determined that there is no deterioration of the device due to the interaction between the surface sealant and the device. Specifically, it can be evaluated by the same method as the deterioration test method described in International Publication No. 2010/035502.
- the metal complex (b1-0) With respect to the metal complex (b1-0), the results of elemental analysis of 1 H NMR, 13 C NMR, FD MS, C, H, and N are shown below. From these results, the metal complex (b1-0) is presumed to have the structure of the general formula (10).
- compositions of the obtained metal complexes (b1-1) to (b1-7) and the 1 HNMR peak transfer amount are summarized in Table 1.
- the numerical value in the column of the metal complex in the table indicates the mass ratio.
- the viscosities of the surface sealants obtained in Examples 1 to 10 and Comparative Example 1 were measured.
- the viscosity immediately after synthesis of the surface sealing agent (0 h) and the viscosity after the surface sealing agent was stored at 25 ° C. for 24 to 48 hours after synthesis were respectively represented by an E-type viscometer (digital rheometer model DII manufactured by BROOKFIEL) -III ULTRA) at 25 ° C. and 1 rpm. Then, the measured value was applied to the following formula to determine the rate of increase in viscosity.
- Increasing rate (%) ( ⁇ viscosity change amount (viscosity after 24 hr or 48 hr ⁇ viscosity immediately after synthesis) / viscosity immediately after synthesis) ⁇ 100
- the curability of the surface sealants obtained in Examples 1 to 10 and Comparative Example 1 was evaluated by the following method.
- the fluidity and tackiness of a cured product obtained by curing each surface sealing agent by heating in the air for 30 minutes were evaluated using pencil hardness.
- the state in which the cured product had no fluidity and no tackiness was evaluated as ⁇ , the fluidity state was evaluated as x, and the state where tackiness remained was evaluated as ⁇ .
- the haze value (%) of the cured product layer was measured using a haze meter (manufactured by Tokyo Denka, model name TC-H3DPK). Then, the glass substrate on which the cured product layer is formed is placed in a plasma processing apparatus (manufactured by Yamato Kagaku, model name PDC210, parallel plate type), and plasma processing is performed for 20 minutes under the conditions of an oxygen flow rate of 20 mL / min and an RF output of 500 W. did. And the haze value (%) of the hardened
- a suitable surface sealing agent in a method of manufacturing an organic EL device including a step of irradiating plasma to a cured product of a surface sealing agent by performing plasma treatment and evaluating a change in haze? It is possible to evaluate whether or not the weather resistance is accelerated.
- Table 2 shows the evaluation results of the surface sealants of Examples 1 to 10 and Comparative Example 1.
- the haze of the cured product layer before the plasma treatment is sufficiently reduced.
- the surface sealants of Examples 1 to 10 have the haze value of the cured layer after plasma treatment suppressed to less than 30%, whereas the surface sealants of Comparative Example 1 have plasma treatments.
- the haze value of the later cured product layer exceeds 40%.
- the surface sealant of Comparative Example 1 has good curability, the storage stability is low, whereas the surface sealants of Examples 1 to 8 have high curability and good storage stability. I know that there is. In particular, it can be seen that the surface sealants of Examples 2 and 5 to 8 have a low rate of increase in viscosity and good curability even after storage for 48 hours.
- Examples 11 to 23 and 25, Comparative Example 2 In a flask replaced with nitrogen, 100 parts by weight of an epoxy resin having a composition shown in Tables 3 to 5, 84 parts by weight of an acid anhydride, 4 parts by weight of a silane coupling agent, and parts by weight of Tables 3 to 5 were added. A metal complex or an amine compound was stirred and mixed to obtain a surface sealing agent.
- the metal complexes used in Examples 11 to 13 were the metal complexes (b1-1) to (b1-3) synthesized above.
- Example 24 A surface sealant was obtained in the same manner as in Example 11 except that zinc bis (2-ethylhexoate) and 1,2-DMZ were added alone in place of the metal complex.
- the viscosities of the surface sealants obtained in Examples 11 to 25 and Comparative Example 2 were measured in the same manner as described above. Furthermore, the degree of stabilization due to complexation was calculated as follows. That is, the rate of increase in viscosity after 24 hours (the rate of increase when not complexed) of the surface sealing agent in which tertiary amine and zinc bis (2-ethylhexoate) were separately blended was determined as The value obtained by dividing the surface sealing agent containing a metal complex complexed with zinc bis (2-ethylhexoate) by the rate of increase in viscosity after 24 hours was calculated as “stability by complexation”. If the degree of stabilization by complexation is greater than 1, it indicates that the stability has been increased by complexation, and if it is less than 1, it indicates that the stability has been reduced by complexation.
- “increase rate when not complexed” is the rate of increase after 24 hr of Example 24 when the tertiary amine is “1,2-DMZ”; In the case of “IBMI12”, the rate of increase after 24 hr of Example 25 was used; in the case of “1B2MZ”, the rate of increase after 24 hr of Example 10 was used.
- the surface sealant obtained in Examples 11 to 23 and Comparative Example 2 was applied to a screen printer (Screen Printer) on a glass substrate (7 cm ⁇ 7 cm ⁇ 0.7 mm thickness) previously cleaned by ozone treatment. Model 2200, manufactured by MITANI) was used for printing.
- the surface sealing agent was applied so as to have a thickness of 5 cm ⁇ 5 cm ⁇ 3 ⁇ m in a dry state.
- the glass substrate on which the surface sealing agent was printed was heated on a hot plate heated to 100 ° C. for 30 minutes to obtain a cured product layer.
- the haze value (%) of the cured product layer was measured using a haze meter (manufactured by Tokyo Denka, model name TC-H3DPK). Thereafter, the glass substrate on which the cured product layer was formed was placed in a sputtered thin film forming apparatus (manufactured by ULVAC, Inc., JSP-8000), and SiO 2 having a thickness of 50 nm was formed under the following conditions. And the haze value (%) of the hardened
- the haze after film-forming treatment was evaluated as ⁇ , when the haze was 25% or less, ⁇ when the haze was more than 25% to 40% or less, and x when the haze exceeded 40%.
