JP2020021714A - Uv curable resin composition for sealing organic el element, method of manufacturing organic el light-emitting device and organic el light-emitting device - Google Patents

Abstract

To provide a UV curable resin composition for sealing organic EL element containing a hygroscopic agent, which hardly increases the viscosity due to the hygroscopic agent and hardly generates outgas from the cured product while suppressing a decrease in the transparency of the cured product due to the hygroscopic agent.SOLUTION: The UV curable resin composition for sealing organic EL element contains a polymerizable compound (A), a photopolymerization initiator (B) and a hygroscopic agent (E) with an average particle size of 200 nm or less. The polymerizable compound (A) contains: a polyfunctional acrylic compound (A1) having a polyoxyalkylene skeleton and having two or more (meth) acryloyloxy groups in one molecule; and a monofunctional acrylic compound (A2) having one (meth) acryloyloxy group and at least one cationically polymerizable group in one molecule.SELECTED DRAWING: Figure 1

Description

  TECHNICAL FIELD The present invention relates to an ultraviolet curable resin composition for sealing an organic EL element, a method for manufacturing an organic EL light emitting device, and an organic EL light emitting device, and more particularly, to an organic material suitable for producing a sealing material in an organic EL light emitting device. The present invention relates to an ultraviolet curable resin composition for sealing an EL element, a method for manufacturing an organic EL light emitting device using the ultraviolet curable resin composition for sealing an organic EL element, and an organic EL light emitting device including the sealing material.

  Organic EL light-emitting devices are applied to lighting, displays, and the like, and are expected to spread further in the future.

  Among the organic EL light-emitting devices, a device called a top emission type has, for example, an organic EL element arranged on a support substrate, a transparent substrate arranged so as to face the support substrate, and a transparent substrate between the support substrate and the transparent substrate. It is configured by filling a suitable sealing material. In this case, light emitted from the organic EL element passes through the sealing material and the transparent substrate and exits to the outside.

  The sealing material suppresses the intrusion of moisture into the organic EL element, thereby suppressing the generation and growth of dark spots in the organic EL element. The dark spot is a portion that does not emit light and is generated when the organic EL element is deteriorated by moisture.

  In some cases, merely providing a sealing material in the organic EL light emitting device may not sufficiently prevent moisture from entering. Therefore, a hygroscopic agent is provided between the supporting substrate and the transparent substrate. However, a process for providing the hygroscopic agent is required, which complicates the structure of the organic EL light emitting device and lowers the manufacturing efficiency. I will.

  It has also been proposed to add a hygroscopic agent to a composition for producing a sealing material to impart hygroscopicity to the sealing material. For example, Patent Document 1 discloses a sealant for an organic electroluminescent display element containing a radically polymerizable compound, a polymerization initiator and / or a curing agent, and a powdery molecular sieve.

JP-A-2012-012559

  Simply dispersing a hygroscopic agent in the sealing material as disclosed in Patent Literature 1 causes a decrease in the transparency of the sealing material, and lowers the luminous efficiency of the organic EL light emitting device. . If the particle size of the hygroscopic agent is reduced, the transparency can be expected to be improved, but the moldability of the composition is deteriorated by increasing the viscosity of the composition for producing the sealing material by the hygroscopic agent.

  In addition, outgassing may be generated from a sealing material manufactured from the composition. This outgas may cause voids in the organic EL light emitting device. Water may reach the organic EL element through the gap.

  SUMMARY OF THE INVENTION An object of the present invention is to provide an organic EL element sealing which can suppress a decrease in transparency of a cured product due to a moisture absorbing agent while containing a moisture absorbing agent, hardly cause an increase in viscosity due to the moisture absorbing agent, and hardly generate outgas from the cured product. An object of the present invention is to provide a UV curable resin composition for stopping.

  The ultraviolet curable resin composition for sealing an organic EL element according to one embodiment of the present invention contains a polymerizable compound (A), a photopolymerization initiator (B), and a moisture absorbent (E) having an average particle diameter of 200 nm or less. A polymerizable compound (A) having a polyoxyalkylene skeleton and having two or more (meth) acryloyloxy groups in one molecule; a polyfunctional acrylic compound (A1) having one compound in one molecule; And a monofunctional acrylic compound (A2) having a (meth) acryloyloxy group and at least one cationically polymerizable group.

  A method for manufacturing an organic EL light-emitting device according to one embodiment of the present invention is a method for manufacturing an organic EL light-emitting device including an organic EL element and a sealing material covering the organic EL element. The method includes molding the ultraviolet-curable resin composition by an inkjet method, and then irradiating the ultraviolet-curable resin composition for sealing an organic EL element with ultraviolet rays to cure the composition, thereby producing the sealing material.

  An organic EL light emitting device according to one embodiment of the present invention includes an organic EL element and a sealing material that covers the organic EL element, and the sealing material is an ultraviolet curable resin composition for sealing the organic EL element. It is a cured product of

  According to one embodiment of the present invention, it is possible to suppress the decrease in the transparency of a cured product due to a moisture absorbent while containing a moisture absorbent, and it is difficult to increase the viscosity due to the moisture absorbent, and it is difficult to generate outgas from the cured product. An ultraviolet curable resin composition for sealing an EL element can be provided.

FIG. 1 is a schematic sectional view of a first example of an organic EL light emitting device. FIG. 2 is a schematic sectional view of a second example of the organic EL light emitting device.

  Hereinafter, an embodiment of the present invention will be described.

1. Overview of Embodiment An organic EL light emitting device 1 according to the present embodiment includes an organic EL element 4 and a sealing material 5 that covers the organic EL element 4. EL is an abbreviation for electroluminescence.

  A first example of the structure of the organic EL light emitting device 1 will be described with reference to FIG. This organic EL light emitting device 1 is a top emission type. The organic EL light emitting device 1 includes a support substrate 2, a transparent substrate 3 facing the support substrate 2 at an interval, an organic EL element 4 on a surface of the support substrate 2 facing the transparent substrate 3, and the support substrate 2. A sealing material filled between the transparent substrate and the transparent substrate. In the example shown in FIG. 1, the organic EL light emitting device 1 includes a passivation layer 6 that covers the surface of the support substrate 2 facing the transparent substrate 3 and the organic EL element 4.

