WO2018074507A1 - Organic el display element sealing agent, and method for producing organic el display element sealing agent - Google Patents

Organic el display element sealing agent, and method for producing organic el display element sealing agent Download PDF

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Publication number
WO2018074507A1
WO2018074507A1 PCT/JP2017/037656 JP2017037656W WO2018074507A1 WO 2018074507 A1 WO2018074507 A1 WO 2018074507A1 JP 2017037656 W JP2017037656 W JP 2017037656W WO 2018074507 A1 WO2018074507 A1 WO 2018074507A1
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Prior art keywords
organic
sealing agent
display element
display elements
meth
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PCT/JP2017/037656
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French (fr)
Japanese (ja)
Inventor
信烈 梁
山本　拓也
範久 赤松
七里　徳重
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積水化学工業株式会社
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Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to KR1020187026418A priority Critical patent/KR102416054B1/en
Priority to KR1020227022052A priority patent/KR20220097552A/en
Priority to CN201780020277.2A priority patent/CN108886849B/en
Priority to JP2017556252A priority patent/JP6427283B2/en
Publication of WO2018074507A1 publication Critical patent/WO2018074507A1/en

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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
    • 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
    • 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
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts

Definitions

  • the present invention relates to an encapsulant for an organic EL display element that can be easily applied by an ink jet method, can provide an organic EL display element that is excellent in low outgassing properties and excellent in reliability. Moreover, this invention relates to the manufacturing method of this sealing agent for organic EL display elements.
  • An organic electroluminescence (organic EL) display element has a laminated structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other, and electrons are injected into the organic light emitting material layer from one electrode. By injecting holes from the other electrode, electrons and holes are combined in the organic light emitting material layer to emit light.
  • the organic EL display element performs self-emission, it has better visibility than a liquid crystal display element that requires a backlight, can be reduced in thickness, and can be driven by a DC low voltage. Has the advantage.
  • Patent Document 1 discloses a method of sealing an organic light emitting material layer and an electrode of an organic EL display element with a laminated film of a silicon nitride film and a resin film formed by a CVD method.
  • the resin film has a role of preventing pressure on the organic layer and the electrode due to internal stress of the silicon nitride film.
  • Patent Document 1 In the method of sealing with a silicon nitride film disclosed in Patent Document 1, organic light emission occurs when a silicon nitride film is formed due to unevenness on the surface of the organic EL display element, adhesion of foreign matters, generation of cracks due to internal stress, or the like. The material layer or electrode may not be completely covered. If the coating with the silicon nitride film is incomplete, moisture will enter the organic light emitting material layer through the silicon nitride film. As a method for preventing moisture from entering into the organic light emitting material layer, Patent Document 2 discloses a method of alternately depositing an inorganic material film and a resin film. Patent Document 3 and Patent Document 4 Discloses a method of forming a resin film on an inorganic material film.
  • a method for forming a resin film there is a method in which a sealing agent is applied on a substrate using an inkjet method and then the sealing agent is cured. If such a coating method by the ink jet method is used, a resin film can be uniformly formed at high speed.
  • the sealant is made to have a low viscosity in order to be suitable for application by the ink jet method, outgas is generated, or moisture penetration cannot be sufficiently prevented in a high temperature and high humidity environment. There is a problem that the organic EL display element to be used is inferior in reliability.
  • An object of the present invention is to provide a sealing agent for organic EL display elements that can be easily applied by an ink jet method, can provide an organic EL display element that is excellent in low outgassing properties and excellent in reliability. And Moreover, an object of this invention is to provide the manufacturing method of this sealing agent for organic EL display elements.
  • the present invention 1 contains a polymerizable compound and a polymerization initiator, has a viscosity at 25 ° C. of 5 to 50 mPa ⁇ s, a surface tension at 25 ° C. of 15 to 35 mN / m, and 25 ° C., 50 It is a sealant for organic EL display elements having a water content at 25 ° C. of 1000 ppm or less after standing in an environment of% RH for 24 hours.
  • the present invention 2 is an organic EL display element sealing agent used for coating by an ink jet method, which contains a polymerizable compound and a polymerization initiator, and is 24 hours in an environment of 25 ° C. and 50% RH.
  • the sealing agent for organic EL display elements whose water content in 25 degreeC after leaving still is 1000 ppm or less.
  • the present invention is described in detail below.
  • the sealing agent for organic EL display elements of this invention 1 and the sealing agent for organic EL display elements of this invention 2 it describes as "the sealing agent for organic EL display elements of this invention”. To do.
  • the inventors of the present invention have further studied to make the moisture content within a specific range for the sealing agent for organic EL display elements having excellent ink jet coating properties. As a result, it has been found that a sealing agent for organic EL display elements can be obtained that can be easily applied by an ink jet method, can provide an organic EL display element that is excellent in low outgassing properties and excellent in reliability.
  • the present invention has been completed.
  • the sealing agent for organic EL display elements of the present invention can be used as an ink jet method for coating by a non-heated ink jet method, or can be used for coating by a heat ink jet method.
  • the “non-heated ink jet method” is a method of ink jet coating at a coating head temperature of less than 28 ° C.
  • the “heated ink jet method” is an ink jet at a coating head temperature of 28 ° C. or higher. It is a method of applying.
  • an ink jet coating head equipped with a heating mechanism is used.
  • the viscosity and the surface tension can be lowered when discharging the sealing agent for organic EL display elements.
  • Examples of the inkjet coating head equipped with the heating mechanism include KM1024 series manufactured by Konica Minolta, SG1024 series manufactured by Fuji Film Dimatix, and the like.
  • the heating temperature of the coating head is preferably in the range of 28 ° C. to 80 ° C.
  • the heating temperature of the coating head is within this range, the increase in the viscosity of the sealant for organic EL display elements over time is suppressed, and the ejection stability is improved.
  • the sealing agent for organic EL display elements of the present invention 1 has a viscosity lower limit of 5 mPa ⁇ s and an upper limit of 50 mPa ⁇ s. When the viscosity is within this range, it can be suitably applied by an ink jet method.
  • the said viscosity in this specification means the value measured on 25 degreeC and 100 rpm conditions using an E-type viscosity meter.
  • the preferable lower limit of the viscosity of the sealing agent for organic EL display elements of the present invention when applied by the non-heating ink jet method is 5 mPa ⁇ s, and the preferable upper limit is 20 mPa.s. s.
  • the more preferable lower limit of the viscosity of the sealing agent for organic EL display elements of the present invention when applied by the non-heating ink jet method is 8 mPa ⁇ s, and the more preferable upper limit is 16 mPa ⁇ s. s, a more preferred lower limit is 10 mPa ⁇ s, and a more preferred upper limit is 13 mPa ⁇ s. s.
  • the preferable lower limit of the viscosity of the sealing agent for organic EL display elements of the present invention when used for coating by the heating ink jet method is 10 mPa ⁇ s, and the preferable upper limit is 50 mPa ⁇ s. s.
  • the viscosity is within this range, it can be suitably applied by a heating ink jet method.
  • the more preferable lower limit of the viscosity of the sealing agent for organic EL display elements of the present invention when used for coating by the heating ink jet method is 20 mPa ⁇ s, and the more preferable upper limit is 40 mPa ⁇ s. s.
  • the sealing agent for organic EL display elements of the present invention 1 has a lower limit of surface tension of 15 mN / m and an upper limit of 35 mN / m. When the surface tension is within this range, it can be suitably applied by an ink jet method.
  • the preferable lower limit of the surface tension is 20 mN / m
  • the preferable upper limit is 30 mN / m
  • the more preferable lower limit is 22 mN / m
  • the more preferable upper limit is 28 mN / m.
  • the sealing agent for organic EL display elements of the present invention 2 has a preferable lower limit of surface tension of 15 mN / m and a preferable upper limit of 35 mN / m.
  • the surface tension When the surface tension is within this range, it can be suitably applied by an ink jet method.
  • the more preferable lower limit of the surface tension is 20 mN / m
  • the more preferable upper limit is 30 mN / m
  • the still more preferable lower limit is 22 mN / m
  • the still more preferable upper limit is 28 mN / m.
  • the surface tension means a value measured by a Wilhelmy method using a dynamic wettability tester at 25 ° C.
  • the sealing agent for organic EL display elements of the present invention has a water content of 1000 ppm or less at 25 ° C. after standing for 24 hours in an environment of 25 ° C. and 50% RH.
  • the moisture content is 1000 ppm or less, the obtained organic EL display element has excellent reliability.
  • a preferable upper limit of the water content is 800 ppm, and a more preferable upper limit is 300 ppm.
  • the water content is most preferably 0 ppm.
  • the said moisture content can be measured on 25 degreeC and the conditions of 50% RH environment using a Karl Fischer apparatus.
  • the measurement of the said moisture content is performed about the sealing agent within 30 minutes, after leaving still for 24 hours.
  • the viscosity, the surface tension, and the water content are described above by selecting these types and adjusting the content ratio of the polymerizable compound, the polymerization initiator, and other components that may be contained, which will be described later. It can be a range. Moreover, the said moisture content can be easily made into 1000 ppm or less by performing a dehydration process after mixing each component of the sealing agent for organic EL display elements.
  • the manufacturing method of the sealing agent for organic EL display elements which has the dehydration process exposed to 15 minutes or more is also one of this invention.
  • the preferable lower limit of the temperature in the dehydration step is 20 ° C, and the preferable upper limit is 80 ° C.
  • the dehydration step is preferably performed for 20 minutes or longer.
  • Other methods for dehydrating the organic EL display element sealant other than the dehydration step in the method for producing an organic EL display element sealant of the present invention include, for example, a method using a dehydrating agent.
  • Specific examples of the method using the dehydrating agent include a method of flowing a sealing agent for an organic EL display element through a column filled with the dehydrating agent at a flow rate of about 2.5 liters per hour, or a sealing for an organic EL display element.
  • Examples include a method of adding a dehydrating agent to the stopper and stirring the mixture, leaving it for about 12 hours, and removing the dehydrating agent by filtration or the like.
  • Examples of the dehydrating agent include molecular sieves, aluminum oxide, calcium chloride, calcium oxide, magnesium oxide, magnesium perchlorate, anhydrous magnesium sulfate, phosphorous oxide (V), anhydrous potassium carbonate, silica gel, sodium hydroxide, and anhydrous sulfuric acid. Examples thereof include sodium and zinc chloride. Of these, molecular sieves are preferable because of their excellent drying ability.
  • the sealing agent for organic EL display elements of the present invention contains a polymerizable compound.
  • the polymerizable compound preferably contains 20 to 90 parts by weight of a compound having an oxygen atom content of 30% or less in the molecule in 100 parts by weight of the entire polymerizable compound.
  • the present inventors have introduced an oxygen atom in a molecule such as a compound having a polyoxyalkylene skeleton in the main chain as a polymerizable compound. The use of a compound with a high content of was studied.
  • the resulting organic EL display element tends to be inferior in reliability, such as generating a dark spot when exposed to a high temperature and high humidity environment.
  • the present inventors have obtained an ink jet coatability by using a compound having an oxygen atom content of 30% or less as a polymerizable compound so as to have a specific content. It has been found that the reliability of the organic EL display element can be easily achieved.
  • the compound having an oxygen atom content in the molecule of 30% or less preferably has an oxygen atom content in the molecule of 25% or less, and more preferably 20% or less.
  • the more preferable lower limit of the content of the compound having an oxygen atom content of 30% or less in 100 parts by weight of the total polymerizable compound is 30 parts by weight, and the more preferable upper limit is 70 parts by weight.
  • a radical polymerizable compound or a cationic polymerizable compound can be used as the polymerizable compound.
  • a (meth) acrylic compound is preferable.
  • the (meth) acrylic compound may be a monofunctional (meth) acrylic compound or a polyfunctional (meth) acrylic compound.
  • the above “(meth) acryl” means acryl or methacryl
  • the above “(meth) acryl compound” means a compound having a (meth) acryloyl group
  • the above “(meth) “Acryloyl” means acryloyl or methacryloyl.
  • the monofunctional (meth) acrylic compound preferably has a cationic polymerizable group from the viewpoint of low outgassing property.
  • the cationic polymerizable group include a vinyl ether group, an epoxy group, an oxetanyl group, an allyl ether group, a vinyl group, and a hydroxyl group.
  • the monofunctional (meth) acrylic compound examples include 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and (meth) acrylic.
  • (meth) acrylate 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and 2- (2-vinyloxyethoxy) ethyl (meth) acrylate are preferable.
  • the “(meth) acrylate” means acrylate or methacrylate.
  • the preferred lower limit of the content of the monofunctional (meth) acrylic compound in 100 parts by weight of the polymerizable compound is 20 parts by weight, and the preferred upper limit is 80. Parts by weight.
  • the content of the monofunctional (meth) acrylic compound is within this range, the obtained sealing agent for organic EL display elements is excellent due to low outgassing properties and the like.
  • the minimum with more preferable content of the said monofunctional (meth) acryl compound is 30 weight part, and a more preferable upper limit is 60 weight part.
  • the polyfunctional (meth) acrylic compound preferably has a polyoxyalkylene skeleton in the main chain from the viewpoint of inkjet coating properties and the like.
  • a compound having a high content of oxygen atoms in the molecule when used, the obtained organic EL display element tends to be inferior in reliability, and thus a polyoxyalkylene skeleton in the main chain is likely to be obtained.
  • a functional (meth) acryl compound it is preferable to adjust the content. That is, the content of the polyfunctional (meth) acrylic compound having a polyoxyalkylene skeleton in the main chain so that the content of the compound having an oxygen atom content in the molecule of 30% or less falls within the above-described range. Is preferably adjusted.
  • the polyoxyalkylene skeleton is preferably a series of 2 to 6 oxyalkylene units. Examples of oxyalkylene units constituting the polyoxyalkylene skeleton include oxyethylene units and oxypropylene units.
  • the polyfunctional (meth) acrylic compound preferably has a structure with less carbon chain branching, and more preferably is a straight chain, from the viewpoint of inkjet coating properties and the like.
  • polyfunctional (meth) acrylic compound examples include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and dipropylene glycol di (meth) acrylate. , Tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, and the like. Of these, tetraethylene glycol di (meth) acrylate is preferable.
  • the preferred lower limit of the content of the polyfunctional (meth) acrylic compound in 100 parts by weight of the polymerizable compound is 20 parts by weight, and the preferred upper limit is 80. Parts by weight.
  • the content of the polyfunctional (meth) acrylic compound is within this range, the obtained sealing agent for organic EL display elements is excellent in ink jet coating properties and the like.
  • the minimum with more preferable content of the said polyfunctional (meth) acryl compound is 30 weight part, and a more preferable upper limit is 60 weight part.
  • the content ratio of the monofunctional (meth) acrylic compound and the polyfunctional (meth) acrylic compound is expressed as a weight ratio.
  • an epoxy compound an oxetane compound, a vinyl ether compound etc. are mentioned, for example.
  • the epoxy compound examples include bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol O type epoxy resin, 2,2′-diallyl bisphenol A type epoxy resin, Alicyclic epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene Epoxy resin, phenol novolac epoxy resin, orthocresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl Examples thereof include a volac type epoxy resin, a naphthalene phenol novolac type epoxy resin, a glycidyl amine type epoxy resin, an alkyl polyol type epoxy resin, a rubber-modified epoxy resin, a glycidyl ester compound, and 1,6-hexan
  • alicyclic epoxy resins are preferred.
  • examples of commercially available alicyclic epoxy resins include Celoxide 2000, Celoxide 2021P, Celoxide 2081, Celoxide 3000, Celoxide 8000 (all manufactured by Daicel), and Sunsizer EPS (manufactured by Shin Nippon Rika Kogyo Co., Ltd.). ) And the like.
  • oxetane compound examples include allyloxyoxetane, phenoxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3-((2-ethylhexyloxy ) Methyl) oxetane, 3-ethyl-3-((3- (triethoxysilyl) propoxy) methyl) oxetane, 3-ethyl-3-((((3-ethyloxetane-3-yl) methoxy) methyl) oxetane, Examples include oxetanylsilsesquioxane, phenol novolac oxetane, 1,4-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) benzene.
  • vinyl ether compound examples include benzyl vinyl ether, cyclohexane dimethanol monovinyl ether, dicyclopentadiene vinyl ether, 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, dipropylene glycol. Examples thereof include divinyl ether and tripropylene glycol divinyl ether.
  • the sealing agent for organic EL display elements of the present invention contains a polymerization initiator.
  • a radical photopolymerization initiator, a thermal radical polymerization initiator, a cationic photopolymerization initiator, or a thermal cationic polymerization initiator is suitably used depending on the type of polymerizable compound used.
  • photo radical polymerization initiator examples include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, benzyl, thioxanthone compounds, and the like.
  • Examples of commercially available photo radical polymerization initiators include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucin TPO (both benzoin methyl ether, benzoin methyl ether) Examples include ethyl ether and benzoin isopropyl ether (both manufactured by Tokyo Chemical Industry Co., Ltd.).
  • thermal radical polymerization initiator what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
  • the azo compound include 2,2′-azobis (2,4-dimethylvaleronitrile), azobisisobutyronitrile, and the like.
  • the organic peroxide include benzoyl peroxide, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
  • thermal radical polymerization initiators examples include VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001, and V-501 (all manufactured by Wako Pure Chemical Industries, Ltd.). ) And the like.
  • the photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid generating type or a nonionic photoacid generating type. May be.