- the low haze after the film forming process by sputtering means that the surface of the cured product layer after the film forming process is smooth (the external haze is low) because the cured layer has a relatively high degree of curing. Means).
- the high haze after the film-forming process by the sputtering method means that the cured layer, particularly the surface thereof, has a relatively low degree of curing, so that the surface of the cured layer is roughened by the film-forming process (external High haze).
- the haze after the film-forming process by a sputtering method does not necessarily mean that the weather resistance of the hardened
- the measurement results of Examples 11 to 16 are shown in Table 3; the measurement results of Examples 17 to 21 are shown in Table 4; the measurement results of Examples 22 to 25 and Comparative Example 2 are shown in Table 5.
- surface shows the radius of an anionic ligand.
- the radius of the anionic ligand was calculated after obtaining a connolly volume using Material Studio 6.0 Dmol3; assuming that the connolly volume is a true spherical volume.
- the radii of chloride ions and sulfate ions used were the ion radii (calculated by Shannon and Prewitt) described in Chemistry Handbook Basic Edition 2nd edition, Japan Chemical Society.
- the surface sealing agents of Examples 11 to 23 showed good curability and had a degree of stabilization by complexation of greater than 1, and the storage stability of the surface sealing agent. Is shown to be high. Specifically, Example 25 in which only the tertiary amine (not complexed) was added and Example 3 in which the tertiary amine and zinc bis (2-ethylhexoate) were added separately (without complexing)
- the surface sealant of Example 24 has a slightly higher viscosity increase rate after 24 hours, whereas the surface sealants of Examples 11 to 12 and 17 to 23 have a lower viscosity increase rate after 24 hours. It is shown that the storage stability of the surface sealant is improved by the complexation of the secondary amine.
- the surface sealing agent of Comparative Example 2 did not contain a tertiary amine, the curability was low and the cured product could not be evaluated.
- the cured products of the surface sealing agents of Examples 11 to 16 and 18 to 20 have a low haze after the film forming treatment and maintain a good transparency. This is presumably because the increase in external haze due to the roughening of the film formation surface could be reduced due to the high curability of the surfaces of the cured products of the surface sealants of Examples 11 to 16 and 18 to 20. .
- the viscosities of the surface sealants obtained in Examples 26 to 34 and Comparative Examples 3 to 4 were measured.
- the viscosity of the surface sealant at 25 ° C. was measured using an E-type viscometer (digital rheometer model DII-III ULTRA manufactured by BROOKFIEL). Table 6 shows the measurement results.
- the curability of the surface sealants obtained in Examples 26 to 34 and Comparative Examples 3 to 4 was evaluated by the following method. Samples were prepared by sandwiching each surface sealing agent between two NaCl crystal plates (thickness 5 mm). A surface sealing agent was sealed between two NaCl crystal plates (2 cm square) so that the distance between NaCl crystal plates was 15 ⁇ m. The infrared transmission spectrum before and after heat-treating this sample for 30 minutes at 100 ° C. was measured with an FT-IR measuring apparatus.
- the height of the absorption peak (near 910 cm ⁇ 1 ) derived from the reverse symmetrical ring stretching of the epoxy group is the height of the absorption peak (near 1600 cm ⁇ 1 ) derived from the intra-CC stretching of the benzene ring. Divided by the standardization. And the reaction rate of the epoxy group was computed from the decreasing degree of the peak derived from the epoxy group by heat processing.
- the haze value (%) of the cured product layer was measured using a haze meter (manufactured by Tokyo Denka, model name TC-H3DPK). Then, the glass substrate on which the cured product layer is formed is placed in a plasma processing apparatus (manufactured by Yamato Kagaku, model name PDC210, parallel plate type), and plasma processing is performed for 20 minutes under the conditions of an oxygen flow rate of 20 mL / min and an RF output of 500 W. did. And the haze value (%) of the hardened
- a suitable surface sealing agent in a method of manufacturing an organic EL device including a step of irradiating plasma to a cured product of the surface sealing agent by performing plasma treatment in this way and evaluating a change in haze. As well as accelerated evaluation of weather resistance.
- the haze of the cured product layer before the plasma treatment is sufficiently reduced. And about the surface sealing agent of Examples 26-34, while the haze value of the hardened
- the haze value of the cured product layer after the plasma treatment is suppressed to less than 20%. This suggests that when the hydrogen atom bonded to the 1-position of the imidazole ring of the curing accelerator is substituted with another substituent, the haze increase due to plasma can be more effectively suppressed.
