WO2013005441A1 - エポキシ重合性組成物、および有機elデバイス - Google Patents
エポキシ重合性組成物、および有機elデバイス Download PDFInfo
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- WO2013005441A1 WO2013005441A1 PCT/JP2012/004380 JP2012004380W WO2013005441A1 WO 2013005441 A1 WO2013005441 A1 WO 2013005441A1 JP 2012004380 W JP2012004380 W JP 2012004380W WO 2013005441 A1 WO2013005441 A1 WO 2013005441A1
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- polymerizable composition
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- 0 C*CC1NC1 Chemical compound C*CC1NC1 0.000 description 5
- YCXJEKZAMLIMIV-UHFFFAOYSA-N C(C1OC1)Oc1ccc(C2(c3ccccc3-c3c2cccc3)c(cc2)ccc2OC2COC2)cc1 Chemical compound C(C1OC1)Oc1ccc(C2(c3ccccc3-c3c2cccc3)c(cc2)ccc2OC2COC2)cc1 YCXJEKZAMLIMIV-UHFFFAOYSA-N 0.000 description 1
- RBCOXGQCDDTMIX-UHFFFAOYSA-N NCNC(CC(NCN)NCN)NCN Chemical compound NCNC(CC(NCN)NCN)NCN RBCOXGQCDDTMIX-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- 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
- C08G59/20—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 epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/302—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing sulfur
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- 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
- C08G59/20—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 epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
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- 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
- C08G59/40—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 curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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- 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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
- H05B33/04—Sealing arrangements, e.g. against humidity
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
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- 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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/841—Self-supporting sealing arrangements
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- 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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the present invention relates to an epoxy polymerizable composition and an organic EL device.
- Organic EL elements are expected as next-generation displays or lighting devices because of low power consumption and low viewing angle dependency.
- the organic EL element has a problem that it is easily degraded by moisture and oxygen in the atmosphere. Therefore, the organic EL element is used after being sealed with a seal member.
- the method for sealing the organic EL element includes a method called “frame sealing” and a method called “surface sealing”.
- Frame sealing is a method in which a peripheral portion of a sealing cap is sealed with a sealing member in a structure in which a sealing cap is disposed on an organic EL element disposed on a substrate (Patent Document 1, etc.) See).
- Surface sealing refers to a method of sealing so as to cover the organic EL element.
- a space that exists between the sealing plate and the substrate and between the organic EL element and the sealing plate there is a method of filling and sealing with a sealing material (see Patent Document 2 and the like).
- the sealing member for surface sealing is arranged at any position in the space formed between the organic EL element and the sealing plate. Therefore, the refractive index of the sealing member is required to be high (the difference in refractive index from the transparent electrode is small). This is because, when the refractive index of the sealing member is low, total reflection occurs between the electrode and the sealing member, and the extraction efficiency of light emission from the organic EL element decreases.
- the sealing material composition When performing surface sealing by a screen printing method or a dispensing method, the sealing material composition is required to be liquid at a temperature near room temperature. If the sealing material composition is not liquid at a temperature near room temperature, workability is poor, and it is necessary to heat and seal the sealing material composition when sealing the organic EL element. When heated, the display member may be thermally distorted and may not be sufficiently sealed. Further, when the sealing material composition is heated, the curing reaction proceeds and the viscosity tends to become unstable.
- a photo-curable adhesive composition containing a thiol compound and an epoxy compound has been proposed as an adhesive composition suitable for bonding optical parts (see Patent Document 3 and the like). Since this photocurable adhesive composition contains a large amount of elemental sulfur, the cured product is said to have a high refractive index. In addition, the photocurable adhesive composition does not have a rigid molecular structure like a fluorene skeleton, and thus has a low softening point and excellent workability at room temperature, but has a problem of low heat resistance. .
- a photocurable adhesive containing an epoxy compound containing a sulfur atom and (meth) acrylic acid has been proposed; it has a high adhesive force and a high refractive index and is said to have excellent heat resistance (Patent Document) 4).
- a curable resin composition containing an epoxy oligomer containing a sulfur atom and a compound copolymerizable therewith is known; the cured product is said to have a high refractive index (Patent Document) 5).
- the refractive index of the surface sealing material of the organic EL element is increased, the light extraction efficiency of the organic EL device is improved.
- the electron density of the cured resin generally constituting the surface sealing material may be increased.
- a part of the polymerization component of the resin polymerizable composition may be a sulfur-containing compound such as a thiol-containing compound.
- the polymerizable resin composition for electronic materials.
- the polymerizable resin composition is often applied to the organic EL element by a printing application method such as screen printing.
- a printing application it is preferable to apply the polymerizable resin composition at a high speed with a high shearing force.
- the viscosity of the polymerizable resin composition is preferably set to a certain value or less.
- a solvent may be added.
- the organic solvent may deteriorate precision electronic members such as organic EL elements.
- the organic solvent in the polymerizable resin composition volatilizes as an outgas when placed in a heating environment, and there is a risk of degrading the precision electronic member.
- a high-boiling organic solvent is contained in the polymerizable resin composition, the solvent remains in the cured product, and thus it is difficult to impart desired characteristics (for example, refractive index) to the cured product.
- a part of the polymerization component may be a low molecular weight component.
- the low molecular weight component may have a low compatibility with other polymerization components, the transparency of the cured product may decrease (become cloudy).
- the viscosity at a high shear force of the polymerizable resin composition is easily influenced by the combination of the components contained therein, and therefore it is necessary to select an appropriate component.
- an object of the present invention is to provide a polymerizable resin composition in which the cured product has a high refractive index and a viscosity at a high shearing force is not more than a certain value.
- the first of the present invention relates to the following epoxy polymerizable composition or a cured product thereof.
- A1 An S-containing epoxy compound represented by the following general formula (i) and having a refractive index of 1.66 to 1.80, and (A2) an epoxy compound having a softening point of 70 ° C. or lower ( However, (A1) excluding S-containing epoxy compound), (B) a curing accelerator, and (C) a thiol compound having two or more thiol groups in one molecule, An epoxy polymerizable composition having a measured viscosity at 25 ° C. and 60 rpm of 100 to 15000 mPa ⁇ s.
- a 1 and A 2 each independently represent a benzene ring or a 1,3,5-triazine ring
- X 11 each independently represents —S—, —SO 2 —, —O—, —C (R 11 ) 2 —
- R 11 represents each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms).
- Y 11 and Y 12 each independently represent —O— or —S—
- Z 1 and Z 2 each independently represent —O— or —S—
- R 11 and R 12 each independently represent an alkyl group having 1 to 6 carbon atoms or a halogen group
- m a represents an integer of 0 to 10
- m c is when A 2 is a benzene ring represents an integer of from 1 to 5, when A 2 is a 1,3,5-triazine ring represents 1 or 2
- If m b and n a is A 1 or A 2 is a benzene ring are each independently an integer of 0 to 4, when A 1 or A 2 is a 1,3,5-triazine ring
- Each independently represents 0 or 1 j and k each independently represent an integer of 1 to 5 when A 1 or A 2 is a benzene ring, and when A 1 or A 2 is a 1,3,5-triazine ring, Each independently represents 1 or 2, The sum of
- the epoxy compound is at least one epoxy compound selected from the group consisting of a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, an amino epoxy compound, and an epoxy compound represented by the following general formula (4)
- Each of R 12 independently represents an alkyl group having 1 to 5 carbon atoms or a halogen atom; s is 0-4]
- [5] The epoxy polymerizable composition according to any one of [1] to [4], wherein (A2) the epoxy compound is a trifunctional epoxy compound.
- the thiol equivalent of the (C) thiol compound is 80 to 100 g / eq, and the sulfur content of the (C) thiol compound is 50 to 80%, according to any one of [1] to [5] Epoxy polymerizable composition.
- the content of (A1) S-containing epoxy compound is 50 parts by mass or more with respect to 100 parts by mass of the epoxy compound contained in the epoxy polymerizable composition.
- the epoxy polymerizable composition according to any one of the above.
- the epoxy according to any one of [1] to [8], wherein the molar ratio of the epoxy group to the thiol group contained in the epoxy polymerizable composition is 1: 0.9 to 1.1.
- Polymerizable composition [10]
- a transparent resin for optical materials comprising the epoxy polymerizable composition according to any one of [1] to [10].
- An organic EL device surface sealing agent comprising the epoxy polymerizable composition according to any one of [1] to [10].