  • Examples of the anion portion of the ionic photoacid-generating photocationic polymerization initiator include BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , and (BX 4 ) ⁇ (wherein X is at least two or more. And a phenyl group substituted with a fluorine or trifluoromethyl group).
  • Examples of the ionic photoacid-generating photocationic polymerization initiator include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts having the above anion moiety, and (2,4-cyclohexane). And pentadien-1-yl) ((1-methylethyl) benzene) -Fe salt.
  • aromatic sulfonium salt examples include bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluoroantimonate, and bis (4- ( Diphenylsulfonio) phenyl) sulfide bistetrafluoroborate, bis (4- (diphenylsulfonio) phenyl) sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- ( Phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetraflu
  • aromatic iodonium salt examples 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, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexa Fluorophosphate, 4-methylphenyl-4- (1-methylethy
  • aromatic diazonium salt examples include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate.
  • aromatic ammonium salt examples include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl -2-Cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl)
  • Examples include -2-cyanopyridinium tetrafluoroborate and 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate.
  • Examples of the (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salt include (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene.
  • nonionic photoacid-generating photocationic polymerization initiator examples include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenol sulfonic acid ester, diazonaphthoquinone, N-hydroxyimide sulfonate, and the like.
  • photocationic polymerization initiators examples include, for example, DTS-200 (manufactured by Midori Chemical Co., Ltd.), UVI6990, UVI6974 (all manufactured by Union Carbide), SP-150, SP-170 (all ADEKA), FC-508, FC-512 (all from 3M), IRGACURE261, IRGACURE290 (all from BASF), PI2074 (from Rhodia), and the like.
  • the anion moiety is BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , or (BX 4 ) ⁇ (where X is substituted with at least two fluorine or trifluoromethyl groups
  • a sulfonium salt, a phosphonium salt, an ammonium salt, and the like are preferable.
  • sulfonium salt examples include triphenylsulfonium tetrafluoroborate and triphenylsulfonium hexafluoroantimonate.
  • Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.
  • ammonium salt examples include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (pentafluorophenyl).
  • thermal cationic polymerization initiators include, for example, Sun-Aid SI-60, Sun-Aid SI-80, Sun-Aid SI-B3, Sun-Aid SI-B3A, Sun-Aid SI-B4 (all of which are Sanshin Chemical Industry Co., Ltd.). CXC1612, CXC1821 (all manufactured by King Industries) and the like.
  • the content of the polymerization initiator is preferably 0.01 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the polymerizable compound.
  • the content of the polymerization initiator is 0.01 parts by weight or more, the obtained sealing agent for organic EL display elements is more excellent in curability.
  • the content of the polymerization initiator is 10 parts by weight or less, the curing reaction of the obtained sealing agent for organic EL display elements does not become too fast, and the workability is improved, and the cured product is more uniform. It can be.
  • the minimum with more preferable content of the said polymerization initiator is 0.05 weight part, and a more preferable upper limit is 5 weight part.
  • the sealing agent for organic EL display elements of the present invention may contain a sensitizer.
  • the sensitizer has a role of further improving the polymerization initiation efficiency of the polymerization initiator and further promoting the curing reaction of the sealing agent for organic EL display elements of the present invention.
  • sensitizer examples include thioxanthone compounds such as 2,4-diethylthioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 2,4-dichlorobenzophenone, o- Examples include methyl benzoylbenzoate, 4,4′-bis (dimethylamino) benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, and the like.
  • thioxanthone compounds such as 2,4-diethylthioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 2,4-dichlorobenzophenone, o- Examples include methyl benzoylbenzoate, 4,4′-bis (dimethylamino) benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, and the like.
  • the content of the sensitizer is preferably 0.01 parts by weight and preferably 3 parts by weight with respect to 100 parts by weight of the polymerizable compound.
  • the content of the sensitizer is 0.01 parts by weight or more, the sensitizing effect is more exhibited.
  • the content of the sensitizer is 3 parts by weight or less, light can be transmitted to a deep part without excessive absorption.
  • the minimum with more preferable content of the said sensitizer is 0.1 weight part, and a more preferable upper limit is 1 weight part.
  • the sealing agent for organic EL display elements of the present invention may contain a silane coupling agent.
  • the said silane coupling agent has a role which improves the adhesiveness of the sealing agent for organic EL display elements of this invention, a board
  • silane coupling agent examples include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, and the like. These silane coupling agents may be used independently and 2 or more types may be used together.
  • the content of the silane coupling agent is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the polymerizable compound. When the content of the silane coupling agent is within this range, the effect of improving the adhesiveness is suppressed while suppressing the excess silane coupling agent from bleeding out.
  • the minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 5 weight part.
  • the sealing agent for organic EL display elements of the present invention may further contain a surface modifier as long as the object of the present invention is not impaired.
  • a surface modifier By containing the surface modifier, the flatness of the coating film can be imparted to the organic EL display element sealant of the present invention.
  • the surface modifier include surfactants and leveling agents.
  • Examples of the surface modifier include silicone-based and fluorine-based ones.
  • Examples of commercially available surface modifiers include BYK-340, BYK-345 (both manufactured by Big Chemie Japan) and Surflon S-611 (manufactured by AGC Seimi Chemical).
  • the encapsulant for organic EL display elements of the present invention may contain a solvent for the purpose of adjusting the viscosity, but problems such as deterioration of the organic light emitting material layer and generation of outgas due to the remaining solvent. Therefore, it is preferable that the solvent is not contained or the solvent content is 0.05% by weight or less.
  • the sealing agent for organic EL display elements of this invention contains well-known various additives, such as a reinforcing agent, a softening agent, a plasticizer, a viscosity modifier, a ultraviolet absorber, antioxidant, as needed. May be.
  • Examples of the method for producing the sealing agent for organic EL display elements of the present invention include a polymerizable compound using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three roll. And a method of mixing a polymerization initiator and an additive such as a silane coupling agent added if necessary.
  • a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three roll.
  • a method of mixing a polymerization initiator and an additive such as a silane coupling agent added if necessary.
  • the preferable lower limit of the total light transmittance of light at a wavelength of 380 to 800 nm of the cured product of the encapsulant for organic EL display elements of the present invention is 80%.
  • the total light transmittance is 80% or more, the obtained organic EL display element has superior optical characteristics.
  • a more preferable lower limit of the total light transmittance is 85%.
  • cured material used for the measurement of the said total light transmittance is a photocurable sealing agent, it will obtain by, for example, irradiating 3000 mJ / cm ⁇ 2 > of ultraviolet rays with a wavelength of 365 nm with a LED lamp to a sealing agent. If it is a thermosetting sealant, it can be obtained by heating at 80 ° C. for 1 hour, for example.
  • the transmittance at 400 nm after irradiating the cured product with ultraviolet rays for 100 hours is preferably 85% or more at an optical path length of 20 ⁇ m.
  • the transmittance after irradiating the ultraviolet rays for 100 hours is 85% or more, the transparency is high, the loss of light emission is small, and the color reproducibility is excellent.
  • a more preferable lower limit of the transmittance after irradiation with the ultraviolet rays for 100 hours is 90%, and a more preferable lower limit is 95%.
  • the light source for irradiating the ultraviolet rays a conventionally known light source such as a xenon lamp or a carbon arc lamp can be used.
  • permeability after irradiating the said ultraviolet-ray for 100 hours is a photocurable sealing agent, for example, ultraviolet rays with a wavelength of 365 nm will be 3000 mJ / cm with a LED lamp to sealing agent. If it is a thermosetting sealant, it can be obtained, for example, by heating at 80 ° C. for 1 hour.
  • the sealant for an organic EL display device of the present invention has a moisture permeability of 100 g / 100 ⁇ m when the cured product is exposed to an environment of 85 ° C. and 85% RH for 24 hours in accordance with JIS Z 0208.
  • m is preferably 2 or less.
  • the moisture permeability is 100 g / m 2 or less, the effect of preventing moisture from reaching the organic light emitting material layer and the generation of dark spots is improved, and the resulting organic EL display element is more reliable. It will be a thing.
  • cured material used for the said moisture permeability measurement is a photocurable sealing agent, for example, it can obtain by irradiating 3000 mJ / cm ⁇ 2 > of ultraviolet rays with a wavelength of 365 nm with a LED lamp to sealing agent. If it is a thermosetting sealing agent, it can obtain by heating at 80 degreeC for 1 hour, for example.
  • the sealing agent for organic EL display elements of the present invention may have a moisture content of less than 0.5% when the cured product is exposed to an environment of 85 ° C. and 85% RH for 24 hours. preferable.
  • the moisture content of the cured product is less than 0.5%, the effect of preventing the deterioration of the organic light emitting material layer due to moisture in the cured product is excellent, and the obtained organic EL display element is excellent in reliability. It becomes.
  • a more preferable upper limit of the moisture content of the cured product is 0.3%.
  • Examples of the method for measuring the moisture content include a method of obtaining by a Karl Fischer method in accordance with JIS K 7251, and a method of obtaining a weight increment after water absorption in accordance with JIS K 7209-2.
  • cured material used for the measurement of the said moisture content is a photocurable sealing agent, it can obtain by irradiating 3000 mJ / cm ⁇ 2 > of ultraviolet rays with a wavelength of 365 nm with a LED lamp to a sealing agent, for example. If it is a thermosetting sealing agent, it can obtain by heating at 80 degreeC for 1 hour, for example.
  • the sealing agent for organic EL display elements of the present invention 1 is suitably used for coating by an ink jet method
  • the sealing agent for organic EL display elements of the present invention 2 is used for coating by an ink jet method.
  • a method for producing an organic EL display element using the sealing agent for organic EL display elements of the present invention for example, a step of applying the sealing agent for organic EL display elements of the present invention to a substrate by an inkjet method, And a method of curing the applied sealing agent for organic EL display elements by light irradiation and / or heating.
  • the organic EL display element sealant of the present invention may be applied to the entire surface of the substrate, or on a part of the substrate. It may be applied.
  • the shape of the sealing portion of the sealing agent for organic EL display elements of the present invention formed by coating is not particularly limited as long as it is a shape that can protect the laminate having the organic light emitting material layer from the outside air. A shape that completely covers the body may be formed, a closed pattern may be formed in the peripheral portion of the laminate, or a pattern having a shape in which a partial opening is provided in the peripheral portion of the laminate. It may be formed.
  • the organic EL display element sealant of the present invention irradiates light having a wavelength of 300 nm to 400 nm and an accumulated light amount of 300 to 3000 mJ / cm 2. Can be suitably cured.
  • Examples of the light source for irradiating the organic EL display element sealant of the present invention with light include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an excimer laser, a chemical lamp, a black light lamp, and a microwave.
  • Examples include an excited mercury lamp, a metal halide lamp, a sodium lamp, a halogen lamp, a xenon lamp, an LED lamp, a fluorescent lamp, sunlight, and an electron beam irradiation device.
  • These light sources may be used independently and 2 or more types may be used together. These light sources are appropriately selected according to the absorption wavelength of the photo radical polymerization initiator or the photo cationic polymerization initiator.
  • Examples of the light irradiation means to the organic EL display element sealant of the present invention include simultaneous irradiation of various light sources, sequential irradiation with a time difference, combined irradiation of simultaneous irradiation and sequential irradiation, and the like. Any irradiation means may be used.
  • the cured product obtained by the step of curing the organic EL display element sealing agent by light irradiation and / or heating may be further coated with an inorganic material film.
  • the inorganic material forming the inorganic material layer can be a conventionally known, for example, silicon nitride (SiN x), silicon oxide (SiO x), and the like.
  • the inorganic material film may be a single layer or may be a laminate of a plurality of types of layers. Moreover, you may coat
  • the method for producing the organic EL display element comprises a step of bonding a base material (hereinafter also referred to as “one base material”) coated with the organic EL display element sealing agent of the present invention and the other base material.
  • the substrate on which the sealing agent for organic EL display elements of the present invention is applied (hereinafter also referred to as “one substrate”) may be a substrate on which a laminate having an organic light emitting material layer is formed. A base material on which the laminate is not formed may be used.
  • the present invention is applied to the one substrate so that the laminate can be protected from the outside air when the other substrate is bonded. What is necessary is just to apply
  • the sealing agent portion having a closed pattern may be formed in a shape that fits in the shape.
  • the step of curing the organic EL display element sealant by light irradiation and / or heating may be performed before the step of bonding the one base material and the other base material, You may perform after the process of bonding a base material and said other base material.
  • the organic EL display of the present invention preferably has a pot life of 1 minute or longer after irradiation with light and / or heating until the curing reaction proceeds and adhesion becomes impossible. When the pot life is 1 minute or longer, higher adhesion strength can be obtained without excessive curing before the one base material and the other base material are bonded together.
  • a method of bonding the one base material and the other base material is not particularly limited, but it is preferable to bond them in a reduced-pressure atmosphere.
  • the preferable lower limit of the degree of vacuum in the reduced-pressure atmosphere is 0.01 kPa, and the preferable upper limit is 10 kPa.
  • the degree of vacuum in the reduced-pressure atmosphere is within this range, the one base material and the other base material are not spent for a long time to achieve a vacuum state due to the airtightness of the vacuum device and the ability of the vacuum pump. Bubbles in the sealing agent for organic EL display elements of the present invention when the material is bonded can be more efficiently removed.
  • an encapsulant for an organic EL display element that can be easily applied by an ink jet method, can obtain an organic EL display element that is excellent in low outgassing properties and excellent in reliability. Can do.
  • the manufacturing method of this sealing agent for organic EL display elements can be provided.
  • Examples 1 to 7, Comparative Examples 1 to 4 In accordance with the blending ratio described in Table 1, each material was uniformly stirred and mixed at a stirring speed of 3000 rpm using a homodisper type stirring mixer (“Primix Corporation,“ Homodisper L type ”). To 7 and Comparative Examples 1 to 4 were prepared. Each sealing agent for organic EL display elements obtained in Examples 1 to 5 and Comparative Examples 1 and 2 was subjected to a dehydration process in which the mixture was stirred and mixed and then exposed to an environment of 50 ° C. and 0.1 MPa for 30 minutes.
  • each sealing agent for organic EL display elements obtained in Examples and Comparative Examples was performed using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., “VISCOMETER TV-22”) at 25 ° C. and 100 rpm.
  • Table 1 shows the measured viscosity and the surface tension measured at 25 ° C. with a dynamic wettability tester (Reska, “WET-6100”).
  • 10 g of each organic EL display element sealant obtained in Examples and Comparative Examples was placed in a high vessel container and allowed to stand in a constant temperature and humidity chamber at 25 ° C. and 50% RH for 24 hours, and then the Karl Fischer device.
  • this substrate is fixed to the substrate folder of the vacuum evaporation apparatus, and 200 mg of N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine ( ⁇ -NPD) is added to the unglazed crucible.
  • 200 mg of tris (8-quinolinolato) aluminum (Alq 3 ) was put in the crucible, and the pressure in the vacuum chamber was reduced to 1 ⁇ 10 ⁇ 4 Pa. Thereafter, the crucible containing ⁇ -NPD was heated, and ⁇ -NPD was deposited on the substrate at a deposition rate of 15 s / s to form a 600 ⁇ ⁇ hole transport layer.
  • the crucible containing Alq 3 was heated to form an organic light emitting material layer having a thickness of 600 ⁇ at a deposition rate of 15 ⁇ / s. Thereafter, the substrate on which the hole transport layer and the organic light emitting material layer are formed is transferred to another vacuum vapor deposition apparatus, and 200 mg of lithium fluoride is added to a tungsten resistance heating boat in the vacuum vapor deposition apparatus, and an aluminum wire is added to another tungsten boat. 1.0 g was added.
  • the inside of the vapor deposition unit of the vacuum vapor deposition apparatus is depressurized to 2 ⁇ 10 ⁇ 4 Pa to form a lithium fluoride film with a thickness of 5 mm at a deposition rate of 0.2 kg / s, and then aluminum with a film thickness of 1000 mm at a rate of 20 kg / s. did.
  • the inside of the vapor deposition unit was returned to normal pressure with nitrogen, and the substrate on which the laminate having the organic light emitting material layer of 10 mm ⁇ 10 mm was arranged was taken out.
  • a mask having an opening of 13 mm ⁇ 13 mm is installed so as to cover the entire laminated body of the substrate on which the obtained laminated body is arranged, and inorganic by plasma CVD method.
  • a material film A was formed.
  • SiH 4 gas and nitrogen gas are used as source gases, the flow rates of each are SiH 4 gas 10 sccm, nitrogen gas 200 sccm, RF power 10 W (frequency 2.45 GHz), chamber temperature 100 ° C., chamber The test was performed under the condition that the internal pressure was 0.9 Torr.
  • the formed inorganic material film A had a thickness of about 1 ⁇ m.
  • each material was uniformly stirred and mixed at a stirring speed of 3000 rpm using a homodisper type stirring mixer (manufactured by Primics Co., Ltd., “Homodisper L type”).
  • the sealing agent for organic EL display elements was produced by performing the spin-drying
  • the surface tension was measured with a dynamic wettability tester (Reska, “WET-6100”). Moreover, after putting 10 g of obtained sealing agents for organic EL display elements in a high vessel container and leaving it still in a thermostat at 25 ° C. and 50% RH for 24 hours, using a Karl Fischer device, The moisture content of the sealing agent for organic EL display elements was measured under the condition of 50% RH. BHB-160 (manufactured by Kinki Container Co., Ltd.) was used as the high vessel container, and MKC-710S (manufactured by Kyoto Electronics Industry Co., Ltd.) was used as the Karl Fischer apparatus.