- the surface sealant of the first aspect of the present invention has good curability and is excellent in storage stability. Therefore, the manufacturing efficiency of the optical semiconductor device can be increased. Moreover, the haze rise of a hardened
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Abstract
Description
[1]1分子内に2個以上のエポキシ基を有するエポキシ樹脂(a)と、Zn、Bi、Ca、Al、Cd、La、Zrからなる群から選ばれる1種類以上の金属イオンと、前記金属イオンと錯形成が可能であって、N-H結合を有さない3級アミンと、分子量が17~200のアニオン性配位子とを含む金属錯体(b1)と、を含み、E型粘度計により25℃、1.0rpmで測定した粘度が10~10000mPa・sである、光半導体用の面封止剤。
[2] 前記アニオン性配位子の価数が前記金属イオンの価数より小さく、かつ前記アニオン性配位子の半径が2.0Å以上である、[1]に記載の光半導体用の面封止剤。
[3] 前記3級アミンが、下記一般式(1)~(6)のいずれかで表される化合物である、[1]または[2]に記載の光半導体用の面封止剤。
[4] 前記アニオン性配位子が、O、S、Pからなる群から選ばれ、前記金属イオンに結合しうる原子を2以上有し、かつ前記金属イオンに配位して3~7員環を形成しうるものである、[1]~[3]のいずれかに記載の光半導体用の面封止剤。
[5] 前記3級アミンが、前記一般式(1)~(3)のいずれかで表される化合物であり、かつ前記アニオン性配位子が、下記一般式(7A)で表されるカルボキシレート化合物である、[3]に記載の光半導体用の面封止剤。
[6] 前記面封止剤の、CDCl3中、25℃、270MHzにおける1HNMRの化学シフトのうち3級アミンに由来する化学シフトが、前記3級アミン単独の、CDCl3中、25℃、270MHzにおける1HNMRの化学シフトに対して0.1ppm以上移動するピークを含む、[1]~[5]のいずれかに記載の光半導体用の面封止剤。
[7] 前記金属イオンに対する前記3級アミンのモル比が、0.5~6.0である、[1]~[6]のいずれかに記載の光半導体用の面封止剤。
[8] 前記カルボキシレート化合物が、2-エチルヘキサン酸、ギ酸、酢酸、ブタン酸、2-エチルブタン酸、2,2-ジメチルブタン酸、3-メチルブタン酸、2,2-ジメチルプロパン酸、安息香酸およびナフテン酸からなる群から選ばれる少なくとも1種類の化合物である、[5]に記載の光半導体用の面封止剤。
[9] 前記3級アミンが、1,8-ジアゾビシクロ[5,4,0]ウンデカ-7-エン、1-メチルイミダゾール、1,2-ジメチルイミダゾール、1-ベンジル-2-メチルイミダゾール、1-イソブチル-2-メチルイミダゾール、1-ブチルイミダゾールおよび1,5-ジアゾビシクロ[4,3,0]ノン-5-エンからなる群から選ばれる少なくとも1種類の化合物である、[1]~[8]のいずれかに記載の光半導体用の面封止剤。
[10] 1分子内に2個以上のエポキシ基を有するエポキシ樹脂(a)と、下記一般式(11)または(12)で表される硬化促進剤(b2)とを含み、E型粘度計により25℃、1.0rpmで測定した粘度が10~10000mPa・sである、光半導体用の面封止剤。
[11] 前記一般式(11)において、R1が、炭素数1~17の脂肪族炭化水素基、水酸基、アリール含有基またはシアノエチル基を示す、[10]に記載の光半導体用の面封止剤。
[13] 前記光半導体用の面封止剤は、前記硬化促進剤(b2)を、3級アミンの活性官能基/エポキシ基の当量比が0.008~0.152となる範囲で含む、[10]または[11]に記載の光半導体用の面封止剤。
[14] 前記光半導体用の面封止剤は、酸無水物を、酸無水物基/エポキシ基の当量比が0.8~1.2となる範囲でさらに含む、[1]~[13]のいずれかに記載の光半導体用の面封止剤。
[15] 含水率が0.1重量%以下である、[1]~[14]のいずれかに記載の光半導体用の面封止剤。
[16] 有機EL素子用の面封止剤である、[1]~[15]のいずれかに記載の光半導体用の面封止剤。
[17] 基板上に有機EL素子を形成する第1の工程と、前記有機EL素子を、[1]~[16]のいずれかに記載の面封止剤で覆う第2の工程と、前記面封止剤を硬化させた硬化物で、前記有機EL素子を面封止する第3の工程と、前記有機EL素子を面封止する前記硬化物上に、パッシベーション膜を成膜する第4の工程と、を含む、有機ELデバイスの製造方法。
[18] 有機EL素子と、前記有機EL素子と接触しており、前記有機EL素子を面封止している[1]~[16]のいずれかに記載の面封止剤の硬化物からなる硬化物層と、前記硬化物層と接するパッシベーション層と、を含む有機ELデバイス。
[19] 有機EL素子と、前記有機EL素子を面封止しており、X線光電子分光法(XPS)で測定されるスペクトルにおいて、Zn、Bi、Ca、Al、Cd、La、Zrからなる群から選ばれる1種類以上の金属原子に由来するピークと、窒素原子に由来するピークとが検出され、前記検出される金属原子と窒素原子とのモル比が、前記金属原子:前記窒素原子=1:0.5~1:6.0であり、かつ前記金属原子の含有量が0.5~15質量%であるエポキシ樹脂組成物の硬化物層と、前記硬化物層と接するパッシベーション層と、を含む、有機ELデバイス。
[20] [18]または[19]に記載の有機ELデバイスを有する、有機ELディスプレイパネル。
本発明のエポキシ樹脂組成物は、エポキシ樹脂(a)と、アミン化合物(b)とを含み;さらに、酸無水物(c)などを含みうる。本発明のエポキシ樹脂組成物は、例えば面封止剤、透明フィル剤などの用途;好ましくは面封止剤として用いられうる。なお、透明フィル剤とは、例えば、タッチパネルなどの基板と液晶パネルなどの画像表示装置の間を埋める透明性が要求される材料のことをいう。以下、本発明のエポキシ樹脂組成物が面封止剤として用いられる例で説明する。本発明の面封止剤には、後述する第一または第二の形態の面封止剤が含まれる。