- the second of the present invention relates to the following organic EL device and method for producing the same.
- An organic EL device is a cured product of the epoxy polymerizable composition according to any one of [1] to [10]
- An organic EL device comprising an organic EL element, a sealing member in contact with the organic EL element, and a passivation film in contact with the sealing member, wherein the sealing member is any one of [1] to [10]
- An organic EL device which is a cured product of the epoxy polymerizable composition according to claim 1.
- An organic EL display panel comprising the organic EL device according to [14] or [15].
- An organic EL device comprising: a third step of laminating the counter substrate so as to face the display substrate and via the composition; and a fourth step of curing the composition to form a sealing member. Manufacturing method.
- a method for producing an organic EL device comprising: a third step of forming a sealing member by curing the composition; and a fourth step of forming a passivation film on the sealing member.
- the epoxy polymerizable composition of the present invention can be molded into a cured product with good workability, and the refractive index of the cured product is high. Therefore, the epoxy polymerizable composition of the present invention is particularly suitably used for forming a surface sealing material for an optical device, particularly a light emitting device.
- Epoxy Polymerizable Composition comprises (A1) an S-containing epoxy compound, (A2) a low softening point epoxy compound having a low softening point (except (A1)), ( B) a curing accelerator and (C) a thiol compound. Furthermore, (A3) a fluorene type epoxy compound may be included.
- the S-containing epoxy compound is represented by the following general formula (i).
- “epoxy group” includes “thioepoxy group”.
- the (A1) S-containing epoxy compound also includes a thioepoxy compound having a thioepoxy group.
- a 1 and A 2 each independently represent a benzene ring or a 1,3,5-triazine ring.
- X 11 is independently —S—, —SO 2 —, —O—, —C (R 21 ) 2 — (R 21 is each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms). Indicates. When a plurality of X 11 are included, each X 11 may be the same or different.
- R 11 and R 12 each independently represents an alkyl group having 1 to 6 carbon atoms or a halogen group.
- the alkyl group having 1 to 6 carbon atoms may be a linear or branched alkyl group; for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl , Pentyl, hexyl and the like.
- the halogen group include chlorine, bromine, iodine and the like.
- m b and n a each represent the number of R 11 and R 12, independently represent an integer of 0 to 4, preferably 0.
- m b and n a is large (A1) lower the softening point of the S-containing epoxy compound, thereby improving the workability in forming the epoxy polymerizable composition.
- the heat resistance and refractive index of the cured product of the epoxy polymerizable composition may become too low.
- m a represents an integer of 0 to 10, and is preferably 1.
- m c is the case A 2 is a benzene ring an integer of 1-5. On the other hand, when A 2 is a 1,3,5-triazine ring, 1 or 2 is indicated.
- the number of m c is large, increases the number of epoxy groups in the compounds of the general formula (i) (including thioepoxy group), although heat resistance of the cured product of the epoxy polymerizable composition is increased, large cure shrinkage Sometimes it becomes too much.
- Y 11 and Y 12 each independently represent —O— or —S—.
- Z 1 and Z 2 each independently represent —O— or —S—.
- j and k each independently represent an integer of 1 to 5. Even when j and k are large, the heat resistance of the cured product of the epoxy polymerizable composition is increased, but the curing shrinkage ratio may be too large.
- m a contained in the general formula (i) when m a contained in the general formula (i) is all 0, at least one of the groups represented by Y 11 , Y 12 , Z 1 , and Z 2 is —S—.
- m a included in the general formula (i) is 1 to 10
- X 11, Y 11, Y 12, Z 1 and at least one of the groups represented by Z 2 include a S; That is, at least one of Y 11 , Y 12 , Z 1 , and Z 2 is —S—, or X 11 is —S— or —SO 2 —. That is, the compound represented by the general formula (i) always contains an S atom.
- n a and k and m c, when A 2 is a benzene ring is 6 or less, when A 2 is a 1,3,5-triazine ring is 3 or less.
- the sum of mb and j in the phenyl group to which the group represented by the following formula is bonded is 5 or less.
- the refractive index of the compound represented by the general formula (i) is 1.66 to 1.80.
- the refractive index of the (A1) S-containing epoxy compound represented by the general formula (i) is 1.66 or more, the refractive index of the cured product of the epoxy polymerizable composition is increased.
- the refractive index refers to a value measured with sodium D line (589 nm). Although the refractive index can be measured by a known method, it can generally be measured by a critical angle method using an Abbe refractometer.
- Examples of the S-containing epoxy compound represented by the general formula (i) include compounds represented by the following general formulas (ii) to (iv).
- R 11, R 12, X 11, Y 11, Y 12, Z 1, Z 2, m b, n a, j, and k are the same as the above general formula (i) is there.
- R 11, R 12, X 11, Y 11, Y 12, Z 1, Z 2, m b, n a, j, and k are the same as the above general formula (i) is there.
- S-containing epoxy compound represented by the general formula (i) include an S-containing epoxy compound represented by the following general formula (1).
- X represents —S— or —SO 2 —.
- Y 1 and Y 2 each independently represent —O— or —S—.
- m represents an integer of 0 to 10, but is preferably 1. When m is 0, at least one of Y 1 and Y 2 is —S—. That is, the compound represented by the general formula (1) always contains an S atom.
- R 1 and R 2 each independently represents an alkyl group having 1 to 6 carbon atoms or a halogen group.
- the alkyl group having 1 to 6 carbon atoms may be a linear or branched alkyl group; for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl , Pentyl, hexyl and the like.
- Examples of the halogen group include chlorine, bromine, iodine and the like.
- m1 and n each independently represents an integer of 0 to 4, preferably 0.
- S-containing epoxy compound represented by the general formula (1) examples include bis [4- (2,3-epoxypropylthio) phenyl] sulfide, bis [4- (2,3-epoxypropylthio) -3.
- S-containing epoxy compound represented by the general formula (1) examples include bis [4- (2,3-epoxypropylthio) phenyl] sulfide, bis [4- (2,3-epoxypropylthio)- 3-methylphenyl] sulfide, bis [4- (2,3-epoxypropylthio) -3,5-dimethylphenyl] sulfide, bis [4- (2,3-epoxypropylthio) -3,5-dibromophenyl ] Sulfides and the like are included.
- the method for producing the S-containing epoxy compound is not particularly limited.
- the S-containing epoxy compound represented by the general formula (ii) is obtained by reacting a trithiol compound represented by the following formula with epihalohydrin.
- the S-containing epoxy compound represented by the general formula (1) is, for example, the following formula (X, Y 1 , Y 2 , m, R 1 , R 2 , m1, n are the same as those in the general formula (1), respectively. It is obtained by reacting a dithiol compound or a diol compound (as defined in 1) with an epihalohydrin.
- the S-containing epoxy compound tends to increase the refractive index of the cured product of the epoxy polymerizable composition.
- the viscosity of the epoxy polymerizable composition is not increased more than necessary.
- it is excellent also in compatibility with the below-mentioned (A2) low softening point epoxy compound.
- the epoxy polymerizable composition of the present application has a low viscosity even when a high shear force is applied.
- m c and m a is 1 or more
- X 11 is a relatively short bridge
- Y 11 and Y 12 is short It is a crosslinked part. Therefore, the degree of freedom of conformation of ring A 1 , ring A 2 , and epoxy group (thioepoxy group) is low, and the (A1) S-containing epoxy compound tends to have a compact structure.
- the ring A 1 and the ring A 2 are relatively small rings such as a benzene ring and a 1,3,5-triazine ring, the bulk of the (A1) S-containing epoxy compound is low. Therefore, it is considered that the viscosity can be kept low even when high shear is applied to the epoxy polymerizable composition. Furthermore, since it has a certain level of ring A 1 and ring A 2 in a molecule, described later (A2) low softening point epoxy compounds (especially compounds having a benzene ring) and, (A3) fluorene epoxy compound compatible And the transparency of the cured product of the epoxy polymerizable composition is high.
- the low softening point epoxy compound preferably has a softening point of 70 ° C. or lower, and may be liquid at room temperature.
- the (A2) low softening point epoxy compound referred to in the present specification does not include (A1) an S-containing epoxy compound.
- the epoxy compound having a low softening point can further improve the workability of the epoxy polymerizable composition. Moreover, it is excellent in compatibility with components such as the aforementioned (A1) S-containing epoxy compound, and also has an effect of preventing the cured product of the composition of the present invention from becoming cloudy.