  • BHB-160 manufactured by Kinki Container Co., Ltd.
  • MKC-710S manufactured by Kyoto Electronics Industry Co., Ltd.
  • the moisture content was measured for the sealant immediately after taking out from the thermo-hygrostat (within 30 minutes) after standing for 24 hours.
  • the obtained sealant for organic EL display element was alkali-washed with an ink-jet discharge device (“NanoPrinter500” manufactured by Microjet Co., Ltd.) with a droplet volume of 30 picoliters (manufactured by Asahi Glass Co., Ltd.). , “AN100”).
  • the ink jet discharge performance was evaluated by assuming that “ ⁇ ” indicates that the liquid droplets were normally discharged from the ink jet nozzle and landed on the substrate, and “X” indicates that the liquid droplets were not normally discharged.
  • IJH-30 manufactured by IJT was used as an inkjet coating head, and inkjet coating was performed without heating (head temperature 25 ° C.).
  • Example 2 The same sealing agent for organic EL display elements as that prepared in Experimental Example 1 was prepared. Inkjet ejection properties were evaluated in the same manner as in Experimental Example 1 except that IJH-30 (manufactured by IJT) was used as an inkjet coating head and inkjet coating was performed while heating (head temperature 60 ° C.).
  • an encapsulant for an organic EL display element that can be easily applied by an ink jet method, can obtain an organic EL display element that is excellent in low outgassing properties and excellent in reliability. Can do.
  • the manufacturing method of this sealing agent for organic EL display elements can be provided.

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Abstract

The purpose of the present invention is to provide an organic EL display element sealing agent which can easily be applied as a coat using the inkjet method, exhibits low outgassing properties, and makes it possible to obtain a highly reliable organic EL display element. In addition, another purpose of the present invention is to provide a method for producing said organic EL display element sealing agent. To this end, the present invention provides an organic EL display element sealing agent which contains a polymerizable compound and a polymerization initiator, and exhibits a viscosity of 5-50mPa·s at 25°C, a surface tension of 15-35mN/m at 25°C, and a water content of 1,000ppm or less at 25°C after being left for 24 hours in a 25°C, 50%RH environment.

Description

有機ＥＬ表示素子用封止剤及び有機ＥＬ表示素子用封止剤の製造方法Sealant for organic EL display element and method for producing sealant for organic EL display element
本発明は、インクジェット法により容易に塗布することができ、低アウトガス性に優れ、かつ、信頼性に優れる有機ＥＬ表示素子を得ることができる有機ＥＬ表示素子用封止剤に関する。また、本発明は、該有機ＥＬ表示素子用封止剤の製造方法に関する。 The present invention relates to an encapsulant for an organic EL display element that can be easily applied by an ink jet method, can provide an organic EL display element that is excellent in low outgassing properties and excellent in reliability. Moreover, this invention relates to the manufacturing method of this sealing agent for organic EL display elements.
有機エレクトロルミネッセンス（有機ＥＬ）表示素子は、互いに対向する一対の電極間に有機発光材料層が挟持された積層体構造を有し、この有機発光材料層に一方の電極から電子が注入されるとともに他方の電極から正孔が注入されることにより有機発光材料層内で電子と正孔とが結合して発光する。このように有機ＥＬ表示素子は自己発光を行うことから、バックライトを必要とする液晶表示素子等と比較して視認性がよく、薄型化が可能であり、しかも直流低電圧駆動が可能であるという利点を有している。 An organic electroluminescence (organic EL) display element has a laminated structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other, and electrons are injected into the organic light emitting material layer from one electrode. By injecting holes from the other electrode, electrons and holes are combined in the organic light emitting material layer to emit light. Thus, since the organic EL display element performs self-emission, it has better visibility than a liquid crystal display element that requires a backlight, can be reduced in thickness, and can be driven by a DC low voltage. Has the advantage.
有機ＥＬ表示素子を構成する有機発光材料層や電極は、水分や酸素等により特性が劣化しやすいという問題がある。従って、実用的な有機ＥＬ表示素子を得るためには、有機発光材料層や電極を大気と遮断して長寿命化を図る必要がある。特許文献１には、有機ＥＬ表示素子の有機発光材料層と電極とを、ＣＶＤ法により形成した窒化珪素膜と樹脂膜との積層膜により封止する方法が開示されている。ここで樹脂膜は、窒化珪素膜の内部応力による有機層や電極への圧迫を防止する役割を有する。 The organic light-emitting material layer and electrodes constituting the organic EL display element have a problem that the characteristics are easily deteriorated by moisture, oxygen, and the like. Therefore, in order to obtain a practical organic EL display element, it is necessary to extend the life by blocking the organic light emitting material layer and the electrode from the atmosphere. Patent Document 1 discloses a method of sealing an organic light emitting material layer and an electrode of an organic EL display element with a laminated film of a silicon nitride film and a resin film formed by a CVD method. Here, the resin film has a role of preventing pressure on the organic layer and the electrode due to internal stress of the silicon nitride film.
特許文献１に開示された窒化珪素膜で封止を行う方法では、有機ＥＬ表示素子の表面の凹凸や異物の付着、内部応力によるクラックの発生等により、窒化珪素膜を形成する際に有機発光材料層や電極を完全に被覆できないことがある。窒化珪素膜による被覆が不完全であると、水分が窒化珪素膜を通して有機発光材料層内に浸入してしまう。
有機発光材料層内への水分の浸入を防止するための方法として、特許文献２には、無機材料膜と樹脂膜とを交互に蒸着する方法が開示されており、特許文献３や特許文献４には、無機材料膜上に樹脂膜を形成する方法が開示されている。 In the method of sealing with a silicon nitride film disclosed in Patent Document 1, organic light emission occurs when a silicon nitride film is formed due to unevenness on the surface of the organic EL display element, adhesion of foreign matters, generation of cracks due to internal stress, or the like. The material layer or electrode may not be completely covered. If the coating with the silicon nitride film is incomplete, moisture will enter the organic light emitting material layer through the silicon nitride film.
As a method for preventing moisture from entering into the organic light emitting material layer, Patent Document 2 discloses a method of alternately depositing an inorganic material film and a resin film. Patent Document 3 and Patent Document 4 Discloses a method of forming a resin film on an inorganic material film.
樹脂膜を形成する方法として、インクジェット法を用いて基材上に封止剤を塗布した後、該封止剤を硬化させる方法がある。このようなインクジェット法による塗布方法を用いれば、高速かつ均一に樹脂膜を形成することができる。しかしながら、インクジェット法による塗布に適したものとするために封止剤を低粘度となるようにした場合、アウトガスが発生したり、高温高湿環境下では水分の浸入を充分に防止できず、得られる有機ＥＬ表示素子が信頼性に劣るものとなったりする等の問題があった。 As a method for forming a resin film, there is a method in which a sealing agent is applied on a substrate using an inkjet method and then the sealing agent is cured. If such a coating method by the ink jet method is used, a resin film can be uniformly formed at high speed. However, when the sealant is made to have a low viscosity in order to be suitable for application by the ink jet method, outgas is generated, or moisture penetration cannot be sufficiently prevented in a high temperature and high humidity environment. There is a problem that the organic EL display element to be used is inferior in reliability.
特開２０００－２２３２６４号公報JP 2000-223264 A 特表２００５－５２２８９１号公報JP 2005-522891 Gazette 特開２００１－３０７８７３号公報JP 2001-307873 A 特開２００８－１４９７１０号公報JP 2008-149710 A
本発明は、インクジェット法により容易に塗布することができ、低アウトガス性に優れ、かつ、信頼性に優れる有機ＥＬ表示素子を得ることができる有機ＥＬ表示素子用封止剤を提供することを目的とする。また、本発明は、該有機ＥＬ表示素子用封止剤の製造方法を提供することを目的とする。 An object of the present invention is to provide a sealing agent for organic EL display elements that can be easily applied by an ink jet method, can provide an organic EL display element that is excellent in low outgassing properties and excellent in reliability. And Moreover, an object of this invention is to provide the manufacturing method of this sealing agent for organic EL display elements.
本発明１は、重合性化合物と重合開始剤とを含有し、２５℃における粘度が５～５０ｍＰａ・ｓであり、２５℃における表面張力が１５～３５ｍＮ／ｍであり、かつ、２５℃、５０％ＲＨの環境下に２４時間静置した後の２５℃における含水率が１０００ｐｐｍ以下である有機ＥＬ表示素子用封止剤である。
また、本発明２は、インクジェット法による塗布に用いられる有機ＥＬ表示素子用封止剤であって、重合性化合物と重合開始剤とを含有し、２５℃、５０％ＲＨの環境下に２４時間静置した後の２５℃における含水率が１０００ｐｐｍ以下である有機ＥＬ表示素子用封止剤である。
以下に本発明を詳述する。なお、本発明１の有機ＥＬ表示素子用封止剤と本発明２の有機ＥＬ表示素子用封止剤とに共通する事項については、「本発明の有機ＥＬ表示素子用封止剤」として記載する。 The present invention 1 contains a polymerizable compound and a polymerization initiator, has a viscosity at 25 ° C. of 5 to 50 mPa · s, a surface tension at 25 ° C. of 15 to 35 mN / m, and 25 ° C., 50 It is a sealant for organic EL display elements having a water content at 25 ° C. of 1000 ppm or less after standing in an environment of% RH for 24 hours.
In addition, the present invention 2 is an organic EL display element sealing agent used for coating by an ink jet method, which contains a polymerizable compound and a polymerization initiator, and is 24 hours in an environment of 25 ° C. and 50% RH. It is the sealing agent for organic EL display elements whose water content in 25 degreeC after leaving still is 1000 ppm or less.
The present invention is described in detail below. In addition, about the matter common to the sealing agent for organic EL display elements of this invention 1 and the sealing agent for organic EL display elements of this invention 2, it describes as "the sealing agent for organic EL display elements of this invention". To do.
本発明者らは、インクジェット塗布性に優れる有機ＥＬ表示素子用封止剤について、更に、含水率を特定の範囲となるようにすることを検討した。その結果、インクジェット法により容易に塗布することができ、低アウトガス性に優れ、かつ、信頼性に優れる有機ＥＬ表示素子を得ることができる有機ＥＬ表示素子用封止剤を得ることができることを見出し、本発明を完成させるに至った。 The inventors of the present invention have further studied to make the moisture content within a specific range for the sealing agent for organic EL display elements having excellent ink jet coating properties. As a result, it has been found that a sealing agent for organic EL display elements can be obtained that can be easily applied by an ink jet method, can provide an organic EL display element that is excellent in low outgassing properties and excellent in reliability. The present invention has been completed.
本発明の有機ＥＬ表示素子用封止剤は、インクジェット法として、非加熱式インクジェット法による塗布に用いることもできるし、加熱式インクジェット法による塗布に用いることもできる。
なお、本明細書において、上記「非加熱式インクジェット法」は、２８℃未満の塗布ヘッド温度でインクジェット塗布する方法であり、上記「加熱式インクジェット法」は、２８℃以上の塗布ヘッド温度でインクジェット塗布する方法である。 The sealing agent for organic EL display elements of the present invention can be used as an ink jet method for coating by a non-heated ink jet method, or can be used for coating by a heat ink jet method.
In the present specification, the “non-heated ink jet method” is a method of ink jet coating at a coating head temperature of less than 28 ° C., and the “heated ink jet method” is an ink jet at a coating head temperature of 28 ° C. or higher. It is a method of applying.
上記加熱式インクジェット法には、加熱機構を搭載したインクジェット用塗布ヘッドが用いられる。インクジェット塗布ヘッドが加熱機構を搭載していることにより、有機ＥＬ表示素子用封止剤を吐出する際に粘度と表面張力を低下させることができる。 In the heating ink jet method, an ink jet coating head equipped with a heating mechanism is used. When the inkjet coating head is equipped with a heating mechanism, the viscosity and the surface tension can be lowered when discharging the sealing agent for organic EL display elements.
上記加熱機構を搭載したインクジェット用塗布ヘッドとしては、例えば、コニカミノルタ社製のＫＭ１０２４シリーズや、富士フィルムＤｉｍａｔｉｘ社製のＳＧ１０２４シリーズ等が挙げられる。 Examples of the inkjet coating head equipped with the heating mechanism include KM1024 series manufactured by Konica Minolta, SG1024 series manufactured by Fuji Film Dimatix, and the like.
本発明の有機ＥＬ表示素子用封止剤を上記加熱式インクジェット法による塗布に用いる場合、塗布ヘッドの加熱温度は、２８℃～８０℃の範囲であることが好ましい。上記塗布ヘッドの加熱温度がこの範囲であることにより、有機ＥＬ表示素子用封止剤の経時的な粘度上昇が抑制され、吐出安定性により優れるものとなる。 When the sealant for organic EL display elements of the present invention is used for coating by the above-described heating ink jet method, the heating temperature of the coating head is preferably in the range of 28 ° C. to 80 ° C. When the heating temperature of the coating head is within this range, the increase in the viscosity of the sealant for organic EL display elements over time is suppressed, and the ejection stability is improved.
本発明１の有機ＥＬ表示素子用封止剤は、粘度の下限が５ｍＰａ・ｓ、上限が５０ｍＰａ・ｓである。上記粘度がこの範囲であることにより、インクジェット法によって好適に塗布することができる。
なお、本明細書において上記粘度は、Ｅ型粘度計を用いて、２５℃、１００ｒｐｍの条件で測定される値を意味する。 The sealing agent for organic EL display elements of the present invention 1 has a viscosity lower limit of 5 mPa · s and an upper limit of 50 mPa · s. When the viscosity is within this range, it can be suitably applied by an ink jet method.
In addition, the said viscosity in this specification means the value measured on 25 degreeC and 100 rpm conditions using an E-type viscosity meter.
上記非加熱式インクジェット法によって塗布する場合の本発明の有機ＥＬ表示素子用封止剤の粘度の好ましい下限は５ｍＰａ・ｓ、好ましい上限は２０ｍＰａ．ｓである。上記粘度がこの範囲であることにより、非加熱式インクジェット法によって好適に塗布することができる。上記非加熱式インクジェット法によって塗布する場合の本発明の有機ＥＬ表示素子用封止剤の粘度のより好ましい下限は８ｍＰａ・ｓ、より好ましい上限は１６ｍＰａ．ｓ、更に好ましい下限は１０ｍＰａ・ｓ、更に好ましい上限は１３ｍＰａ．ｓである。 The preferable lower limit of the viscosity of the sealing agent for organic EL display elements of the present invention when applied by the non-heating ink jet method is 5 mPa · s, and the preferable upper limit is 20 mPa.s. s. When the viscosity is within this range, it can be suitably applied by a non-heating ink jet method. The more preferable lower limit of the viscosity of the sealing agent for organic EL display elements of the present invention when applied by the non-heating ink jet method is 8 mPa · s, and the more preferable upper limit is 16 mPa · s. s, a more preferred lower limit is 10 mPa · s, and a more preferred upper limit is 13 mPa · s. s.
一方、上記加熱式インクジェット法による塗布に用いる場合の本発明の有機ＥＬ表示素子用封止剤の粘度の好ましい下限は１０ｍＰａ・ｓ、好ましい上限は５０ｍＰａ．ｓである。上記粘度がこの範囲であることにより、加熱式インクジェット法によって好適に塗布することができる。上記加熱式インクジェット法による塗布に用いる場合の本発明の有機ＥＬ表示素子用封止剤の粘度のより好ましい下限は２０ｍＰａ・ｓ、より好ましい上限は４０ｍＰａ．ｓである。 On the other hand, the preferable lower limit of the viscosity of the sealing agent for organic EL display elements of the present invention when used for coating by the heating ink jet method is 10 mPa · s, and the preferable upper limit is 50 mPa · s. s. When the viscosity is within this range, it can be suitably applied by a heating ink jet method. The more preferable lower limit of the viscosity of the sealing agent for organic EL display elements of the present invention when used for coating by the heating ink jet method is 20 mPa · s, and the more preferable upper limit is 40 mPa · s. s.
本発明１の有機ＥＬ表示素子用封止剤は、表面張力の下限が１５ｍＮ／ｍ、上限が３５ｍＮ／ｍである。上記表面張力がこの範囲であることにより、インクジェット法によって好適に塗布することができる。上記表面張力の好ましい下限は２０ｍＮ／ｍ、好ましい上限は３０ｍＮ／ｍ、より好ましい下限は２２ｍＮ／ｍ、より好ましい上限は２８ｍＮ／ｍである。
また、本発明２の有機ＥＬ表示素子用封止剤は、表面張力の好ましい下限が１５ｍＮ／ｍ、好ましい上限が３５ｍＮ／ｍである。上記表面張力がこの範囲であることにより、インクジェット法によって好適に塗布することができる。上記表面張力のより好ましい下限は２０ｍＮ／ｍ、より好ましい上限は３０ｍＮ／ｍ、更に好ましい下限は２２ｍＮ／ｍ、更に好ましい上限は２８ｍＮ／ｍである。
なお、上記表面張力は、２５℃において動的濡れ性試験機によりＷｉｌｈｅｌｍｙ法によって測定された値を意味する。 The sealing agent for organic EL display elements of the present invention 1 has a lower limit of surface tension of 15 mN / m and an upper limit of 35 mN / m. When the surface tension is within this range, it can be suitably applied by an ink jet method. The preferable lower limit of the surface tension is 20 mN / m, the preferable upper limit is 30 mN / m, the more preferable lower limit is 22 mN / m, and the more preferable upper limit is 28 mN / m.