本発明の面封止剤に含まれるエポキシ樹脂(a)は、1分子内に2個以上のエポキシ基を有するエポキシ樹脂であればよく、分子量などは特に限定されず、分子量分布がないエポキシ樹脂も、分子量分布があるエポキシ樹脂も用いることができる。
本発明の面封止剤に含まれるアミン化合物(b)は、3級アミンの金属錯体(b1)または特定のアミン化合物(b2)でありうる。これらのアミン化合物(b)は、硬化促進剤として機能しうる。
R1-(C=O)-CH=C(O)-R2 …(8)
R3-(C=S)-CH=C(S)-R4 …(9)
本発明の面封止剤は、酸無水物(c)を含んでいてもよい。特に、硬化性樹脂であるエポキシ樹脂と、酸無水物とを含む面封止剤からは、透明性の高い硬化物が得られることがある。芳香族系の酸無水物は着色しているものが多いので、脂肪族系(芳香族系の水添物)の酸無水物が好ましい。封止剤に含まれる酸無水物の例には、無水フタル酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水トリメリット酸、無水ヘキサクロロエンドメチレンテトラヒドロフタル酸、無水ベンゾフェノンテトラカルボン酸などが含まれる。透明性が高いのは脂肪族系の酸無水物であり、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸が用いられる。
本発明の面封止剤は、シランカップリング剤、チタン系カップリング剤、ジルコニウム系カップリング剤、アルミニウム系カップリング剤などのカップリング剤を含有してもよい。カップリング剤を含む面封止剤は、ガラス基板との密着性が高まる。
本発明の面封止剤には、本発明の効果を損なわない範囲で、その他の任意成分(e)を含有させることができる。その他の任意成分(e)としては、樹脂成分、充填剤、改質剤、酸化防止剤、安定剤等を挙げることができる。樹脂成分の具体例としては、ポリアミド、ポリアミドイミド、ポリウレタン、ポリブタジェン、ポリクロロプレン、ポリエーテル、ポリエステル、スチレン-ブタジエン-スチレンブロック共重合体、石油樹脂、キシレン樹脂、ケトン樹脂、セルロース樹脂、フッ素系オリゴマー、シリコン系オリゴマー、ポリスルフィド系オリゴマー等を挙げることができる。これらの樹脂成分は、一種単独で又は二種以上を組み合わせて用いることができる。ただし、本発明の面封止剤の硬化物に透明性が求められる場合には、エポキシ樹脂と相分離し、かつエポキシ樹脂との屈折率差が大きい成分;具体的には、エポキシ樹脂の硬化物との屈折率差が0.1以上でかつ直径が0.1μm以上の無機フィラーや有機フィラーなどを実質的に含まないことが好ましい。
本発明の面封止剤は、溶剤(f)を含んでもよい。溶剤(f)は、各成分を均一に分散または溶解させる機能を有する。溶剤(f)は、各種有機溶剤であってもよく、トルエン、キシレン等の芳香族溶媒;アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶媒;エーテル、ジブチルエーテル、テトラヒドロフラン、ジオキサン、エチレングリコ-ルモノアルキルエーテル等のエーテル類;N-メチルピロリドン等の非プロトン性極性溶媒;酢酸エチル、酢酸ブチル等のエステル類等が含まれる。特に、本発明の面封止剤に、任意成分である高分子量のエポキシ樹脂(a-2)を添加して、面封止成形物を得る場合は、高分子量のエポキシ樹脂(a-2)を溶解し易い点から、メチルエチルケトン等のケトン系溶媒(ケト基を有する溶媒)がより好ましい。
粘度上昇率=粘度変化量(24hr後の粘度-合成直後の粘度)/合成直後の粘度×100
1)面封止剤を、基材上に塗布および乾燥させた後、硬化させて、厚み100μmの硬化物を得る。
2)得られた硬化物の、波長450nmにおける光線透過率を、紫外/可視光光度計(島津製作所製のMULTISPEC-1500)を用いて測定する。
本発明の有機ELデバイスは、基板上に配置された有機EL素子と、有機EL素子と接触して、かつ有機EL素子を覆う(面封止する)樹脂硬化物層と、さらに樹脂硬化物層を覆う封止基板とを含む。有機ELデバイスは、それを含む有機ELディスプレイパネルとして用いられうる。
1-1.金属錯体(b1)の合成
金属錯体(b1-0)の合成
国際公開第2006/022899号に記載された金属アミジン錯体の合成方法に従って、Znイオンを中心金属にして、1つのZnイオンにカルボキシレート化合物として2分子の2-エチルヘキサン酸と、3級アミンとして2分子の1-メチルイミダゾールが配位した金属錯体(b1-0)を合成した。得られた金属錯体(b1-0)における金属イオンに対する3級アミンのモル比は、2.0であった。前記金属錯体(b1-0)について、1H NMR、13C NMR、FD MS、C,H,Nの元素分析の結果を以下に示す。これらの結果から、金属錯体(b1-0)は上記一般式(10)の構造であると推定される。
13C NMR (68 MHz, CDCl3): d 183.7, 139.9, 129.0, 120.0, 49.1, 32.6, 30.1, 26.1,22.9, 14.1, 12.3.FD MS m/z (relative intensity): 82.1 (60), 127.1 (30), 725.3 (100), 1427.6 (20).Anal. Calcd for ZnC24H42N4O4: C, 55.9; H, 8.2; N, 10.9.
5Lフラスコに、亜鉛ビス(2-エチルヘキソエート)を768.19g(2.18mol)投入し、イソプロピルアルコールを1500g加えて、常温常圧下、約150rpmで撹拌した。次いで、亜鉛ビス(2-エチルヘキソエート)が完全に溶解したのを確認後、1,2-DMZ(1,2-ジメチルイミダゾール)を210g(2.18mol)加えて、撹拌を続けた。次いで、1,2-DMZを42g(0.44mol)さらに加えて、撹拌を続けた。その後、撹拌を停止し、得られた溶液を3Lのフラスコに移してエバポレーションによりイソプロピルアルコールを留去し、液状の金属錯体(b1-1)を得た。金属イオンに対する3級アミンのモル比は1.2であった。
1H NMR(270 MHz、CDCl3): δ 0.82 (t, J = 6.8 Hz, 12 H), 1.18-1.23 (m, 8 H), 1.30-1.57 (m, 8H), 2.22 (td, J = 6.9Hz, 3.0Hz, 2 H), 2.51 (s, 3.7 H), 3.57 (s, 3.7 H), 6.76(s, 1.2 H), 7.06(s, 1.2H).