  The support substrate 2 is made of, for example, a resin material, but is not limited to this. The transparent substrate 3 is made of a light-transmitting material. The transparent substrate 3 is, for example, a glass substrate or a transparent resin substrate. The organic EL element 4 is also called an organic light emitting diode. The organic EL element 4 includes, for example, a pair of electrodes and an organic light emitting layer between the electrodes. The passivation layer 6 is preferably made of silicon nitride or silicon oxide.

  A second example of the structure of the organic EL light emitting device 1 will be described with reference to FIG. Elements common to those in the first example shown in FIG. 1 are denoted by the same reference numerals as in FIG. 1, and detailed description will be omitted as appropriate. The organic EL light emitting device 1 shown in FIG. 2 is also a top emission type. The organic EL light emitting device 1 includes a support substrate 2, a transparent substrate 3 facing the support substrate 2 at an interval, an organic EL element 4 on a surface of the support substrate 2 facing the transparent substrate 3, and an organic EL element 4. Is provided.

  As in the case of the first example, the organic EL element 4 includes, for example, a pair of electrodes 41 and 43 and an organic light emitting layer 42 between the electrodes 41 and 43. The organic light emitting layer 42 includes, for example, a hole injection layer 421, a hole transport layer 422, a light emitting layer 423, and an electron transport layer 424, and these layers are stacked in the order described above.

  The organic EL device 1 includes a plurality of organic EL elements 4, and the plurality of organic EL elements 4 form an array 9 (hereinafter, referred to as an element array 9) on the support substrate 2. The element array 9 also includes the partition wall 7. The partition wall 7 is on the support substrate 2 and partitions between two adjacent organic EL elements 4. The partition 7 is produced by, for example, molding a photosensitive resin material by a photolithography method. The element array 9 also includes connection wirings 8 that electrically connect the electrodes 43 and the electron transport layers 424 of the adjacent organic EL elements 4. The connection wiring 8 is provided on the partition wall 7.

  The organic EL light emitting device 1 also includes a passivation layer 6 that covers the organic EL element 4. The passivation layer 6 is preferably made of silicon nitride or silicon oxide. Passivation layer 6 includes a first passivation layer 61 and a second passivation layer 62. The first passivation layer 61 covers the organic EL element 4 by covering the element array 9 in a state of being in direct contact with the element array 9. The second passivation layer 62 is disposed at a position opposite to the element array 9 with respect to the first passivation layer 61, and a space is provided between the second passivation layer 62 and the first passivation layer 61. ing. The sealing material 5 is filled between the first passivation layer 61 and the second passivation layer 62. That is, the first passivation layer 61 is interposed between the organic EL element 4 and the sealing material 5 covering the organic EL element 4.

  Further, a second sealing material 52 is filled between the second passivation layer 62 and the transparent substrate 3. The second sealing material 52 is made of, for example, a transparent resin material. The material of the second sealing material 52 is not particularly limited. The material of the second sealing material 52 may be the same as or different from that of the sealing material 5.

  The sealing material 5 can be made from the ultraviolet-curable resin composition according to the present embodiment. That is, the ultraviolet curable resin composition is used for producing the sealing material 5 for the organic EL element 4. In other words, the ultraviolet curable resin composition is preferably a composition for producing a sealing material, a composition for sealing an organic EL element, or a composition for producing an organic EL light emitting device.

2. About ultraviolet curable resin composition The ultraviolet curable resin composition (hereinafter, referred to as composition (X)) according to the present embodiment includes a polymerizable compound (A), a photopolymerization initiator (B), and an average particle diameter of 200 nm or less. (E).

  The polymerizable compound (A) contains a polyfunctional acrylic compound (A1) and a monofunctional acrylic compound (A2). The polyfunctional acrylic compound (A1) is an acrylic compound having a polyoxyalkylene skeleton and having two or more (meth) acryloyloxy groups in one molecule. The monofunctional acrylic compound (A2) is an acrylic compound having one (meth) acryloyloxy group and at least one cationically polymerizable group in one molecule. The acrylic compound is a compound having at least one (meth) acryloyl group. Further, “(meth) acryl” is at least one of “acryl” and “methacryl”.

  By having a polyoxyalkylene skeleton, the polyfunctional acrylic compound (A1) can enhance the moldability of the composition (X), particularly when the composition (X) is molded by an inkjet method. In addition, the polyfunctional acrylic compound (A1) makes it difficult for the composition (X) to penetrate into an adhesive or a rubber material in a head portion or the like of an ink jet device, thereby making it difficult to damage the ink jet device. Further, the polyfunctional acrylic compound (A1) can enhance the adhesion between the sealing material 5 and a member made of an inorganic material, for example, the passivation layer 6.

  The polyoxyalkylene skeleton in the polyfunctional acrylic compound (A1) preferably has 2 to 6 oxyalkylene units. In this case, the polyfunctional acrylic compound (A1) can particularly enhance the moldability of the composition (X) by the inkjet method, and particularly enhances the adhesion of the cured product to the member made of an inorganic material and the flexibility of the cured product. Can be enhanced. The oxyalkylene unit in the polyfunctional acrylic compound (A1) contains, for example, at least one of an oxyethylene unit and an oxypropylene unit.

  The polyfunctional acrylic compound (A1) preferably has a structure in which the carbon chain has no or few branches. In this case, the polyfunctional acrylic compound (A1) can particularly reduce the viscosity of the composition (X).

  Examples of the polyfunctional acrylic compound (A1) include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate. ) At least one compound selected from the group consisting of acrylate, tetrapropylene glycol di (meth) acrylate and polytetramethylene glycol di (meth) acrylate.

  The percentage of the amount of the polyfunctional acrylic compound (A1) to the entire polymerizable compound (A) is, for example, 10% by mass or more and 90% by mass or less. In this case, the polyfunctional acrylic compound (A1) can particularly enhance the moldability when the composition (X) is molded by the inkjet method, and the composition (X) is less likely to damage the inkjet device. In addition, the adhesion between the sealing material 5 and the member made of an inorganic material can be particularly enhanced. The percentage of the amount of the polyfunctional acrylic compound (A1) is preferably 40% by mass or more, and more preferably 70% by mass or less.

  The monofunctional acrylic compound (A2) improves the flexibility of the sealing material 5 so that stress is less likely to remain in the sealing material 5, thereby improving the adhesion between the sealing material 5 and a member made of an inorganic material. Can be increased. Further, the monofunctional acrylic compound (A2) can make it difficult to generate outgas due to unreacted components and the like in the sealing material 5. This is because the monofunctional acrylic compound (A2) has a cationically polymerizable group, so that the cationically polymerizable group derived from the monofunctional acrylic compound (A2) in the encapsulating material 5 has an acid component that is an unreacted component. It is presumed that it is possible to trap. The acid component is derived from an acrylic compound such as the polyfunctional acrylic compound (A1) in the composition (X). If the monofunctional acrylic compound (A2) is not present in the composition (X), the acid component increases with the passage of time, increasing the risk of outgassing.