- the softening point is measured by the ring and ball method (based on JIS K7234).
- the low softening point epoxy compound is not particularly limited, and includes a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, an amino epoxy compound, an epoxy compound represented by the following general formula (4), and the like.
- the bisphenol A type epoxy compound and the bisphenol F type epoxy compound can be represented by the following formulas, respectively.
- R 10 in the formula is each independently an alkyl group having 1 to 5 carbon atoms, preferably a methyl group;
- p in the formula represents the number of substitution of the substituent R 10 and is 0 to 4, preferably 0. It is.
- the amino epoxy compound is typically the following aniline type epoxy compound, and examples of the aniline type epoxy compound include the following compounds.
- R 11 in the formula represents an alkyl group having 1 to 5 carbon atoms or a halogen atom, q is 0 to 5, and r is 0 to 4.
- R 12 in the general formula (4) independently represents an alkyl group having 1 to 5 carbon atoms or a halogen atom, and s is 0 to 4.
- At least a part of the epoxy compound having a low softening point is preferably a trifunctional epoxy compound. If it is a trifunctional epoxy compound, the crosslinking degree of the hardened
- the fluorene type epoxy compound can increase the refractive index of the cured product of the polymerizable resin composition containing the fluorene type epoxy compound. Moreover, since fluorene is a rigid aromatic group, the glass transition temperature Tg of the hardened
- the softening point of the fluorene type epoxy compound is preferably 50 ° C to 200 ° C, and more preferably 80 ° C to 160 ° C. This is for improving the workability of the composition of the present invention and enhancing the heat resistance of the cured product. Moreover, plasma resistance and a weather resistance can be improved by containing (A3) component.
- the fluorene type epoxy compound is represented by the general formula (2) or (3).
- R 1 in the general formula (2) independently represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom in order to increase the reactivity of the epoxy group.
- R 2 in the general formula (2) is independently a hydrogen atom or a methyl group, but R 2 is preferably a hydrogen atom because of excellent reactivity of the epoxy group.
- N in the general formula (2) represents the number of repeating alkylene ether units.
- n is each independently an integer of 0 to 3. Since the softening point of a compound falls, so that n is large, workability
- M in the general formula (2) represents the number of substitutions of the epoxy group-containing substituent, is an integer of 2 or more, and is usually 4 or less.
- the “epoxy group-containing substituent” means a substituent containing an epoxy group bonded to a benzene ring.
- the epoxy group-containing substituent may be bonded to any benzene ring.
- m is preferably 2.
- P in the general formula (2) represents the number of substitutions of R 3 and is independently an integer of 0 to 4.
- p is preferably 0 or 1, and more preferably 0.
- R 3 in the general formula (2) independently represents an alkyl group having 1 to 5 carbon atoms. When the number of carbon atoms is large, the softening point is lowered and the workability is improved. However, since the heat resistance and refractive index of the cured product may be too low, R 3 is preferably a methyl group.
- Q in the general formula (2) represents the number of substitutions of R 4 and is independently an integer of 0 to 5.
- q is preferably 0 or 1, and more preferably 0.
- R 4 in the general formula (2) independently represents an alkyl group having 1 to 5 carbon atoms.
- R 4 is preferably a methyl group.
- the fluorene type epoxy compound represented by the general formula (2) is preferably a compound represented by the following general formula (2-1).
- m a independently represents an integer of 1 to 3, and is preferably 1.
- Q in the general formula (2-1) each independently represents an integer of 0 to 4.
- R 1 to R 4 , n, and p in the general formula (2-1) are defined in the same manner as in the general formula (2).
- Y in the general formula (3) represents a single bond, an oxygen atom or a sulfur atom.
- Q in the general formula (3) each independently represents an integer of 0 to 4.
- R 1 to R 4 , m, n, and p in the general formula (3) are defined in the same manner as in the general formula (2).
- the fluorene type epoxy compound represented by the general formula (3) is preferably a compound represented by the following general formula (3-1).
- M b in the general formula (3-1) are each independently an integer of 1 to 3, preferably 1.
- R 1 to R 4 , n, and p in the general formula (3-1) are defined in the same manner as in the general formula (3).
- the compound represented by the general formula (3) has a rigid molecular structure as compared with the molecular structure of the compound represented by the general formula (2). Therefore, the heat resistance of the cured product of the compound represented by the general formula (3) is increased. In particular, when Y is a single bond, the heat resistance of the cured product is significantly improved, but the softening point becomes too high and workability may be reduced. On the other hand, when Y is an oxygen atom or a sulfur atom, the above balance is excellent.
- the fluorene type epoxy compound can be obtained, for example, by reacting phenol having a fluorene skeleton with epichlorohydrin (also referred to as “3-chloro-1,2-epoxypropane”) by a known method.
- a desired epoxy compound can be synthesized by appropriately selecting the structure of a phenol having epichlorohydrin and a fluorene skeleton. That is, R 1 in the general formula (2) can be appropriately changed by using an epichlorohydrin derivative instead of epichlorohydrin as a raw material.
- Phenol having a fluorene skeleton can be synthesized according to the method described in JP-A-2001-206862. If a phenol skeleton having a fluorene skeleton is selected, m, R 3 and p in the general formula (2) can be appropriately changed. If the polyfunctional hydroxyl group-containing fluorene compound described in Patent Document 3 is used as a raw material, a fluorene type epoxy compound in which R 2 in the general formula (2) is a hydrogen atom or a methyl group and n is not 0 can be synthesized.
- the epoxy polymerizable composition of the present invention includes (A1) an S-containing epoxy compound and (A2) a low softening point epoxy compound, and more preferably includes (A3) a fluorene type epoxy compound. It is.
- the total content of (A1) S-containing epoxy compound and (A2) epoxy compound having a low softening point contained in the epoxy polymerizable composition, or (A3) component (A1) when containing a fluorene type epoxy compound and (A3) When the total content of the component (A2) and the component (A3) is 100 parts by mass, the content of the component (A1) is preferably 50 parts by mass or more.
- the content of the (A1) S-containing epoxy compound is 50 parts by mass or more, the refractive index of the cured product can be easily adjusted to 1.68 or more.
- composition of this invention contains (A3) fluorene type epoxy compound
- (A3) fluorene type epoxy compound when the total content of (A1) component, (A2) component, and (A3) component is 100 mass parts, (A3) The fluorene type epoxy compound is preferably 1 to 60 parts by weight, more preferably 5 to 50 parts by weight or more, and further preferably 10 to 30 parts by weight.
- content of a fluorene type epoxy compound shall be the said range, the heat resistance of the hardened
- (B) Curing accelerator examples of the (B) curing accelerator that promotes curing of the epoxy compound include imidazole compounds and amine compounds. Examples of imidazole compounds include 2-ethyl-4-methylimidazole, and examples of amine compounds include trisdimethylaminomethylphenol.
- the curing accelerator may be a Lewis base compound.
- the (B) curing accelerator is preferably a thermosetting accelerator, and the composition of the present invention is light. It is preferable that the curing accelerator is not substantially contained. This is because the photocuring accelerator often generates a gas that decomposes and degrades the light emitting element when accelerating the curing as compared with the thermosetting accelerator.
- the content of the (B) curing accelerator in the epoxy polymerizable composition is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of epoxy compounds. This is because the epoxy polymerizable composition has an excellent balance between curability and storage stability.
- the thiol compound has two or more thiol groups in one molecule.
- the thiol compound can act as a curing agent for the epoxy compound.
- the thiol group of the thiol compound reacts with the epoxy group of the epoxy compound (including the thioepoxy group) to cause these epoxy compounds to cross-link with each other, resulting in a cured product having excellent heat resistance and adhesive strength. It can be.
- the transparency of the cured product of the epoxy polymerizable composition can be enhanced by the thiol compound.
- the (C) thiol compound crosslinks the epoxy compound, thereby preventing accumulation of the benzene ring or 1,3,5-triazine ring in the epoxy compound.
- the (C) thiol compound is preferably a compound having no benzene ring or 1,3,5-triazine ring.
- the thiol compound is not particularly limited as long as it has two or more thiol groups in one molecule.
- the number of thiol groups is large, the crosslink density of a cured product (hereinafter, also simply referred to as “cured product”) of the resulting epoxy composition is improved, so that the heat resistance of the cured product is improved.
- cured product also simply referred to as “cured product”
- thiol groups are close to each other in the molecule of the thiol compound, and steric hindrance is likely to occur, and the reactivity with epoxy groups (including thioepoxy groups) decreases.