1HNMR(270 MHz、CDCl3): δ 2.34 (s, 3 H), 3.54 (s, 3 H), 6.76 (s, 1 H), 6.85 (s, 1 H).
3級アミンを1B2MZ(1-ベンジル-2-メチルイミダゾール)に変更し、かつ金属イオンに対する3級アミンのモル比が0.8となるように、2-エチルヘキサノエート亜鉛や3級アミンの仕込み量を変更した以外は合成例1と同様にして液状の金属錯体(b1-2)を得た。
1H NMR(270 MHz、CDCl3、標準物質TMS): δ 0.83 (t, J = 8.1 Hz, 12 H), 1.19-1.28 (m, 8 H), 1.34-1.61 (m, 8 H), 2.22 (td, J = 4.8 Hz, 1.9 Hz, 2 H), 2.50(s, 1.8 H), 5.04 (s, 1.2 H), 6.80 (d, J = 1.6 Hz, 0.6 H), 7.06-7.11 (m, 1.8 H), 7.32-7.38 (m,2.4 H).
1H NMR(270 MHz、CDCl3) : d 2.31 (s, 3H), 5.02 (s, 2 H), 6.82 (d, J = 0.68 Hz, 1 H), 6.94 (d, J = 0.68 Hz,1 H), 7.05 (dd, J = 8.5 Hz, 0.8 Hz, 2 H), 7.27-7.36 (m, 4 H).
3級アミンを1BMI12(1-イソブチル-2-メチルイミダゾール)に変更し、かつ金属イオンに対する3級アミンのモル比が0.8となるように亜鉛ビス(2-エチルヘキソエート)や3級アミンの仕込み量を変更した以外は合成例1と同様にして液状の金属錯体(b1-3)を得た。
1H NMR(270 MHz、CDCl3): δ 0.83 (t, J = 7.0 Hz, 12 H), 0.91 (t, J = 4.1 Hz, 3 H), 0.94 (d, J = 6.5 Hz, 3 H), 1.18-1.26 (m, 8 H), 1.26-1.58 (m, 8 H), 2.03 (qt, J = 13.5, 0.5 Hz, 1 H), 2.23 (td, J = 4.8 Hz, 1.9 Hz, 2 H), 2.50 (s, 3 H), 3.63 (d, 7.3 Hz, 2 H), 6.74 (d, J = 9.7 Hz, 1 H), 7.10 (d, J = 1.4 Hz, 1 H).
1H NMR(270MHz、CDCl3、標準物質TMS): δ 0.90 (t, J = 4.1 Hz, 3 H), 0.91 (d, J = 6.5 Hz, 3 H), 1.97 (qt, J = 13.5, 0.5 Hz, 1 H), 2.35 (s, 3 H), 3.61 (d, J = 7.3 Hz, 2 H), 6.77 (d, J = 1.4 Hz, 1 H), 6.87 (d, J = 1.4 Hz, 1 H).
3級アミンを1MI(1-メチルイミダゾール)に変更し、かつ金属イオンに対する3級アミンのモル比が2.0となるように2-エチルヘキサノエート亜鉛や3級アミンの仕込み量を変更した以外は合成例1と同様にして液状の金属錯体(b1-4)を得た。
1H NMR(270MHz、CDCl3): δ = 0.89 (t, J = 7.6 Hz, 12 H), 1.22-1.30 (m, 8 H), 1.42-1.67 (m, 8 H), 2.32(td, J = 6.9 Hz, 3.0 Hz, 2 H), 3.69 (s, 6 H), 6.84(s, 2 H),7.37 (s, 2 H), 8.15(s, 2 H).
1H NMR(270MHz、CDCl3、標準物質TMS):δ= 3.66 (s, 3 H), 6.87 (s, 1 H), 7.02 (s, 1 H), 7.40 (s, 1 H).
3級アミンを1B2PZ(1-ベンジル-2-フェニルイミダゾール)に変更し、かつ金属イオンに対する3級アミンのモル比が0.2となるように2-エチルヘキサノエート亜鉛や3級アミンの仕込み量を変更した以外は合成例1と同様にして液状の金属錯体(b1-5)を得た。
1H NMR(270MHz、CDCl3): δ 0.82 (t, J = 7.8 Hz, 12 H), 1.15-1.25 (m, 8 H), 1.29-1.61 (m, 8 H), 2.23 (td, J = 8.4, 5.7 Hz, 2 H), 5.14 (s, 0.4 H), 7.01 (d, J = 1.4 Hz, 0.2 H), 7.07 (dd, J= 6.5, 1.6 Hz, 0.4 H), 7.27 (d, J = 3.8 Hz, 0.2 H), 7.33-7.45 (m, 1.2 H), 7.58-7.61 (m, 2 H).
1H NMR(270MHz、CDCl3):δ = 5.18 (s, 2 H), 6.93 (d, J = 3.2 Hz, 1 H), 7.03 (dd, J = 3.2, 1.4 Hz, 2 H), 7.18 (d, J = 3.8 Hz, 1 H), 7.23-7.41 (m, 6 H), 7.51-7.58 (m, 2 H).
3級アミンをDBU(1,8-ジアザビシクロ[5,4,0]ウンデカ-7-エン)に変更し、かつ金属イオンに対する3級アミンのモル比が1.0となるように2-エチルヘキサノエート亜鉛や3級アミンの仕込み量を変更した以外は合成例1と同様にして液状の金属錯体(b1-6)を得た。
1H NMR(270 MHz、CDCl3):δ 0.85 (t, J = 7.3 Hz, 12 H), 1.19-1.27 (m, 8 H), 1.29-1.67 (m, 14 H), 1.82 (quin, J = 5.9 Hz, 2 H), 2.21 (td, J = 8.1, 3.2 Hz, 2 H), 2.63-2.65 (m, 2 H), 3.21-3.41 (m, 6 H).