  The cationically polymerizable group in the monofunctional acrylic compound (A2) is, for example, a vinyl ether group, an epoxy group, an oxetanyl group, an allyl ether group, a vinyl group, or a hydroxyl group.

  The monofunctional acrylic compound (A2) is, for example, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 2- (2-vinyl methacrylate) Roxyethoxy) ethyl, 3-ethyl-3- (meth) acryloxymethyloxetane, allyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxytri It can contain at least one compound selected from the group consisting of ethylene glycol (meth) acrylate and 2- (2-vinyloxyethoxy) ethyl (meth) acrylate.

  The percentage of the amount of the monofunctional acrylic compound (A2) based on the entire polymerizable compound (A) is, for example, 10% by mass or more and 90% by mass or less. In this case, the monofunctional acrylic compound (A2) can particularly enhance the flexibility of the sealing material 5 and the adhesion to the inorganic material member of the sealing material 5 and reduce outgas from the sealing material 5. In particular, it can hardly occur. The percentage of the amount of the monofunctional acrylic compound (A2) is preferably 20% by mass or more, and more preferably 50% by mass or less.

  The mass ratio of the polyfunctional acrylic compound (A1) to the monofunctional acrylic compound (A2) is preferably from 8: 2 to 5: 5. In this case, the moldability of the composition (X) by the inkjet method, the heat resistance of the sealing material 5, the adhesion of the sealing material 5, and the flexibility of the sealing material are particularly enhanced. More preferably, the mass ratio is from 7: 3 to 6: 4.

  The polymerizable compound (A) may further contain a compound other than the polyfunctional acrylic compound (A1) and the monofunctional acrylic compound (A2). Such a compound is used, for example, for the purpose of adjusting the viscosity of the composition (X) and further improving the adhesion of the sealing material 5.

  The polymerizable compound (A) may further contain an acrylic compound (A3) other than the polyfunctional acrylic compound (A1) and the monofunctional acrylic compound (A2). The acrylic compound (A3) includes, for example, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, And at least one compound selected from the group consisting of 1,9-nonanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate and trimethylolpropane tri (meth) arylate.

  The polymerizable compound (A) may further contain a radical polymerizable compound (A4) that is not an acrylic compound (that is, has no (meth) acryloyl group). The radical polymerizable compound (A4) includes a polyfunctional radical polymerizable compound (A41) having two or more radical polymerizable functional groups in one molecule and a monofunctional compound having only one radical polymerizable functional group in one molecule. Any one or both of the radically polymerizable compound (A42) can be contained.

  The percentage of the amount of the radical polymerizable compound (A4) to the total amount of the polymerizable compound (A) and the radical polymerizable compound (A4) is, for example, 10% by mass or less.

  The polyfunctional radically polymerizable compound (A41) is, for example, a group consisting of an aromatic urethane oligomer, an aliphatic urethane oligomer, an epoxy acrylate oligomer, a polyester acrylate oligomer and other special oligomers having two or more ethylenic double bonds in one molecule. And at least one compound selected from the group consisting of: More specifically, the polyfunctional radical polymerizable compound (A41) is, for example, UV-2000B, UV-2750B, UV-3000B, UV-3010B, UV-3200B, UV-3300B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd. UV-3700B, UV-6640B, UV-8630B, UV-7000B, UV-7610B, UV-1700B, UV-7630B, UV-6300B, UV-6640B, UV-7550B, UV-7600B, UV-7605B, UV- 7610B, UV-7630B, UV-7640B, UV-7650B, UT-5449, UT-5454; Sartomer CN902, CN902J75, CN929, CN940, CN944, CN944B85, CN959, CN961E75, CN961H81, N962, CN963, CN963A80, CN963B80, CN963E75, CN963E80, CN963J85, CN964, CN965, CN965A80, CN966, CN966A80, CN966B85, CN966H90, CN966J75, CN968, CN969, CN1970, CN1970A, CN1970A, CN1970A CN973A80, CN973H85, CN973J75, CN975, CN977, CN977C70, CN978, CN980, CN981, CN981A75, CN981B88, CN982, CN982A75, CN982B88, CN982E75, CN983, CN984, CN985, CN985B 8, CN986, CN989, CN991, CN992, CN994, CN996, CN997, CN999, CN9001, CN9002, CN9004, CN9005, CN9006, CN9007, CN9008, CN9009, CN9010, CN9011, CN9013, CN9018, CN9019, CN9024, CN9025, 9090 CN9028, CN9029, CN9030, CN9060, CN9165, CN9167, CN9178, CN9290, CN9782, CN9783, CN9788, CN9893; and EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, KERMYL200, and KERMYL200, manufactured by Daicel Scitech Co., Ltd. RYL8210;

  The monofunctional radically polymerizable compound (A42) includes, for example, N-vinylformamide, vinylcaprolactam, vinylpyrrolidone, phenylglycidyl ether, p-tert-butylphenylglycidylether, butylglycidylether, 2-ethylhexylglycidylether, allylglycidylether, 1,2-butylene oxide, 1,3-butadiene monoxide, 1,2-epoxide decane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-vinylcyclohexene oxide, 4-vinylcyclohexene It contains at least one compound selected from the group consisting of oxide, N-vinylpyrrolidone and N-vinylcaprolactam.

  The polymerizable compound (A) may further contain a cationic polymerizable compound (A5). The cationically polymerizable compound (A5) contains, for example, at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, vinyl ether compounds, and other cationically polymerizable compounds. However, the polymerizable compound (A) does not contain the cationic polymerizable compound (A5), or the percentage of the amount of the cationic polymerizable compound (A5) to the polymerizable compound (A) is 1% by mass or less. More preferred. In this case, outgassing from the sealing material 5 is less likely to be generated.