Moreover, the sealing agent for organic EL display elements of the present invention 2 has a preferable lower limit of surface tension of 15 mN / m and a preferable upper limit of 35 mN / m. When the surface tension is within this range, it can be suitably applied by an ink jet method. The more preferable lower limit of the surface tension is 20 mN / m, the more preferable upper limit is 30 mN / m, the still more preferable lower limit is 22 mN / m, and the still more preferable upper limit is 28 mN / m.
The surface tension means a value measured by a Wilhelmy method using a dynamic wettability tester at 25 ° C.
本発明の有機ＥＬ表示素子用封止剤は、２５℃、５０％ＲＨの環境下に２４時間静置した後の２５℃における含水率が１０００ｐｐｍ以下である。上記含水率が１０００ｐｐｍ以下であることにより、得られる有機ＥＬ表示素子が信頼性に優れるものとなる。上記含水率の好ましい上限は８００ｐｐｍ、より好ましい上限は３００ｐｐｍである。
上記含水率は、０ｐｐｍであることが最も好ましい。
なお、上記含水率は、カールフィッシャー装置を用いて、２５℃、５０％ＲＨの環境下の条件で測定することができる。また、上記含水率の測定は、２４時間静置した後３０分以内の封止剤について行う。 The sealing agent for organic EL display elements of the present invention has a water content of 1000 ppm or less at 25 ° C. after standing for 24 hours in an environment of 25 ° C. and 50% RH. When the moisture content is 1000 ppm or less, the obtained organic EL display element has excellent reliability. A preferable upper limit of the water content is 800 ppm, and a more preferable upper limit is 300 ppm.
The water content is most preferably 0 ppm.
In addition, the said moisture content can be measured on 25 degreeC and the conditions of 50% RH environment using a Karl Fischer apparatus. Moreover, the measurement of the said moisture content is performed about the sealing agent within 30 minutes, after leaving still for 24 hours.
上記粘度、上記表面張力、及び、上記含水率は、後述する、重合性化合物、重合開始剤並びに、含有してもよいその他の成分について、これらの種類の選択及び含有割合の調整により、上述した範囲とすることができる。また、上記含水率は、有機ＥＬ表示素子用封止剤の各成分を混合した後に脱水処理を行うことにより容易に１０００ｐｐｍ以下とすることができる。
本発明の有機ＥＬ表示素子用封止剤を製造する方法であって、重合性化合物と重合開始剤及び／又は熱硬化剤とを含有する混合物を１０℃～１００℃、０．１ＭＰａ以下の環境に１５分以上曝す脱水工程を有する有機ＥＬ表示素子用封止剤の製造方法もまた、本発明の１つである。 The viscosity, the surface tension, and the water content are described above by selecting these types and adjusting the content ratio of the polymerizable compound, the polymerization initiator, and other components that may be contained, which will be described later. It can be a range. Moreover, the said moisture content can be easily made into 1000 ppm or less by performing a dehydration process after mixing each component of the sealing agent for organic EL display elements.
A method for producing a sealing agent for an organic EL display device according to the present invention, wherein a mixture containing a polymerizable compound and a polymerization initiator and / or a thermosetting agent is placed in an environment of 10 to 100 ° C. and 0.1 MPa or less. The manufacturing method of the sealing agent for organic EL display elements which has the dehydration process exposed to 15 minutes or more is also one of this invention.
上記脱水工程における温度の好ましい下限は２０℃、好ましい上限は８０℃である。
また、上記脱水工程は２０分以上行うことが好ましい。 The preferable lower limit of the temperature in the dehydration step is 20 ° C, and the preferable upper limit is 80 ° C.
The dehydration step is preferably performed for 20 minutes or longer.
本発明の有機ＥＬ表示素子用封止剤の製造方法における脱水工程以外で有機ＥＬ表示素子用封止剤を脱水処理する他の方法としては、例えば、脱水剤を用いる方法等が挙げられる。
上記脱水剤を用いる方法としては、具体的には例えば、脱水剤を充填したカラムに有機ＥＬ表示素子用封止剤を毎時２．５リットル程度の流速で流す方法や、有機ＥＬ表示素子用封止剤に脱水剤を加えて撹拌した後に１２時間程度放置し、ろ過等によって脱水剤を取り除く方法等が挙げられる。 Other methods for dehydrating the organic EL display element sealant other than the dehydration step in the method for producing an organic EL display element sealant of the present invention include, for example, a method using a dehydrating agent.
Specific examples of the method using the dehydrating agent include a method of flowing a sealing agent for an organic EL display element through a column filled with the dehydrating agent at a flow rate of about 2.5 liters per hour, or a sealing for an organic EL display element. Examples include a method of adding a dehydrating agent to the stopper and stirring the mixture, leaving it for about 12 hours, and removing the dehydrating agent by filtration or the like.
上記脱水剤としては、例えば、モレキュラーシーブス、酸化アルミニウム、塩化カルシウム、酸化カルシウム、酸化マグネシウム、過塩素酸マグネシウム、無水硫酸マグネシウム、酸化燐（Ｖ）、無水炭酸カリウム、シリカゲル、水酸化ナトリウム、無水硫酸ナトリウム、塩化亜鉛等が挙げられる。なかでも、乾燥能力に優れることからモレキュラーシーブスが好ましい。 Examples of the dehydrating agent include molecular sieves, aluminum oxide, calcium chloride, calcium oxide, magnesium oxide, magnesium perchlorate, anhydrous magnesium sulfate, phosphorous oxide (V), anhydrous potassium carbonate, silica gel, sodium hydroxide, and anhydrous sulfuric acid. Examples thereof include sodium and zinc chloride. Of these, molecular sieves are preferable because of their excellent drying ability.
本発明の有機ＥＬ表示素子用封止剤は、重合性化合物を含有する。
上記重合性化合物は、分子内の酸素原子の含有割合が３０％以下である化合物を、重合性化合物全体１００重量部中に２０～９０重量部含有することが好ましい。
本発明者らは、インクジェット法による塗布に適したものとするために封止剤を低粘度とする目的で、重合性化合物として主鎖にポリオキシアルキレン骨格を有する化合物等の分子内の酸素原子の含有割合が多い化合物を用いることを検討した。しかしながら、分子内の酸素原子の含有割合が多い化合物を用いた場合、得られる有機ＥＬ表示素子が、高温高湿環境下に曝した場合にダークスポットを発生させる等、信頼性に劣るものとなりやすくなるという問題があった。そこで本発明者らは鋭意検討した結果、重合性化合物として上記分子内の酸素原子の含有割合が３０％以下である化合物を特定の含有量となるように用いることで、インクジェット塗布性と得られる有機ＥＬ表示素子の信頼性とを容易に両立することができることを見出した。 The sealing agent for organic EL display elements of the present invention contains a polymerizable compound.
The polymerizable compound preferably contains 20 to 90 parts by weight of a compound having an oxygen atom content of 30% or less in the molecule in 100 parts by weight of the entire polymerizable compound.
In order to make the sealing agent low-viscosity in order to make it suitable for coating by an ink jet method, the present inventors have introduced an oxygen atom in a molecule such as a compound having a polyoxyalkylene skeleton in the main chain as a polymerizable compound. The use of a compound with a high content of was studied. However, when a compound having a high oxygen atom content in the molecule is used, the resulting organic EL display element tends to be inferior in reliability, such as generating a dark spot when exposed to a high temperature and high humidity environment. There was a problem of becoming. Therefore, as a result of intensive studies, the present inventors have obtained an ink jet coatability by using a compound having an oxygen atom content of 30% or less as a polymerizable compound so as to have a specific content. It has been found that the reliability of the organic EL display element can be easily achieved.
上記分子内の酸素原子の含有割合が３０％以下である化合物は、分子内の酸素原子の含有割合が２５％以下であることが好ましく、２０％以下であることがより好ましい。
また、上記重合性化合物全体１００重量部中における上記分子内の酸素原子の含有割合が３０％以下である化合物の含有量のより好ましい下限は３０重量部、より好ましい上限は７０重量部である。 The compound having an oxygen atom content in the molecule of 30% or less preferably has an oxygen atom content in the molecule of 25% or less, and more preferably 20% or less.
Moreover, the more preferable lower limit of the content of the compound having an oxygen atom content of 30% or less in 100 parts by weight of the total polymerizable compound is 30 parts by weight, and the more preferable upper limit is 70 parts by weight.
上記重合性化合物としては、ラジカル重合性化合物やカチオン重合性化合物を用いることができる。 As the polymerizable compound, a radical polymerizable compound or a cationic polymerizable compound can be used.
上記ラジカル重合性化合物としては、（メタ）アクリル化合物が好ましい。
上記（メタ）アクリル化合物は、単官能（メタ）アクリル化合物であってもよいし、多官能（メタ）アクリル化合物であってもよく、上記単官能（メタ）アクリル化合物と上記多官能（メタ）アクリル化合物とを組み合わせて用いてもよい。
なお、本明細書において、上記「（メタ）アクリル」は、アクリル又はメタクリルを意味し、上記「（メタ）アクリル化合物」は、（メタ）アクリロイル基を有する化合物を意味し、上記「（メタ）アクリロイル」は、アクリロイル又はメタクリロイルを意味する。 As the radical polymerizable compound, a (meth) acrylic compound is preferable.
The (meth) acrylic compound may be a monofunctional (meth) acrylic compound or a polyfunctional (meth) acrylic compound. The monofunctional (meth) acrylic compound and the polyfunctional (meth) You may use it in combination with an acrylic compound.
In the present specification, the above “(meth) acryl” means acryl or methacryl, the above “(meth) acryl compound” means a compound having a (meth) acryloyl group, and the above “(meth) “Acryloyl” means acryloyl or methacryloyl.
上記単官能（メタ）アクリル化合物は、低アウトガス性等の観点から、カチオン重合性基を有することが好ましい。
上記カチオン重合性基としては、例えば、ビニルエーテル基、エポキシ基、オキセタニル基、アリルエーテル基、ビニル基、水酸基等が挙げられる。 The monofunctional (meth) acrylic compound preferably has a cationic polymerizable group from the viewpoint of low outgassing property.
Examples of the cationic polymerizable group include a vinyl ether group, an epoxy group, an oxetanyl group, an allyl ether group, a vinyl group, and a hydroxyl group.
上記単官能（メタ）アクリル化合物としては、具体的には例えば、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート、グリシジル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレートグリシジルエーテル、（メタ）アクリル酸２－（２－ビニロキシエトキシ）エチル、３－エチル－３－（メタ）アクリルオキシメチルオキセタン、アリル（メタ）アクリレート、メトキシジエチレングリコール（メタ）アクリレート、メトキシトリエチレングリコール（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、エトキシトリエチレングリコール（メタ）アクリレート、２－（２－ビニルオキシエトキシ）エチル（メタ）アクリレート等が挙げられる。なかでも、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレートグリシジルエーテル、（メタ）アクリル酸２－（２－ビニロキシエトキシ）エチルが好ましい。
なお、本明細書において上記「（メタ）アクリレート」は、アクリレート又はメタクリレートを意味する。 Specific examples of the monofunctional (meth) acrylic compound include 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and (meth) acrylic. Acid 2- (2-vinyloxyethoxy) ethyl, 3-ethyl-3- (meth) acryloxymethyloxetane, allyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (Meth) acrylate, ethoxytriethylene glycol (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate and the like. Of these, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and 2- (2-vinyloxyethoxy) ethyl (meth) acrylate are preferable.
In the present specification, the “(meth) acrylate” means acrylate or methacrylate.
上記重合性化合物が上記単官能（メタ）アクリル化合物を含有する場合、上記重合性化合物１００重量部中における上記単官能（メタ）アクリル化合物の含有量の好ましい下限は２０重量部、好ましい上限は８０重量部である。上記単官能（メタ）アクリル化合物の含有量がこの範囲であることにより、得られる有機ＥＬ表示素子用封止剤が低アウトガス性等により優れるものとなる。上記単官能（メタ）アクリル化合物の含有量のより好ましい下限は３０重量部、より好ましい上限は６０重量部である。 When the polymerizable compound contains the monofunctional (meth) acrylic compound, the preferred lower limit of the content of the monofunctional (meth) acrylic compound in 100 parts by weight of the polymerizable compound is 20 parts by weight, and the preferred upper limit is 80. Parts by weight. When the content of the monofunctional (meth) acrylic compound is within this range, the obtained sealing agent for organic EL display elements is excellent due to low outgassing properties and the like. The minimum with more preferable content of the said monofunctional (meth) acryl compound is 30 weight part, and a more preferable upper limit is 60 weight part.
上記多官能（メタ）アクリル化合物は、インクジェット塗布性等の観点から、主鎖にポリオキシアルキレン骨格を有することが好ましい。ただし、上述したように、分子内の酸素原子の含有割合が多い化合物を用いた場合、得られる有機ＥＬ表示素子が信頼性に劣るものとなりやすくなるため、主鎖にポリオキシアルキレン骨格を有する多官能（メタ）アクリル化合物を用いる場合は、その含有量を調整することが好ましい。即ち、上記分子内の酸素原子の含有割合が３０％以下である化合物の含有量が上述した範囲となるように、該主鎖にポリオキシアルキレン骨格を有する多官能（メタ）アクリル化合物の含有量を調整することが好ましい。
上記ポリオキシアルキレン骨格は、オキシアルキレン単位が２～６個連続したものであることが好ましい。
上記ポリオキシアルキレン骨格を構成するオキシアルキレン単位としては、オキシエチレン単位、オキシプロピレン単位等が挙げられる。 The polyfunctional (meth) acrylic compound preferably has a polyoxyalkylene skeleton in the main chain from the viewpoint of inkjet coating properties and the like. However, as described above, when a compound having a high content of oxygen atoms in the molecule is used, the obtained organic EL display element tends to be inferior in reliability, and thus a polyoxyalkylene skeleton in the main chain is likely to be obtained. When using a functional (meth) acryl compound, it is preferable to adjust the content. That is, the content of the polyfunctional (meth) acrylic compound having a polyoxyalkylene skeleton in the main chain so that the content of the compound having an oxygen atom content in the molecule of 30% or less falls within the above-described range. Is preferably adjusted.
The polyoxyalkylene skeleton is preferably a series of 2 to 6 oxyalkylene units.
Examples of oxyalkylene units constituting the polyoxyalkylene skeleton include oxyethylene units and oxypropylene units.
上記多官能（メタ）アクリル化合物は、インクジェット塗布性等の観点から、炭素鎖の分岐が少ない構造であることが好ましく、直鎖状であることがより好ましい。 The polyfunctional (meth) acrylic compound preferably has a structure with less carbon chain branching, and more preferably is a straight chain, from the viewpoint of inkjet coating properties and the like.
上記多官能（メタ）アクリル化合物としては、具体的には例えば、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、テトラプロピレングリコールジ（メタ）アクリレート、ポリテトラメチレングリコールジ（メタ）アクリレート等が挙げられる。なかでも、テトラエチレングリコールジ（メタ）アクリレートが好ましい。 Specific examples of the polyfunctional (meth) acrylic compound include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and dipropylene glycol di (meth) acrylate. , Tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, and the like. Of these, tetraethylene glycol di (meth) acrylate is preferable.
上記重合性化合物が上記多官能（メタ）アクリル化合物を含有する場合、上記重合性化合物１００重量部中における上記多官能（メタ）アクリル化合物の含有量の好ましい下限は２０重量部、好ましい上限は８０重量部である。上記多官能（メタ）アクリル化合物の含有量がこの範囲であることにより、得られる有機ＥＬ表示素子用封止剤がインクジェット塗布性等により優れるものとなる。上記多官能（メタ）アクリル化合物の含有量のより好ましい下限は３０重量部、より好ましい上限は６０重量部である。 When the polymerizable compound contains the polyfunctional (meth) acrylic compound, the preferred lower limit of the content of the polyfunctional (meth) acrylic compound in 100 parts by weight of the polymerizable compound is 20 parts by weight, and the preferred upper limit is 80. Parts by weight. When the content of the polyfunctional (meth) acrylic compound is within this range, the obtained sealing agent for organic EL display elements is excellent in ink jet coating properties and the like. The minimum with more preferable content of the said polyfunctional (meth) acryl compound is 30 weight part, and a more preferable upper limit is 60 weight part.