1HNMR(270 MHz、CDCl3、標準物質TMS):δ 1.58-1.68 (m, 6 H), 1.78 (quin, J = 6.2 Hz, 2 H), 2.36-2.40 (m, 2 H), 3.17-3.29 (m, 6 H).
3級アミンをDBN(1,5-ジアゾビシクロ[4,3,0]ノン-5-エン)に変更し、かつ金属イオンに対する3級アミンのモル比が1.0となるように2-エチルヘキサノエート亜鉛や3級アミンの仕込み量を変更した以外は合成例1と同様にして液状の金属錯体(b1-7)を得た。
1H NMR(270 MHz、CDCl3):δ 0.85 (t, J = 6.8 Hz, 12 H), 1.19-1.29 (m, 8 H), 1.33-1.64 (m, 8 H), 1.82 (quin, J = 5.7 Hz, 2 H), 1.94 (quin, J = 7.8 Hz, 2 H), 2.21 (td, J = 8.1, 3.2 Hz, 2 H), 2.81 (t, J = 8.1 Hz, 2 H), 3.19 (t, J = 5.9 Hz, 2 H), 3.33-3.41 (m, 4 H).
1H NMR(270 MHz、CDCl3):δ 1.76 (quin, J = 3.2 Hz, 2 H), 1.89 (quin, J = 3.0 Hz, 2 H), 2.42 (t, J = 8.1 Hz, 2 H), 3.18 (t, J = 5.9 Hz, 2 H), 3.23-3.34 (m, 4 H).
以下の原料を用いて、面封止剤を調製した。
3官能エポキシ樹脂:分子量592(VG-3101L、プリンテック社製)
ビスフェノールF型エポキシ樹脂:分子量338(YL-983U、ジャパンエポキシレジン社製)
ビスフェノールE型エポキシ樹脂:エポキシ当量155~175(R1710、プリンテック社製)
前述で合成した金属錯体(b1-0)~(b1-1)を用いた。
<アミン化合物(b2)>
1,2-ジメチルイミダゾール(キュアゾール 1.2DMZ、四国化成製)
1-ベンジル-2-メチルイミダゾール(キュアゾール 1B2MZ、四国化成製)
1-ベンジル-2-フェニルイミダゾール(キュアゾール 1B2PZ、四国化成製)
1-イソブチル-2-メチルイミダゾール(JERキュアIBMI12、ジャパンエポキシレジン製)
2,4,6-トリス[(ジメチルアミノ)メチル]フェノール(JERキュア 3010、ジャパンエポキシレジン製)
トリス(ジメチルアミノメチル)フェノール・トリ(2-エチルヘキソシエート)(K-61B、エアプロダクツジャパン製)
2-フェニル-4-メチルイミダゾール(キュアゾール 2P4MZ、四国化成製)
2-エチル-4-メチルイミダゾール(キュアゾール 2E4MZ、四国化成製)
ジアザシクロウンデセンフタル酸塩(SA-810、サンアプロ製)
メチルヘキサヒドロ無水フタル酸とヘキサヒドロ無水フタル酸との混合物(リカシッドMH-700、新日本理化製)
3-グリシドキシプロピルトリメトキシシラン、分子量236(KBM-403、信越化学製)
窒素で置換したフラスコで、表2に示す組成のエポキシ樹脂100重量部と、84重量部の酸無水物と、4重量部のシランカップリング剤と、表2に示す重量部の金属錯体(b1-0)または比較用アミン化合物とを攪拌混合して、面封止剤を得た。
上昇率(%)=(Δ粘度変化量(24hrまたは48hr後の粘度-合成直後の粘度)/合成直後の粘度)×100
実施例1~10および比較例1で得られた面封止剤を、予めオゾン処理によって洗浄したガラス基板(7cm×7cm×0.7mm厚)に、スクリーン印刷機(Screen Printer Model 2200、MITANI製)を用いて印刷した。面封止剤の塗布は、乾燥状態で5cm×5cm×3μm厚となるように行った。印刷したガラス基板を、100℃に加熱したホットプレート上で30分間加熱して、硬化物層とした。
窒素で置換したフラスコで、表3~5に示す組成のエポキシ樹脂100重量部と、84重量部の酸無水物と、4重量部のシランカップリング剤と、表3~5に示す重量部の金属錯体またはアミン化合物とを攪拌混合して、面封止剤を得た。なお、実施例11~13で用いた金属錯体は、前述で合成した金属錯体(b1-1)~(b1-3)を用いた。
金属錯体に代えて、亜鉛ビス(2-エチルヘキソエート)と1,2-DMZとをそれぞれ単独で添加した以外は、実施例11と同様にして面封止剤を得た。
実施例11~23および比較例2で得られた面封止剤を、予めオゾン処理によって洗浄したガラス基板(7cm×7cm×0.7mm厚)に、スクリーン印刷機(Screen Printer Model 2200、MITANI製)を用いて印刷した。面封止剤の塗布は、乾燥状態で5cm×5cm×3μm厚となるように行った。面封止剤を印刷したガラス基板を、100℃に加熱したホットプレート上で30分間加熱して、硬化物層とした。
<プレスパッタ条件>
ターゲット:SiO2
ガス種:Ar
ガス流量:15sccm
圧力:4.8×10-1Pa
電源:交流電源(周波数13.56MHz)
入力電力:300W
時間:120秒間
温度:室温
<成膜条件>
ターゲット:SiO2
ガス種:Ar
ガス流量:15sccm
圧力:4.8×10-1Pa
電源:交流電源(周波数13.56MHz)
入力電力:300W
時間:2500秒間
温度:室温
(実施例26~34、比較例3~4)
窒素で置換したフラスコで、表6に示す組成のエポキシ樹脂100重量部と、85重量部の酸無水物と、4重量部のシランカップリング剤と、表6に示す重量部のアミン化合物とを攪拌混合して、面封止剤を得た。
実施例26~34および比較例3~4で得られた面封止剤を、予めオゾン処理によって洗浄したガラス基板(7cm×7cm×0.7mm厚)に、スクリーン印刷機(Screen Printer Model 2200、MITANI製)を用いて印刷した。面封止剤の塗布は、乾燥状態で5cm×5cm×3μm厚となるように行った。印刷したガラス基板を100℃に加熱したホットプレート上で30分間加熱して硬化物層とした。