  When the polymerizable compound (A) contains an epoxy compound, the epoxy compound includes, for example, bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol O epoxy resin, 2,2'-diallylbisphenol 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 Epoxy resin, dicyclopentadiene epoxy resin, naphthalene epoxy resin, phenol novolak epoxy resin, orthocresol novolak epoxy resin, dicyclopentadi At least one selected from the group consisting of nonvolak epoxy resin, biphenyl novolak epoxy resin, naphthalenephenol novolak epoxy resin, glycidylamine epoxy resin, alkyl polyol epoxy resin, rubber-modified epoxy resin, and glycidyl ester compound Of the compound. The epoxy compound preferably contains an alicyclic epoxy resin. Specific examples of the alicyclic epoxy resin include Celloxide 2000, Celloxide 2021P, Celloxide 2081, Celloxide 3000, Celloxide 8000, Cyclomer M100 (all manufactured by Daicel Corporation), and Sansosizer EPS (manufactured by Nippon Rika Kogyo). Including.

  When the polymerizable compound (A) contains an oxetane compound, examples of the oxetane compound include phenoxymethyl oxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, and 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, oxetanylsilsesquioxane, phenol novolak oxetane and 1,4-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) benzene at least one compound selected from the group consisting of contains.

  When the polymerizable compound (A) contains a vinyl ether compound, 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, and diethylene glycol. It contains at least one compound selected from the group consisting of divinyl ether, triethylene glycol divinyl ether, dipropylene glycol divinyl ether, and tripropylene glycol divinyl ether.

  When the polymerizable compound (A) contains a compound other than the polyfunctional acrylic compound (A1) and the monofunctional acrylic compound (A2), the total of the compounds other than the polyfunctional acrylic compound (A1) and the monofunctional acrylic compound (A2) The percentage of the amount is preferably 1% by mass or more and 20% by mass or less based on the polymerizable compound (A). In this case, the effects of adjusting the viscosity of the composition (X) and further improving the adhesion of the sealing material 5 can be achieved without generating a large amount of outgas or deteriorating the flexibility of the sealing material 5. Can be demonstrated. The percentage of the total amount of the compounds other than the polyfunctional acrylic compound (A1) and the monofunctional acrylic compound (A2) is more preferably 3% by mass or more, and even more preferably 10% by mass or less.

  The photopolymerization initiator (B) contains a photoradical polymerization initiator. The photo-radical polymerization initiator is not particularly limited as long as it is a compound that generates a radical species when irradiated with ultraviolet rays. Examples of the photopolymerization initiator (B) include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds , A ketoxime ester compound, a borate compound, an azinium compound, a metallocene compound, an active ester compound, a compound having a carbon-halogen bond, and an alkylamine compound.

  The photopolymerization initiator (B) preferably contains an acylphosphine oxide-based photopolymerization initiator. Examples of the acylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphinate. Examples of product names of the acylphosphine oxide-based photopolymerization initiator include Irgacure TPO, Irgacure TPO-L and Irgacure 819 manufactured by BASF.

  The amount of the photopolymerization initiator (B) is, for example, 1 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the composition (X). The amount of the photopolymerization initiator (B) is, for example, 0.5 part by mass or more and 20 parts by mass or less, preferably 10 parts by mass or more and 15 parts by mass or less based on 100 parts by mass of the polymerizable compound.

  The photopolymerization initiator (B) may contain a sensitizer as a part of the photopolymerization initiator (B). The sensitizer can promote the radical generation reaction of the photopolymerization initiator (B), improve the reactivity of radical polymerization, and increase the crosslink density. The sensitizer is, for example, 9,10-dibutoxyanthracene, 9-hydroxymethylanthracene, thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, anthraquinone, 1,2- Dihydroxyanthraquinone, 2-ethylanthraquinone, 1,4-diethoxynaphthalene, p-dimethylaminoacetophenone, p-diethylaminoacetophenone, p-dimethylaminobenzophenone, p-diethylaminobenzophenone, 4,4′-bis (dimethylamino) benzophenone, At least one selected from the group consisting of 4,4'-bis (diethylamino) benzophenone, p-dimethylaminobenzaldehyde, and p-diethylaminobenzaldehyde It may contain one compound.

  The content of the sensitizer in the composition (X) is, for example, 0.1 part by mass or more and 5 parts by mass or less, preferably 0.1 part by mass, based on 100 parts by mass of the solid content of the composition (X). To 3 parts by mass. When the content of the sensitizer is in such a range, the composition (X) can be cured in the air, and the composition (X) needs to be cured under an inert atmosphere such as a nitrogen atmosphere. Disappears.

  The composition (X) may contain a polymerization accelerator in addition to the photopolymerization initiator (B). Examples of the polymerization accelerator include, for example, ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and butoxy p-dimethylaminobenzoate. Contains amine compounds such as ethyl.

  Note that the monofunctional acrylic compound (A2) in the composition (X) has at least one cationically polymerizable group, and this cationically polymerizable group is for trapping an acid component as described above. It may not be involved in the curing of the composition (X). Therefore, the composition (X) may not contain a component for initiating or promoting a cationic polymerization reaction, for example, a cationic curing catalyst and a photo-cationic polymerization initiator.

  As described above, the composition (X) contains the moisture absorbent (E) having an average particle size of 200 nm or less. The hygroscopic agent (E) is preferably inorganic particles having hygroscopicity, and contains at least one component selected from the group consisting of zeolite particles, silica gel particles, calcium chloride particles, and titanium oxide nanotube particles. Is preferred. It is particularly preferred that the desiccant (E) contains zeolite particles.

  The zeolite particles having an average particle size of 200 nm or less can be produced by, for example, grinding a general industrial zeolite. In producing the zeolite particles, the zeolite may be pulverized and then crystallized by hydrothermal synthesis or the like. In this case, the zeolite particles can have particularly high hygroscopicity. Methods for producing such zeolite particles are known from JP-A-2006-69266, JP-A-2013-049602, and the like.

  The zeolite particles preferably contain sodium ions. For that purpose, the zeolite particles are preferably manufactured from a zeolite containing sodium ions, and may be manufactured from at least one material selected from the group consisting of A-type zeolite, X-type zeolite and Y-type zeolite. More preferred. It is particularly preferred that the zeolite particles are produced from 4A zeolite of the A zeolite. In these cases, the zeolite particles have a crystal structure suitable for adsorbing moisture.

  One specific example of a method for producing zeolite particles having an average particle size of 200 nm or less will be described. First, a zeolite powder as a raw material is prepared, and this zeolite powder is physically pulverized. For example, the zeolite powder can be physically pulverized by mixing the zeolite powder with water to prepare a slurry and applying the slurry to a bead mill pulverizer.

