WO2022230748A1 - 硬化性組成物および有機el表示装置 - Google Patents
硬化性組成物および有機el表示装置 Download PDFInfo
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- WO2022230748A1 WO2022230748A1 PCT/JP2022/018382 JP2022018382W WO2022230748A1 WO 2022230748 A1 WO2022230748 A1 WO 2022230748A1 JP 2022018382 W JP2022018382 W JP 2022018382W WO 2022230748 A1 WO2022230748 A1 WO 2022230748A1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
- C08G65/18—Oxetanes
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
- H05B33/04—Sealing arrangements, e.g. against humidity
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—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
- H10K50/844—Encapsulations
-
- 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
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
- H10K59/873—Encapsulations
Definitions
- the present invention relates to a curable composition and an organic EL display device.
- Organic EL elements are being used in displays and lighting devices due to their low power consumption. Since organic EL elements are easily deteriorated by moisture and oxygen in the air, it is being considered to use them after being sealed with a sealing material.
- Patent Document 1 International Publication No. 2015/129670 describes a curable resin composition for encapsulating an organic electroluminescence display element containing a cycloalkene oxide type alicyclic epoxy compound, a phenoxy resin, and a curing agent. It is said that a cured product having excellent transparency, flex resistance and barrier properties can be obtained from such a composition.
- the composition used for encapsulating the organic EL element is a liquid curable composition containing specific components, and the dielectric constant and hysteresis loss are within specific ranges, thereby solving the above problems.
- a liquid curable composition used for sealing an organic EL element The following components (a) and (b): (a) a polymerizable compound, (b) a polymerization initiator, The cured product of the curable composition cured with a UV-LED having a wavelength of 395 nm at an illuminance of 1500 mW/cm 2 and an integrated light amount of 1500 mJ/cm 2 has a dielectric constant of 3.6 or less at a frequency of 100 kHz, A curable composition having a hysteresis loss of 0% or more and 45% or less when a sample obtained under Condition 1 below is measured under Condition 2 below.
- the component (a) is a (meth)acrylic compound having two (meth)acrylic groups in one molecule, an epoxy compound having two epoxy groups in one molecule, and two The curable composition according to [1], comprising one or more selected from the group consisting of oxetane compounds having an oxetanyl group.
- the component (a) is a (meth)acrylic compound having two (meth)acrylic groups in one molecule, an epoxy compound having two epoxy groups in one molecule, and two The curable composition according to [1] or [2], comprising two or more selected from the group consisting of oxetane compounds having an oxetanyl group.
- Composition. [10] a substrate; an organic EL element arranged on the substrate; a sealing layer covering the organic EL element; wherein the sealing layer is composed of a cured product of the curable composition according to any one of [1] to [9].
- FIG. 1 is a cross-sectional view showing a configuration example of an organic EL display device according to an embodiment
- FIG. It is a diagram schematically showing an example of a stress-strain curve in the embodiment. It is a top view for demonstrating the bending-resistant evaluation method in an Example.
- the curable composition is a liquid composition used for encapsulating an organic EL device, and contains the following components (a) and (b).
- (a) Polymerizable compound (b) Polymerization initiator
- the curable composition is cured with a UV-LED having a wavelength of 395 nm at an illumination intensity of 1500 mW/cm 2 and an integrated light intensity of 1500 mJ/cm 2 Dielectric constant at a frequency of 100 kHz is less than or equal to 3.6.
- the hysteresis loss when a sample obtained from the curable composition under the following condition 1 is measured under the following condition 2 is 0% or more and 45% or less.
- the state in which no sample is attached is set to 0 mN, and the load is pulled until it reaches 0.05 N in order to eliminate the initial strain, and that point is taken as the starting point.
- the present inventors have found that the dielectric constant and hysteresis loss of the cured product of the liquid curable composition containing components (a) and (b) are as follows during long-term use of the organic EL display device. We have found that this is effective as a design guideline for realizing a sealing material that can improve durability. Further, the inventors of the present invention made further intensive studies based on the above findings, and found that a curable composition having a dielectric constant of 3.6 or less and a hysteresis loss of 0% or more and 45% or less was used. As a result, the inventors have found that a sealing material for improving durability during long-term use can be realized. The reason why the durability of the organic EL display device can be improved during long-term use by using such a curable composition is not necessarily clear. This is thought to be due to the fact that strain tends to occur because it is difficult to return to its original state.
- the cured product of the curable composition has a dielectric constant of 3.6 or less, for example, 1.0 or more and 3.6 or less, preferably 1.0 to 3.6, from the viewpoint of improving the sealing properties of the sealing material. It is 0 or more and 3.5 or less, more preferably 1.0 or more and 3.3 or less.
- the dielectric constant of the cured product is obtained by curing the curable composition under the conditions of a UV-LED with a wavelength of 395 nm and an illuminance of 1500 mW/cm 2 and an integrated light intensity of 1500 mJ/cm 2 at a frequency of 100 kHz. is the measured dielectric constant.
- the hysteresis loss of the cured product of the curable composition is 0% or more and 45% or less, preferably 0% or more and 40% or less, more preferably 0%. 35% or more, more preferably 0% or more and 25% or less, and even more preferably 0% or more and 20% or less.
- the hysteresis loss of the cured product of the curable composition may be, for example, 5% or more.
- the hysteresis loss of the cured product of the curable composition is obtained by measuring the sample obtained using the curable composition under condition 1 above under condition 2 above.
- condition 1 first, the curable composition is enclosed in two glasses sandwiching a Teflon (registered trademark) sheet having a thickness of 100 ⁇ m. Then, it is cured with a UV-LED having a wavelength of 395 nm at an illuminance of 1000 mW/cm 2 and an integrated amount of light of 1500 mJ/cm 2 to obtain a cured product having a thickness of approximately 100 ⁇ m.
- the obtained cured product is cut into a size of 10 mm width ⁇ 55 mm length.
- a cured product having a thickness in the range of 90 to 110 ⁇ m at a total of 5 points every 10 mm in the length direction is used as a sample for hysteresis loss measurement.
- Hysteresis loss is measured based on Condition 2.
- a device capable of a tensile test such as a universal material testing machine can be used. One end of the sample is fixed to the chuck of the measuring device, and the other end is fixed so that the distance between the chucks is 30 mm.
- a tensile test is performed by pulling the other end in the direction of 180 degrees at 23° C. and 10 mm/sec (pulling speed) to obtain a curve (stress-strain curve) with stress as the vertical axis and strain as the horizontal axis.
- the state in which no sample is attached is set to 0 mN, and the load is pulled until it reaches 0.05 N in order to cancel the initial strain, and that point is taken as the starting point.
- FIG. 2 is a diagram schematically showing an example of a stress-strain curve.
- the curable composition in order to adjust the dielectric constant and hysteresis loss of the cured product of the curable composition within the above range, for example, the types and content ratios of components (a) and (b), the curable composition It is necessary to highly control the manufacturing method of Among them, in the present embodiment, for example, as the component (a), a (meth)acrylic compound having two or more (meth)acrylic groups in one molecule, an epoxy compound having two or more epoxy groups in one molecule, and using one or more selected from the group consisting of oxetane compounds having two or more oxetanyl groups in one molecule; Using, for example, a photocationic polymerization initiator as component (b); adjusting the mixing ratio of components (a) and (b); adjusting the viscosity of the curable composition; After heating and stirring materials other than the polymerization initiator under reduced pressure, for example at a temperature of 40° C.
- adjusting the oxygen concentration during film formation (for example, coating) and curing of the curable composition; and the like are factors for controlling the dielectric constant and hysteresis loss of the cured product of the curable composition within the above ranges.
- mixing and stirring are performed under a reduced pressure of, for example, 200 Pa at a temperature of, for example, 40° C. or higher. If the pressure is not reduced during stirring, oxygen in the gas dissolves into the liquid and the oxygen concentration in the liquid increases, which may result in failure to obtain desirable curing characteristics.
- coating for film formation from the viewpoint of improving the reliability of the cured product during long-term use, coating is performed in an atmosphere with an oxygen concentration of 20.0 to 21.1%, for example. Curing is performed at an oxygen concentration of 50 ppm to 1000 ppm.
- the curable composition is preferably a sealant used for coating, more preferably a sealant used for coating by an inkjet method.
- the viscosity of the curable composition measured at 25° C. and 20 rpm using an E-type viscometer is preferably 3 mPa ⁇ s or more, more preferably 5 mPa ⁇ s or more, and further preferably It is preferably 8 mPa ⁇ s or more, and more preferably 10 mPa ⁇ s or more.
- the viscosity of the curable composition is preferably 50 mPa ⁇ s or less, more preferably 30 mPa ⁇ s or less, still more preferably 27 mPa ⁇ s or less, and even more preferably 25 mPa ⁇ s or less. s or less.
- Component (a) is a polymerizable compound.
- component (a) include compounds having radically polymerizable functional groups such as (meth)acryloyl groups and vinyl groups (hereinafter also referred to as “radical polymerizable compounds”); and epoxy groups, oxetanyl groups, Examples thereof include compounds having a cationically polymerizable functional group such as a vinyl ether group (hereinafter also referred to as “cationically polymerizable compound”).
- the component (a) is preferably a (meth)acrylic compound having two or more (meth)acrylic groups in one molecule. and epoxy compounds having more than one epoxy group, and one or more selected from the group consisting of oxetane compounds having two or more oxetanyl groups in one molecule; more preferably two (meth) acrylics in one molecule a (meth) acrylic compound having a group, an epoxy compound having two epoxy groups in one molecule, and one or more selected from the group consisting of an oxetane compound having two oxetanyl groups in one molecule;
- the radically polymerizable compound is preferably a (meth)acrylic compound.
- the (meth)acrylic compound is preferably a (meth)acrylic compound having two or more (meth)acrylic groups in one molecule. Acrylic compounds are mentioned.