22 基板
24 有機EL素子
26 封止基板
28 面封止層
28-1 硬化物層
28-2 パッシベーション層
28-3 第2の樹脂硬化物層
30 反射画素電極層
32 有機EL層
34 透明対向電極層
Claims (20)
- 1分子内に2個以上のエポキシ基を有するエポキシ樹脂(a)と、
Zn、Bi、Ca、Al、Cd、La、Zrからなる群から選ばれる1種類以上の金属イオンと、前記金属イオンと錯形成が可能であって、N-H結合を有さない3級アミンと、分子量が17~200のアニオン性配位子とを含む金属錯体(b1)と、
を含み、
E型粘度計により25℃、1.0rpmで測定した粘度が10~10000mPa・sである、光半導体用の面封止剤。 - 前記アニオン性配位子の価数が前記金属イオンの価数より小さく、かつ
前記アニオン性配位子の半径が2.0Å以上である、請求項1に記載の光半導体用の面封止剤。 - 前記3級アミンが、下記一般式(1)~(6)のいずれかで表される化合物である、請求項1に記載の光半導体用の面封止剤。
R1は、炭素数1~17の脂肪族炭化水素基、水酸基、アリール含有基またはシアノエチル基を示し;
R2、R3、R4は、それぞれ独立に水素基、炭素数1~17の脂肪族炭化水素基、水酸基、アリール含有基またはシアノエチル基を示す)
RB1、RB3、RB4、RB5は、それぞれ独立に水素基、炭素数1~17のヘテロ原子を含有してもよい脂肪族炭化水素基、水酸基、アリール含有基またはシアノエチル基を示し;
RB2は、炭素数1~17のヘテロ原子を含有してもよい脂肪族炭化水素基、水酸基、アリール含有基またはシアノエチル基を示し;
RB1、RB2、RB3、RB4、RB5から選択された複数の基が互いに連結して、脂環式環、芳香族環、または酸素、窒素、硫黄から選ばれるヘテロ原子を含有する複素環を形成してもよい)
RC1、RC3、RC4、RC5は、それぞれ独立に水素基、炭素数1~17のヘテロ原子を含有してもよい脂肪族炭化水素基、水酸基、アリール含有基またはシアノエチル基を示し;
RC2は、炭素数1~17のヘテロ原子を含有してもよい脂肪族炭化水素基、水酸基、アリール含有基またはシアノエチル基を示し;
RC1、RC2、RC3、RC4、RC5から選択された複数の基が互いに連結し、脂環式環、芳香族環、または酸素、窒素、硫黄から選ばれるヘテロ原子を含有する複素環を形成してもよい)
RE1、RE2、RE3、RE4、RE5は、それぞれ独立に水素基、炭素数1~17のヘテロ原子を含有してもよい脂肪族炭化水素基、水酸基、アリール含有基またはシアノエチル基を示し;
RE1、RE2、RE3、RE4、RE5から選択された複数の基が互いに連結し、脂環式環、芳香族環、または酸素、窒素、硫黄から選ばれるヘテロ原子を含有する複素環を形成してもよい)
RF1、RF2、RF3、RF4、RF5、RF6、RF7は、それぞれ独立に水素基、炭素数1~17のヘテロ原子を含有してもよい脂肪族炭化水素基、水酸基、アリール含有基またはシアノエチル基を示し;
RF1、RF2、RF3、RF4、RF5、RF6、RF7から選択された複数の基が互いに連結し、脂環式環、芳香族環、または酸素、窒素、硫黄から選ばれるヘテロ原子を含有する複素環を形成してもよい)
RG1、RG2、RG3、RG4は、それぞれ独立に水素基、炭素数1~17のヘテロ原子を含有してもよい脂肪族炭化水素基、水酸基、アリール含有基またはシアノエチル基を示し;
RG1、RG2、RG3、RG4から選択された複数の基が互いに連結し、脂環式環、芳香族環、または酸素、窒素、硫黄から選ばれるヘテロ原子を含有する複素環を形成してもよい) - 前記アニオン性配位子が、O、S、Pからなる群から選ばれ、前記金属イオンに結合しうる原子を2以上有し、かつ前記金属イオンに配位して3~7員環を形成しうるものである、請求項2に記載の光半導体用の面封止剤。
- 前記面封止剤の、CDCl3中、25℃、270MHzにおける1HNMRの化学シフトのうち3級アミンに由来する化学シフトが、前記3級アミン単独の、CDCl3中、25℃、270MHzにおける1HNMRの化学シフトに対して0.05ppm以上移動するピークを含む、請求項1に記載の光半導体用の面封止剤。
- 前記金属イオンに対する前記3級アミンのモル比が、0.5~6.0である、請求項1に記載の光半導体用の面封止剤。
- 前記カルボキシレート化合物が、2-エチルヘキサン酸、ギ酸、酢酸、ブタン酸、2-エチルブタン酸、2,2-ジメチルブタン酸、3-メチルブタン酸、2,2-ジメチルプロパン酸、安息香酸およびナフテン酸からなる群から選ばれる少なくとも1種類の化合物である、請求項5に記載の光半導体用の面封止剤。
- 前記3級アミンが、1,8-ジアゾビシクロ[5,4,0]ウンデカ-7-エン、1-メチルイミダゾール、1,2-ジメチルイミダゾール、1-ベンジル-2-メチルイミダゾール、1-イソブチル-2-メチルイミダゾール、1-ブチルイミダゾールおよび1,5-ジアゾビシクロ[4,3,0]ノン-5-エンからなる群から選ばれる少なくとも1種類の化合物である、請求項1に記載の光半導体用の面封止剤。
- 1分子内に2個以上のエポキシ基を有するエポキシ樹脂(a)と、下記一般式(11)または(12)で表される硬化促進剤(b2)とを含み、
E型粘度計により25℃、1.0rpmで測定した粘度が10~10000mPa・sである、光半導体用の面封止剤。
- 前記一般式(11)において、R1が、炭素数1~17の脂肪族炭化水素基、水酸基、アリール含有基またはシアノエチル基を示す、請求項10に記載の光半導体用の面封止剤。
- 前記光半導体用の面封止剤は、前記金属錯体(b1)を、3級アミンの活性官能基/エポキシ基の当量比が0.008~0.3となる範囲で含む、請求項1に記載の光半導体用の面封止剤。
- 前記光半導体用の面封止剤は、前記硬化促進剤(b2)を、3級アミンの活性官能基/エポキシ基の当量比が0.008~0.152となる範囲で含む、請求項10に記載の光半導体用の面封止剤。