- the content of thiol groups in one molecule is represented by thiol equivalent (g / eq).
- the thiol equivalent of the thiol compound is 80 to 100 g / eq, preferably 85 to 95 g / eq, more preferably 86 to 92 g / eq.
- the thiol equivalent is a value obtained by dividing the molecular weight of the (C) thiol compound by the number of thiol groups contained in the molecule.
- the thiol equivalent is less than 80 g / eq, the distance between the cross-linking points of the cured product is shortened, so the reactivity with the epoxy group (including the thioepoxy group) is lowered, and the conversion rate may not increase.
- the thiol equivalent exceeds 100 g / eq, the distance between the crosslinking points of the cured product becomes too long, and the heat resistance of the cured product may be reduced.
- the thiol compound may contain a sulfur atom other than a thiol group in the molecule.
- the thiol compound containing sulfur element in the molecule increases the refractive index of the cured product of the epoxy polymerizable composition. Therefore, the sulfur content of the (C) thiol compound in the epoxy polymerizable composition is 50 to 80%, preferably 60 to 75%.
- the sulfur content is obtained from the ratio of each element obtained by mass spectrometry of the thiol compound (the ratio of sulfur element to all elements).
- the sulfur content is less than 50%, the refractive index of the cured product of the resin composition containing the sulfur content may not be sufficiently increased.
- the cured product of the resin composition containing the thiol compound since many thiol compounds having a sulfur content exceeding 80% contain an SS bond in the molecule, the cured product of the resin composition containing the thiol compound generates radicals or has chemical stability. May be inferior.
- the molecular weight of the thiol compound is preferably 140 to 500.
- the molecular weight may be obtained by mass spectrometry.
- (C) A thiol compound will not be specifically limited if a thiol equivalent and a sulfur content rate are in the said range.
- Specific examples of (C) thiol compounds include compounds represented by the following formulas (4), (5) and (6).
- the compounds represented by the formulas (4), (5) and (6) can be synthesized by known methods, but are also commercially available.
- the thiol equivalent of the compound of formula (4) is 87 g / eq and the sulfur content is 62%; the thiol equivalent of the compound of formula (5) is 91 g / eq and the sulfur content is 61%;
- the compound has a thiol equivalent of 89 g / eq and a sulfur content of 72%.
- the content of the (C) thiol compound in the epoxy polymerizable composition of the present invention is not particularly limited, but the ratio of the molar amount of the thiol group and the epoxy group (including the thioepoxy group) contained in the epoxy polymerizable composition. May be determined.
- the thiol compound acts as a curing agent for the epoxy compound.
- the thiol group is excessively contained in the epoxy polymerizable composition, the thiol group that has not reacted with the epoxy group (including the thioepoxy group) remains in the cured product. Therefore, there is a possibility of contaminating a member near the cured product.
- the thiol group is too small, the crosslinking density cannot be sufficiently increased, and the heat resistance of the obtained cured product may be lowered.
- the epoxy group (including the thioepoxy group) contained in the epoxy polymerizable composition of the present invention is 1 mole, 0.9 to 1.1 moles of thiol group is preferably contained, and 0.95 More preferably, ⁇ 1.05 mol of thiol group is contained, and 1 mol of thiol group is particularly preferred.
- Silane coupling agent may be contained in the epoxy polymerizable composition.
- the epoxy polymerizable composition containing a silane coupling agent has high adhesion to a substrate or the like when used as a sealing material composition for organic EL.
- Examples of silane coupling agents include silane compounds having reactive groups such as epoxy groups, carboxyl groups, methacryloyl groups, and isocyanate groups.
- silane compounds include trimethoxysilylbenzoic acid, ⁇ -methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxy.
- Silane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like are included.
- the silane coupling agent may be a single type or a combination of two or more types.
- the content of the (D) silane coupling agent in the epoxy polymerizable composition is preferably 0.05 to 30 parts by mass, preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the epoxy polymerizable composition. More preferably, it is 0.3 to 10 parts by mass.
- the epoxy polymerizable composition can further contain optional components such as other resin components, fillers, modifiers, stabilizers and the like within a range not impairing the effects of the present invention.
- optional components include polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene-styrene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine series Oligomer, silicon oligomer and polysulfide oligomer are included. These 1 type can be contained individually or in combination of multiple types.
- Examples of the filler include glass beads, styrene polymer particles, methacrylate polymer particles, ethylene polymer particles, and propylene polymer particles.
- the filler may be a combination of a plurality of types.
- Examples of the modifier include polymerization initiation aids, anti-aging agents, leveling agents, wettability improvers, surfactants, plasticizers, and the like. You may use these in combination of multiple types.
- Examples of the stabilizer include ultraviolet absorbers, preservatives, and antibacterial agents.
- the modifier may be a combination of a plurality of types.
- a component that is phase-separated from the epoxy compound and has a large refractive index difference from the epoxy compound specifically, a cured product of the epoxy compound and It is preferable that an inorganic filler or an organic filler having a refractive index difference of 0.1 or more and a diameter of 0.1 ⁇ m or more is substantially not contained.
- the water content of the epoxy polymerizable composition of the present invention is preferably 0.1% by mass or less, and more preferably 0.06% by mass or less, particularly when used as a sealant for a light emitting device. Since the electric circuit in which the organic EL element itself and the light emitting element are arranged is easily deteriorated by moisture, it is preferable to reduce the water content of the epoxy polymerizable composition as much as possible.
- the water content of the epoxy polymerizable composition can be determined 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 epoxy polymerizable composition of the present invention preferably has a viscosity at 25 ° C. of 100 to 15000 mPa ⁇ s, more preferably 100 to 10000 mPa ⁇ s, from the viewpoint of ease of application work and the like. More preferably, it is 6000 mPa ⁇ s.
- the viscosity of the composition at 25 ° C. is measured with a B-type viscometer (BL type manufactured by Toki Sangyo Co., Ltd.) under the condition of a rotational speed of 60 rpm.
- BL type manufactured by Toki Sangyo Co., Ltd.
- the epoxy polymerizable composition of the present invention preferably has a small curing shrinkage rate.
- the cure shrinkage is preferably 10% or less, and more preferably 8% or less.
- a sealing material composition for producing a surface-sealing sealing member has a low cure shrinkage rate. This is because if the cure shrinkage rate is high, a fine gap is formed between the sealing member, which is a cured product, and the substrate due to internal stress, adhesive strength is reduced, and moisture resistance is further reduced.
- the cured product of the epoxy polymerizable composition of the present invention has a high refractive index.
- the refractive index of the cured product is preferably more than 1.60, more preferably 1.64 or more, further preferably 1.66 or more, and particularly preferably 1.68 or more.
- the refractive index refers to a value measured with sodium D line (589 nm). Although the refractive index can be measured by a known method, it can generally be measured by a critical angle method using an Abbe refractometer.
- the cured product of the epoxy polymerizable composition of the present invention is preferably transparent in the visible light region. Transparency can be evaluated by light transmittance using an ultraviolet / visible spectrophotometer.
- the light transmittance of the cured product of the present invention is preferably 30% or more at 450 nm, more preferably 50% or more, and still more preferably 80% or more. This is for improving the display properties when used as a sealing member of an optical device (including an organic EL element).
- the light transmittance of the epoxy polymerizable cured product can be measured by the following procedure. 1) An epoxy polymerizable cured product 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).
- the epoxy polymerizable composition of the present invention can be used as a seal member by being cured. Further, it is preferably applied to a seal member or an optical material through which light from the optical device passes.
- optical devices include organic EL panels, liquid crystal displays, LEDs, electronic paper, solar cells, CCDs, and the like.
- the optical material include an optical adhesive, an optical film, a hologram material, a photonic crystal, a diffraction grating, a prism, a refractive index distribution lens, an optical fiber, and an optical waveguide film.
- the epoxy polymerizable composition of the present invention is preferably used as a sealing material composition (or a transparent resin composition for optical materials) that serves as a sealing member of a light emitting device (in particular, an organic EL device having a top emission structure).
- a sealing material composition or a transparent resin composition for optical materials
- This is to improve the extraction efficiency of light emitted from the organic EL element when used as a seal member for the organic EL element having a top emission structure. That is, in the organic EL element having the top emission structure, a transparent cathode electrode layer such as ITO is disposed on the organic EL layer. Since the refractive index of ITO is about 1.8, if the refractive index of the seal member disposed on the cathode electrode layer is too low, the extraction efficiency of light emitted from the organic EL element is lowered.