- di(meth)acryl compound examples include one or more selected from the group consisting of aliphatic di(meth)acryl compounds and alicyclic di(meth)acryl compounds.
- aliphatic di(meth)acrylic compounds include diol di(meth)acrylates and (poly)alkylene glycol di(meth)acrylates, and more specifically, 1,6-hexanediol diacrylate ( For example, A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (eg, A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,10-decanediol diacrylate (eg, A -DOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), neopentyl glycol diacrylate (for example, A-NPG, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol diacrylate (for
- the content of the di(meth)acrylic compound in the (meth)acrylic compound is preferably 50 parts by mass or more when the total amount of the (meth)acrylic compound is 100 parts by mass, from the viewpoint of keeping the crosslink density high. It is preferably 70 parts by mass or more, more preferably 80 parts by mass or more, and even more preferably 90 parts by mass or more. Also, the content of the di(meth)acrylic compound in the (meth)acrylic compound is, for example, 100 parts by mass or less, and may be, for example, 95 parts by mass or less.
- tri- or higher polyfunctional (meth)acrylic compounds include trimethylolpropane triacrylate (eg A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethoxylated trimethylolpropane triacrylate (eg A-TMPT-EO, Shin-Nakamura Chemical Co., Ltd.), ethoxylated glycerin triacrylate (eg, A-GLY-6E, manufactured by Shin-Nakamura Chemical Co., Ltd.), propoxylated glycerin triacrylate (eg, A-GLY-3P, manufactured by Shin-Nakamura Chemical Co., Ltd.), etc.
- A-TMPT manufactured by Shin-Nakamura Chemical Co., Ltd.
- ethoxylated trimethylolpropane triacrylate eg A-TMPT-EO, Shin-Nakamura Chemical Co., Ltd.
- ethoxylated glycerin triacrylate eg, A-GLY-6E, manufactured
- Pentaerythritol tetraacrylate eg, A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.
- monofunctional (meth)acrylic compounds include monofunctional aliphatic (meth)acrylic compounds such as isostearyl acrylate; and monofunctional aromatic (meth)acrylic compounds such as benzyl acrylate and ethoxylated o-phenylphenol acrylate. mentioned.
- the (meth)acrylic compound having two or more (meth)acrylic groups in one molecule is preferably a di(meth)acrylate of an aliphatic diol having 8 to 12 carbon atoms, More preferably one or two selected from the group consisting of 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, 1,9-nonanediol dimethacrylate and 1,10-decanediol dimethacrylate That's it.
- the (meth)acrylic compound having two or more (meth)acrylic groups in one molecule preferably includes an aliphatic di(meth)acrylic compound and an alicyclic di(meth)acrylic compound, One or more selected from the group consisting of 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, 1,9-nonanediol dimethacrylate and 1,10-decanediol dimethacrylate and di and cyclopentanyl dimethacrylate.
- the content of the monofunctional acrylate compound in the (meth)acrylic compound is preferably 30% by mass or less, more preferably 20% by mass or less, and more preferably 15% by mass relative to the entire (meth)acrylic compound. % by mass or less, still more preferably 12% by mass or less, even more preferably 8% by mass or less, still more preferably 5% by mass or less, even more preferably 2% by mass or less, ( It is even more preferred that the meth)acrylic compounds do not contain monofunctional acrylate compounds.
- component (a) is a cationically polymerizable compound
- component (a) is preferably at least one selected from the group consisting of epoxy compounds and oxetane compounds, more preferably epoxy compounds and oxetane compounds.
- the epoxy compound is preferably an epoxy compound having two or more epoxy groups in one molecule, and specific examples thereof include bifunctional epoxy compounds and trifunctional or higher epoxy compounds.
- bifunctional epoxy compounds include bifunctional alicyclic epoxy compounds and bifunctional aliphatic epoxy compounds.
- the bifunctional alicyclic epoxy compound an alicyclic epoxy compound having a cycloalkene oxide structure is preferred.
- Examples of alicyclic epoxy compounds having a cycloalkene oxide structure include compounds represented by the following general formula (1).
- X is a single bond or a linking group.
- the linking group is, for example, a divalent hydrocarbon group, a carbonyl group, an ether group (ether bond), a thioether group (thioether bond), an ester group (ester bond), a carbonate group (carbonate bond), an amide group (amide bond), Alternatively, it can be a group in which a plurality of these are linked.
- the divalent hydrocarbon group includes, for example, an alkylene group having 1 to 18 carbon atoms and a divalent alicyclic hydrocarbon group.
- alkylene group having 1 to 18 carbon atoms include methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group and trimethylene group.
- divalent alicyclic hydrocarbon groups include 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene and 1,3-cyclohexylene.
- Divalent cycloalkylene groups (including cycloalkylidene groups) such as silene group, 1,4-cyclohexylene group and cyclohexylidene group can be mentioned.
- X is preferably a linking group having a single bond or an oxygen atom.
- a linking group having an oxygen atom includes -CO- (carbonyl group), -O-CO-O- (carbonate group), -COO- (ester group), -O- (ether group), -CONH- (amide group ), a group in which a plurality of these groups are linked, or a group in which one or more of these groups and one or more of divalent hydrocarbon groups are linked. More preferably, X is a single bond.
- epoxy compounds represented by general formula (1) are shown below.
- l represents an integer of 1-10 and m represents an integer of 1-30.
- R represents an alkylene group having 1 to 8 carbon atoms (preferably an alkylene group having 1 to 3 carbon atoms such as methylene group, ethylene group, propylene group and isopropylene group).
- alicyclic epoxy compounds having a cycloalkene oxide structure include, for example, Celoxide 2021P (3′,4′-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate), Celoxide 2081 ( ⁇ -caprolactone-modified 3′, 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate), Celoxide 8000, and Celoxide 8010 (manufactured by Daicel Corporation).
- Bifunctional aliphatic epoxy compounds include neopentyl glycol diglycidyl ether (eg NPG (D), manufactured by Yokkaichi Gosei Co., Ltd.), 1,6-hexanediol diglycidyl ether (eg ED-503, manufactured by ADEKA), and propylene glycol.
- Diglycidyl ether eg, SR-PG, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.
- hydrogenated bisphenol A diglycidyl ether eg, EX252, manufactured by Nagase ChemteX Corporation
- tri- or more functional epoxy compounds include trimethylolpropane polyglycidyl ether (eg EX-321L, manufactured by Nagase ChemteX), diglycerol polyglycidyl ether (eg EX-421, manufactured by Nagase ChemteX). Functional epoxy compounds are mentioned.
- the epoxy compound having two or more epoxy groups in one molecule is preferably a compound in which X is a single bond in the above general formula (1), 3',4'-epoxycyclohexylmethyl 3, One or more selected from the group consisting of 4-epoxycyclohexane carboxylate and neopentyl glycol diglycidyl ether.
- the content of the epoxy compound in the cationically polymerizable compound is preferably 5 parts by mass or more, more preferably 15 parts by mass or more, when the total cationically polymerizable compound is 100 parts by mass. More preferably, it is 25 parts by mass or more. Further, from the viewpoint of increasing the elongation reaction rate, the content of the epoxy compound in the cationically polymerizable compound is, for example, 100 parts by mass or less, preferably 50 parts by mass or less when the total cationically polymerizable compound is 100 parts by mass. , more preferably 40 parts by mass or less, and still more preferably 30 parts by mass or less.
- the oxetane compound is preferably an oxetane compound having two or more oxetanyl groups in one molecule, more preferably a bifunctional oxetane compound, more preferably represented by the following general formula (6) or (7) It is a bifunctional oxetane compound.
- R 5 is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, an aralkyl group, a furyl group or a thienyl group, preferably is an alkyl group having 1 to 6 carbon atoms.
- R6 is a divalent organic residue.
- u is a number of 1 to 5, preferably a number of 1 to 3 on average.
- the alkyl group having 1 to 6 carbon atoms specifically includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a cyclohexyl group.
- aryl groups include phenyl, naphthyl, tolyl, and xylyl groups.
- Specific examples of the aralkyl group include a benzyl group and a phenethyl group.
- R 6 examples include an alkylene group, a polyoxyalkylene group, a phenylene group, a xylylene group, and structures represented by the following general formulas.
- R 3 is an oxygen atom, a sulfur atom, —CH 2 —, —NH—, —SO—, —SO 2 —, —C(CF 3 ) 2 — or —C(CH 3 ) 2 —.
- R 4 is an alkylene or arylene group having 1 to 6 carbon atoms. Specific examples of the alkylene group having 1 to 6 carbon atoms include methylene group, ethylene group, propylene group, butylene group and cyclohexylene group.
- the polyoxyalkylene group preferably has 4 to 30 carbon atoms, more preferably 4 to 8 carbon atoms.
- Specific examples of polyoxyalkylene groups include polyoxyethylene groups and polyoxypropylene groups.
- Specific examples of the compound represented by the general formula (6) include 3-ethyl-3 ⁇ [(3-ethyloxetan-3-yl)methoxy]methyl ⁇ oxetane (for example, OXT-221, manufactured by Toagosei Co., Ltd.).
- the oxetane compound having two or more oxetanyl groups in one molecule is preferably 3-ethyl-3 ⁇ [(3-ethyloxetan-3-yl)methoxy]methyl ⁇ oxetane.
- the oxetane compound may include a monofunctional oxetane compound.
- monofunctional oxetane compounds include monofunctional aliphatic oxetane compounds such as 3-ethyl-3-[(2-ethylhexyloxy)methyl]oxetane.
- the content of the oxetane compound in the cationically polymerizable compound is preferably 30 parts by mass or more when the total cationically polymerizable compound is 100 parts by mass, from the viewpoint of reducing the dielectric constant of the cured product of the curable composition. , more preferably 50 parts by mass or more, and still more preferably 70 parts by mass or more. From the same viewpoint, the content of the oxetane compound in the cationically polymerizable compound is, for example, 100 parts by mass or less, preferably 95 parts by mass or less, more preferably 100 parts by mass of the total cationically polymerizable compound. is 90 parts by mass or less, more preferably 85 parts by mass or less.