- 前記光半導体用の面封止剤は、酸無水物を、酸無水物基/エポキシ基の当量比が0.8~1.2となる範囲でさらに含む、請求項1または10に記載の光半導体用の面封止剤。
- 含水率が0.1重量%以下である、請求項1または10に記載の光半導体用の面封止剤。
- 有機EL素子用の面封止剤である、請求項1または10に記載の光半導体用の面封止剤。
- 基板上に有機EL素子を形成する第1の工程と、
前記有機EL素子を、請求項1または10に記載の面封止剤で覆う第2の工程と、
前記面封止剤を硬化させた硬化物で、前記有機EL素子を面封止する第3の工程と、
前記有機EL素子を面封止する前記硬化物上に、パッシベーション膜を成膜する第4の工程と、を含む、有機ELデバイスの製造方法。 - 有機EL素子と、
前記有機EL素子と接触しており、前記有機EL素子を面封止している請求項1または10に記載の面封止剤の硬化物からなる硬化物層と、
前記硬化物層と接するパッシベーション層と、を含む有機ELデバイス。 - 有機EL素子と、
前記有機EL素子を面封止しており、X線光電子分光法(XPS)で測定されるスペクトルにおいて、Zn、Bi、Ca、Al、Cd、La、Zrからなる群から選ばれる1種類以上の金属原子に由来するピークと、窒素原子に由来するピークとが検出され、検出される前記金属原子と前記窒素原子とのモル比が、前記金属原子:前記窒素原子=1:0.5~1:6.0であり、かつ前記金属原子の含有量が0.5~15質量%であるエポキシ樹脂組成物の硬化物層と、
前記硬化物層と接するパッシベーション層と、を含む、有機ELデバイス。 - 請求項18に記載の有機ELデバイスを有する、有機ELディスプレイパネル。
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- 2012-06-22 US US13/818,202 patent/US9013049B2/en not_active Expired - Fee Related
- 2012-06-22 CN CN201280030854.3A patent/CN103636286B/zh active Active
- 2012-06-22 TW TW101122505A patent/TWI621650B/zh active
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WO2013187394A1 (ja) * | 2012-06-15 | 2013-12-19 | 古河電気工業株式会社 | 有機エレクトロルミネッセンス素子封止用樹脂組成物、有機エレクトロルミネッセンス素子用封止フィルム、有機エレクトロルミネッセンス素子用ガスバリアフィルムおよびこれを用いた有機エレクトロルミネッセンス素子 |
JP2014002875A (ja) * | 2012-06-15 | 2014-01-09 | Furukawa Electric Co Ltd:The | 有機エレクトロルミネッセンス素子封止用樹脂組成物、有機エレクトロルミネッセンス素子用封止フィルム、有機エレクトロルミネッセンス素子用ガスバリアフィルムおよびこれを用いた有機エレクトロルミネッセンス素子 |
US9913324B2 (en) | 2012-06-15 | 2018-03-06 | Furukawa Electric Co., Ltd. | Resin composition for sealing organic electroluminescent element, sealing film for organic electroluminescent element, gas-barrier film for organic electroluminescent element, and organic electroluminescent element using these films |
WO2014097647A1 (ja) * | 2012-12-21 | 2014-06-26 | 三井化学株式会社 | シート状エポキシ樹脂組成物、それを用いた有機elデバイスの製造方法、有機elデバイスおよび有機elディスプレイパネル |
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JP2018097943A (ja) * | 2016-12-08 | 2018-06-21 | コニカミノルタ株式会社 | 有機エレクトロルミネッセンス発光装置 |
WO2019220896A1 (ja) * | 2018-05-18 | 2019-11-21 | 日本ゼオン株式会社 | 印刷用樹脂溶液及びデバイス構造体の製造方法 |
Also Published As
Publication number | Publication date |
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US20130153880A1 (en) | 2013-06-20 |
JP5237507B1 (ja) | 2013-07-17 |
CN103636286B (zh) | 2017-02-15 |
KR101604896B1 (ko) | 2016-03-18 |
JP2013166949A (ja) | 2013-08-29 |
CN103636286A (zh) | 2014-03-12 |
KR20140024432A (ko) | 2014-02-28 |
TW201311791A (zh) | 2013-03-16 |
JPWO2012176472A1 (ja) | 2015-02-23 |
US9013049B2 (en) | 2015-04-21 |
TWI621650B (zh) | 2018-04-21 |
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