  Subsequently, the zeolite powder is crystallized by hydrothermal synthesis. For example, hydrothermal synthesis can be performed by heating a slurry containing zeolite powder after physical pulverization in an autoclave. The conditions for the hydrothermal synthesis are, for example, a heating temperature of 150 to 200 ° C. and a heating time of 15 to 24 hours.

  Subsequently, the zeolite powder is dried. The drying temperature is, for example, in the range of 150 to 200 ° C., and the drying time is, for example, in the range of 2 to 3 hours. Subsequently, if necessary, the dried zeolite powder is crushed using a mortar or the like and then sieved to adjust the particle size.

  Subsequently, if necessary, the zeolite powder may be subjected to an ion exchange treatment. The ion exchange treatment is performed, for example, by dispersing zeolite powder in an aqueous solution containing magnesium ions to prepare a mixture, and heating the mixture. More specifically, the ion exchange treatment is performed, for example, as follows. First, the zeolite powder is mixed with magnesium chloride and water, and the resulting mixture is stirred while being heated. During this treatment, the operation of temporarily stopping the stirring, discarding the supernatant of the mixture, subsequently replenishing the mixture with water, and then restarting the stirring is preferably repeated a plurality of times at appropriate intervals. . The heating temperature in this treatment is preferably in the range of 40 to 80 ° C, and the treatment time is preferably in the range of 6 to 8 hours.

  When the ion exchange treatment is performed, the zeolite powder is subsequently dried. The drying temperature is, for example, in the range of 150 to 200 ° C., and the drying time is, for example, in the range of 2 to 3 hours. Subsequently, if necessary, the dried zeolite powder is crushed using a mortar or the like and then sieved to adjust the particle size. Thereby, zeolite particles having an average particle size of 200 nm or less can be obtained.

Crystallization of the zeolite powder can also be performed in the presence of silicate and alkali metal oxide. A specific example of a method for producing zeolite particles having an average particle size of 200 nm or less in that case will be described. First, a zeolite powder is prepared. Zeolite powder preferably has a composition of _{aM1 2 O · bSiO 2 · Al} 2 O 3 · cMe. M1 is an alkali metal, proton or ammonium ion (NH ₄ ⁺ ), Me is an alkaline earth metal, a is a number in the range of 0.01 to 1, and b is in the range of 20 to 80 And c is a number in the range of 0 to 1. The zeolite powder preferably contains zeolite containing sodium ions, and more preferably contains at least one material selected from the group consisting of A-type zeolite, X-type zeolite and Y-type zeolite among sodium ions. It is particularly preferred that the zeolite powder contains 4A zeolite among A zeolite. The zeolite powder is physically pulverized. For example, zeolite powder can be physically pulverized by passing it through a bead mill pulverizer.

The zeolite powder after the physical pulverization is dispersed in a solution containing M2 ₂ O, SiO ₂ and H ₂ O to prepare a slurry. M2 is an alkali metal, preferably K or Na. The molar ratio of M2 ₂ O / H ₂ O is, for example, in the range of 0.003 to 0.01, and the molar ratio of SiO ₂ / H ₂ O is, for example, in the range of 0.006 to 0.025. The amount of the zeolite powder is, for example, 0.5 to 10 g per 100 ml of the solution.

  The zeolite powder can be crystallized by heating the slurry in an autoclave. The conditions are, for example, a heating temperature of 100 to 230 ° C. and a heating time of 1 to 24 hours. Subsequently, the zeolite powder is washed and dried. Thereby, zeolite particles having an average particle size of 200 nm or less can be obtained.

  The pH of the zeolite particles is preferably from 7 to 10. When the pH of the zeolite particles is 7 or more, the crystals of the zeolite particles are less likely to be broken, so that the sealing material made from the composition (X) containing the zeolite particles can have particularly high hygroscopicity. When the pH of the zeolite particles is 10 or less, the zeolite particles hardly inhibit the curing when the composition (X) is cured.

  The pH of the zeolite particles was determined by heating a dispersion obtained by adding 0.05 g of zeolite particles to 99.95 g of ion-exchanged water at 90 ° C. for 24 hours, and then measuring the pH of the supernatant of the dispersion with a pH meter. It is a value obtained by measuring with. As the pH measuring device, for example, a compact pH meter <LAQUATwin> B-711 manufactured by Horiba, Ltd. can be used.

  In order for the pH of the zeolite particles to be 7 or more and 10 or less, it is preferable that the zeolite particles be made of a FAU Y-type zeolite having a proton as a counter cation.

  In the process of producing the zeolite particles, when performing hydrothermal synthesis of zeolite, a treatment for adjusting pH may be performed. The treatment for adjusting the pH is performed, for example, before heating the slurry containing the zeolite powder prepared for hydrothermal synthesis, during heating the slurry, or after heating the slurry. The pH is adjusted by, for example, adding an acid to the slurry. The acid contains at least one component selected from the group consisting of inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid and organic acids such as formic acid, acetic acid and oxalic acid.

  The average particle size of the moisture absorbent (E) is preferably 10 nm or more and 200 nm or less. When the average particle size is 200 nm or less, the cured product can have particularly high transparency. When the average particle size is 10 nm or more, good hygroscopicity of the hygroscopic agent (E) can be maintained. The average particle diameter is a median diameter calculated from the measurement result by the dynamic light scattering method, that is, a cumulative 50% diameter (D50). As a measuring device, a Nanotrac Wave series manufactured by Microtrac Bell Co., Ltd. can be used.

  The average particle size of the moisture absorbent (E) is more preferably 150 nm or less, further preferably 100 nm or less, and particularly preferably 70 nm or less. The average particle size of the moisture absorbent (E) is preferably 20 nm or more, more preferably 50 nm or more. In this case, the cured product can have particularly good transparency and hygroscopicity.

  The 90% cumulative diameter (D90) of the moisture absorbent (E) is also preferably 100 nm or less. In this case, the cured product can have particularly high transparency.

  The ratio of the moisture absorbent (E) to the total amount of the composition (X) is preferably from 1% by mass to 20% by mass. When the proportion of the hygroscopic agent (E) is 1% by mass or more, the cured product can have particularly high hygroscopicity. When the proportion of the moisture absorbent (E) is 20% by mass or less, the viscosity of the composition (X) can be particularly reduced, and the composition (X) has a sufficiently low viscosity that can be applied by an inkjet method. Can also. The proportion of the moisture absorbent (E) is more preferably 3% by mass or more, particularly preferably 5% by mass or more. The proportion of the moisture absorbent (E) is more preferably 15% by mass or less, particularly preferably 13% by mass or less.