- the component (a) is preferably a compound in which X is a single bond in the general formula (1), neopentyl glycol diglycidyl ether, 3' , 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3-ethyl-3 ⁇ [(3-ethyloxetan-3-yl)methoxy]methyl ⁇ oxetane, 1,9-nonanediol diacrylate, 1, One or more selected from the group consisting of 9-nonanediol dimethacrylate and trimethylolpropane triacrylate, more preferably 3-ethyl-3 ⁇ [(3-ethyloxetan-3-yl) methoxy ] methyl ⁇ oxetane, 1,9-nonanediol diacrylate and 1,9-nonanediol dim
- component (a) may contain one or more selected from the group consisting of monofunctional (meth)acrylate compounds, monofunctional epoxy compounds and monofunctional oxetane compounds.
- the curable composition preferably contains one or more selected from the group consisting of monofunctional (meth)acrylate compounds and monofunctional oxetane compounds. Contains compounds.
- the content of component (a) in the curable composition is preferably 60 to 99.9% by mass, more preferably 80 to 99.9% by mass, more preferably 85 to 99.9% by mass, even more preferably 90 to 99.9% by mass, and even more preferably 90 to 98.0% by mass.
- Component (b) is a polymerization initiator.
- polymerization initiators include one or more selected from the group consisting of thermal radical initiators and photopolymerization initiators.
- the component (b) is a polymerization initiator that generates radicals or ions when irradiated with light such as ultraviolet rays (a photoradical polymerization initiator such as a UV radical initiator or a photocationic polymerization initiator such as a UV cationic initiator), more preferably a photocationic polymerization initiator.
- the photocationic polymerization initiator include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts and the like from the viewpoint of stably forming a cured product.
- the anionic moieties of these salts are, for example, BF 4 ⁇ , (R f ) n PF 6-n (R f is an organic group and n is an integer from 1 to 5), PF 6 ⁇ , SbF 6 ⁇ , or BY 4 ⁇ (Y is a phenyl group substituted with at least two or more fluorine or trifluoromethyl groups).
- aromatic sulfonium salts include bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluoroantimonate, bis[4-(diphenyl sulfonio)phenyl]sulfide bistetrafluoroborate, bis[4-(diphenylsulfonio)phenyl]sulfidetetrakis(pentafluorophenyl)borate, diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate, diphenyl-4-(phenylthio ) phenylsulfonium hexafluoroantimonate, diphenyl-4-(phenylthio)phenylsulfonium tetrafluoroborate.
- aromatic iodonium salts include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis(pentafluorophenyl)borate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis( dodecylphenyl)iodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium tetrafluoroborate, bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate.
- aromatic diazonium salts include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis(pentafluorophenyl)borate.
- aromatic ammonium salts include 1-benzyl-2-cyanopyridinium hexafluorophosphate and 1-benzyl-2-cyanopyridinium hexafluoroantimonate.
- photocationic polymerization initiators include Irgacure250, Irgacure270, Irgacure290 (manufactured by BASF), CPI-100P, CPI-101A, CPI-200K, CPI-210S, CPI-310B, CPI- 400PG (manufactured by San-Apro), SP-150, SP-170, SP-171, SP-056, SP-066, SP-130, SP-140, SP-601, SP-606, SP-701 (above , manufactured by ADEKA).
- the photocationic polymerization initiator is preferably Irgacure270, Irgacure290, CPI-100P, CPI-101A, CPI-200K, CPI-210S, CPI-310B, CPI-400PG, SP-150. , SP-170, SP-171, SP-056, SP-066, SP-601, SP-606, SP-701 and the like.
- photoradical polymerization initiators include acylphosphine oxide photopolymerization initiators such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
- the content of component (b) in the curable composition is preferably 0.1% by mass or more, more preferably 0.3, based on the total composition of the curable composition. It is at least 0.5% by mass, more preferably at least 0.5% by mass. Further, from the viewpoint of suppressing coloring of the curable composition, the content of the component (b) in the curable composition is preferably 10% by mass or less, more preferably 10% by mass or less, based on the total composition of the curable composition. is 6% by mass or less, more preferably 4% by mass or less.
- the curable composition may contain components other than components (a) and (b), for example, the curable composition may further contain component (c): a leveling agent.
- component (c) By including the leveling agent of component (c) in the curable composition, the flatness of the film formed from the curable composition can be improved.
- component (c) include silicone-based leveling agents such as polyester-modified polydimethylsiloxane (eg BYK-310, manufactured by BYK-Chemie Japan) and polyether-modified siloxane (eg BYK-345, manufactured by BYK-Chemie Japan); Acrylic leveling agents such as acrylic copolymers (for example, BYK-350, manufactured by BYK-Chemie Japan; KL700, manufactured by Kyoeisha Chemical Co., Ltd.); Fluorinated leveling agents such as fluorine-modified polymers (eg, BYK-340, manufactured by BYK-Chemie Japan) and perfluoroalkyl-containing oligomers (eg, Surflon S-611 (manufactured by AGC Seimi Chemical Co., Ltd.) can be mentioned.
- component (c) is preferably selected from the group consisting of acrylic copolymers, polyester-modified polydimethylsiloxanes and fluorine-modified polymers. One or two or more. From the same point of view, it is also preferable that the component (c) is an acrylic leveling agent.
- the content of component (c) in the curable composition is preferably 0.01% by mass based on the total composition of the curable composition from the viewpoint of improving the flatness of the film formed by the curable composition. or more, more preferably 0.03% by mass or more, and still more preferably 0.05% by mass or more. Further, from the viewpoint of stabilizing the surface hardness of the cured product, the content of component (c) in the curable composition is preferably 5% by mass or less, more preferably It is 3% by mass or less, more preferably 2% by mass or less.
- Examples of other components in the curable composition include tackifiers, sensitizers, and coupling agents such as silane coupling agents.
- a tackifier in the curable composition, it is possible to adjust the viscosity of the curable composition without significantly changing the dielectric constant of the cured product of the curable composition, such as preferably increasing the viscosity be able to.
- the tackifier include petroleum resins such as aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, and aromatic hydrocarbon resins; terpene resins; phenols such as phenolic resins; and rosin resins. 1 type or 2 types or more are mentioned.
- C5 monomers or oligomers thereof obtained from, for example, pentene, pentadiene, isoprene, etc. as petroleum resins; C9 monomers or oligomers thereof obtained from indene, methylindene, vinyltoluene, styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, etc.; Copolymers of C5 and C9 monomers (C5-C9 copolymer resins); Alicyclic monomers or polymers thereof obtained from cyclopentadiene, dicyclopentadiene, etc.; aromatic monomers such as isopropenyl toluene or polymers thereof; hydrides of the above various monomers or polymers thereof; Modified petroleum resins obtained by modifying the above various monomers or polymers thereof with maleic anhydride, maleic acid, fumaric acid, (meth)acrylic acid, phenol, or the like can be mentioned.
- the petroleum resin used as the tackifier is preferably a styrene-based oligomer.
- the component (a) is a petroleum resin produced using dicyclopentadiene as a main raw material, more preferably a petroleum resin produced using dicyclopentadiene as a main raw material, and having an ester group in the molecule. It is a petroleum resin (for example, QTN1500, manufactured by Nippon Zeon Co., Ltd.).
- Terpene-based resins include, for example, ⁇ -pinene resin, ⁇ -pinene resin, ⁇ -pinene monomer, ⁇ -pinene monomer, and other aromatic-modified terpene resins obtained by copolymerizing terpenes with aromatic monomers such as styrene. resin.
- phenols include phenol compounds such as phenol, m-cresol, 3,5-xylenol, p-alkylphenol and resorcinol.
- phenolic resins include resoles obtained by addition reaction of these phenolic compounds and formaldehyde with an alkali catalyst, and novolacs obtained by condensation reaction with an acid catalyst.
- Phenolic resins also include rosin phenol resins obtained by adding phenol to rosin with an acid catalyst and thermally polymerizing the resulting mixture.
- rosin resins examples include gum rosin, wood rosin, tall oil rosin, stabilized rosin and polymerized rosin obtained by disproportionation or hydrogenation using these rosins, maleic anhydride, maleic acid, fumaric acid, Modified rosins modified with (meth)acrylic acid, phenol or the like, esters thereof, and the like can be mentioned.
- a polyhydric alcohol is preferred as the alcohol used to obtain the esterified product.
- polyhydric alcohols examples include dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and neopentyl glycol; trihydric alcohols such as glycerin, trimethylolethane and trimethylolpropane; tetrahydric alcohols such as pentaerythritol and diglycerin; Examples include hexahydric alcohols such as pentaerythritol.
- the content of the tackifier in the curable composition is preferably 1% by mass or more, more preferably It is 3% by mass or more, more preferably 5% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less.
- Sensitizers include, for example, photocationic sensitizers.
- Specific examples of sensitizers include thioxanthone compounds such as 2,4-diethylthioxanthone, 2,2-dimethoxy-1,2-diphenylethan-1-one, benzophenone, 2,4-dichlorobenzophenone, o- methyl benzoylbenzoate, 4,4'-bis(dimethylamino)benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 9,10-dibutoxyanthracene.
- the content of the sensitizer in the curable composition is preferably 0.01% by mass or more, more preferably 0.01% by mass or more, based on the total composition of the curable composition. is 0.03% by mass or more, more preferably 0.05% by mass or more.
- the content of the sensitizer in the curable composition is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably is 5% by mass or less, and more preferably 1% by mass or less.
- the method for producing a curable composition includes, for example, a step of obtaining a liquid curable composition by mixing components (a) and (b) and other components.
- a cured product can be obtained by curing the obtained curable composition.