上記単官能（メタ）アクリル化合物と上記多官能（メタ）アクリル化合物とを組み合わせて用いる場合、上記単官能（メタ）アクリル化合物と上記多官能（メタ）アクリル化合物との含有割合は、重量比で、単官能（メタ）アクリル化合物：多官能（メタ）アクリル化合物＝７：３～３：７であることが好ましい。上記単官能（メタ）アクリル化合物と上記多官能（メタ）アクリル化合物との含有割合をこの範囲とすることにより、得られる有機ＥＬ表示素子用封止剤を、インクジェット塗布性等により優れるものとすることができる。上記単官能（メタ）アクリル化合物と上記多官能（メタ）アクリル化合物との含有割合は、重量比で、単官能（メタ）アクリル化合物：多官能（メタ）アクリル化合物＝６：４～４：６であることがより好ましい。 When the monofunctional (meth) acrylic compound and the polyfunctional (meth) acrylic compound are used in combination, the content ratio of the monofunctional (meth) acrylic compound and the polyfunctional (meth) acrylic compound is expressed as a weight ratio. Monofunctional (meth) acrylic compound: polyfunctional (meth) acrylic compound = 7: 3 to 3: 7 is preferable. By setting the content ratio of the monofunctional (meth) acrylic compound and the polyfunctional (meth) acrylic compound in this range, the obtained sealing agent for organic EL display elements is excellent in ink jet coating properties and the like. be able to. The content ratio of the monofunctional (meth) acrylic compound and the polyfunctional (meth) acrylic compound is, by weight ratio, monofunctional (meth) acrylic compound: polyfunctional (meth) acrylic compound = 6: 4 to 4: 6. It is more preferable that
上記カチオン重合性化合物としては、例えば、エポキシ化合物、オキセタン化合物、ビニルエーテル化合物等が挙げられる。 As said cationically polymerizable compound, an epoxy compound, an oxetane compound, a vinyl ether compound etc. are mentioned, for example.
上記エポキシ化合物としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＥ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビスフェノールＯ型エポキシ樹脂、２，２’－ジアリルビスフェノールＡ型エポキシ樹脂、脂環式エポキシ樹脂、水添ビスフェノール型エポキシ樹脂、プロピレンオキシド付加ビスフェノールＡ型エポキシ樹脂、レゾルシノール型エポキシ樹脂、ビフェニル型エポキシ樹脂、スルフィド型エポキシ樹脂、ジフェニルエーテル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ナフタレン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、オルトクレゾールノボラック型エポキシ樹脂、ジシクロペンタジエンノボラック型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、ナフタレンフェノールノボラック型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、アルキルポリオール型エポキシ樹脂、ゴム変性型エポキシ樹脂、グリシジルエステル化合物、１，６－ヘキサンジオールジグリシジルエーテル等が挙げられる。なかでも、脂環式エポキシ樹脂が好ましい。
上記脂環式エポキシ樹脂のうち市販されているものとしては、例えば、セロキサイド２０００、セロキサイド２０２１Ｐ、セロキサイド２０８１、セロキサイド３０００、セロキサイド８０００（いずれもダイセル社製）、サンソサイザーＥＰＳ（新日本理化工業社製）等が挙げられる。 Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol O type epoxy resin, 2,2′-diallyl bisphenol A type epoxy resin, Alicyclic epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene Epoxy resin, phenol novolac epoxy resin, orthocresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl Examples thereof include a volac type epoxy resin, a naphthalene phenol novolac type epoxy resin, a glycidyl amine type epoxy resin, an alkyl polyol type epoxy resin, a rubber-modified epoxy resin, a glycidyl ester compound, and 1,6-hexanediol diglycidyl ether. Of these, alicyclic epoxy resins are preferred.
Examples of commercially available alicyclic epoxy resins include Celoxide 2000, Celoxide 2021P, Celoxide 2081, Celoxide 3000, Celoxide 8000 (all manufactured by Daicel), and Sunsizer EPS (manufactured by Shin Nippon Rika Kogyo Co., Ltd.). ) And the like.
上記オキセタン化合物としては、例えば、アリルオキシオキセタン、フェノキシメチルオキセタン、３－エチル－３－ヒドロキシメチルオキセタン、３－エチル－３－（フェノキシメチル）オキセタン、３－エチル－３－（（２－エチルヘキシルオキシ）メチル）オキセタン、３－エチル－３－（（３－（トリエトキシシリル）プロポキシ）メチル）オキセタン、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、オキセタニルシルセスキオキサン、フェノールノボラックオキセタン、１，４－ビス（（（３－エチル－３－オキセタニル）メトキシ）メチル）ベンゼン等が挙げられる。 Examples of the oxetane compound include allyloxyoxetane, phenoxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3-((2-ethylhexyloxy ) Methyl) oxetane, 3-ethyl-3-((3- (triethoxysilyl) propoxy) methyl) oxetane, 3-ethyl-3-((((3-ethyloxetane-3-yl) methoxy) methyl) oxetane, Examples include oxetanylsilsesquioxane, phenol novolac oxetane, 1,4-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) benzene.
上記ビニルエーテル化合物としては、例えば、ベンジルビニルエーテル、シクロヘキサンジメタノールモノビニルエーテル、ジシクロペンタジエンビニルエーテル、１，４－ブタンジオールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、ジプロピレングリコールジビニルエーテル、トリプロピレングリコールジビニルエーテル等が挙げられる。 Examples of the vinyl ether compound include benzyl vinyl ether, cyclohexane dimethanol monovinyl ether, dicyclopentadiene vinyl ether, 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, dipropylene glycol. Examples thereof include divinyl ether and tripropylene glycol divinyl ether.
本発明の有機ＥＬ表示素子用封止剤は、重合開始剤を含有する。
上記重合開始剤としては、用いる重合性化合物の種類等に応じて、光ラジカル重合開始剤や、熱ラジカル重合開始剤や、光カチオン重合開始剤や、熱カチオン重合開始剤が好適に用いられる。 The sealing agent for organic EL display elements of the present invention contains a polymerization initiator.
As the polymerization initiator, a radical photopolymerization initiator, a thermal radical polymerization initiator, a cationic photopolymerization initiator, or a thermal cationic polymerization initiator is suitably used depending on the type of polymerizable compound used.
上記光ラジカル重合開始剤としては、例えば、ベンゾフェノン系化合物、アセトフェノン系化合物、アシルフォスフィンオキサイド系化合物、チタノセン系化合物、オキシムエステル系化合物、ベンゾインエーテル系化合物、ベンジル、チオキサントン系化合物等が挙げられる。 Examples of the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, benzyl, thioxanthone compounds, and the like.
上記光ラジカル重合開始剤のうち市販されているものとしては、例えば、ＩＲＧＡＣＵＲＥ１８４、ＩＲＧＡＣＵＲＥ３６９、ＩＲＧＡＣＵＲＥ３７９、ＩＲＧＡＣＵＲＥ６５１、ＩＲＧＡＣＵＲＥ８１９、ＩＲＧＡＣＵＲＥ９０７、ＩＲＧＡＣＵＲＥ２９５９、ＩＲＧＡＣＵＲＥ　ＯＸＥ０１、ルシリンＴＰＯ（いずれもＢＡＳＦ社製）、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル（いずれも東京化成工業社製）等が挙げられる。 Examples of commercially available photo radical polymerization initiators include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucin TPO (both benzoin methyl ether, benzoin methyl ether) Examples include ethyl ether and benzoin isopropyl ether (both manufactured by Tokyo Chemical Industry Co., Ltd.).
上記熱ラジカル重合開始剤としては、例えば、アゾ化合物、有機過酸化物等からなるものが挙げられる。
上記アゾ化合物としては、例えば、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、アゾビスイソブチロニトリル等が挙げられる。
上記有機過酸化物としては、例えば、過酸化ベンゾイル、ケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、パーオキシエステル、ジアシルパーオキサイド、パーオキシジカーボネート等が挙げられる。 As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
Examples of the azo compound include 2,2′-azobis (2,4-dimethylvaleronitrile), azobisisobutyronitrile, and the like.
Examples of the organic peroxide include benzoyl peroxide, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
上記熱ラジカル重合開始剤のうち市販されているものとしては、例えば、ＶＰＥ－０２０１、ＶＰＥ－０４０１、ＶＰＥ－０６０１、ＶＰＳ－０５０１、ＶＰＳ－１００１、Ｖ－５０１（いずれも和光純薬工業社製）等が挙げられる。 Examples of commercially available thermal radical polymerization initiators include VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001, and V-501 (all manufactured by Wako Pure Chemical Industries, Ltd.). ) And the like.
上記光カチオン重合開始剤は、光照射によりプロトン酸又はルイス酸を発生するものであれば特に限定されず、イオン性光酸発生型であってもよいし、非イオン性光酸発生型であってもよい。 The photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid generating type or a nonionic photoacid generating type. May be.
上記イオン性光酸発生型の光カチオン重合開始剤のアニオン部分としては、例えば、ＢＦ４ －、ＰＦ６ －、ＳｂＦ６ －、又は、（ＢＸ４）－（但し、Ｘは、少なくとも２つ以上のフッ素又はトリフルオロメチル基で置換されたフェニル基を表す）等が挙げられる。
上記イオン性光酸発生型の光カチオン重合開始剤としては、例えば、上記アニオン部分を有する、芳香族スルホニウム塩、芳香族ヨードニウム塩、芳香族ジアゾニウム塩、芳香族アンモニウム塩、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ塩等が挙げられる。 Examples of the anion portion of the ionic photoacid-generating photocationic polymerization initiator include BF 4 − , PF 6 − , SbF 6 − , and (BX 4 ) − (wherein X is at least two or more. And a phenyl group substituted with a fluorine or trifluoromethyl group).
Examples of the ionic photoacid-generating photocationic polymerization initiator include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts having the above anion moiety, and (2,4-cyclohexane). And pentadien-1-yl) ((1-methylethyl) benzene) -Fe salt.
上記芳香族スルホニウム塩としては、例えば、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロホスフェート、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロアンチモネート、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドビステトラフルオロボレート、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドテトラキス（ペンタフルオロフェニル）ボレート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムヘキサフルオロホスフェート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムヘキサフルオロアンチモネート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムテトラフルオロボレート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムテトラキス（ペンタフルオロフェニル）ボレート、トリフェニルスルホニウムヘキサフルオロホスフェート、トリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムテトラフルオロボレート、トリフェニルスルホニウムテトラキス（ペンタフルオロフェニル）ボレート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロホスフェート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロアンチモネート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドビステトラフルオロボレート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドテトラキス（ペンタフルオロフェニル）ボレート、トリス（４－（４－アセチルフェニル）チオフェニル）スルホニウムテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。 Examples of the aromatic sulfonium salt include bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluoroantimonate, and bis (4- ( Diphenylsulfonio) phenyl) sulfide bistetrafluoroborate, bis (4- (diphenylsulfonio) phenyl) sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- ( Phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) Phenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis (4- (di ( 4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bishexafluoroantimonate, Bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bistetrafluoroborate, bis (4- (di ( - (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide tetrakis (pentafluorophenyl) borate, tris (4- (4-acetylphenyl) thiophenyl) sulfonium tetrakis (pentafluorophenyl) borate, and the like.
上記芳香族ヨードニウム塩としては、例えば、ジフェニルヨードニウムヘキサフルオロホスフェート、ジフェニルヨードニウムヘキサフルオロアンチモネート、ジフェニルヨードニウムテトラフルオロボレート、ジフェニルヨードニウムテトラキス（ペンタフルオロフェニル）ボレート、ビス（ドデシルフェニル）ヨードニウムヘキサフルオロホスフェート、ビス（ドデシルフェニル）ヨードニウムヘキサフルオロアンチモネート、ビス（ドデシルフェニル）ヨードニウムテトラフルオロボレート、ビス（ドデシルフェニル）ヨードニウムテトラキス（ペンタフルオロフェニル）ボレート、４－メチルフェニル－４－（１－メチルエチル）フェニルヨードニウムヘキサフルオロホスフェート、４－メチルフェニル－４－（１－メチルエチル）フェニルヨードニウムヘキサフルオロアンチモネート、４－メチルフェニル－４－（１－メチルエチル）フェニルヨードニウムテトラフルオロボレート、４－メチルフェニル－４－（１－メチルエチル）フェニルヨードニウムテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。 Examples of the aromatic iodonium salt 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, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexa Fluorophosphate, 4-methylphenyl-4- (1-methylethyl) Such as phenyl iodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate Can be mentioned.
上記芳香族ジアゾニウム塩としては、例えば、フェニルジアゾニウムヘキサフルオロホスフェート、フェニルジアゾニウムヘキサフルオロアンチモネート、フェニルジアゾニウムテトラフルオロボレート、フェニルジアゾニウムテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。 Examples of the aromatic diazonium salt include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate.
上記芳香族アンモニウム塩としては、例えば、１－ベンジル－２－シアノピリジニウムヘキサフルオロホスフェート、１－ベンジル－２－シアノピリジニウムヘキサフルオロアンチモネート、１－ベンジル－２－シアノピリジニウムテトラフルオロボレート、１－ベンジル－２－シアノピリジニウムテトラキス（ペンタフルオロフェニル）ボレート、１－（ナフチルメチル）－２－シアノピリジニウムヘキサフルオロホスフェート、１－（ナフチルメチル）－２－シアノピリジニウムヘキサフルオロアンチモネート、１－（ナフチルメチル）－２－シアノピリジニウムテトラフルオロボレート、１－（ナフチルメチル）－２－シアノピリジニウムテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。 Examples of the aromatic ammonium salt include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl -2-Cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) Examples include -2-cyanopyridinium tetrafluoroborate and 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate.
上記（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ塩としては、例えば、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ（ＩＩ）ヘキサフルオロホスフェート、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ（ＩＩ）ヘキサフルオロアンチモネート、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ（ＩＩ）テトラフルオロボレート、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ（ＩＩ）テトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。 Examples of the (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salt include (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene. ) -Fe (II) hexafluorophosphate, (2,4-cyclopentadiene-1-yl) ((1-methylethyl) benzene) -Fe (II) hexafluoroantimonate, (2,4-cyclopentadiene-1 -Yl) ((1-methylethyl) benzene) -Fe (II) tetrafluoroborate, (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe (II) tetrakis (penta Fluorophenyl) borate and the like.
上記非イオン性光酸発生型の光カチオン重合開始剤としては、例えば、ニトロベンジルエステル、スルホン酸誘導体、リン酸エステル、フェノールスルホン酸エステル、ジアゾナフトキノン、Ｎ－ヒドロキシイミドスルホネート等が挙げられる。 Examples of the nonionic photoacid-generating photocationic polymerization initiator include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenol sulfonic acid ester, diazonaphthoquinone, N-hydroxyimide sulfonate, and the like.
上記光カチオン重合開始剤のうち市販されているものとしては、例えば、ＤＴＳ－２００（みどり化学社製）、ＵＶＩ６９９０、ＵＶＩ６９７４（いずれもユニオンカーバイド社製）、ＳＰ－１５０、ＳＰ－１７０（いずれもＡＤＥＫＡ社製）、ＦＣ－５０８、ＦＣ－５１２（いずれも３Ｍ社製）、ＩＲＧＡＣＵＲＥ２６１、ＩＲＧＡＣＵＲＥ２９０（いずれもＢＡＳＦ社製）、ＰＩ２０７４（ローディア社製）等が挙げられる。 Examples of commercially available photocationic polymerization initiators include, for example, DTS-200 (manufactured by Midori Chemical Co., Ltd.), UVI6990, UVI6974 (all manufactured by Union Carbide), SP-150, SP-170 (all ADEKA), FC-508, FC-512 (all from 3M), IRGACURE261, IRGACURE290 (all from BASF), PI2074 (from Rhodia), and the like.
上記熱カチオン重合開始剤としては、アニオン部分がＢＦ４ －、ＰＦ６ －、ＳｂＦ６ －、又は、（ＢＸ４）－（但し、Ｘは、少なくとも２つ以上のフッ素又はトリフルオロメチル基で置換されたフェニル基を表す）で構成される、スルホニウム塩、ホスホニウム塩、アンモニウム塩等が挙げられる。なかでも、スルホニウム塩、アンモニウム塩が好ましい。 As the thermal cationic polymerization initiator, the anion moiety is BF 4 − , PF 6 − , SbF 6 − , or (BX 4 ) − (where X is substituted with at least two fluorine or trifluoromethyl groups A sulfonium salt, a phosphonium salt, an ammonium salt, and the like. Of these, sulfonium salts and ammonium salts are preferable.
上記スルホニウム塩としては、トリフェニルスルホニウムテトラフルオロボレート、トリフェニルスルホニウムヘキサフルオロアンチモネート等が挙げられる。 Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate and triphenylsulfonium hexafluoroantimonate.
上記ホスホニウム塩としては、エチルトリフェニルホスホニウムヘキサフルオロアンチモネート、テトラブチルホスホニウムヘキサフルオロアンチモネート等が挙げられる。 Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.
上記アンモニウム塩としては、例えば、ジメチルフェニル（４－メトキシベンジル）アンモニウムヘキサフルオロホスフェート、ジメチルフェニル（４－メトキシベンジル）アンモニウムヘキサフルオロアンチモネート、ジメチルフェニル（４－メトキシベンジル）アンモニウムテトラキス（ペンタフルオロフェニル）ボレート、ジメチルフェニル（４－メチルベンジル）アンモニウムヘキサフルオロホスフェート、ジメチルフェニル（４－メチルベンジル）アンモニウムヘキサフルオロアンチモネート、ジメチルフェニル（４－メチルベンジル）アンモニウムヘキサフルオロテトラキス（ペンタフルオロフェニル）ボレート、メチルフェニルジベンジルアンモニウムヘキサフルオロホスフェート、メチルフェニルジベンジルアンモニウムヘキサフルオロアンチモネート、メチルフェニルジベンジルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、フェニルトリベンジルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、ジメチルフェニル（３，４－ジメチルベンジル）アンモニウムテトラキス（ペンタフルオロフェニル）ボレート、Ｎ，Ｎ－ジメチル－Ｎ－ベンジルアニリニウムヘキサフルオロアンチモネート、Ｎ，Ｎ－ジエチル－Ｎ－ベンジルアニリニウムテトラフルオロボレート、Ｎ，Ｎ－ジメチル－Ｎ－ベンジルピリジニウムヘキサフルオロアンチモネート、Ｎ，Ｎ－ジエチル－Ｎ－ベンジルピリジニウムトリフルオロメタンスルホン酸等が挙げられる。 Examples of the ammonium salt include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (pentafluorophenyl). Borate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) borate, methylphenyl Dibenzylammonium hexafluorophosphate, methylphenyldibenzylammonium Safluoroantimonate, methylphenyldibenzylammonium tetrakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3,4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) borate, N , N-dimethyl-N-benzylanilinium hexafluoroantimonate, N, N-diethyl-N-benzylanilinium tetrafluoroborate, N, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N, N-diethyl -N-benzylpyridinium trifluoromethanesulfonic acid and the like.