  The composition (X) may further contain an inorganic filler other than the moisture absorbent (E). Particularly, the composition (X) preferably contains nano-sized high refractive index particles. Examples of high refractive index particles include zirconia particles. When the composition (X) contains high refractive index particles, the cured product can have a high refractive index while maintaining good transparency of the cured product. Therefore, when the cured product is applied to the sealing material 5 in the organic EL light emitting device 1, the efficiency of extracting light that passes through the sealing material 5 and is emitted to the outside can be improved. The average particle size of the high refractive index particles is preferably in the range of 5 to 30 nm, and more preferably in the range of 10 to 20 nm.

  The ratio of the high refractive index particles in the composition (X) is appropriately designed so that the cured product has a desired refractive index. In particular, the high refractive index particles are preferably contained in the composition (X) such that the refractive index of the cured product is in the range of 1.45 or more and less than 1.55. In this case, the light extraction efficiency of the organic EL light emitting device 1 is particularly improved.

  It is preferable that the composition (X) does not contain a solvent. In this case, when preparing a cured product from the composition (X), there is no need to dry the composition (X) to volatilize the solvent.

  The composition (X) may further contain a dispersant (F). The dispersant (F) is a surfactant that can be adsorbed on the moisture absorbent (E). The dispersant (F) includes, for example, an adsorptive group (also referred to as an anchor) that can be adsorbed to the particles of the hygroscopic agent (E) and a chain-like adhering to the particles of the hygroscopic agent (E) by the adsorption of the adsorbable group to the particles of the hygroscopic agent (E) Or a tail that is a comb-shaped molecular skeleton. The dispersant (F) includes, for example, an acrylic dispersant having a tail having an acrylic molecular chain, a urethane dispersant having a tail having a urethane molecular chain, and a polyester dispersing agent having a polyester molecular chain having a tail. The composition contains at least one component selected from the group consisting of the agent and the agent.

  When the composition (X) contains the dispersant (F), the moisture absorbent (E) can be favorably dispersed in the composition (X) and the cured product. For this reason, even though the cured product and the sealing material 5 contain the moisture absorbent (E), the transparency of the cured product and the sealing material 5 is not easily reduced by the moisture absorbent (E). Further, the dispersant (F) can effectively suppress aggregation of the moisture absorbent (E) during storage of the composition (X). Therefore, the storage stability of the composition (X) is not easily reduced by the moisture absorbent (E). Further, the adhesion between the cured product, silicon nitride and silicon oxide is not easily reduced by the dispersant (F). This is because the dispersant (F) is easily adsorbed to the moisture absorbent (E) as described above, and thus the dispersant (F) is unlikely to affect the interface between the cured product and silicon nitride and silicon oxide. It is believed that there is. For this reason, the sealing material 5 can have high adhesion to the glass base material. Further, silicon nitride and silicon oxide may be used as the material of the passivation layer 6 in the organic EL light emitting device 1 in some cases. Therefore, when the passivation layer 6 is made of silicon nitride or silicon oxide, the sealing material 5 can have high adhesion to the passivation layer 6.

  The dispersant (F) preferably has a boiling point of 200 ° C. or higher. In this case, since the dispersant (F) hardly volatilizes from the composition (X), the storage stability of the composition (X) is further improved.

  The dispersant (F) preferably has one or both of a basic polar functional group and an acidic polar functional group as an adsorptive group. In this case, the desiccant (E) can be dispersed particularly well in the composition (X) and the cured product. This is because the dispersant (F) has one or both of a basic polar functional group and an acidic polar functional group, so that the dispersant (F) is easily adsorbed on the moisture absorbent (E). It is considered that the effect of dispersing phenomena is remarkably exhibited.

  Dispersant (F) may include a polymer. The weight average molecular weight of the polymer is, for example, 1000 or more. Polymers include, for example, hydroxyl group-containing carboxylic acid esters, salts of long-chain polyaminoamides and high-molecular-weight acid esters, salts of high-molecular-weight polycarboxylic acids, salts of long-chain polyaminoamides and polar acid esters, and high-molecular-weight unsaturated acid esters , Modified polyurethane, modified polyacrylate, polyetherester type anionic surfactant, salt of naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl phosphate, polyoxyethylene nonylphenyl ether, polyesterpolyamine, and stearylamine acetate It contains at least one component selected from the group. When the dispersant (F) contains a polymer, the steric hindrance effect that occurs when the polymer is adsorbed on the particles of the moisture absorbent (E) is improved, so that the dispersibility of the moisture absorbent (E) can be improved.

  The dispersant (F) can contain, for example, one or both of a dispersant (F1) having a basic polar functional group and a dispersant (F2) having an acidic polar functional group.

  The basic polar functional group in the dispersant (F1) having a basic polar functional group is, for example, at least one selected from the group consisting of an amino group, an imino group, an amide group, an imide group, and a nitrogen-containing heterocyclic group. Including the group of When the dispersant (F1) has a basic polar functional group, the dispersant (F1) is easily adsorbed to the moisture absorbent (E), and thus the dispersibility of the moisture absorbent (E) can be improved. The basic polar functional group can particularly enhance the ability of the dispersant (F1) to adsorb to the hygroscopic agent (E), can particularly improve the dispersibility of the hygroscopic agent (E), and can improve the dispersibility of the composition (X). It is preferable to include an amino group since the viscosity can be particularly reduced.

  The dispersant (F1) having a basic polar functional group is, for example, trade name: Solsperse 24000 (amine value: 41.6 mg KOH / g), trade name: Solsperse 32000 (amine value: 31.2 mg KOH / g), trade name : Solsperse 39000 (amine value: 25.7 mgKOH / g), trade name: Solsperse J100, trade name: Solsperse series manufactured by Japan Louvre Resol Co., Ltd. such as Solsperse J200; trade names: DisperBYK-108, DisperBYK-2013, DisperBYK -180, DISPERBYK-106, DisperBYK-162 (amine value: 13 mgKOH / g), trade name: DisperBYK-163 (amine value: 10 mgKOH / g), trade name: DISPERBYK-168 (amine value: DisperBYK series manufactured by BYK Japan KK, such as 1 mgKOH / g), trade name: DISPERBYK-2050 (amine value: 30.7 mgKOH / g), trade name: DISPERBYK-2150 (amine value: 56.7 mgKOH / g); Trade name: BYKJET-9151 (amine value: 17.2 mgKOH / g), trade name: BYKJET-9152 (amine value: 27.3 mgKOH / g), etc .; BYKJET series manufactured by BYK Japan KK; and trade name: Ajinomoto Fine-Techno stocks such as Ajispar PB821 (amine value: 11.2 mgKOH / g), trade name: Ajispar PB822 (amine value: 18.2 mgKOH / g), trade name: Ajispar PB881 (amine value: 17.4 mgKOH / g) Company made Including di-spar series.