- the method for producing the curable composition, etc. by highly controlling the type and content ratio of components (a) and (b), the method for producing the curable composition, etc., the dielectric constant and hysteresis loss of the cured product of the curable composition can be stably adjusted within the above range.
- the curable composition can be obtained by mixing the above components and mixing using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roller.
- a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roller.
- the curable composition obtained in the present embodiment is suitably used, for example, for sealing display devices, preferably organic EL display devices.
- a sealing material for a display device preferably an organic EL display device
- a display device having excellent durability during long-term use can be obtained.
- An example of the configuration of the display device will be described below using the organic EL display device as an example.
- FIG. 1 is a cross-sectional view showing a configuration example of an organic EL display device according to this embodiment.
- the display device 100 shown in FIG. 1 is an organic EL display device, and includes a substrate (base layer 50), an organic EL element (light emitting element 10) arranged on the base layer 50, and the light emitting element 10.
- an overlying sealing layer 22 (which may be an overcoat layer 22 or a barrier layer 22);
- the sealing layer 22 is composed of a cured product of the curable composition of the present embodiment.
- FIG. 1 is a cross-sectional view showing a configuration example of an organic EL display device according to this embodiment.
- the display device 100 shown in FIG. 1 is an organic EL display device, and includes a substrate (base layer 50), an organic EL element (light emitting element 10) arranged on the base layer 50, and the light emitting element 10.
- an overlying sealing layer 22 (which may be an overcoat layer 22 or a barrier layer 22);
- the sealing layer 22 is composed of
- the display device 100 includes a barrier layer 21 (which may be the touch panel layer 21 or the surface protective layer 21) and a sealing layer 22 (which may be the touch panel layer 21 or the surface protective layer 21) as layers located on the observation side of the light emitting element 10. It has an overcoat layer 22 or a barrier layer 22 ), a planarizing layer 23 (which may be a sealing layer 23 ), and a barrier layer 24 .
- the planarization layer 23 is provided on the base layer 50 so as to cover the light emitting element 10
- the barrier layer 24 is provided on the surface of the planarization layer 23 .
- the sealing layer 22 is provided on the base layer 50 so as to cover the planarizing layer 23 and the barrier layer 24 .
- a barrier layer 21 is provided on the sealing layer 22 .
- each layer is not limited, and an appropriate configuration can be adopted based on generally known information. Moreover, such a display device 100 can be manufactured based on generally known information.
- Polymerizable compound 2 bifunctional aliphatic epoxy compound, NPG (D), manufactured by Yokkaichi Gosei Co., Ltd., neopentyl glycol diglycidyl ether
- Polymerizable compound 3 bifunctional aliphatic oxetane compound, OXT221, Toagosei Co., Ltd., 3-ethyl -3 ⁇ [(3-ethyloxetan-3-yl)methoxy]methyl ⁇ oxetane polymerizable compound 4: Bifunctional alicyclic methacrylate compound, DCP, manufactured by Shin-Nakamura Chemical Co., Ltd., dicyclopentanyl dimethacrylate polymerizable compound 5: Bifunctional aliphatic methacrylate compound, NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd., 1,9-nonanediol dimethacrylate polymerizable compound 6: Bifunctional aliphatic acrylate compound, A-NO
- component 1 tackifier
- IPT isopropenyl toluene
- component 2 photocationic sensitizer
- Examples 1 to 8, Comparative Examples 1 to 3 A liquid curable composition was obtained by blending each component on a scale of 11 kg in total so as to obtain the composition shown in Table 1. At that time, all the components other than the polymerization initiator are mixed, the system is decompressed with a vacuum pump, and the mixture and stirring are performed at 80 ° C. for 4 hours in an atmosphere of a decompression degree of 190 Pa to 210 Pa. After lowering to room temperature, oxygen In order to prevent contamination, the solution was transferred to a tank containing a polymerization initiator by nitrogen extrusion, and mixed and stirred at 40° C. for 1 hour under an atmosphere of 190 Pa to 210 Pa in pressure reduction.
- Coating for film formation was performed in an atmosphere with an oxygen concentration of 20.0 to 21.1%, and UV curing was performed in an oxygen concentration of 50 ppm to 1000 ppm.
- the physical properties of the curable composition obtained in each example or its cured product were measured by the following methods. The measurement results are also shown in Table 1.
- Viscosity of curable composition The viscosity of the curable composition obtained in each example was measured at 25° C. and 20 rpm using an E-type viscometer (LV-DV-II+, manufactured by BROOKFIELD).
- the viscosity evaluation criteria shown in Table 1 are as follows. A: 3 mPa s or more and 50 mPa s or less B: less than 3 mPa s or more than 50 mPa s
- Hysteresis loss of cured product of curable composition A cured product of the curable composition was produced according to the method described above, and the hysteresis loss was obtained from the results of a tensile test of the cured product. That is, first, the curable composition was enclosed in two sheets of glass sandwiching a Teflon (registered trademark) sheet (MSF-100, manufactured by Chukoh Kasei Kogyo Co., Ltd.) having a thickness of 100 ⁇ m.
- Teflon (registered trademark) sheet MSF-100, manufactured by Chukoh Kasei Kogyo Co., Ltd.
- a UV-LED having a wavelength of 395 nm at an illuminance of 1000 mW/cm 2 and an integrated amount of light of 1500 mJ/cm 2 to obtain a cured product having a thickness of about 100 ⁇ m.
- the obtained cured product was cut into a size of 10 mm width ⁇ 55 mm length.
- a cured product having a thickness in the range of 90 to 110 ⁇ m at a total of 5 points every 10 mm in the length direction was used as a sample for hysteresis loss measurement.
- One end of the sample is fixed to a chuck, and a universal material testing machine AG-X-Plus manufactured by Shimadzu Corporation is used to perform a tensile test in which the other end is pulled in the direction of 180 degrees at 23 ° C. and 10 mm / sec (tension speed).
- a curve stress-strain curve
- the state in which no sample was attached was set to 0 mN, and the load was pulled until it reached 0.05 N in order to eliminate the initial strain, and that point was taken as the starting point. Therefore, the strain was 0 mm and the load was 0.05 N at the starting point.
- a coating film for obtaining a cured product for dielectric constant measurement was produced by the following method. That is, the resulting curable composition was introduced into an inkjet cartridge DMC-11610 (manufactured by Fuji Film Dimatix). The inkjet cartridge was set in an inkjet device DMP-2831 (manufactured by Fujifilm Dimatix), and the ejection state was adjusted. It was applied in a size of 5 cm ⁇ 5 cm so as to be 10 ⁇ m. The oxygen concentration at this time was 20.6%.
- the resulting coating film was allowed to stand at room temperature (25° C.) for 1 minute, and then cured with a UV-LED with a wavelength of 395 nm at an illuminance of 1500 mW/cm 2 , an integrated light intensity of 1500 mJ/cm 2 and an oxygen concentration of 1000 ppm or less.
- a UV-LED with a wavelength of 395 nm at an illuminance of 1500 mW/cm 2 , an integrated light intensity of 1500 mJ/cm 2 and an oxygen concentration of 1000 ppm or less.
- aluminum was vapor-deposited on the ink-jet coated surface to a thickness of 100 nm, and the dielectric constant was measured at 100 kHz with an LCR meter HP4284A (manufactured by Agilent Technologies) by an automatic balanced bridge method.
- the evaluation criteria for the dielectric constant shown in Table 1 are as follows. A: 3.6 or less B: greater than 3.6
- the curable composition obtained in each example was evaluated for flex resistance and EL element damage as an index of long-term durability when used as a sealing material for a display device.
- the evaluation method is as follows.
- the evaluation results are also shown in Table 1.
- FIG. 3 is a top view for explaining a bending resistance evaluation method.
- a bending tester DML HP, manufactured by Yuasa System Co., Ltd.
- the bending radius was set to 1 mm, and as shown in FIG.
- EL element damage As an index of EL element damage, the reliability of the organic EL display element was evaluated by the following method.
- the substrate was treated with a UV-ozone treatment device (PL21-200 (S) / UVE-200J manufactured by Sen Special Light Source Co., Ltd.), and then an alkaline aqueous solution and pure water. , acetone, and isopropyl alcohol for 15 minutes each, and finally, ultrasonic cleaning was performed for 10 minutes with acetone.
- PL21-200 (S) / UVE-200J manufactured by Sen Special Light Source Co., Ltd.
- this substrate was fixed to a substrate holder of a vacuum deposition apparatus, and Dipyrazino[2,3-f:2′,3′-h]quinoxaline-2,3,6,7,10,11, was placed in an unglazed crucible.
- HAT-CN hexacarbonitrile
- Tris-PCz 9-phenyl-3,6-bis(9-phenyl-9Hcarbazol-3-yl)-9H-carbazole
- the crucible containing HAT-CN was heated to deposit HAT-CN on the substrate at a deposition rate of 0.4 ⁇ /s to form a film having a thickness of 100 nm.
- the crucible containing Tris-PCz was heated and deposited on the substrate at a deposition rate of 1.0 ⁇ /s to form a film with a thickness of 400 nm.
- 200 mg of Tris(8-hydroxyquinolinato)aluminum (Alq3) was placed in another unglazed crucible, and the pressure in the vacuum chamber was reduced to 1 ⁇ 10 4 Pa again.
- the crucible containing Alq3 tris(8-quinolinolato)aluminum
- the vacuum chamber was evacuated to 1 ⁇ 10 ⁇ 4 Pa, and a lithium fluoride film of 5 nm was deposited at a deposition rate of 0.03 ⁇ /s.
- magnesium and 200 mg of silver were placed in a tungsten resistance heating boat, the vacuum chamber was evacuated to 1 ⁇ 10 ⁇ 4 Pa, and magnesium was deposited at a deposition rate of 0.9 ⁇ /s and silver at a deposition rate of 0.1 ⁇ /s. A film of 150 nm was formed so that the magnesium/silver ratio was 1/9. The inside of the evaporator was returned to normal pressure with nitrogen, and the substrate on which the laminate having the 8 mm ⁇ 8 mm organic light-emitting material layer was placed was taken out.