- the epoxy polymerizable composition of the present invention can be produced by any method as long as the effects of the invention are not impaired.
- each epoxy compound including (A1) to (A3)
- the epoxy mixture and (C) thiol compound are mixed at 30 ° C. or less.
- Step 2 of 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.
- the curing accelerator and other optional components are preferably mixed with the mixture obtained in step 2.
- Step 1 may be performed under heating conditions.
- the heating temperature is set according to the softening point of each epoxy component.
- Process 2 mixes an epoxy mixture and (C) thiol compound, for example on non-heating conditions (30 degrees C or less). It is for suppressing progress (gelation etc.) of hardening reaction of an epoxy mixture and (C) thiol compound.
- (B) It is preferable that a hardening accelerator is similarly mixed at 30 degrees C or less.
- the epoxy polymerizable composition of this invention is useful as a composition for producing the sealing member of an organic EL element. That is, the organic EL device of the present invention includes a display substrate on which an organic EL element is disposed, a counter substrate that is paired with the display substrate, and the organic EL element that is disposed between the display substrate and the counter substrate. And a sealing member for sealing.
- the method of sealing so as to cover the organic EL element is called surface sealing, and an example thereof is a method of sealing by filling a space formed between the organic EL element and the counter substrate with a sealing member.
- placing a sealing member around the periphery of the counter substrate and sealing it is called frame sealing.
- the epoxy polymerizable composition of the present invention may be applied to any sealing member for surface sealing and frame sealing, but is preferably applied to a sealing member for surface sealing, and an organic EL having a top emission structure. More preferably, it is applied to a surface sealing type sealing member of a device.
- FIG. 1A is a cross-sectional view schematically showing a first example of a surface-sealing type organic EL device.
- the organic EL device 20 shown in FIG. 1A includes a display substrate 22, an organic EL element 24, a sealing substrate 26, and a sealing member 28 for surface sealing.
- the organic EL element 24 includes a pixel electrode 30, an organic EL layer 32, and a counter electrode 34.
- the sealing member 28 in FIG. 1A is a cured product of the aforementioned epoxy polymerizable composition.
- the counter electrode 34 may be covered with a passivation film made of an orientation compound such as silicon oxide or silicon nitride.
- FIG. 1B is a cross-sectional view schematically showing a second example of the surface-sealing type organic EL device.
- the organic EL device 20 ′ shown in FIG. 1B includes a display substrate 22, an organic EL element 24, a sealing substrate 26, and a sealing member 28 that performs surface sealing.
- the organic EL element 24 includes a pixel electrode 30, an organic EL layer 32, and a counter electrode 34.
- the sealing member 28 in FIG. 1B includes a cured resin layer 28-1, a passivation layer 28-2 made of an inorganic compound such as silicon oxide or silicon nitride, and an adhesive resin layer 28-3.
- a cured product layer 28-1 of the resin in FIG. 1B can be a cured product of the aforementioned epoxy polymerizable composition.
- Organic EL device can be manufactured by any method.
- the sealing material composition is applied to the display substrate 22 on which the organic EL elements 24 are laminated, and the display substrate 22 on which the sealing material composition is applied.
- the sealing substrate 26 to be paired is overlapped to obtain a laminate, and the sealing material composition (the above-described epoxy polymerizable composition) of the obtained laminate is cured to form the sealing member 28.
- Each step may be performed according to a known method. Examples of the method of applying the sealing material composition include screen printing and a method using a dispenser. Since the viscosity of the epoxy polymerizable composition of the present invention is adjusted to 100 to 15000 mPa ⁇ s, it is easy to apply.
- the curing step is preferably performed at 25 to 100 ° C. for 0.1 to 2 hours.
- FIG. 2 schematically shows a manufacturing process of the organic EL device 20 'shown in FIG. 1B.
- the display substrate 22 on which the organic EL element 24 is laminated is prepared (FIG. 2A).
- the organic EL element includes the pixel electrode 30, the organic EL layer 32, and the counter electrode 34, but may further include another functional layer.
- a sealing material composition (the aforementioned epoxy polymerizable composition) is applied on the organic EL element 24 laminated on the display substrate 22 (so as to cover the counter electrode 34), and then cured to be a cured product layer. 28-1 is deposited (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, but can be formed by plasma CVD or sputtering. Further, 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. The sealing substrate 26 is attached (FIG. 2E). In this way, the organic EL device 20 'of the present invention is obtained.
- the transparency of the cured product of the epoxy resin composition of the present invention is not easily lowered even when exposed to plasma. Therefore, if the cured product layer 28-1 is a cured product of the epoxy polymerizable composition of the present invention, the cured product layer 28-1 is turned into plasma when the passivation layer 28-2 is formed by plasma CVD or the like. Despite being exposed, the transparency of the cured product layer 28-1 is maintained. In addition, since the organic EL device is often used in a form exposed to sunlight for a long time, the cured product of the organic EL element surface sealing material is also required to have weather resistance. Since the cured product of the composition maintains transparency even when exposed to plasma as described above, it can be seen that the cured product is also excellent in weather resistance.
- FIG. 2 shows a flow of forming one organic EL element 24 on the display substrate 22 and sealing it; the plurality of organic EL elements 24 formed on the display substrate 22 are processed in the same procedure. It can be sealed with a single flow.
- the organic EL device of the present invention can be applied to an organic EL display panel.
- organic EL devices are arranged in a matrix on a substrate.
- An epoxy polymerizable composition was produced using the components shown below.
- Example 1 In a flask, 50 parts by mass of TBBT epoxy ((A1) S-containing epoxy), 20 parts by mass of EP3950S ((A2) low softening point epoxy), and 30 parts by mass of PG-100 ((A3) fluorene type epoxy) And mixed while warming. To this, 52 parts by mass of GST ((C) thiol compound) was added and mixed at room temperature, and further 0.4 parts by mass of 2E4MZ ((B) curing accelerator) was added and stirred at room temperature for epoxy. A polymerizable composition was obtained.
- Examples 2 to 9 As shown in Table 1, (A1) the amount of S-containing epoxy, (A2) the type and amount of low softening point epoxy, (A3) the amount of fluorene type epoxy, (C) the type and amount of thiol compound, An epoxy polymerizable composition was obtained in the same procedure as in Example 1.
- the epoxy polymerizable compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 6 were poured into a mold and heated at 90 ° C. for 1 h to obtain a cured product having a thickness of 0.2 mm. Further, the epoxy polymerizable composition obtained in Comparative Example 7 was poured into a mold, and 10 mW / cm 2 of UV light was heated for 5 minutes at 60 ° C. for 2 hours to obtain a cured product having a thickness of 0.2 mm. The epoxy polymerizable composition obtained in Comparative Example 8 could not be cured.
- the refractive index of the obtained cured product was measured by irradiating sodium D-line (589 nm) using a refractometer (multi-wavelength Abbe refractometer DR-M4 manufactured by Atago Co., Ltd.).
- the haze value (%) of the obtained cured product was measured using a haze meter (manufactured by Tokyo Denka, model name TC-H3DPK). Thereafter, the cured product was placed in a plasma processing apparatus (manufactured by Yamato Kagaku, model name PDC210, parallel plate type), and plasma processing was performed for 20 minutes under conditions of an oxygen flow rate of 20 mL / min and an RF output of 500 W. The haze value (%) of the cured product layer after the plasma treatment was measured using a haze meter (manufactured by Tokyo Denka, model name TC-H3DPK).
- the viscosity of the surface sealant obtained in Comparative Examples 9 and 10 was measured.
- the viscosity of the epoxy polymerizable composition at 25 ° C. was measured using an E-type viscometer (digital rheometer model DII-III ULTRA manufactured by BROOKFIEL). The measurement results are shown in Table 1.
- the curability of the surface sealant obtained in Comparative Examples 9 and 10 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. Based on the obtained spectrum, 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
- YL-983U Bisphenol F type epoxy resin (manufactured by Japan Epoxy Resin)
- VG-3101L Trifunctional epoxy resin: Molecular weight 592 (manufactured by Printec)
- MH-700 Methylhexahydrophthalic anhydride and hexahydrophthalic anhydride Mixture (manufactured by Shin Nippon Chemical Co., Ltd.)