  The amine value of the dispersant (F1) is preferably 10 mgKOH / g or more, more preferably 10 mgKOH / g or more and 30 mgKOH / g, and still more preferably 15 mgKOH / g or more and 30 mgKOH / g or less. Further, the dispersant (F1) preferably does not have a phosphate group. When the dispersant (F1) has a phosphate group, the acid value derived from the phosphate group is preferably equal to or less than the amine value. In this case, the dispersant (F1) can disperse the hygroscopic agent (E) particularly favorably, can particularly enhance the storage stability of the composition (X), and particularly enhance the transparency of the cured product. In addition, the adhesion between the cured product and silicon nitride and silicon oxide can be particularly enhanced. Among the components that can be included in the dispersant (F1), examples of the dispersant having an amino group and no phosphate group include DISPERBYK-108 manufactured by BYK Chemie. Examples of the dispersant having an amino group and a phosphate group and having an acid value derived from the phosphate group equal to or less than the amine value include DISPERBYK-2013 manufactured by BYK-Chemie and DISPERBYK-180 manufactured by BYK-Chemie.

  The acidic polar functional group in the dispersant (F2) having an acidic polar functional group is, for example, a carboxyl group. The dispersant (F2) contains, for example, DISPERBYK-P105 manufactured by Big Chemie.

  The amount of the dispersant (F) is preferably 5 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the moisture absorbent (E). When the amount of the dispersant (F) is 5 parts by mass or more, the advantage of the dispersant (F) can be particularly exhibited. When the amount of the dispersant (F) is 60 parts by mass or less, the adhesion between the cured product, silicon nitride, and silicon oxide can be further increased. The amount of the dispersant (F) is more preferably at least 15 parts by mass. The amount of the dispersant (F) is more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less.

  The composition (X) may further contain a silane coupling agent. The silane coupling agent can further enhance the adhesion between the sealing material 5 and the member made of an inorganic material. The silane coupling agent is at least selected from the group consisting of, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-isocyanatopropyltrimethoxysilane. It can contain one compound.

  The percentage of the amount of the silane coupling agent to the polymerizable compound (A) is, for example, 0.1% by mass or more and 10% by mass or less. In this case, excess silane coupling agent can be prevented from bleeding out from the sealing material 5. The percentage of the silane coupling agent is more preferably 0.5% by mass or more and 5% by mass or less.

  The composition (X) may further contain a surface modifier. In this case, a film formed from the composition (X) can be easily flattened. The surface modifier contains, for example, at least one compound selected from the group consisting of a surfactant and a leveling agent. Examples of the compound contained in the surface modifier include a silicone compound and a fluorine compound. More specific examples of the surface modifier include BYK-340, BYK-345 (all manufactured by BYK Japan KK), and Surflon S-611 (AGC Seimi Chemical Co., Ltd.).

  The composition (X) is selected from the group consisting of appropriate additives other than the above components, if necessary, for example, a reinforcing agent, a softener, a plasticizer, a viscosity modifier, an ultraviolet absorber, and an antioxidant. At least one compound may be contained.

  The composition (X) may contain a solvent, but preferably does not contain a solvent. When the composition (X) does not contain a solvent, there is no need to dry the composition (X) to evaporate the solvent when preparing a cured product from the composition (X). In addition, the deterioration of the sealing material 5 due to the solvent and the generation of outgas from the sealing material 5 can be suppressed.

  The composition (X) can be prepared by mixing the above components. The composition (X) is preferably liquid at 25 ° C.

  The viscosity of the composition (X) at 25 ° C. is preferably 50 mPa · s or less. In this case, the composition (X) can be easily formed at ordinary temperature by a method such as a casting method, and the composition (X) can be formed at ordinary temperature by an inkjet method. The viscosity at 25 ° C. of the composition (X) is more preferably 20 mPa · s or less, and particularly preferably 13 mPa · s or less. The viscosity of the composition (X) is, for example, 1 mPa · s or more, 5 mPa · s or more, or 10 mPa · s or more.

  It is also preferable that the viscosity at 40 ° C. of the composition (X) is 50 mPa · s or less. In this case, even if the viscosity of the composition (X) at room temperature is any value, it is possible to lower the viscosity by slightly heating the composition (X). Therefore, when heated, the composition (X) can be easily formed by a method such as a casting method, and the composition (X) can be formed by an ink jet method. The viscosity is more preferably 20 mPa · s or less, particularly preferably 13 mPa · s or less. The viscosity of the composition (X) at 40 ° C. is, for example, 1 mPa · s or more, 5 mPa · s or more, or 10 mPa · s or more.

  Such a low viscosity at 25 ° C. or 40 ° C. of the composition (X) can be achieved by the composition of the composition (X) described in detail above.

  When the thickness of the cured product of the composition (X) is 10 μm, the total light transmittance is preferably 90% or more. In this case, when the cured product is applied to the sealing material 5 in the organic EL light emitting device 1, the efficiency of extracting light that passes through the sealing material 5 and is emitted to the outside can be particularly improved. Such a high light transmittance of the cured product can be achieved by the composition of the composition (X) described in detail above.

  When the cured product of the composition (X) has a thickness of 20 μm, the transmittance of light having a wavelength of 400 nm after irradiation with ultraviolet rays for 100 hours is preferably 85% or more. In this case, the transparency of the sealing material 5 can be increased, the loss of light emission in the organic EL light emitting device 1 can be reduced, and the color reproducibility of light emitted from the organic EL light emitting device 1 can be improved. The light transmittance is more preferably 90% or more, and even more preferably 95% or more.

The cured product having a thickness of 100 μm of the composition (X) is exposed to an environment of 85 ° C. and 85% RH for 24 hours in accordance with JIS Z 0208, and has a moisture permeability of 100 g / m ² or less. Is preferred. In this case, defects such as dark spots in the organic EL element can be further reduced by the sealing material 5 made of the composition (X).