- the dielectric constant of the cured product was 3.6 or less and the hysteresis loss was within the range of 0% to 45%.
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Abstract
Description
すなわち、特定の成分を含む液状の硬化性組成物において、誘電率およびヒステリシスロスという尺度が、有機EL表示装置の長期使用時の耐久性を向上するための設計指針として有効であることを見出し、本発明に到達した。
[1] 有機EL素子の封止に用いる、液状の硬化性組成物であって、
以下の成分(a)および(b):
(a)重合性化合物、
(b)重合開始剤
を含み、
波長395nmのUV-LEDで照度1500mW/cm2、積算光量1500mJ/cm2で硬化させた当該硬化性組成物の硬化物の周波数100kHzにおける誘電率が3.6以下であり、
以下の条件1にて得られる試料を、以下の条件2にて測定したときのヒステリシスロスが0%以上45%以下である、硬化性組成物。
(条件1)当該硬化性組成物を、厚さ100μmのテフロン(登録商標)シートを挟み込んだ2枚のガラス中へ封入し、波長395nmのUV-LEDで照度1000mW/cm2、積算光量1500mJ/cm2にて硬化して得られる硬化物を、幅10mm×長さ55mmの大きさにカットし、長さ方向に10mm毎合計5点での厚みがすべて90~110μmの範囲である硬化物を前記試料とする。
(条件2)前記試料の一端を固定し、チャック間距離が30mmになるよう他端を固定する。このとき前記試料を何も取り付けていない状態を0mNと設定し、また、初期ひずみ解消のため、荷重が0.05Nに達するまで引っ張り、その点を開始点とする。23℃、10mm/秒(引っ張り速度)にて前記他端を180度方向へ引っ張る引っ張り試験をおこなったときの応力を縦軸とし、ひずみを横軸とした曲線(応力-ひずみ曲線)において、前記引っ張り試験の前記開始点から2%伸張時までのグラフ1、前記縦軸、''ひずみ=2%''の直線および前記横軸に囲まれる領域の面積をAとし、前記2%伸張時から前記応力がゼロとなるまでのグラフ2、''ひずみ=2%''の前記直線および前記横軸に囲まれる領域の面積をBとし、{(A-B)/A}×100で計算される解を前記ヒステリシスロスとする。
[2] 前記成分(a)が、一分子中に2つの(メタ)アクリル基を有する(メタ)アクリル化合物、一分子中に2つのエポキシ基を有するエポキシ化合物、および、一分子中に2つのオキセタニル基を有するオキセタン化合物からなる群から選択される1種以上を含む、[1]に記載の硬化性組成物。
[3] 前記成分(a)が、一分子中に2つの(メタ)アクリル基を有する(メタ)アクリル化合物、一分子中に2つのエポキシ基を有するエポキシ化合物、および、一分子中に2つのオキセタニル基を有するオキセタン化合物からなる群から選択される2種以上を含む、[1]または[2]に記載の硬化性組成物。
[4] 前記成分(b)が、光カチオン重合開始剤である、[1]乃至[3]いずれか1つに記載の硬化性組成物。
[5] 前記成分(b)が、光ラジカル重合開始剤である、[1]乃至[3]のいずれか1つに記載の硬化性組成物。
[6] 成分(c):レベリング剤をさらに含む、[1]乃至[5]いずれか1つに記載の硬化性組成物。
[7] 前記成分(c)が、アクリル系レベリング剤である、[6]に記載の硬化性組成物。
[8] E型粘度計を用いて25℃、20rpmにて測定される当該硬化性組成物の粘度が、3mPa・s以上50mPa・s以下である、[1]乃至[7]いずれか1つに記載の硬化性組成物。
[9] 前記成分(a)が、一分子中に2つの(メタ)アクリル基を有する(メタ)アクリル化合物を2種以上含む、[1]乃至[8]いずれか1つに記載の硬化性組成物。
[10] 基板と、
前記基板上に配置された有機EL素子と、
前記有機EL素子を被覆する封止層と、
を含み、前記封止層が、[1]乃至[9]いずれか1つに記載の硬化性組成物の硬化物により構成されている、有機EL表示装置。
本実施形態において、硬化性組成物は、有機EL素子の封止に用いる、液状の組成物であって、以下の成分(a)および(b)を含む。
(a)重合性化合物
(b)重合開始剤
また、硬化性組成物を波長395nmのUV-LEDで照度1500mW/cm2、積算光量1500mJ/cm2で硬化させた硬化物の周波数100kHzにおける誘電率は、3.6以下である。
また、硬化性組成物を用いて以下の条件1にて得られる試料を、以下の条件2にて測定したときのヒステリシスロスは、0%以上45%以下である。
(条件1)硬化性組成物を、厚さ100μmのテフロン(登録商標)シートを挟み込んだ2枚のガラス中へ封入し、波長395nmのUV-LEDで照度1000mW/cm2、積算光量1500mJ/cm2にて硬化して得られる硬化物を、幅10mm×長さ55mmの大きさにカットし、長さ方向に10mm毎合計5点での厚みがすべて90~110μmの範囲である硬化物を試料とする。
(条件2)試料の一端を固定し、チャック間距離が30mmになるよう他端を固定する。このとき試料を何も取り付けていない状態を0mNと設定し、また、初期ひずみ解消のため、荷重が0.05Nに達するまで引っ張り、その点を開始点とする。23℃、10mm/秒(引っ張り速度)にて他端を180度方向へ引っ張る引っ張り試験をおこなったときの応力を縦軸とし、ひずみを横軸とした曲線(応力-ひずみ曲線)において、引っ張り試験の開始点から2%伸張時までのグラフ1、縦軸、''ひずみ=2%''の直線および横軸に囲まれる領域の面積をAとし、2%伸張時から応力がゼロとなるまでのグラフ2、''ひずみ=2%''の直線および横軸に囲まれる領域の面積をBとし、{(A-B)/A}×100で計算される解をヒステリシスロスとする。
このような硬化性組成物を用いることにより、有機EL表示装置の長期使用時の耐久性を向上することができる理由は必ずしも明らかではないが、有機EL素子の電界の影響を受けにくい点や樹脂がもとに戻りにくいためひずみが起きやすい点が考えられる。
ここで、硬化物の誘電率は、波長395nmのUV-LEDで照度1500mW/cm2、積算光量1500mJ/cm2の条件で硬化性組成物を硬化させて得られる硬化物について、周波数100kHzにて測定される誘電率である。
条件1においては、まず、硬化性組成物を、厚さ100μmのテフロン(登録商標)シートを挟み込んだ2枚のガラス中へ封入する。そして、波長395nmのUV-LEDで照度1000mW/cm2、積算光量1500mJ/cm2にて硬化して、厚みが概ね100μmの硬化物を得る。
得られた硬化物を、幅10mm×長さ55mmの大きさにカットする。カットした硬化物のうち、長さ方向に10mm毎合計5点での厚みがすべて90~110μmの範囲である硬化物をヒステリシスロス測定のための試料とする。
ここで、ひずみとは、((引っ張り距離)/(チャック間距離))である。このチャック間距離は、開始点におけるチャック間距離のことを示し、引っ張り距離とは、開始点から180度方向に引っ張った距離を示す。
図2は、応力-ひずみ曲線の一例を模式的に示す図である。
引っ張り試験で得られた応力-ひずみ曲線において、引っ張り試験の開始点から2%伸張時までのグラフ1、縦軸、''ひずみ=2%''の直線および横軸に囲まれる領域の面積をAとし、2%伸張時から応力がゼロとなるまでのグラフ2とする。そして、グラフ2、''ひずみ=2%''の直線および上記横軸に囲まれる領域の面積をBとし、下記式によりヒステリシスロスを算出する。
ヒステリシスロス={(A-B)/A}×100
中でも、本実施形態においては、たとえば成分(a)として一分子中に2以上の(メタ)アクリル基を有する(メタ)アクリル化合物、一分子中に2以上のエポキシ基を有するエポキシ化合物、および、一分子中に2以上のオキセタニル基を有するオキセタン化合物からなる群から選択される1種以上を用いること;
成分(b)として、たとえば光カチオン重合開始剤を用いること;
成分(a)および(b)の配合割合を調整すること;
硬化性組成物の粘度を調整すること;
重合開始剤以外の材料を減圧下、たとえば40℃以上の温度で加熱攪拌した後、重合開始剤を添加すること;
硬化物組成物の硬化物を得るにあたり、硬化性組成物の成膜(たとえば、塗布)時および硬化時の酸素濃度を調整すること;
等が硬化性組成物の硬化物の誘電率やヒステリシスロスを上述の範囲内に制御するための因子として挙げられる。
このうち、硬化物組成物の調製時は、たとえば200Paの減圧下、たとえば40℃以上の温度で混合および攪拌をおこなう。攪拌時に減圧状態ではない場合、気体中の酸素が液へ溶け込み、液中酸素濃度が高くなってしまうため好ましい硬化特性が得られない場合がある。また、温度が低すぎる場合、液中の酸素が取り除かれにくくなるため、好ましい硬化特性が得られない場合がある。
また成膜のための塗布時は、硬化物の長期使用時の信頼性を向上する観点から、たとえば酸素濃度20.0~21.1%雰囲気下で塗布を行い、硬化時においては、たとえばUV硬化時は酸素濃度50ppm~1000ppmにて硬化を行う。
E型粘度計を用いて25℃、20rpmにて測定される硬化性組成物の粘度は、インクジェット吐出性向上の観点から、好ましくは3mPa・s以上であり、より好ましくは5mPa・s以上、さらに好ましくは8mPa・s以上、さらにより好ましくは10mPa・s以上である。
また、インクジェット吐出性向上の観点から、上記硬化性組成物の粘度は、好ましくは50mPa・s以下であり、より好ましくは30mPa・s以下、さらに好ましくは27mPa・s以下、さらにより好ましくは25mPa・s以下である。