上記熱カチオン重合開始剤のうち市販されているものとしては、例えば、サンエイドＳＩ－６０、サンエイドＳＩ－８０、サンエイドＳＩ－Ｂ３、サンエイドＳＩ－Ｂ３Ａ、サンエイドＳＩ－Ｂ４（いずれも三新化学工業社製）、ＣＸＣ１６１２、ＣＸＣ１８２１（いずれもＫｉｎｇ　Ｉｎｄｕｓｔｒｉｅｓ社製）等が挙げられる。 Commercially available thermal cationic polymerization initiators include, for example, Sun-Aid SI-60, Sun-Aid SI-80, Sun-Aid SI-B3, Sun-Aid SI-B3A, Sun-Aid SI-B4 (all of which are Sanshin Chemical Industry Co., Ltd.). CXC1612, CXC1821 (all manufactured by King Industries) and the like.
上記重合開始剤の含有量は、上記重合性化合物１００重量部に対して、好ましい下限が０．０１重量部、好ましい上限が１０重量部である。上記重合開始剤の含有量が０．０１重量部以上であることにより、得られる有機ＥＬ表示素子用封止剤が硬化性により優れるものとなる。上記重合開始剤の含有量が１０重量部以下であることにより、得られる有機ＥＬ表示素子用封止剤の硬化反応が速くなり過ぎず、作業性により優れるものとなり、硬化物をより均一なものとすることができる。上記重合開始剤の含有量のより好ましい下限は０．０５重量部、より好ましい上限は５重量部である。 The content of the polymerization initiator is preferably 0.01 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the polymerizable compound. When the content of the polymerization initiator is 0.01 parts by weight or more, the obtained sealing agent for organic EL display elements is more excellent in curability. When the content of the polymerization initiator is 10 parts by weight or less, the curing reaction of the obtained sealing agent for organic EL display elements does not become too fast, and the workability is improved, and the cured product is more uniform. It can be. The minimum with more preferable content of the said polymerization initiator is 0.05 weight part, and a more preferable upper limit is 5 weight part.
本発明の有機ＥＬ表示素子用封止剤は、増感剤を含有してもよい。上記増感剤は、上記重合開始剤の重合開始効率をより向上させて、本発明の有機ＥＬ表示素子用封止剤の硬化反応をより促進させる役割を有する。 The sealing agent for organic EL display elements of the present invention may contain a sensitizer. The sensitizer has a role of further improving the polymerization initiation efficiency of the polymerization initiator and further promoting the curing reaction of the sealing agent for organic EL display elements of the present invention.
上記増感剤としては、例えば、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や、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等が挙げられる。 Examples of the sensitizer include thioxanthone compounds such as 2,4-diethylthioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 2,4-dichlorobenzophenone, o- Examples include methyl benzoylbenzoate, 4,4′-bis (dimethylamino) benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, and the like.
上記増感剤の含有量は、上記重合性化合物１００重量部に対して、好ましい下限が０．０１重量部、好ましい上限が３重量部である。上記増感剤の含有量が０．０１重量部以上であることにより、増感効果がより発揮される。上記増感剤の含有量が３重量部以下であることにより、吸収が大きくなり過ぎずに深部まで光を伝えることができる。上記増感剤の含有量のより好ましい下限は０．１重量部、より好ましい上限は１重量部である。 The content of the sensitizer is preferably 0.01 parts by weight and preferably 3 parts by weight with respect to 100 parts by weight of the polymerizable compound. When the content of the sensitizer is 0.01 parts by weight or more, the sensitizing effect is more exhibited. When the content of the sensitizer is 3 parts by weight or less, light can be transmitted to a deep part without excessive absorption. The minimum with more preferable content of the said sensitizer is 0.1 weight part, and a more preferable upper limit is 1 weight part.
本発明の有機ＥＬ表示素子用封止剤は、シランカップリング剤を含有してもよい。上記シランカップリング剤は、本発明の有機ＥＬ表示素子用封止剤と基板等との接着性を向上させる役割を有する。 The sealing agent for organic EL display elements of the present invention may contain a silane coupling agent. The said silane coupling agent has a role which improves the adhesiveness of the sealing agent for organic EL display elements of this invention, a board | substrate, etc.
上記シランカップリング剤としては、例えば、３－アミノプロピルトリメトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－イソシアネートプロピルトリメトキシシラン等が挙げられる。これらのシランカップリング剤は単独で用いられてもよいし、２種以上が併用されてもよい。 Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, and the like. These silane coupling agents may be used independently and 2 or more types may be used together.
上記シランカップリング剤の含有量は、上記重合性化合物１００重量部に対して、好ましい下限が０．１重量部、好ましい上限が１０重量部である。上記シランカップリング剤の含有量がこの範囲であることにより、余剰のシランカップリング剤がブリードアウトすることを抑制しつつ、接着性を向上させる効果により優れるものとなる。上記シランカップリング剤の含有量のより好ましい下限は０．５重量部、より好ましい上限は５重量部である。 The content of the silane coupling agent is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the polymerizable compound. When the content of the silane coupling agent is within this range, the effect of improving the adhesiveness is suppressed while suppressing the excess silane coupling agent from bleeding out. The minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 5 weight part.
本発明の有機ＥＬ表示素子用封止剤は、更に、本発明の目的を阻害しない範囲において、表面改質剤を含有してもよい。上記表面改質剤を含有することにより、本発明の有機ＥＬ表示素子用封止剤に塗膜の平坦性を付与することができる。
上記表面改質剤としては、例えば、界面活性剤やレベリング剤等が挙げられる。 The sealing agent for organic EL display elements of the present invention may further contain a surface modifier as long as the object of the present invention is not impaired. By containing the surface modifier, the flatness of the coating film can be imparted to the organic EL display element sealant of the present invention.
Examples of the surface modifier include surfactants and leveling agents.
上記表面改質剤としては、例えば、シリコーン系やフッ素系等のものが挙げられる。
上記表面改質剤のうち市販されているものとしては、例えば、ＢＹＫ－３４０、ＢＹＫ－３４５（いずれもビックケミー・ジャパン社製）、サーフロンＳ－６１１（ＡＧＣセイミケミカル社製）等が挙げられる。 Examples of the surface modifier include silicone-based and fluorine-based ones.
Examples of commercially available surface modifiers include BYK-340, BYK-345 (both manufactured by Big Chemie Japan) and Surflon S-611 (manufactured by AGC Seimi Chemical).
本発明の有機ＥＬ表示素子用封止剤は、粘度調整等を目的として溶剤を含有してもよいが、残存した溶剤により、有機発光材料層が劣化したりアウトガスが発生したりする等の問題が生じるおそれがあるため、溶剤を含有しない、又は、溶剤の含有量が０．０５重量％以下であることが好ましい。 The encapsulant for organic EL display elements of the present invention may contain a solvent for the purpose of adjusting the viscosity, but problems such as deterioration of the organic light emitting material layer and generation of outgas due to the remaining solvent. Therefore, it is preferable that the solvent is not contained or the solvent content is 0.05% by weight or less.
また、本発明の有機ＥＬ表示素子用封止剤は、必要に応じて、補強剤、軟化剤、可塑剤、粘度調整剤、紫外線吸収剤、酸化防止剤等の公知の各種添加剤を含有してもよい。 Moreover, the sealing agent for organic EL display elements of this invention contains well-known various additives, such as a reinforcing agent, a softening agent, a plasticizer, a viscosity modifier, a ultraviolet absorber, antioxidant, as needed. May be.
本発明の有機ＥＬ表示素子用封止剤を製造する方法としては、例えば、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本ロール等の混合機を用いて、重合性化合物と、重合開始剤と、必要に応じて添加するシランカップリング剤等の添加剤とを混合する方法等が挙げられる。 Examples of the method for producing the sealing agent for organic EL display elements of the present invention include a polymerizable compound using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three roll. And a method of mixing a polymerization initiator and an additive such as a silane coupling agent added if necessary.
本発明の有機ＥＬ表示素子用封止剤の硬化物の波長３８０～８００ｎｍにおける光の全光線透過率の好ましい下限は８０％である。上記全光線透過率が８０％以上であることにより、得られる有機ＥＬ表示素子が光学特性により優れるものとなる。上記全光線透過率のより好ましい下限は８５％である。
上記全光線透過率は、例えば、ＡＵＴＯＭＡＴＩＣ　ＨＡＺＥ　ＭＡＴＥＲ　ＭＯＤＥＬ　ＴＣ＝ＩＩＩ　ＤＰＫ（東京電色社製）等の分光計を用いて測定することができる。
また、上記全光線透過率の測定に用いる硬化物は、光硬化性の封止剤であれば、例えば、封止剤にＬＥＤランプにて波長３６５ｎｍの紫外線を３０００ｍＪ／ｃｍ２照射することにより得ることができ、熱硬化性の封止剤であれば、例えば、８０℃で１時間加熱することにより得ることができる。 The preferable lower limit of the total light transmittance of light at a wavelength of 380 to 800 nm of the cured product of the encapsulant for organic EL display elements of the present invention is 80%. When the total light transmittance is 80% or more, the obtained organic EL display element has superior optical characteristics. A more preferable lower limit of the total light transmittance is 85%.
The total light transmittance can be measured using a spectrometer such as AUTOMATIC HAZE MATER MODEL TC = III DPK (manufactured by Tokyo Denshoku Co., Ltd.).
Moreover, if the hardened | cured material used for the measurement of the said total light transmittance is a photocurable sealing agent, it will obtain by, for example, irradiating 3000 mJ / cm < 2 > of ultraviolet rays with a wavelength of 365 nm with a LED lamp to a sealing agent. If it is a thermosetting sealant, it can be obtained by heating at 80 ° C. for 1 hour, for example.
本発明の有機ＥＬ表示素子用封止剤は、硬化物に紫外線を１００時間照射した後の４００ｎｍにおける透過率が２０μｍの光路長にて８５％以上であることが好ましい。上記紫外線を１００時間照射した後の透過率が８５％以上であることにより、透明性が高く、発光の損失が小さくなり、かつ、色再現性により優れるものとなる。上記紫外線を１００時間照射した後の透過率のより好ましい下限は９０％、更に好ましい下限は９５％である。
上記紫外線を照射する光源としては、例えば、キセノンランプ、カーボンアークランプ等、従来公知の光源を用いることができる。
また、上記紫外線を１００時間照射した後の透過率の測定に用いる硬化物は、光硬化性の封止剤であれば、例えば、封止剤にＬＥＤランプにて波長３６５ｎｍの紫外線を３０００ｍＪ／ｃｍ２照射することにより得ることができ、熱硬化性の封止剤であれば、例えば、８０℃で１時間加熱することにより得ることができる。 In the sealing agent for organic EL display elements of the present invention, the transmittance at 400 nm after irradiating the cured product with ultraviolet rays for 100 hours is preferably 85% or more at an optical path length of 20 μm. When the transmittance after irradiating the ultraviolet rays for 100 hours is 85% or more, the transparency is high, the loss of light emission is small, and the color reproducibility is excellent. A more preferable lower limit of the transmittance after irradiation with the ultraviolet rays for 100 hours is 90%, and a more preferable lower limit is 95%.
As the light source for irradiating the ultraviolet rays, a conventionally known light source such as a xenon lamp or a carbon arc lamp can be used.
Moreover, if the hardened | cured material used for the measurement of the transmittance | permeability after irradiating the said ultraviolet-ray for 100 hours is a photocurable sealing agent, for example, ultraviolet rays with a wavelength of 365 nm will be 3000 mJ / cm with a LED lamp to sealing agent. If it is a thermosetting sealant, it can be obtained, for example, by heating at 80 ° C. for 1 hour.
本発明の有機ＥＬ表示素子用封止剤は、ＪＩＳ　Ｚ　０２０８に準拠して、硬化物を８５℃、８５％ＲＨの環境下に２４時間暴露して測定した１００μｍ厚での透湿度が１００ｇ／ｍ２以下であることが好ましい。上記透湿度が１００ｇ／ｍ２以下であることにより、有機発光材料層に水分が到達してダークスポットが発生することを防止する効果により優れるものとなり、得られる有機ＥＬ表示素子が信頼性により優れるものとなる。
また、上記透湿度の測定に用いる硬化物は、光硬化性の封止剤であれば、例えば、封止剤にＬＥＤランプにて波長３６５ｎｍの紫外線を３０００ｍＪ／ｃｍ２照射することにより得ることができ、熱硬化性の封止剤であれば、例えば、８０℃で１時間加熱することにより得ることができる。 The sealant for an organic EL display device of the present invention has a moisture permeability of 100 g / 100 μm when the cured product is exposed to an environment of 85 ° C. and 85% RH for 24 hours in accordance with JIS Z 0208. m is preferably 2 or less. When the moisture permeability is 100 g / m 2 or less, the effect of preventing moisture from reaching the organic light emitting material layer and the generation of dark spots is improved, and the resulting organic EL display element is more reliable. It will be a thing.
Moreover, if the hardened | cured material used for the said moisture permeability measurement is a photocurable sealing agent, for example, it can obtain by irradiating 3000 mJ / cm < 2 > of ultraviolet rays with a wavelength of 365 nm with a LED lamp to sealing agent. If it is a thermosetting sealing agent, it can obtain by heating at 80 degreeC for 1 hour, for example.
更に、本発明の有機ＥＬ表示素子用封止剤は、硬化物を８５℃、８５％ＲＨの環境下に２４時間暴露したときに、硬化物の含水率が０．５％未満であることが好ましい。上記硬化物の含水率が０．５％未満であることにより、硬化物中の水分による有機発光材料層の劣化を防止する効果により優れるものとなり、得られる有機ＥＬ表示素子が信頼性により優れるものとなる。上記硬化物の含水率のより好ましい上限は０．３％である。
上記含水率の測定方法としては、例えば、ＪＩＳ　Ｋ　７２５１に準拠してカールフィッシャー法により求める方法や、ＪＩＳ　Ｋ　７２０９－２に準拠して吸水後の重量増分を求める等の方法が挙げられる。
また、上記含水率の測定に用いる硬化物は、光硬化性の封止剤であれば、例えば、封止剤にＬＥＤランプにて波長３６５ｎｍの紫外線を３０００ｍＪ／ｃｍ２照射することにより得ることができ、熱硬化性の封止剤であれば、例えば、８０℃で１時間加熱することにより得ることができる。 Furthermore, the sealing agent for organic EL display elements of the present invention may have a moisture content of less than 0.5% when the cured product is exposed to an environment of 85 ° C. and 85% RH for 24 hours. preferable. When the moisture content of the cured product is less than 0.5%, the effect of preventing the deterioration of the organic light emitting material layer due to moisture in the cured product is excellent, and the obtained organic EL display element is excellent in reliability. It becomes. A more preferable upper limit of the moisture content of the cured product is 0.3%.
Examples of the method for measuring the moisture content include a method of obtaining by a Karl Fischer method in accordance with JIS K 7251, and a method of obtaining a weight increment after water absorption in accordance with JIS K 7209-2.
Moreover, if the hardened | cured material used for the measurement of the said moisture content is a photocurable sealing agent, it can obtain by irradiating 3000 mJ / cm < 2 > of ultraviolet rays with a wavelength of 365 nm with a LED lamp to a sealing agent, for example. If it is a thermosetting sealing agent, it can obtain by heating at 80 degreeC for 1 hour, for example.
本発明１の有機ＥＬ表示素子用封止剤は、インクジェット法による塗布に好適に用いられ、本発明２の有機ＥＬ表示素子用封止剤は、インクジェット法による塗布に用いられる。
本発明の有機ＥＬ表示素子用封止剤を用いて有機ＥＬ表示素子を製造する方法としては、例えば、インクジェット法により、本発明の有機ＥＬ表示素子用封止剤を基材に塗布する工程と、塗布した有機ＥＬ表示素子用封止剤を光照射及び／又は加熱により硬化させる工程とを有する方法等が挙げられる。 The sealing agent for organic EL display elements of the present invention 1 is suitably used for coating by an ink jet method, and the sealing agent for organic EL display elements of the present invention 2 is used for coating by an ink jet method.
As a method for producing an organic EL display element using the sealing agent for organic EL display elements of the present invention, for example, a step of applying the sealing agent for organic EL display elements of the present invention to a substrate by an inkjet method, And a method of curing the applied sealing agent for organic EL display elements by light irradiation and / or heating.