- KBM-403 3-glycidoxypropyltrimethoxysilane, molecular weight 236 (manufactured by Shin-Etsu Chemical) 2E4MZ: 2-phenyl-4-methylimidazole (Cureazole 2P4MZ, manufactured by Shikoku Kasei) SA-810: Diazacycloundecenphthalate (San-Apro)
- the epoxy polymerizable composition obtained in each example is colorless and transparent, and its viscosity is kept low (14000 mPa ⁇ s or less). Moreover, it can be seen that the refractive index of the cured product is high (over 1.67). On the other hand, it can be seen that the epoxy polymerizable compositions obtained in Comparative Examples 1 to 4 have a low refractive index (1.67 or less).
- the epoxy polymerizable compositions obtained in Comparative Examples 5 to 6 were cloudy, and the cured products were also cloudy.
- the epoxy polymerizable composition obtained in Comparative Example 7 had a high cure shrinkage, a refractive index of 1.65 or less, oxygen inhibition during thin film curing, and insufficient curing, and a thin film could not be formed.
- the epoxy polymerizable composition obtained in Comparative Example 8 was pasty and difficult to cure.
- FIG. 3 is a graph in which the viscosity and the refractive index of the cured product are plotted for the epoxy polymerizable compositions of Examples 1 to 9 and the epoxy polymerizable compositions of Comparative Examples 1 to 4. As shown in FIG. 3, it can be seen that the epoxy polymerizable composition obtained in the examples increases the refractive index of the cured product while maintaining the viscosity low.
- the glass transition temperatures (51 ° C. to 78 ° C.) of the cured products of the epoxy polymerizable compositions obtained in Examples 1 to 6 are the glass transition temperatures of the cured products of the epoxy polymerizable compositions obtained in Examples 7 to 9 ( 42-59 ° C). From this, it can be seen that a cured epoxy resin with good heat resistance can be obtained by adding a fluorene type epoxy resin.
- the plasma resistance of the cured products of the epoxy polymerizable compositions obtained in Examples 1 to 9 is higher than that of Comparative Examples 9 and 10. From this, it can be seen that the composition of the present invention is suitable for the production of an organic EL device exposed to plasma, and the cured product of the composition of the present invention is also excellent in weather resistance.
- the epoxy polymerizable composition of the present invention has a low viscosity even when subjected to high shear, and the cured product has a high refractive index even though it can be easily molded by a technique such as a printing method. Therefore, it is particularly suitably used as a sealing material for optical devices, particularly light emitting devices.
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Abstract
Description
[1] (A1)下記一般式(i)で表され、かつ屈折率が1.66~1.80である、S含有エポキシ化合物と、(A2)70℃以下の軟化点を有するエポキシ化合物(ただし、前記(A1)S含有エポキシ化合物を除く)と、(B)硬化促進剤と、(C)1分子内に2つ以上のチオール基を有するチオール化合物と、を含み、B型粘度計で測定された25℃、60rpmでの粘度が100~15000mPa・sである、エポキシ重合性組成物。
A1及びA2は、それぞれ独立にベンゼン環、または1,3,5-トリアジン環を示し、
X11はそれぞれ独立に-S-、-SO2-、-O-、-C(R11)2-(R11は、それぞれ独立に水素原子、または炭素数1~3のアルキル基)を示し、
Y11およびY12は、それぞれ独立に-O-又は-S-を示し、
Z1及びZ2は、それぞれ独立に、-O-又は-S-を示し、
R11およびR12は、それぞれ独立に炭素数1~6のアルキル基またはハロゲン基を示し、
maは0~10のいずれかの整数を示し、
mcはA2がベンゼン環である場合には1~5の整数を示し、A2が1,3,5-トリアジン環である場合には1または2を示し、
mb及びnaはA1またはA2がベンゼン環である場合には、それぞれ独立に0~4の整数を示し、A1またはA2が1,3,5-トリアジン環である場合には、それぞれ独立に0または1を示し、
j及びkは、A1またはA2がベンゼン環である場合には、それぞれ独立に1~5の整数を示し、A1またはA2が1,3,5-トリアジン環である場合には、それぞれ独立に1または2を示し、
mbとjとの和は、A1がベンゼン環である場合には5以下であり、A1が1,3,5-トリアジン環である場合には2以下であり、
naとkとmcとの和は、A2がベンゼン環である場合には6以下であり、A2が1,3,5-トリアジン環である場合には3以下であり、
maが0のとき、Y11、Y12、Z1、及びZ2で表される基の少なくとも一つが-S-であり、
maが1~10のとき、X11、Y11、Y12、Z1、及びZ2で表される基の少なくとも一つがSを含む基である。]
Xは-S-または-SO2-を示し、
Y1およびY2は、それぞれ独立に-O-又は-S-を示し、
mは0~10のいずれかの整数を示し、
m1及びnは、それぞれ独立に0~4のいずれかの整数を示し、
R1およびR2は、それぞれ独立に炭素数1~6のアルキル基またはハロゲン基を示し、
mが0のとき、Y1およびY2の少なくとも一方が-S-である]
R1は、それぞれ独立に水素原子またはメチル基を表し;
R2は、それぞれ独立に水素原子またはメチル基を表し;
R3は、それぞれ独立に炭素数が1~5のアルキル基を表し;
R4は、それぞれ独立に炭素数が1~5のアルキル基を表し;
mは、2以上の整数を表し;
nは、それぞれ独立に0~3の整数を表し;
pは、それぞれ独立に0~4の整数を表し;
qは、それぞれ独立に0~5の整数を表す]
Yは、単結合、酸素原子または硫黄原子を表し;
qは、それぞれ独立に0~4の整数を表し;
R1~R4、m、n、及びpは、一般式(2)と同様に定義される]
R12は、それぞれ独立して、炭素数1~5のアルキル基またはハロゲン原子を表し、
sは0~4である]
[5](A2)エポキシ化合物が3官能エポキシ化合物である、[1]~[4]のいずれかに記載のエポキシ重合性組成物。
[7](C)チオール化合物の分子量が、140~500である、[6]に記載のエポキシ重合性組成物。
[9]前記エポキシ重合性組成物に含まれる、エポキシ基とチオール基とのモル比が、1:0.9~1.1である、[1]~[8]のいずれかに記載のエポキシ重合性組成物。
[10]含水率が0.1質量%以下である、[1]~[9]のいずれかに記載のエポキシ重合性組成物。
[12]前記[1]~[10]のいずれかに記載のエポキシ重合性組成物を含む、有機EL素子面封止剤。
[13]前記[1]~[10]のいずれかに記載のエポキシ重合性組成物の硬化物であって、屈折率が1.68以上の硬化物。