成分(a)は、重合性化合物である。成分(a)として、具体的には、(メタ)アクリロイル基、ビニル基等のラジカル重合性官能基を有する化合物(以下、「ラジカル重合性化合物」とも呼ぶ。);および
エポキシ基、オキセタニル基、ビニルエーテル基等のカチオン重合性の官能基を有する化合物(以下、「カチオン重合性化合物」とも呼ぶ。)が挙げられる。
なお、本実施形態において、(メタ)アクリルとは、アクリルまたはメタクリルを意味する。
(メタ)アクリル化合物は、好ましくは一分子中に2以上の(メタ)アクリル基を有する(メタ)アクリル化合物であり、その具体例として、ジ(メタ)アクリル化合物、3官能以上の(メタ)アクリル化合物が挙げられる。
脂肪族ジ(メタ)アクリル化合物として、たとえば、ジオールのジ(メタ)アクリレート、(ポリ)アルキレングリコールのジ(メタ)アクリレートが挙げられ、さらに具体的には、1,6-ヘキサンジオールジアクリレート(たとえばA-HD-N、新中村化学工業社製)、1,9-ノナンジオールジアクリレート(たとえばA-NOD-N、新中村化学工業社製)、1,10-デカンジオールジアクリレート(たとえばA-DOD-N、新中村化学工業社製)、ネオペンチルグリコールジアクリレート(たとえばA-NPG、新中村化学工業社製)、エチレングリコールジアクリレート(たとえばSR206NS、アルケマ社製)、ポリエチレングリコールジアクリレート(たとえばA-400、新中村化学工業社製)、ポリプロピレングリコールジアクリレート(たとえばAPG-400、新中村化学工業社製)、トリシクロデカンジメタノールジアクリレート(たとえばA-DCP)、1,3-ブタンジオールジメタクリレート(たとえばBG、新中村化学工業社製)、1,4-ブタンジオールジメタクリレート(たとえばBD、新中村化学工業社製)、1,6-ヘキサンジオールジメタクリレート(たとえばHD-N、新中村化学工業社製)、1,9-ノナンジオールジメタクリレート(たとえばNOD-N、新中村化学工業社製)、1,10-デカンジオールジメタクリレート(たとえばDOD-N、新中村化学工業社製)、ネオペンチルグリコールジメタクリレート(たとえばNPG、新中村化学工業社製)が挙げられる。
脂環式ジ(メタ)アクリル化合物として、たとえば、ジシクロペンタニルジメタクリレート(たとえばDCP、新中村化学工業社製)が挙げられる。
ペンタエリスリトールテトラアクリレート(たとえばA-TMMT、新中村化学工業社製)、エトキシ化ペンタエリスリトールテトラアクリレート(たとえばATM-4E、新中村化学工業社製)、ジトリメチロールプロパンテトラアクリレート(たとえばAD-TMP-L、新中村化学工業社製)等の4官能(メタ)アクリル化合物;
ジペンタエリスリトールペンタアクリレート(たとえばM-402、東亞合成社製)等の5官能脂肪族アクリレート化合物;および
ジペンタエリスリトールペンタヘキサアクリレート(たとえばGM66G0H、國精化學社製)等の6官能(メタ)アクリル化合物が挙げられる。
一方、単官能(メタ)アクリル化合物として、たとえば、イソステアリルアクリレート等の単官能脂肪族(メタ)アクリル化合物;ベンジルアクリレート、エトキシ化o-フェニルフェノールアクリレート等の単官能芳香族(メタ)アクリル化合物が挙げられる。
同様の観点から、一分子中に2以上の(メタ)アクリル基を有する(メタ)アクリル化合物が、脂肪族ジ(メタ)アクリル化合物および脂環式ジ(メタ)アクリル化合物を含むことも好ましく、1,9-ノナンジオールジアクリレート、1,10-デカンジオールジアクリレート、1,9-ノナンジオールジメタクリレートおよび1,10-デカンジオールジメタクリレートからなる群から選択される1種または2種以上とジシクロペンタニルジメタクリレートとを含むことがより好ましい。
また、(メタ)アクリル化合物中の単官能アクリレート化合物の含有量は、(メタ)アクリル化合物全体に対して好ましくは30質量%以下であり、さらに好ましくは20質量%以下であり、より好ましくは15質量%以下であり、さらにより好ましくは12質量%以下であり、いっそう好ましくは8質量%以下であり、さらに好ましくは5質量%以下であり、さらによりいっそう好ましくは2質量%以下であり、(メタ)アクリル化合物が単官能アクリレート化合物を含まないことがことさら好ましい。
2官能脂環式エポキシ化合物としては、シクロアルケンオキサイド構造を有する脂環式エポキシ化合物が好ましい。
3官能以上のエポキシ化合物の具体例として、トリメチロールプロパンポリグリシジルエーテル(たとえばEX-321L、ナガセケムテックス社製)、ジグリセロールポリグリシジルエーテル(たとえばEX-421、ナガセケムテックス社製)等の多官能エポキシ化合物が挙げられる。
また、伸長反応速度を高める観点から、カチオン重合性化合物中のエポキシ化合物の含有量は、カチオン重合性化合物全体を100質量部としたとき、たとえば100質量部以下であり、好ましくは50質量部以下、より好ましくは40質量部以下、さらに好ましくは30質量部以下である。
オキセタン化合物は、好ましくは一分子中に2以上のオキセタニル基を有するオキセタン化合物であり、より好ましくは2官能オキセタン化合物であり、さらに好ましくは以下の一般式(6)または(7)で表される2官能オキセタン化合物である。
アリール基の例として、具体的には、フェニル基、ナフチル基、トリル基、キシリル基が挙げられる。
アラルキル基として、具体的には、ベンジル基、フェネチル基が挙げられる。
また、R4は、炭素原子数1~6のアルキレン基またはアリーレン基である。炭素原子数1~6のアルキレン基として、具体的には、メチレン基、エチレン基、プロピレン基、ブチレン基、シクロヘキシレン基が挙げられる。
硬化性向上の観点から、一分子中に2以上のオキセタニル基を有するオキセタン化合物は、好ましくは3-エチル-3{[(3-エチルオキセタン-3-イル)メトキシ]メチル}オキセタンである。
また、同様の観点から、カチオン重合性化合物中のオキセタン化合物の含有量は、カチオン重合性化合物全体を100質量部としたとき、たとえば100質量部以下であり、好ましくは95質量部以下、より好ましくは90質量部以下、さらに好ましくは85質量部以下である。
成分(b)は、重合開始剤である。重合開始剤の具体例として、熱ラジカル開始剤および光重合開始剤からなる群から選択される1種以上が挙げられる。低温で安定的に硬化物を形成する観点から、成分(b)は、紫外線等の光が照射されることでラジカルまたはイオンを生成する重合開始剤(UVラジカル開始剤等の光ラジカル重合開始剤またはUVカチオン開始剤等の光カチオン重合開始剤)を含み、より好ましくは光カチオン重合開始剤である。
また、硬化性組成物の着色を抑制する観点から、硬化性組成物中の成分(b)の含有量は、硬化性組成物の全組成に対し、好ましくは10質量%以下であり、より好ましくは6質量%以下、さらに好ましくは4質量%以下である。
硬化性組成物が成分(c)のレベリング剤を含むことにより、硬化性組成物により形成される膜の平坦性を向上することができる。
成分(c)の具体例として、ポリエステル変性ポリジメチルシロキサン(たとえばBYK-310、ビックケミー・ジャパン社製)、ポリエーテル変性シロキサン(たとえばBYK-345、ビックケミー・ジャパン社製)等のシリコーン系レベリング剤;
アクリル系共重合体(たとえばBYK-350、ビックケミー・ジャパン社製;KL700、共栄社化学社製)等のアクリル系レベリング剤;
フッ素変性ポリマー(たとえばBYK-340、ビックケミー・ジャパン社製)、パーフルオロアルキル含有オリゴマー(たとえばサーフロンS-611(AGCセイミケミカル社製)等のフッ素系レベリング剤が挙げられる。
同様の観点から、成分(c)がアクリル系レベリング剤であることも好ましい。
また、硬化物の表面硬度を安定させる観点から、硬化性組成物中の成分(c)の含有量は、硬化性組成物の全組成に対し、好ましくは5質量%以下であり、より好ましくは3質量%以下、さらに好ましくは2質量%以下である。
粘着性付与剤の具体例として、脂肪族炭化水素樹脂、脂環式炭化水素樹脂、芳香族炭化水素樹脂等の石油樹脂;テルペン樹脂;フェノール樹脂等のフェノール類;およびロジン樹脂からなる群から選択される1種または2種以上が挙げられる。
インデン、メチルインデン、ビニルトルエン、スチレン、α-メチルスチレン、β-メチルスチレン等から得られるC9モノマーまたはそのオリゴマー;
C5モノマーおよびC9モノマーの共重合体(C5-C9共重合樹脂);
シクロペンタジエン、ジシクロペンタジエン等から得られる脂環式モノマーまたはその重合体;
イソプロペニルトルエン等の芳香族モノマーまたはその重合体;
上記各種モノマーもしくはその重合体の水素化物;
上記各種モノマーもしくはその重合体を、無水マレイン酸やマレイン酸、フマル酸、(メタ)アクリル酸、フェノール等で変性した変性石油樹脂が挙げられる。
成分(a)との相溶性に優れる観点から、粘着付与剤として用いられる石油樹脂は、好ましくはスチレン系オリゴマーである。同様の観点から、成分(a)がジシクロペンタジエンを主原料に製造された石油樹脂であることも好ましく、より好ましくはジシクロペンタジエンを主原料に製造され、分子内にエステル基を有している石油樹脂(たとえばQTN1500、日本ゼオン社製)である。
また、フェノール樹脂の具体例として、これらのフェノール化合物とホルムアルデヒドとをアルカリ触媒で付加反応させたレゾールや、酸触媒で縮合反応させて得られるノボラック等が含まれる。また、フェノール樹脂には、ロジンにフェノールを酸触媒で付加させ熱重合することにより得られるロジンフェノール樹脂等も含まれる。