本発明の有機ＥＬ表示素子用封止剤を基材に塗布する工程において、本発明の有機ＥＬ表示素子用封止剤は、基材の全面に塗布してもよく、基材の一部に塗布してもよい。塗布により形成される本発明の有機ＥＬ表示素子用封止剤の封止部の形状としては、有機発光材料層を有する積層体を外気から保護しうる形状であれば特に限定されず、該積層体を完全に被覆する形状であってもよいし、該積層体の周辺部に閉じたパターンを形成してもよいし、該積層体の周辺部に一部開口部を設けた形状のパターンを形成してもよい。 In the step of applying the organic EL display element sealant of the present invention to the substrate, the organic EL display element sealant of the present invention may be applied to the entire surface of the substrate, or on a part of the substrate. It may be applied. The shape of the sealing portion of the sealing agent for organic EL display elements of the present invention formed by coating is not particularly limited as long as it is a shape that can protect the laminate having the organic light emitting material layer from the outside air. A shape that completely covers the body may be formed, a closed pattern may be formed in the peripheral portion of the laminate, or a pattern having a shape in which a partial opening is provided in the peripheral portion of the laminate. It may be formed.
上記有機ＥＬ表示素子用封止剤を光照射により硬化させる場合、本発明の有機ＥＬ表示素子用封止剤は、３００ｎｍ～４００ｎｍの波長及び３００～３０００ｍＪ／ｃｍ２の積算光量の光を照射することによって好適に硬化させることができる。 When the organic EL display element sealant is cured by light irradiation, the organic EL display element sealant of the present invention irradiates light having a wavelength of 300 nm to 400 nm and an accumulated light amount of 300 to 3000 mJ / cm 2. Can be suitably cured.
本発明の有機ＥＬ表示素子用封止剤に光を照射するための光源としては、例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、エキシマレーザ、ケミカルランプ、ブラックライトランプ、マイクロウェーブ励起水銀灯、メタルハライドランプ、ナトリウムランプ、ハロゲンランプ、キセノンランプ、ＬＥＤランプ、蛍光灯、太陽光、電子線照射装置等が挙げられる。これらの光源は、単独で用いられてもよく、２種以上が併用されてもよい。
これらの光源は、上記光ラジカル重合開始剤や光カチオン重合開始剤の吸収波長に合わせて適宜選択される。 Examples of the light source for irradiating the organic EL display element sealant of the present invention with light include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an excimer laser, a chemical lamp, a black light lamp, and a microwave. Examples include an excited mercury lamp, a metal halide lamp, a sodium lamp, a halogen lamp, a xenon lamp, an LED lamp, a fluorescent lamp, sunlight, and an electron beam irradiation device. These light sources may be used independently and 2 or more types may be used together.
These light sources are appropriately selected according to the absorption wavelength of the photo radical polymerization initiator or the photo cationic polymerization initiator.
本発明の有機ＥＬ表示素子用封止剤への光の照射手段としては、例えば、各種光源の同時照射、時間差をおいての逐次照射、同時照射と逐次照射との組み合わせ照射等が挙げられ、いずれの照射手段を用いてもよい。 Examples of the light irradiation means to the organic EL display element sealant of the present invention include simultaneous irradiation of various light sources, sequential irradiation with a time difference, combined irradiation of simultaneous irradiation and sequential irradiation, and the like. Any irradiation means may be used.
上記有機ＥＬ表示素子用封止剤を光照射及び／又は加熱により硬化させる工程により得られる硬化物は、更に無機材料膜で被覆されていてもよい。
上記無機材料膜を構成する無機材料としては、従来公知のものを用いることができ、例えば、窒化珪素（ＳｉＮｘ）や酸化珪素（ＳｉＯｘ）等が挙げられる。上記無機材料膜は、１層からなるものであってもよく、複数種の層を積層したものであってもよい。また、上記無機材料膜と本発明の有機ＥＬ表示素子用封止剤からなる樹脂膜とを、交互に繰り返して上記積層体を被覆してもよい。 The cured product obtained by the step of curing the organic EL display element sealing agent by light irradiation and / or heating may be further coated with an inorganic material film.
As the inorganic material forming the inorganic material layer can be a conventionally known, for example, silicon nitride (SiN x), silicon oxide (SiO x), and the like. The inorganic material film may be a single layer or may be a laminate of a plurality of types of layers. Moreover, you may coat | cover the said laminated body by repeating alternately the said inorganic material film | membrane and the resin film which consists of the sealing agent for organic EL display elements of this invention.
上記有機ＥＬ表示素子を製造する方法は、本発明の有機ＥＬ表示素子用封止剤を塗布した基材（以下、「一方の基材」ともいう）と他方の基材とを貼り合わせる工程を有していてもよい。
本発明の有機ＥＬ表示素子用封止剤を塗布する基材（以下、「一方の基材」ともいう）は、有機発光材料層を有する積層体の形成されている基材であってもよく、該積層体の形成されていない基材であってもよい。
上記一方の基材が上記積層体の形成されていない基材である場合、上記他方の基材を貼り合わせた際に、上記積層体を外気から保護できるように上記一方の基材に本発明の有機ＥＬ表示素子用封止剤を塗布すればよい。即ち、他方の基材を貼り合わせた際に上記積層体の位置となる場所に全面的に塗布するか、又は、他方の基材を貼り合わせた際に上記積層体の位置となる場所が完全に収まる形状に、閉じたパターンの封止剤部を形成してもよい。 The method for producing the organic EL display element comprises a step of bonding a base material (hereinafter also referred to as “one base material”) coated with the organic EL display element sealing agent of the present invention and the other base material. You may have.
The substrate on which the sealing agent for organic EL display elements of the present invention is applied (hereinafter also referred to as “one substrate”) may be a substrate on which a laminate having an organic light emitting material layer is formed. A base material on which the laminate is not formed may be used.
When the one substrate is a substrate on which the laminate is not formed, the present invention is applied to the one substrate so that the laminate can be protected from the outside air when the other substrate is bonded. What is necessary is just to apply | coat the sealing agent for organic EL display elements. That is, apply the entire surface to the location of the laminate when the other substrate is bonded, or the location of the laminate is complete when the other substrate is bonded. The sealing agent portion having a closed pattern may be formed in a shape that fits in the shape.
上記有機ＥＬ表示素子用封止剤を光照射及び／又は加熱により硬化させる工程は、上記一方の基材と上記他方の基材とを貼り合わせる工程の前に行なってもよいし、上記一方の基材と上記他方の基材とを貼り合わせる工程の後に行なってもよい。
上記有機ＥＬ表示素子用封止剤を光照射及び／又は加熱により硬化させる工程を、上記一方の基材と上記他方の基材とを貼り合わせる工程の前に行なう場合、本発明の有機ＥＬ表示素子用封止剤は、光照射及び／又は加熱してから硬化反応が進行して接着ができなくなるまでの可使時間が１分以上であることが好ましい。上記可使時間が１分以上であることにより、上記一方の基材と上記他方の基材とを貼り合わせる前に硬化が進行し過ぎることなく、より高い接着強度を得ることができる。 The step of curing the organic EL display element sealant by light irradiation and / or heating may be performed before the step of bonding the one base material and the other base material, You may perform after the process of bonding a base material and said other base material.
When the step of curing the organic EL display element sealant by light irradiation and / or heating is performed before the step of bonding the one base material and the other base material, the organic EL display of the present invention. The device sealant preferably has a pot life of 1 minute or longer after irradiation with light and / or heating until the curing reaction proceeds and adhesion becomes impossible. When the pot life is 1 minute or longer, higher adhesion strength can be obtained without excessive curing before the one base material and the other base material are bonded together.
上記一方の基材と上記他方の基材とを貼り合わせる工程において、上記一方の基材と上記他方の基材とを貼り合わせる方法は特に限定されないが、減圧雰囲気下で貼り合わせることが好ましい。
上記減圧雰囲気下の真空度の好ましい下限は０．０１ｋＰａ、好ましい上限は１０ｋＰａである。上記減圧雰囲気下の真空度がこの範囲であることにより、真空装置の気密性や真空ポンプの能力から真空状態を達成するのに長時間を費やすことなく、上記一方の基材と上記他方の基材とを貼り合わせる際の本発明の有機ＥＬ表示素子用封止剤中の気泡をより効率的に除去することができる。 In the step of bonding the one base material and the other base material, a method of bonding the one base material and the other base material is not particularly limited, but it is preferable to bond them in a reduced-pressure atmosphere.
The preferable lower limit of the degree of vacuum in the reduced-pressure atmosphere is 0.01 kPa, and the preferable upper limit is 10 kPa. When the degree of vacuum in the reduced-pressure atmosphere is within this range, the one base material and the other base material are not spent for a long time to achieve a vacuum state due to the airtightness of the vacuum device and the ability of the vacuum pump. Bubbles in the sealing agent for organic EL display elements of the present invention when the material is bonded can be more efficiently removed.
本発明によれば、インクジェット法により容易に塗布することができ、低アウトガス性に優れ、かつ、信頼性に優れる有機ＥＬ表示素子を得ることができる有機ＥＬ表示素子用封止剤を提供することができる。また、本発明によれば、該有機ＥＬ表示素子用封止剤の製造方法を提供することができる。 According to the present invention, there is provided an encapsulant for an organic EL display element that can be easily applied by an ink jet method, can obtain an organic EL display element that is excellent in low outgassing properties and excellent in reliability. Can do. Moreover, according to this invention, the manufacturing method of this sealing agent for organic EL display elements can be provided.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（実施例１～７、比較例１～４）
表１に記載された配合比に従い、各材料を、ホモディスパー型撹拌混合機（プライミクス社製、「ホモディスパーＬ型」）を用い、撹拌速度３０００ｒｐｍで均一に撹拌混合することにより、実施例１～７、比較例１～４の各有機ＥＬ表示素子用封止剤を作製した。実施例１～５及び比較例１、２で得られた各有機ＥＬ表示素子用封止剤については、撹拌混合した後、５０℃、０．１ＭＰａの環境に３０分曝す脱水工程を行った。
実施例及び比較例で得られた各有機ＥＬ表示素子用封止剤について、Ｅ型粘度計（東機産業社製、「ＶＩＳＣＯＭＥＴＥＲ　ＴＶ－２２」）を用いて、２５℃、１００ｒｐｍの条件において測定した粘度、及び、２５℃において動的濡れ性試験機（レスカ社製、「ＷＥＴ－６１００型」）により測定した表面張力を表１に示した。
また、実施例及び比較例で得られた各有機ＥＬ表示素子用封止剤１０ｇをハイベッセル容器に入れ、２５℃、５０％ＲＨの恒温恒湿機内に２４時間静置した後、カールフィッシャー装置を用いて、２５℃、５０％ＲＨの条件で各有機ＥＬ表示素子用封止剤の含水率を測定した。上記ハイベッセル容器としては、ＢＨＢ－１６０（近畿容器社製）を用い、上記カールフィッシャー装置としては、ＭＫＣ－７１０Ｓ（京都電子工業社製）を用いた。また、含水率の測定は、２４時間静置した後、恒温恒湿機から取り出した直後（３０分以内）の封止剤について行った。結果を表１に示した。 (Examples 1 to 7, Comparative Examples 1 to 4)
In accordance with the blending ratio described in Table 1, each material was uniformly stirred and mixed at a stirring speed of 3000 rpm using a homodisper type stirring mixer (“Primix Corporation,“ Homodisper L type ”). To 7 and Comparative Examples 1 to 4 were prepared. Each sealing agent for organic EL display elements obtained in Examples 1 to 5 and Comparative Examples 1 and 2 was subjected to a dehydration process in which the mixture was stirred and mixed and then exposed to an environment of 50 ° C. and 0.1 MPa for 30 minutes.
About each sealing agent for organic EL display elements obtained in Examples and Comparative Examples, measurement was performed using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., “VISCOMETER TV-22”) at 25 ° C. and 100 rpm. Table 1 shows the measured viscosity and the surface tension measured at 25 ° C. with a dynamic wettability tester (Reska, “WET-6100”).
Further, 10 g of each organic EL display element sealant obtained in Examples and Comparative Examples was placed in a high vessel container and allowed to stand in a constant temperature and humidity chamber at 25 ° C. and 50% RH for 24 hours, and then the Karl Fischer device. Was used to measure the water content of each organic EL display element sealant under the conditions of 25 ° C. and 50% RH. BHB-160 (manufactured by Kinki Container Co., Ltd.) was used as the high vessel container, and MKC-710S (manufactured by Kyoto Electronics Industry Co., Ltd.) was used as the Karl Fischer apparatus. Moreover, the moisture content was measured for the sealant immediately after taking out from the thermo-hygrostat (within 30 minutes) after standing for 24 hours. The results are shown in Table 1.
＜評価＞
実施例及び比較例で得られた各有機ＥＬ表示素子用封止剤について以下の評価を行った。結果を表１に示した。
なお、インクジェット吐出性、濡れ広がり性、及び、有機ＥＬ表示素子の信頼性の各評価において、インクジェット用塗布ヘッドとしてはＩＪＨ－３０（ＩＪＴ社製）を用い、インクジェット塗布は加熱を行わずに行った（ヘッド温度２５℃）。 <Evaluation>
The following evaluation was performed about each sealing agent for organic EL display elements obtained by the Example and the comparative example. The results are shown in Table 1.
In each evaluation of ink jet discharge property, wettability and organic EL display element reliability, IJH-30 (manufactured by IJT) was used as the ink jet coating head, and the ink jet coating was performed without heating. (Head temperature 25 ° C.).
（１）インクジェット塗布性
（１－１）インクジェット吐出性
実施例及び比較例で得られた各有機ＥＬ表示素子用封止剤を、インクジェット吐出装置（マイクロジェット社製、「ＮａｎｏＰｒｉｎｔｅｒ５００」）を用いて、３０ピコリットルの液滴量にて、アルカリ洗浄した無アルカリガラス（旭硝子社製、「ＡＮ１００」）上に塗布した。インクジェットノズルから液滴が正常に吐出されて基板に着弾した場合を「○」、正常に吐出されなかった場合を「×」としてインクジェット吐出性を評価した。 (1) Inkjet applicability (1-1) Inkjet ejection properties Each of the organic EL display element sealants obtained in Examples and Comparative Examples was used with an inkjet ejection device (“NanoPrinter500” manufactured by Microjet Co., Ltd.). The solution was applied on alkali-washed non-alkali glass (“AN100” manufactured by Asahi Glass Co., Ltd.) with a droplet volume of 30 picoliters. The ink jet discharge performance was evaluated by assuming that “◯” indicates that the liquid droplets were normally discharged from the ink jet nozzle and landed on the substrate, and “X” indicates that the liquid droplets were not normally discharged.
（１－２）濡れ広がり性
実施例１～７及び比較例３、４で得られた各有機ＥＬ表示素子用封止剤を、インクジェット吐出装置（マイクロジェット社製、「ＮａｎｏＰｒｉｎｔｅｒ５００」）を用いて、３０ピコリットルの液滴量にて、アルカリ洗浄した無アルカリガラス（旭硝子社製、「ＡＮ１００」）上に、５ｍ／秒の速度にて５００μｍピッチで１０００滴塗布した。塗布から１０分後の無アルカリガラス上の液滴の直径を測定し、液滴の直径が１５０μｍ以上であった場合を「○」、液滴の直径が５０μｍ以上１５０μｍ未満であった場合を「△」、液滴の直径が５０μｍ未満であった場合を「×」として濡れ広がり性を評価した。 (1-2) Wetting and spreading property Each of the organic EL display element sealants obtained in Examples 1 to 7 and Comparative Examples 3 and 4 was used using an inkjet discharge device (“NanoPrinter500” manufactured by Microjet). Then, 1000 drops were applied at a speed of 5 m / second at a pitch of 500 μm on alkali-washed non-alkali glass (“AN100” manufactured by Asahi Glass Co., Ltd.) with a drop volume of 30 picoliters. The diameter of the droplet on the alkali-free glass 10 minutes after the coating was measured. The case where the diameter of the droplet was 150 μm or more was “◯”, and the case where the diameter of the droplet was 50 μm or more and less than 150 μm was “ “Δ”, the case where the diameter of the droplet was less than 50 μm was evaluated as “×”, and the wetting and spreading property was evaluated.
（２）低アウトガス性
実施例１～７及び比較例３、４で得られた各有機ＥＬ表示素子用封止剤の硬化物の加熱時に発生するアウトガスをヘッドスペース法によるガスクロマトグラフ（JＥＯＬ社製、「ＪＭＳ－Ｑ１０５０ＧＣ」）により測定した。各有機ＥＬ表示素子用封止剤１００ｍｇをアプリケーターにて３００μｍの厚さに塗工した。次いで、ＬＥＤランプにて波長３６５ｎｍの紫外線を３０００ｍＪ／ｃｍ２照射して封止剤を硬化した後、ヘッドスペース用バイアルに硬化させた封止剤硬化物を入れてバイアルを封止し、１００℃で３０分間加熱して、ヘッドスペース法により発生ガスを測定した。
発生したガスが３００ｐｐｍ未満であった場合を「○」、３００ｐｐｍ以上５００ｐｐｍ未満であった場合を「△」、５００ｐｐｍ以上であった場合を「×」として低アウトガス性を評価した。 (2) Low outgassing performance Outgas generated during heating of the cured products of the sealants for organic EL display elements obtained in Examples 1 to 7 and Comparative Examples 3 and 4 is gas chromatograph by headspace method (manufactured by JEOL) , “JMS-Q1050GC”). 100 mg of each organic EL display element sealant was applied to a thickness of 300 μm with an applicator. Next, after curing the sealant by irradiating UV light having a wavelength of 365 nm with an LED lamp at 3000 mJ / cm 2 , the cured sealant was put in a headspace vial, and the vial was sealed, For 30 minutes, and the generated gas was measured by the headspace method.