[14]有機EL素子が配置された表示基板と、前記表示基板と対になる対向基板と、前記表示基板と前記対向基板との間に介在し、かつ前記有機EL素子と前記対向基板との間に形成される空間に充填されているシール部材と、を含む有機ELパネルであって、前記シール部材は、[1]~[10]のいずれかに記載のエポキシ重合性組成物の硬化物である、有機ELデバイス。
[15]有機EL素子と、前記有機EL素子と接するシール部材と、前記シール部材と接するパッシベーション膜と、を含む有機ELデバイスであって、前記シール部材は、[1]~[10]のいずれかに記載のエポキシ重合性組成物の硬化物である、有機ELデバイス。
[16]前記[14]または[15]に記載の有機ELデバイスを具備する有機ELディスプレイパネル。
[18]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]~[10]のいずれかに記載の組成物で封止する第2の工程と;前記組成物を硬化させて封止部材を形成する第3の工程と;前記封止部材にパッシベーション膜を形成する第4の工程とを含む、有機ELデバイスの製造方法。
本発明のエポキシ重合性組成物は、(A1)S含有エポキシ化合物と、(A2)低軟化点を有する低軟化点エポキシ化合物((A1)を除く)と、(B)硬化促進剤と、(C)チオール化合物とを含む。さらに、(A3)フルオレン型エポキシ化合物を含んでいてもよい。
X11はそれぞれ独立に-S-、-SO2-、-O-、-C(R21)2-(R21は、それぞれ独立に水素原子、または炭素数1~3のアルキル基である)を示す。複数のX11が含まれる場合、各X11は同一であってもよく、異なっていてもよい。
mcは、A2がベンゼン環である場合には1~5の整数を示す。一方、A2が1,3,5-トリアジン環である場合には1または2を示す。mcの数が大きいと、一般式(i)の化合物中のエポキシ基(チオエポキシ基も含む)の数が増え、エポキシ重合性組成物の硬化物の耐熱性が高まるが、硬化収縮率が大きくなり過ぎる場合がある。
j及びkは、それぞれ独立に1~5の整数を示す。j及びkが大きい場合にも、エポキシ重合性組成物の硬化物の耐熱性が高まるが、硬化収縮率が大きくなりすぎる場合がある。
エポキシ化合物の硬化を促進する(B)硬化促進剤の例には、イミダゾール化合物やアミン化合物が含まれる。イミダゾール化合物の例には、2-エチル-4-メチルイミダゾールなどが含まれ、アミン化合物の例には、トリスジメチルアミノメチルフェノールなどが含まれる。(B)硬化促進剤は、ルイス塩基化合物であってもよい。本発明のエポキシ重合性組成物を発光素子、特に有機EL素子の封止剤として用いる場合には、(B)硬化促進剤は熱硬化促進剤であることが好ましく、本発明の組成物は光硬化促進剤を実質的に含まない方が好ましい。熱硬化促進剤に比べて光硬化促進剤は、硬化を促進する際に分解して発光素子を劣化させるガスなどを発生する場合が多いためである。
(C)チオール化合物は、1分子内に2以上のチオール基を有することを特徴とする。(C)チオール化合物は、エポキシ化合物の硬化剤として作用しうる。つまり(C)チオール化合物のチオール基は、エポキシ化合物のエポキシ基(チオエポキシ基も含む)と反応することにより、これらのエポキシ化合物を互いに架橋反応させて、耐熱性や接着強度等に優れた硬化物とすることができる。チオール化合物によって、エポキシ重合性組成物の硬化物の透明性を高めることもできる。これは(C)チオール化合物がエポキシ化合物を架橋することで、エポキシ化合物中のベンゼン環、または1,3,5-トリアジン環が集積するのを防ぐことができるからだと推測される。硬化物の透明性を高めるという観点からは、(C)チオール化合物はベンゼン環や1,3,5-トリアジン環を有さない化合物の方が好ましい。
エポキシ重合性組成物には、(D)シランカップリング剤が含まれていてもよい。(D)シランカップリング剤を含むエポキシ重合性組成物は、有機EL用シール材組成物としたときに基板などとの密着性が高い。(D)シランカップリング剤の例には、エポキシ基、カルボキシル基、メタクリロイル基、イソシアネート基などの反応性基を有するシラン化合物が含まれる。シラン化合物の具体例には、トリメトキシシリル安息香酸、γ-メタクリロキシプロピルトリメトキシシラン、ビニルトリアセトキシシラン、ビニルトリメトキシシラン、γ-イソシアナトプロピルトリエトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランなどが含まれる。シランカップリング剤は、1種単独であっても、2種以上の組み合わせであってもよい。
エポキシ重合性組成物は、本発明の効果を損なわない範囲で、その他樹脂成分、充填剤、改質剤、安定剤などの任意成分をさらに含有することができる。他の樹脂成分の例には、ポリアミド、ポリアミドイミド、ポリウレタン、ポリブタジエン、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が含まれる。これらの1種単独を、または複数種の組み合わせを含有することができる。
硬化収縮率(%)={(硬化物の比重-未硬化の組成物の比重)/硬化物の比重}×100
1)エポキシ重合性硬化物を、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。
前記の通り、本発明のエポキシ重合性組成物は、有機EL素子のシール部材を作製するための組成物として有用である。つまり本発明の有機ELデバイスは、有機EL素子が配置された表示基板と、表示基板と対になる対向基板と、表示基板と対向基板との間のいずれかに配置された前記有機EL素子を封止するシール部材とを有する。
(A2)低軟化点エポキシ:VG3101(プリンテック社製)軟化点 38~46℃
(B)硬化促進剤:TMDPO(2,4,6-トリメチルベンゾイルジフェニルホスフィンオキサイド)
アクリル酸:アクリル酸 (東京化成社製)
フラスコに、50質量部のTBBTエポキシ((A1)S含有エポキシ)と、20質量部のEP3950S((A2)低軟化点エポキシ)と、30質量部のPG-100((A3)フルオレン型エポキシ)とを装入し、加温しながら混合した。これに、52質量部のGST((C)チオール化合物)を添加して室温で混合し、さらに0.4質量部の2E4MZ((B)硬化促進剤)を添加して室温で攪拌してエポキシ重合性組成物を得た。
表1に示すように、(A1)S含有エポキシの量、(A2)低軟化点エポキシの種類および量、(A3)フルオレン型エポキシの量、(C)チオール化合物の種類および量を変更し、実施例1と同様の手順でエポキシ重合性組成物を得た。
表2に示す組成で、実施例1と同様の手順でエポキシ重合性組成物を得た。(C)チオール化合物の代わりに、酸無水物を配合した。
表2に示す組成で、実施例1と同様の手順でエポキシ重合性組成物を得た。(C)チオール化合物を配合しなかった。
表2に示す組成で、実施例1と同様の手順でエポキシ重合性組成物を得た。(A1)S含有エポキシを配合しなかった。
表2に示す組成で、実施例1と同様の手順でエポキシ重合性組成物を得た。(A2)低軟化点エポキシを配合しなかった。
表2に示す組成で、実施例1と同様の手順でエポキシ重合性組成物を得た。(A2)低軟化点エポキシおよび(A3)フルオレン型エポキシを配合しなかった。
表2に示す組成で、実施例1と同様の手順でエポキシ重合性組成物を得た。(A2)低軟化点エポキシ、(A3)フルオレン型エポキシおよび(C)チオール化合物を配合せず、アクリル酸を配合した。
表2に示す組成で、実施例1と同様の手順でエポキシ重合性組成物を得た。(A2)低軟化点エポキシおよび(A3)フルオレン型エポキシを配合しなかった。
エポキシ重合性組成物を目視観察して、無色透明であるかどうかを確認した。
B型粘度計(東機産業社製のBL型VISCOMETER/ローターNo4)を用いて、60rpmの回転条件で、25℃におけるエポキシ重合性組成物の粘度を測定した。
得られた硬化物を目視観察して、無色透明かどうかを確認した。
硬化前の組成物の比重と、硬化後の硬化物の比重とを、下記式に当てはめることにより硬化収縮率を求めた。
硬化収縮率(%)={(硬化物の比重-未硬化の組成物の比重)/硬化物の比重}×100
得られた硬化物の屈折率を、屈折率測定計(アタゴ社製の多波長アッベ屈折計DR-M4)を用いて、ナトリウムD線(589nm)を照射して測定した。
得られた硬化物について、TMA(セイコーインスツルメンツ社製のTMA/SS6000)を用いて、昇温速度5℃/分の条件で線膨張係数を測定し、その変曲点からTgを求めた。
得られた硬化物のヘイズ値(%)を、ヘイズメーター(東京電飾製、機種名TC-H3DPK)を用いて測定した。その後、硬化物をプラズマ処理装置(ヤマト科学製、機種名PDC210、平行平板型)に設置し、酸素流量20mL/分、RF出力500Wの条件で20分間プラズマ処理を実施した。プラズマ処理後の硬化物層のヘイズ値(%)を、ヘイズメーター(東京電飾製、機種名TC-H3DPK)を用いて測定した。
エポキシ重合性組成物の含水量をカールフィッシャー法で測定したところ、実施例1~9および比較例1~8の組成物の含水率は、いずれも0.1重量%以下であった。
窒素で置換したフラスコで、表3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3に示す重量部の硬化促進剤とを攪拌混合して、面封止剤を得た。
比較例9および10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(5cm×5cm×3μm厚)。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分間加熱し硬化物層とした。
22 表示基板
24 有機EL素子
26 封止基板
28 封止部材
28-1 硬化物層
28-2 パッシベーション層
28-3 接着樹脂層
30 画素電極
32 有機EL層
34 対向電極
Claims (18)
- (A1)下記一般式(i)で表され、かつ屈折率が1.66~1.80である、S含有エポキシ化合物と、
A1及びA2は、それぞれ独立にベンゼン環、または1,3,5-トリアジン環を示し、
X11はそれぞれ独立に-S-、-SO2-、-O-、-C(R21)2-(R21は、それぞれ独立に水素原子、または炭素数1~3のアルキル基)を示し、
Y11およびY12は、それぞれ独立に-O-又は-S-を示し、
Z1及びZ2は、それぞれ独立に、-O-又は-S-を示し、