また、増感剤の具体例として、2,4-ジエチルチオキサントン等のチオキサントン系化合物、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、ベンゾフェノン、2,4-ジクロロベンゾフェノン、o-ベンゾイル安息香酸メチル、4,4'-ビス(ジメチルアミノ)ベンゾフェノン、4-ベンゾイル-4'-メチルジフェニルサルファイド、9,10-ジブトキシアントラセンが挙げられる。
また、硬化物の可視光透過性を好ましいものとする観点から、硬化性組成物中の増感剤の含有量は、好ましくは20質量%以下であり、より好ましくは10質量%以下、さらに好ましくは5質量%以下、さらにより好ましくは1質量%以下である。
本実施形態において、硬化性組成物の製造方法は、たとえば、成分(a)および(b)ならびにその他の成分を混合することによって、液状の硬化性組成物を得る工程を含む。また、得られた硬化性組成物を硬化することにより硬化物が得られる。
このとき、前述のとおり、成分(a)および(b)の種類や含有割合、硬化性組成物の製造方法等を高度に制御することにより、硬化性組成物の硬化物の誘電率やヒステリシスロスを上述の範囲内に安定的に調整することができる。たとえば、硬化性組成物は、上述の成分を混合し、たとえばホモディスパー、ホモミキサー、万能ミキサー、プラネタリーミキサー、ニーダー、3本ロールなどの混合機を用いて混合して得ることができる。なお、硬化性組成物を安定に混合する観点では、成分(b)以外の成分を混合した後、成分(b)を混合することがより好ましい。また、硬化性組成物の原料を混合および撹拌する際の減圧度、混合温度ならびに硬化物を得る際の酸素濃度を調整することも好ましい。こうした方法により、均一に液が調整可能で、ムラがない硬化物を得ることができ、硬化性組成物の硬化物の誘電率およびヒステリシスロスを上述の範囲に制御しやすくなる。
本実施形態に得られる硬化性組成物の硬化物をたとえば表示装置、好ましくは有機EL表示装置の封止材として用いることにより、長期使用時の耐久性に優れる表示装置を得ることができる。
以下、有機EL表示装置を例に、表示装置の構成例を挙げる。
本実施形態において、有機EL表示装置は、硬化性組成物の硬化物に構成された層を有する。
図1は、本実施形態における有機EL表示装置の構成例を示す断面図である。図1に示した表示装置100は、有機EL表示装置であって、基板(基材層50)と、基材層50上に配置された有機EL素子(発光素子10)と、発光素子10を被覆する封止層22(オーバーコート層22またはバリア性層22であってもよい)と、を含む。そして、たとえば封止層22が、本実施形態における硬化性組成物の硬化物により構成されている。
また、図1においては、表示装置100が、発光素子10よりも観察側に位置する層として、バリア性層21(タッチパネル層21または表面保護層21であってもよい)、封止層22(オーバーコート層22またはバリア性層22であってもよい)、平坦化層23(封止層23であってもよい)、バリア性層24を有している。平坦化層23は、発光素子10を覆うように基材層50上に設けられており、バリア性層24は、平坦化層23の表面に設けられている。封止層22は、平坦化層23およびバリア性層24を覆うように基材層50上に設けられている。また、封止層22上にバリア性層21が設けられている。
((a)重合性化合物)
重合性化合物1:2官能脂環式エポキシ化合物、セロキサイド CEL8010(ダイセル社製、下記式で表される化合物(推定))
重合性化合物3:2官能脂肪族オキセタン化合物、OXT221、東亞合成社製、3-エチル-3{[(3-エチルオキセタン-3-イル)メトキシ]メチル}オキセタン
重合性化合物4:2官能脂環式メタクリレート化合物、DCP、新中村化学工業社製、ジシクロペンタニルジメタクリレート
重合性化合物5:2官能脂肪族メタクリレート化合物、NOD-N、新中村化学工業社製、1,9-ノナンジオールジメタクリレート
重合性化合物6:2官能脂肪族アクリレート化合物、A-NOD-N、新中村化学工業社製、1,9-ノナンジオールジアクリレート
重合性化合物7:単官能脂肪族アクリレート化合物、新中村化学株式工業社製、イソステアリルアクリレート
重合性化合物8:3官能脂肪族アクリレート化合物、A-TMPT、新中村化学工業社製、トリメチロールプロパントリアクリレート
重合性化合物9:5官能脂肪族アクリレート化合物、M-402、東亞合成社製、ジペンタエリスリトールペンタアクリレート
重合性化合物10:単官能脂肪族オキセタン化合物、OXT212、東亞合成社製、3-エチル-3-〔(2-エチルヘキシルオキシ)メチル〕オキセタン
重合性化合物11:単官能芳香族アクリレート化合物、A-LEN-10、新中村化学工業社製、エトキシ化o-フェニルフェノールアクリレート
重合性化合物12:単官能芳香族アクリレート化合物、ビスコート160、大阪有機化学工業社製、ベンジルアクリレート
((b)重合開始剤)
重合開始剤1:光カチオン開始剤、CPI210S、サンアプロ社製
重合開始剤2:光ラジカル開始剤、TPO、BASF社製、2,4,6-trimethylbenzoyl-diphenyl phosphine oxide
((c)レベリング剤)
レベリング剤1:アクリル系共重合物、KL700、共栄社化学社製
(その他成分)
その他成分1(粘着性付与剤):スチレン系オリゴマー(イソプロぺニルトルエン(IPT)の単独重合体(スチレン系オリゴマー、重量平均分子量:1200、数平均分子量:800))
その他成分2(光カチオン増感剤):9,10-ジブトキシアントラセン、UVS-1331、川崎化成工業社製
表1に示した配合組成となるように各成分を合計11kgスケールで配合して液状の硬化性組成物を得た。その際、重合開始剤以外の成分を全て混合し、真空ポンプにて系内を減圧し、減圧度190Pa~210Paの雰囲気下80℃で4時間混合および攪拌を行い、室温まで下げた後、酸素の混入を防ぐため窒素押し出しによって重合開始剤の入ったタンクへ移液を行い、減圧度190Pa~210Paの雰囲気下40℃で1時間混合および攪拌を行った。また成膜のための塗布時は酸素濃度20.0~21.1%雰囲気下で行い、UV硬化時は酸素濃度50ppm~1000ppmにて硬化を行った。
各例で得られた硬化性組成物またはその硬化物の物性を以下の方法で測定した。測定結果を表1にあわせて示す。
各例で得られた硬化性組成物の粘度を、E型粘度計(LV-DV-II+、BROOKFIELD社製)を用いて25℃、20rpmにて測定した。
表1に示した粘度の評価基準は以下のとおりである。
A:3mPa・s以上50mPa・s以下
B:3mPa・s未満または50mPa・s超
前述の方法に従い、硬化性組成物の硬化物を作製し、硬化物の引っ張り試験結果からヒステリシスロスを求めた。
すなわち、まず、硬化性組成物を、厚さ100μmのテフロン(登録商標)シート(MSF-100、中興化成工業社製)を挟み込んだ2枚のガラス中へ封入した。そして、波長395nmのUV-LEDで照度1000mW/cm2、積算光量1500mJ/cm2にて硬化して、厚み約100μmの硬化物を得た。
得られた硬化物を、幅10mm×長さ55mmの大きさにカットした。カットした硬化物のうち、長さ方向に10mm毎合計5点での厚みがすべて90~110μmの範囲である硬化物をヒステリシスロス測定のための試料とした。
試料の一端をチャックに固定し、万能材料試験機 AG-X-Plus、島津製作所社製を用いて、23℃、10mm/秒(引っ張り速度)にて他端を180度方向へ引っ張る引っ張り試験をおこない、応力を縦軸とし、ひずみを横軸とした曲線(応力-ひずみ曲線)を得た。なお試料を何も取り付けていない状態を0mNと設定し、また、初期ひずみ解消のため、荷重が0.05Nに達するまで引っ張り、その点を開始点とした。したがって、開始点においては、ひずみ0mm、荷重0.05Nとした。応力-ひずみ曲線において、引っ張り試験の開始点から2%伸張時までのグラフ1、縦軸、''ひずみ=2%''の直線および横軸に囲まれる領域の面積をAとし、2%伸張時から応力がゼロとなるまでのグラフ2とした。そして、''ひずみ=2%''の直線および横軸に囲まれる領域の面積をBとし、下記式によりヒステリシスロスを算出した。
ヒステリシスロス={(A-B)/A}×100
表1に示したヒステリシスロスの評価基準は以下のとおりである。
A:0%以上45%以下
B:45%超
誘電率測定のための硬化物を得るための塗膜を以下の方法により作製した。すなわち、得られた硬化性組成物を、インクジェットカートリッジDMC-11610(富士フイルムDimatix社製)に導入した。そのインクジェットカートリッジをインクジェット装置DMP-2831(富士フイルムDimatix社製)にセットし、吐出状態の調整を行った後、無アルカリガラス上にアルミを100nmの厚みで蒸着した基板に、硬化後の厚みが10μmとなるように、5cm×5cmのサイズで塗布した。この時の酸素濃度は20.6%で行った。
得られた塗膜を1分間、室温(25℃)で放置した後、波長395nmのUV-LEDで照度1500mW/cm2、積算光量1500mJ/cm2、酸素濃度1000ppm以下で硬化させた。
その後インクジェット塗布面にアルミを100nmの厚みで蒸着し、LCRメーターHP4284A(アジレント・テクノロジー社製)にて、自動平衡ブリッジ法により条件100kHzにて誘電率を測定した。
表1に示した誘電率の評価基準は以下のとおりである。
A:3.6以下
B:3.6超
(耐屈曲性)
耐屈曲性の指標として、以下の方法で、30万回耐折試験後のヘイズに関する評価をおこなった。