The case where the generated gas was less than 300 ppm was evaluated as “◯”, the case where it was 300 ppm or more and less than 500 ppm as “Δ”, and the case where it was 500 ppm or more as “x”, and the low outgassing property was evaluated.
（３）有機ＥＬ表示素子の信頼性
（３－１）有機発光材料層を有する積層体が配置された基板の作製
ガラス基板（長さ２５ｍｍ、幅２５ｍｍ、厚さ０．７ｍｍ）にＩＴＯ電極を１０００Åの厚さで成膜したものを基板とした。上記基板をアセトン、アルカリ水溶液、イオン交換水、イソプロピルアルコールにてそれぞれ１５分間超音波洗浄した後、煮沸させたイソプロピルアルコールにて１０分間洗浄し、更に、ＵＶ－オゾンクリーナ（日本レーザー電子社製、「ＮＬ－ＵＶ２５３」）にて直前処理を行った。
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Ｎ，Ｎ’－ジ（１－ナフチル）－Ｎ，Ｎ’－ジフェニルベンジジン（α－ＮＰＤ）を２００ｍｇ、別の素焼き坩堝にトリス（８－キノリノラト）アルミニウム（Ａｌｑ３）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、α－ＮＰＤの入った坩堝を加熱し、α－ＮＰＤを蒸着速度１５Å／ｓで基板に堆積させ、膜厚６００Åの正孔輸送層を成膜した。次いで、Ａｌｑ３の入った坩堝を加熱し、１５Å／ｓの蒸着速度で膜厚６００Åの有機発光材料層を成膜した。その後、正孔輸送層及び有機発光材料層が形成された基板を別の真空蒸着装置に移し、この真空蒸着装置内のタングステン製抵抗加熱ボートにフッ化リチウム２００ｍｇ、別のタングステン製ボートにアルミニウム線１．０ｇを入れた。その後、真空蒸着装置の蒸着器内を２×１０－４Ｐａまで減圧してフッ化リチウムを０．２Å／ｓの蒸着速度で５Å成膜した後、アルミニウムを２０Å／ｓの速度で１０００Å成膜した。窒素により蒸着器内を常圧に戻し、１０ｍｍ×１０ｍｍの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。 (3) Reliability of organic EL display element (3-1) Fabrication of a substrate on which a laminate having an organic light emitting material layer is disposed An ITO electrode is placed on a glass substrate (length 25 mm, width 25 mm, thickness 0.7 mm). A substrate having a thickness of 1000 mm was used as a substrate. The substrate was ultrasonically washed with acetone, an aqueous alkali solution, ion-exchanged water, and isopropyl alcohol for 15 minutes, respectively, then washed with boiled isopropyl alcohol for 10 minutes, and a UV-ozone cleaner (manufactured by Nippon Laser Electronics Co., Ltd.). The last treatment was performed with “NL-UV253”).
Next, this substrate is fixed to the substrate folder of the vacuum evaporation apparatus, and 200 mg of N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine (α-NPD) is added to the unglazed crucible. 200 mg of tris (8-quinolinolato) aluminum (Alq 3 ) was put in the crucible, and the pressure in the vacuum chamber was reduced to 1 × 10 −4 Pa. Thereafter, the crucible containing α-NPD was heated, and α-NPD was deposited on the substrate at a deposition rate of 15 ｓ / s to form a 600 正 孔 hole transport layer. Next, the crucible containing Alq 3 was heated to form an organic light emitting material layer having a thickness of 600 で at a deposition rate of 15 Å / s. Thereafter, the substrate on which the hole transport layer and the organic light emitting material layer are formed is transferred to another vacuum vapor deposition apparatus, and 200 mg of lithium fluoride is added to a tungsten resistance heating boat in the vacuum vapor deposition apparatus, and an aluminum wire is added to another tungsten boat. 1.0 g was added. After that, the inside of the vapor deposition unit of the vacuum vapor deposition apparatus is depressurized to 2 × 10 −4 Pa to form a lithium fluoride film with a thickness of 5 mm at a deposition rate of 0.2 kg / s, and then aluminum with a film thickness of 1000 mm at a rate of 20 kg / s. did. The inside of the vapor deposition unit was returned to normal pressure with nitrogen, and the substrate on which the laminate having the organic light emitting material layer of 10 mm × 10 mm was arranged was taken out.
（３－２）無機材料膜Ａによる被覆
得られた積層体が配置された基板の該積層体全体を覆うように、１３ｍｍ×１３ｍｍの開口部を有するマスクを設置し、プラズマＣＶＤ法にて無機材料膜Ａを形成した。
プラズマＣＶＤ法は、原料ガスとしてＳｉＨ４ガス及び窒素ガスを用い、各々の流量をＳｉＨ４ガス１０ｓｃｃｍ、窒素ガス２００ｓｃｃｍとし、ＲＦパワーを１０Ｗ（周波数２．４５ＧＨｚ）、チャンバー内温度を１００℃、チャンバー内圧力を０．９Ｔｏｒｒとする条件で行った。
形成された無機材料膜Ａの厚さは、約１μｍであった。 (3-2) Coating with Inorganic Material Film A A mask having an opening of 13 mm × 13 mm is installed so as to cover the entire laminated body of the substrate on which the obtained laminated body is arranged, and inorganic by plasma CVD method. A material film A was formed.
In the plasma CVD method, SiH 4 gas and nitrogen gas are used as source gases, the flow rates of each are SiH 4 gas 10 sccm, nitrogen gas 200 sccm, RF power 10 W (frequency 2.45 GHz), chamber temperature 100 ° C., chamber The test was performed under the condition that the internal pressure was 0.9 Torr.
The formed inorganic material film A had a thickness of about 1 μm.
（３－３）樹脂保護膜の形成
得られた基板に対し、実施例１～７及び比較例３、４で得られた各有機ＥＬ表示素子用封止剤を、インクジェット吐出装置（マイクロジェット社製、「ＮａｎｏＰｒｉｎｔｅｒ５００」）を使用して基板にパターン塗布した。
その後、ＬＥＤランプを用いて波長３６５ｎｍの紫外線を３０００ｍＪ／ｃｍ２照射して有機ＥＬ表示素子用封止剤を硬化させて樹脂保護膜を形成した。 (3-3) Formation of Resin Protective Film Each of the organic EL display element sealants obtained in Examples 1 to 7 and Comparative Examples 3 and 4 was applied to the obtained substrate using an inkjet discharge device (Microjet Corporation). A pattern was applied to the substrate using “NanoPrinter500”).
Thereafter, an ultraviolet ray having a wavelength of 365 nm was irradiated with 3000 mJ / cm 2 using an LED lamp to cure the organic EL display element sealant to form a resin protective film.
（３－４）無機材料膜Ｂによる被覆
樹脂保護膜を形成した後、該樹脂保護膜の全体を覆うように、１２ｍｍ×１２ｍｍの開口部を有するマスクを設置し、プラズマＣＶＤ法にて無機材料膜Ｂを形成して有機ＥＬ表示素子を得た。
プラズマＣＶＤ法は、上記「（３－２）無機材料膜Ａによる被覆」と同様の条件で行った。
形成された無機材料膜Ｂの厚さは、約１μｍであった。 (3-4) After forming the coating resin protective film with the inorganic material film B, a mask having an opening of 12 mm × 12 mm is installed so as to cover the entire resin protective film, and the inorganic material is formed by plasma CVD. Film B was formed to obtain an organic EL display element.
The plasma CVD method was performed under the same conditions as in “(3-2) Coating with inorganic material film A”.
The formed inorganic material film B had a thickness of about 1 μm.
（３－５）有機ＥＬ表示素子の発光状態
得られた有機ＥＬ表示素子を、温度８５℃、湿度８５％の環境下で１００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（ダークスポット及び画素周辺消光の有無）を目視で観察した。ダークスポットや周辺消光が無く均一に発光した場合を「○」、ダークスポットや周辺消光はないものの輝度に僅かな低下が認められた場合を「△」、ダークスポットや周辺消光が認められた場合を「×」として有機ＥＬ表示素子の表示性能を評価した。 (3-5) Light-emitting state of organic EL display element The obtained organic EL display element was exposed for 100 hours in an environment of a temperature of 85 ° C. and a humidity of 85%, and then a voltage of 3 V was applied to the organic EL display element. The light emission state (the presence or absence of dark spots and pixel periphery quenching) was visually observed. “○” when there is no dark spot or peripheral quenching, and “△” when there is no dark spot or peripheral quenching, but “△” when there is a slight decrease in brightness, when dark spot or peripheral quenching is observed The display performance of the organic EL display element was evaluated with “×”.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
非加熱式インクジェット法と加熱式インクジェット法とにおける、有機ＥＬ表示素子用封止剤の粘度によるインクジェット塗布性への効果を確認するため、以下の実験を行った。結果を表２に示した。 In order to confirm the effect of the viscosity of the sealing agent for organic EL display elements on the inkjet applicability in the non-heated inkjet method and the heated inkjet method, the following experiment was performed. The results are shown in Table 2.
（実験例１）
表２に記載された配合比に従い、各材料を、ホモディスパー型撹拌混合機（プライミクス社製、「ホモディスパーＬ型」）を用い、撹拌速度３０００ｒｐｍで均一に撹拌混合した後、５０℃、０．１ＭＰａの環境に３０分曝す脱水工程を行うことにより、有機ＥＬ表示素子用封止剤を作製した。
得られた有機ＥＬ表示素子用封止剤について、Ｅ型粘度計（東機産業社製、「ＶＩＳＣＯＭＥＴＥＲ　ＴＶ－２２」）を用いて、２５℃、１００ｒｐｍの条件において測定した粘度、及び、２５℃において動的濡れ性試験機（レスカ社製、「ＷＥＴ－６１００型」）により表面張力を測定した。
また、得られた有機ＥＬ表示素子用封止剤１０ｇをハイベッセル容器に入れ、２５℃、５０％ＲＨの恒温恒湿機内に２４時間静置した後、カールフィッシャー装置を用いて、２５℃、５０％ＲＨの条件で有機ＥＬ表示素子用封止剤の含水率を測定した。上記ハイベッセル容器としては、ＢＨＢ－１６０（近畿容器社製）を用い、上記カールフィッシャー装置としては、ＭＫＣ－７１０Ｓ（京都電子工業社製）を用いた。また、含水率の測定は、２４時間静置した後、恒温恒湿機から取り出した直後（３０分以内）の封止剤について行った。
得られた有機ＥＬ表示素子用封止剤を、インクジェット吐出装置（マイクロジェット社製、「ＮａｎｏＰｒｉｎｔｅｒ５００」）を用いて、３０ピコリットルの液滴量にて、アルカリ洗浄した無アルカリガラス（旭硝子社製、「ＡＮ１００」）上に塗布した。インクジェットノズルから液滴が正常に吐出されて基板に着弾した場合を「○」、正常に吐出されなかった場合を「×」としてインクジェット吐出性を評価した。なお、インクジェット用塗布ヘッドとしてはＩＪＨ－３０（ＩＪＴ社製）を用い、インクジェット塗布は加熱を行わずに行った（ヘッド温度２５℃）。 (Experimental example 1)
In accordance with the blending ratio described in Table 2, each material was uniformly stirred and mixed at a stirring speed of 3000 rpm using a homodisper type stirring mixer (manufactured by Primics Co., Ltd., “Homodisper L type”). The sealing agent for organic EL display elements was produced by performing the spin-drying | dehydration process exposed to a 0.1 MPa environment for 30 minutes.
About the obtained sealing agent for organic EL display elements, viscosity measured at 25 ° C. and 100 rpm using an E-type viscometer (“VISCOMETER TV-22” manufactured by Toki Sangyo Co., Ltd.), and 25 ° C. The surface tension was measured with a dynamic wettability tester (Reska, “WET-6100”).
Moreover, after putting 10 g of obtained sealing agents for organic EL display elements in a high vessel container and leaving it still in a thermostat at 25 ° C. and 50% RH for 24 hours, using a Karl Fischer device, The moisture content of the sealing agent for organic EL display elements was measured under the condition of 50% RH. BHB-160 (manufactured by Kinki Container Co., Ltd.) was used as the high vessel container, and MKC-710S (manufactured by Kyoto Electronics Industry Co., Ltd.) was used as the Karl Fischer apparatus. Moreover, the moisture content was measured for the sealant immediately after taking out from the thermo-hygrostat (within 30 minutes) after standing for 24 hours.
The obtained sealant for organic EL display element was alkali-washed with an ink-jet discharge device (“NanoPrinter500” manufactured by Microjet Co., Ltd.) with a droplet volume of 30 picoliters (manufactured by Asahi Glass Co., Ltd.). , “AN100”). The ink jet discharge performance was evaluated by assuming that “◯” indicates that the liquid droplets were normally discharged from the ink jet nozzle and landed on the substrate, and “X” indicates that the liquid droplets were not normally discharged. Note that IJH-30 (manufactured by IJT) was used as an inkjet coating head, and inkjet coating was performed without heating (head temperature 25 ° C.).
（実験例２）
実験例１で作製したものと同じ有機ＥＬ表示素子用封止剤を用意した。
インクジェット用塗布ヘッドとしてＩＪＨ－３０（ＩＪＴ社製）を用い、加熱しながらインクジェット塗布を行った（ヘッド温度６０℃）こと以外は、実験例１と同様にしてインクジェット吐出性を評価した。 (Experimental example 2)
The same sealing agent for organic EL display elements as that prepared in Experimental Example 1 was prepared.
Inkjet ejection properties were evaluated in the same manner as in Experimental Example 1 except that IJH-30 (manufactured by IJT) was used as an inkjet coating head and inkjet coating was performed while heating (head temperature 60 ° C.).
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
本発明によれば、インクジェット法により容易に塗布することができ、低アウトガス性に優れ、かつ、信頼性に優れる有機ＥＬ表示素子を得ることができる有機ＥＬ表示素子用封止剤を提供することができる。また、本発明によれば、該有機ＥＬ表示素子用封止剤の製造方法を提供することができる。 According to the present invention, there is provided an encapsulant for an organic EL display element that can be easily applied by an ink jet method, can obtain an organic EL display element that is excellent in low outgassing properties and excellent in reliability. Can do. Moreover, according to this invention, the manufacturing method of this sealing agent for organic EL display elements can be provided.

Claims (5)

  1. 重合性化合物と重合開始剤とを含有し、２５℃における粘度が５～５０ｍＰａ・ｓであり、２５℃における表面張力が１５～３５ｍＮ／ｍであり、かつ、２５℃、５０％ＲＨの環境下に２４時間静置した後の２５℃における含水率が１０００ｐｐｍ以下である
    ことを特徴とする有機ＥＬ表示素子用封止剤。     Contains a polymerizable compound and a polymerization initiator, has a viscosity at 25 ° C. of 5 to 50 mPa · s, a surface tension at 25 ° C. of 15 to 35 mN / m, and an environment of 25 ° C. and 50% RH. And a water content at 25 ° C. after being allowed to stand for 24 hours at 1000 ppm or less.
  2. インクジェット法による塗布に用いられる有機ＥＬ表示素子用封止剤であって、
    重合性化合物と重合開始剤とを含有し、２５℃、５０％ＲＨの環境下に２４時間静置した後の２５℃における含水率が１０００ｐｐｍ以下である
    ことを特徴とする有機ＥＬ表示素子用封止剤。     An organic EL display element sealing agent used for coating by an inkjet method,
    A seal for an organic EL display device, comprising a polymerizable compound and a polymerization initiator, and having a water content at 25 ° C. of 1000 ppm or less after standing in an environment of 25 ° C. and 50% RH for 24 hours. Stopper.
  3. 重合性化合物は、分子内の酸素原子の含有割合が３０％以下である化合物を、重合性化合物全体１００重量部中に２０～９０重量部含有することを特徴とする請求項１又は２記載の有機ＥＬ表示素子用封止剤。 3. The polymerizable compound according to claim 1, wherein 20 to 90 parts by weight of a compound having an oxygen atom content ratio of 30% or less in the molecule is contained in 100 parts by weight of the whole polymerizable compound. Sealant for organic EL display elements.
  4. 溶剤を含有しない、又は、溶剤の含有量が０．０５重量％以下であることを特徴とする請求項１、２又は３記載の有機ＥＬ表示素子用封止剤。 The encapsulant for organic EL display elements according to claim 1, 2 or 3, which does not contain a solvent or has a solvent content of 0.05% by weight or less.
  5. 請求項１、２、３又は４記載の有機ＥＬ表示素子用封止剤を製造する方法であって、
    重合性化合物と重合開始剤及び／又は熱硬化剤とを含有する混合物を１０℃～１００℃、０．１ＭＰａ以下の環境に１５分以上曝す脱水工程を有する
    有機ＥＬ表示素子用封止剤の製造方法。     A method for producing a sealing agent for organic EL display elements according to claim 1, 2, 3, or 4,
    Production of sealing agent for organic EL display device having dehydration step of exposing mixture containing polymerizable compound and polymerization initiator and / or thermosetting agent to environment of 10 to 100 ° C. and 0.1 MPa or less for 15 minutes or more Method.
PCT/JP2017/037656 2016-10-19 2017-10-18 Organic el display element sealing agent, and method for producing organic el display element sealing agent WO2018074507A1 (en)

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