R11およびR12は、それぞれ独立に炭素数1~6のアルキル基またはハロゲン基を示し、
maは0~10のいずれかの整数を示し、
mcはA2がベンゼン環である場合には1~5の整数を示し、A2が1,3,5-トリアジン環である場合には1または2を示し、
mb及びnaはA1またはA2がベンゼン環である場合には、それぞれ独立に0~4の整数を示し、A1またはA2が1,3,5-トリアジン環である場合には、それぞれ独立に0または1を示し、
j及びkは、A1またはA2がベンゼン環である場合には、それぞれ独立に1~5の整数を示し、A1またはA2が1,3,5-トリアジン環である場合には、それぞれ独立に1または2を示し、
mbとjとの和は、A1がベンゼン環である場合には5以下であり、A1が1,3,5-トリアジン環である場合には2以下であり、
naとkとmcとの和は、A2がベンゼン環である場合には6以下であり、A2が1,3,5-トリアジン環である場合には3以下であり、
maが0のとき、Y11、Y12、Z1、及びZ2で表される基の少なくとも一つが-S-であり、
maが1~10のとき、X11、Y11、Y12、Z1、及びZ2で表される基の少なくとも一つがSを含む基である。]
(A2)70℃以下の軟化点を有するエポキシ化合物(ただし、前記(A1)S含有エポキシ化合物を除く)と、
(B)硬化促進剤と、
(C)1分子内に2つ以上のチオール基を有するチオール化合物と、を含み、
B型粘度計で測定された25℃、60rpmでの粘度が100~15000mPa・sである、エポキシ重合性組成物。 - (A3)下記一般式(2)または一般式(3)で表されるフルオレン型エポキシ化合物
R1は、それぞれ独立に水素原子またはメチル基を表し;
R2は、それぞれ独立に水素原子またはメチル基を表し;
R3は、それぞれ独立に炭素数が1~5のアルキル基を表し;
R4は、それぞれ独立に炭素数が1~5のアルキル基を表し;
mは、2以上の整数を表し;
nは、それぞれ独立に0~3の整数を表し;
pは、それぞれ独立に0~4の整数を表し;
qは、それぞれ独立に0~5の整数を表す]
Yは、単結合、酸素原子または硫黄原子を表し;
qはそれぞれ独立に0~4の整数を表し;
R1~R4、m、n、及びpは、一般式(2)と同様に定義される]
をさらに含む、請求項1または2に記載のエポキシ重合性組成物。 - (A2)エポキシ化合物が3官能エポキシ化合物である、請求項3に記載のエポキシ重合性組成物。
- (C)チオール化合物のチオール当量が、80~100g/eqであり、かつ、
(C)チオール化合物の硫黄含有率が、50~80%である、請求項3に記載のエポキシ重合性組成物。 - (C)チオール化合物の分子量が、140~500である、請求項3に記載のエポキシ重合性組成物。
- 前記エポキシ重合性組成物に含まれるエポキシ化合物の含有量100質量部に対して、(A1)S含有エポキシ化合物の含有量が50質量部以上である、請求項3に記載のエポキシ重合性組成物。
- 前記エポキシ重合性組成物に含まれる、エポキシ基とチオール基とのモル比が、1:0.9~1.1である、請求項3に記載のエポキシ重合性組成物。
- 含水率が0.1質量%以下である、請求項3に記載のエポキシ重合性組成物。
- 請求項3に記載のエポキシ重合性組成物を含む、光学材料用透明樹脂。
- 請求項3に記載のエポキシ重合性組成物を含む、有機EL素子面封止剤。
- 請求項3に記載のエポキシ重合性組成物の硬化物であって、屈折率が1.68以上の硬化物。
- 有機EL素子が配置された表示基板と、前記表示基板と対になる対向基板と、前記表示基板と前記対向基板との間に介在し、かつ前記有機EL素子と前記対向基板との間に形成される空間に充填されているシール部材と、を含む有機ELパネルであって、
前記シール部材は、請求項3に記載のエポキシ重合性組成物の硬化物である、有機ELデバイス。 - 有機EL素子と、前記有機EL素子と接するシール部材と、前記シール部材と接するパッシベーション膜と、を含む有機ELデバイスであって、
前記シール部材は、請求項3に記載のエポキシ重合性組成物の硬化物である、有機ELデバイス。 - 請求項14または15に記載の有機ELデバイスを具備する有機ELディスプレイパネル。
- 表示基板上に有機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3に記載のエポキシ重合性組成物で封止する第2の工程と、
前記表示基板に対向し、かつ前記組成物を介するように対向基板を積層する第3の工程と、
前記組成物を硬化させて封止部材を形成する第4の工程と、を含む、有機ELデバイスの製造方法。 - 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3に記載のエポキシ重合性組成物で封止する第2の工程と、
前記組成物を硬化させて封止部材を形成する第3の工程と、
前記封止部材にパッシベーション膜を形成する第4の工程と、を含む、有機ELデバイスの製造方法。
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KR1020147000129A KR101563827B1 (ko) | 2011-07-06 | 2012-07-05 | 에폭시 중합성 조성물, 및 유기 el 디바이스 |
JP2013522476A JP6006720B2 (ja) | 2011-07-06 | 2012-07-05 | エポキシ重合性組成物、および有機elデバイス |
US14/130,699 US20140131691A1 (en) | 2011-07-06 | 2012-07-05 | Polymerizable epoxy composition and organic el device |
CN201280033215.2A CN103649159B (zh) | 2011-07-06 | 2012-07-05 | 环氧聚合性组合物及有机el器件 |
HK14105308.0A HK1191965A1 (zh) | 2011-07-06 | 2014-06-06 | 環氧聚合性組合物及有機 器件 |
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JP (1) | JP6006720B2 (ja) |
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CN (1) | CN103649159B (ja) |
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Cited By (7)
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JP2015117358A (ja) * | 2013-12-16 | 2015-06-25 | サムソン エレクトロ−メカニックス カンパニーリミテッド. | プリント回路基板用絶縁樹脂組成物およびこれを用いた製品 |
JP2016018163A (ja) * | 2014-07-10 | 2016-02-01 | チェイル インダストリーズ インコーポレイテッド | 偏光板用接着剤およびこれを用いた表示装置 |
WO2018190347A1 (ja) * | 2017-04-13 | 2018-10-18 | Jnc株式会社 | 熱硬化性樹脂組成物、硬化膜、硬化膜付き基板、電子部品およびインクジェット用インク |
KR101908179B1 (ko) | 2016-04-07 | 2018-12-10 | 삼성에스디아이 주식회사 | 반도체 밀봉용 에폭시 수지 조성물 및 이를 이용하여 밀봉된 반도체 장치 |
JP2019156952A (ja) * | 2018-03-12 | 2019-09-19 | 三井化学株式会社 | 光学材料用組成物およびその用途 |
JP2020164628A (ja) * | 2019-03-29 | 2020-10-08 | 株式会社Adeka | 樹脂組成物 |
JP2023024361A (ja) * | 2021-08-06 | 2023-02-16 | イノックス・アドバンスト・マテリアルズ・カンパニー・リミテッド | 有機発光素子の封止材用熱硬化性液状組成物 |
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TWI548130B (zh) * | 2014-07-03 | 2016-09-01 | 逢甲大學 | 有機發光裝置及其製作方法 |
CN110028919B (zh) * | 2019-04-01 | 2021-08-06 | 中昊(大连)化工研究设计院有限公司 | 一种高折射率led环氧灌封胶及其制备方法 |
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JP2015117358A (ja) * | 2013-12-16 | 2015-06-25 | サムソン エレクトロ−メカニックス カンパニーリミテッド. | プリント回路基板用絶縁樹脂組成物およびこれを用いた製品 |
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JP7445714B2 (ja) | 2021-08-06 | 2024-03-07 | イノックス・アドバンスト・マテリアルズ・カンパニー・リミテッド | 有機発光素子の封止材用熱硬化性液状組成物 |
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CN103649159B (zh) | 2016-03-30 |
US20140131691A1 (en) | 2014-05-15 |
HK1191965A1 (zh) | 2014-08-08 |
JP6006720B2 (ja) | 2016-10-12 |
TW201305234A (zh) | 2013-02-01 |
KR101563827B1 (ko) | 2015-10-27 |
CN103649159A (zh) | 2014-03-19 |
JPWO2013005441A1 (ja) | 2015-02-23 |
TWI537299B (zh) | 2016-06-11 |
KR20140034275A (ko) | 2014-03-19 |
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