各例で得られた硬化性組成物を、インクジェットカートリッジDMC-11610(富士フイルムDimatix社製)に導入した。そのインクジェットカートリッジをインクジェット装置DMP-2831(富士フイルムDimatix社製)にセットし、吐出状態の調整を行った後、6cm×6cmのPETフィルム(25μm、A31)に、硬化後の厚みが10μmとなるように、5cm×5cmのサイズで塗布した。この時の酸素濃度は20.0%から21.1%の範囲内で行った。得られた塗膜を1分間、室温(25℃)で放置した後、波長395nmのUV-LEDで照度1000mW/cm2、積算光量1500mJ/cm2、酸素濃度1000ppm以下で硬化させた。
得られた硬化物を測定試料として耐屈曲性を評価した。図3は、耐屈曲性の評価方法を説明するための上面図である。屈曲試験機(DML HP、ユアサシステム社製)にて、屈曲半径を1mmに設定し、図3に示したように測定試料(図3のサンプル31、PETフィルムが下面、硬化膜が上面となるよう配置した。)を両面テープ35(ナイスタックNW-15、ニチバン社製)にてサンプル固定用プレート33に固定し、1分間に30回の屈曲速度で30万回屈曲試験を行った。1000回屈曲終了後、10分以内に外観を目視にて確認を行い、白濁の有無を評価した。さらに30万回屈曲終了後、10分以内に外観を目視にて確認を行い、白濁の有無を評価した。1000回屈曲終了時に白濁の無いもの(以下のAおよびB)を合格とした。
評価基準を以下に示す。
A:白濁なし
B:1000回屈曲終了後は白濁が無かったが、30万回屈曲終了後に白濁あり
C:1000回屈曲終了後に白濁あり
EL素子ダメージの指標として、以下の方法で有機EL表示素子の信頼性を評価した。
ITO電極を製膜したガラス基板に対し、上記基板をUV-オゾン処理装置(セン特殊光源社製、PL21-200(S)/UVE-200J)にて処理を行った後、アルカリ水溶液、純水、アセトン、イソプロピルアルコールにてそれぞれ15分間超音波洗浄を行い、最後にアセトンにて10分間超音波洗浄を行った。
次に、この基板を真空蒸着装置の基板フォルダに固定し、素焼きの坩堝にDipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11,hexacarbonitrile(HAT-CN)を200mg、別の素焼き坩堝に9-Phenyl-3,6-bis(9-phenyl-9Hcarbazol-3-yl)-9H-carbazole(Tris-PCz)を200mg入れ、真空チャンバー内を1×10-4Paまで減圧した。その後、HAT-CNの入った坩堝を加熱し、HAT-CNを蒸着速度0.4Å/sで基板に堆積させ、膜厚100nmを製膜した。続いて、Tris-PCzの入った坩堝を加熱し、蒸着速度1.0Å/sで基板に堆積させ、膜厚400nmを製膜した。次に、別の素焼き坩堝にTris(8-hydroxyquinolinato)aluminium(Alq3)を200mg入れ、真空チャンバー内を、再び1×104Paまで減圧した。次いでAlq3(トリス(8-キノリノラト)アルミニウム)の入った坩堝を加熱し、蒸着速度0.5Å/sで厚膜700nmを製膜した。その後、タングステン製抵抗加熱ボートにフッ化リチウム200mgを入れ、真空チャンバーを1×10-4Paまで減圧し、フッ化リチウムを0.03Å/sの蒸着速度で5nm製膜した。最後に、タングステン製抵抗加熱ボートにマグネシウムを1g、銀を200mg入れ、真空チャンバーを1×10-4Paまで減圧し、マグネシムを0.9Å/s、銀を0.1Å/sの蒸着速度でマグネシウム/銀=1/9の比率となるよう150nm製膜した。窒素により蒸着器内を常圧に戻し、8mm×8mm有機発光材料層を有する積層体が配置された基板を取り出した。
この有機発光材料層を有する積層体に対し、窒素雰囲気下でシール材となる各例で得られた硬化性組成物を30mg滴下し、ガラスを被せ、UV照射装置にて395nmを400mWで4秒間照射し、シール材を硬化させた。
得られた有機EL表示素子を、温度85℃の環境下で96時間暴露した後、3Vの電圧を印加し、有機EL表示素子の発光状態を目視にて確認した。
評価基準を以下に示す。以下のAおよびBを合格とした。
A:素子発光時にダークスポット無し。
B:素子発光時にダークスポットが部分的に存在する。
C:素子発光時にダークスポットが全面的に存在し、発光領域の縮小も見られる。
21 バリア性層、タッチパネル層または表面保護層
22 封止層、オーバーコート層、またはバリア性層
23 平坦化層または封止層
24 バリア性層
31 サンプル
33 サンプル固定用プレート
35 両面テープ
50 基材層
100 表示装置
Claims (10)
- 有機EL素子の封止に用いる、液状の硬化性組成物であって、
以下の成分(a)および(b):
(a)重合性化合物、
(b)重合開始剤
を含み、
波長395nmのUV-LEDで照度1500mW/cm2、積算光量1500mJ/cm2で硬化させた当該硬化性組成物の硬化物の周波数100kHzにおける誘電率が3.6以下であり、
以下の条件1にて得られる試料を、以下の条件2にて測定したときのヒステリシスロスが0%以上45%以下である、硬化性組成物。
(条件1)当該硬化性組成物を、厚さ100μmのテフロン(登録商標)シートを挟み込んだ2枚のガラス中へ封入し、波長395nmのUV-LEDで照度1000mW/cm2、積算光量1500mJ/cm2にて硬化して得られる硬化物を、幅10mm×長さ55mmの大きさにカットし、長さ方向に10mm毎合計5点での厚みがすべて90~110μmの範囲である硬化物を前記試料とする。
(条件2)前記試料の一端を固定し、チャック間距離が30mmになるよう他端を固定する。このとき前記試料を何も取り付けていない状態を0mNと設定し、また、初期ひずみ解消のため、荷重が0.05Nに達するまで引っ張り、その点を開始点とする。23℃、10mm/秒(引っ張り速度)にて前記他端を180度方向へ引っ張る引っ張り試験をおこなったときの応力を縦軸とし、ひずみを横軸とした曲線(応力-ひずみ曲線)において、前記引っ張り試験の前記開始点から2%伸張時までのグラフ1、前記縦軸、''ひずみ=2%''の直線および前記横軸に囲まれる領域の面積をAとし、前記2%伸張時から前記応力がゼロとなるまでのグラフ2、''ひずみ=2%''の前記直線および前記横軸に囲まれる領域の面積をBとし、{(A-B)/A}×100で計算される解を前記ヒステリシスロスとする。 - 前記成分(a)が、一分子中に2つの(メタ)アクリル基を有する(メタ)アクリル化合物、一分子中に2つのエポキシ基を有するエポキシ化合物、および、一分子中に2つのオキセタニル基を有するオキセタン化合物からなる群から選択される1種以上を含む、請求項1に記載の硬化性組成物。
- 前記成分(a)が、一分子中に2つの(メタ)アクリル基を有する(メタ)アクリル化合物、一分子中に2つのエポキシ基を有するエポキシ化合物、および、一分子中に2つのオキセタニル基を有するオキセタン化合物からなる群から選択される2種以上を含む、請求項1または2に記載の硬化性組成物。
- 前記成分(b)が、光カチオン重合開始剤である、請求項1乃至3いずれか1項に記載の硬化性組成物。
- 前記成分(b)が、光ラジカル重合開始剤である、請求項1乃至3いずれか1項に記載の硬化性組成物。
- 成分(c):レベリング剤をさらに含む、請求項1乃至5いずれか1項に記載の硬化性組成物。
- 前記成分(c)が、アクリル系レベリング剤である、請求項6に記載の硬化性組成物。
- E型粘度計を用いて25℃、20rpmにて測定される当該硬化性組成物の粘度が、3mPa・s以上50mPa・s以下である、請求項1乃至7いずれか1項に記載の硬化性組成物。
- 前記成分(a)が、一分子中に2つの(メタ)アクリル基を有する(メタ)アクリル化合物を2種以上含む、請求項1乃至8いずれか1項に記載の硬化性組成物。
- 基板と、
前記基板上に配置された有機EL素子と、
前記有機EL素子を被覆する封止層と、
を含み、前記封止層が、請求項1乃至9いずれか1項に記載の硬化性組成物の硬化物により構成されている、有機EL表示装置。
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JP2020057580A (ja) * | 2018-09-27 | 2020-04-09 | パナソニックIpマネジメント株式会社 | 有機el素子封止用紫外線硬化性樹脂組成物、有機el発光装置の製造方法、有機el発光装置、及びタッチパネル |
WO2021006070A1 (ja) * | 2019-07-05 | 2021-01-14 | 三井化学株式会社 | 有機el表示素子用封止剤および有機el表示装置 |
JP2021064541A (ja) * | 2019-10-15 | 2021-04-22 | パナソニックIpマネジメント株式会社 | 紫外線硬化性樹脂組成物、発光装置の製造方法、発光装置、及びタッチパネル |
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WO2021006070A1 (ja) * | 2019-07-05 | 2021-01-14 | 三井化学株式会社 | 有機el表示素子用封止剤および有機el表示装置 |
JP2021064541A (ja) * | 2019-10-15 | 2021-04-22 | パナソニックIpマネジメント株式会社 | 紫外線硬化性樹脂組成物、発光装置の製造方法、発光装置、及びタッチパネル |
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