  When the cured product of the composition (X) is exposed to an environment of 85 ° C. and 85% RH for 24 hours, the moisture content of the cured product is preferably less than 0.5%. In this case, in this case, the sealing material 5 made of the composition (X) can further prevent defects such as dark spots in the organic EL element from occurring. The moisture content is more preferably 0.3% or less. The water content can be determined by, for example, the Karl Fischer method in accordance with JIS K 7251, and can also be determined from the weight increase after water absorption in accordance with JIS K 7209-2.

3. Method for Manufacturing Sealing Material and Method for Manufacturing Organic EL Light-Emitting Device A method for manufacturing the sealing material 5 using the composition (X) and a method for manufacturing the organic EL light-emitting device 1 will be described.

  In the present embodiment, it is preferable to form the sealing material 5 by molding the composition (X) by an inkjet method and then irradiating the composition (X) with ultraviolet rays to cure the composition (X). In this embodiment, since the viscosity of the composition (X) can be reduced, the composition (X) can be formed by an inkjet method.

  In applying the composition (X) by the inkjet method, when the composition (X) has a sufficiently low viscosity at room temperature, for example, when the viscosity at 25 ° C. is 50 mPa · s or less, particularly 20 mPa · s or less. Can be formed by applying the composition (X) by an inkjet method without heating.

  When the composition (X) has a property of being reduced in viscosity by being heated, the composition (X) may be heated and then applied to the composition (X) by an ink-jet method to form the composition. When the viscosity at 40 ° C. of the composition (X) is 50 mPa · s or less, particularly 20 mPa · s or less, the viscosity can be reduced by only slightly heating the composition (X). The composition (X) can be discharged by an inkjet method. The heating temperature of the composition (X) is, for example, 20 ° C or higher and 50 ° C or lower.

  A method for manufacturing the organic EL light emitting device 1 of the first example shown in FIG. 1 will be described. For example, first, the support substrate 2 is prepared. The organic EL element 4 is provided on one surface of the support substrate 2. The organic EL element 4 can be manufactured by an appropriate method such as an evaporation method and a coating method. In particular, it is preferable to manufacture the organic EL element 4 by a coating method such as an ink jet method.

  Next, a passivation layer 6 is provided. The passivation layer 6 can be manufactured by, for example, an evaporation method.

  Next, the composition (X) is formed by an inkjet method so as to cover one surface of the support substrate 2 and the organic EL element 4. When the passivation layer 6 is provided, the composition (X) is formed so as to cover the passivation layer 6. If the inkjet method is applied to both the formation of the organic EL element 4 and the application of the composition (X), the manufacturing efficiency of the organic EL light emitting device 1 can be particularly improved.

  Next, the transparent substrate 3 is overlaid on the composition (X). The transparent substrate 3 is, for example, a glass substrate or a transparent resin substrate.

  Next, ultraviolet rays are applied to the transparent substrate 3 from the outside. The ultraviolet rays pass through the transparent substrate 3 and reach the composition (X). Thereby, the radical polymerization reaction proceeds in the composition (X), the composition (X) is cured, and the sealing material 5 made of a cured product is produced. The thickness of the sealing material 5 is, for example, 5 μm or more and 50 μm or less.

  The composition (X) may be formed by a method other than the inkjet method, and may be formed by, for example, a casting method.

  A method for manufacturing the organic EL light emitting device 1 of the second example shown in FIG. 2 will be described.

  First, the support substrate 2 is prepared. A partition 7 is formed on one surface of the support substrate 2 by a photolithography method using, for example, a photosensitive resin material. Subsequently, a plurality of organic EL elements 4 are provided on one surface of the support substrate 2. The organic EL element 4 can be manufactured by an appropriate method such as an evaporation method and a coating method. In particular, it is preferable to manufacture the organic EL element 4 by a coating method such as an ink jet method. Thereby, the element array 9 is manufactured on the support substrate 2.

  Next, a first passivation layer 61 is provided on the element array 9. The first passivation layer 61 can be manufactured by an evaporation method such as a plasma CVD method.

  Next, the composition (X) is formed on the first passivation layer 61 by, for example, an inkjet method to form a coating film. If the inkjet method is applied to both the formation of the organic EL element 4 and the application of the composition (X), the manufacturing efficiency of the organic EL light emitting device 1 can be particularly improved. Subsequently, the coating film is cured by irradiating the coating material with ultraviolet rays to produce the sealing material 5. The thickness of the sealing material 5 is, for example, not less than 5 μm and not more than 50 μm.

  Next, a second passivation layer 62 is provided on the sealing material 5. The second passivation layer 62 can be manufactured by an evaporation method such as a plasma CVD method.

  Next, an ultraviolet curable resin material is provided on one surface of the support substrate 2 so as to cover the second passivation layer 62, and then the transparent substrate 3 is overlaid on the resin material. The transparent substrate 3 is, for example, a glass substrate or a transparent resin substrate.

  Next, ultraviolet light is applied to the transparent substrate 3 from the outside. The ultraviolet light passes through the transparent substrate 3 and reaches the ultraviolet-curable resin material. Thereby, the ultraviolet curable resin material is cured, and the second sealing material 52 is manufactured.

  Hereinafter, specific examples of the present invention will be described. However, the present invention is not limited only to the examples.

1. Preparation of Compositions The compositions of Examples and Comparative Examples were prepared by mixing the components shown in the following table. The details of the components shown in the table are as follows.
-Tetraethylene glycol diacrylate: TEGDA, manufactured by Osaka Organic Chemicals.
-Polytetramethylene glycol # 650 diacrylate: manufactured by Shin-Nakamura Chemical Co., Ltd., product number A-PTMG-65.
-4-hydroxybutyl acrylate glycidyl ether: manufactured by Nippon Kasei, part number 4HBAGE.
-2- (2-vinyloxyethoxy) ethyl acrylate: manufactured by Nippon Shokubai, part number VEEA.
-3-Ethyl-3 methacryloxymethyl oxetane: manufactured by Ube Industries, part number ETERNACOLL OXMA.
-3,4-epoxycyclohexylmethyl methacrylate: manufactured by Daicel, product number M100.
-2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide: Lucylin TPO, manufactured by BASF.
・ Hygroscopic agent 1:
The hygroscopic agent 1 is a zeolite particle produced by the following method and having a D50 of 60 nm, a D90 of 110 nm, and a pH of 10.

  As a starting material zeolite powder, sodium 4A zeolite having an average particle size of 5 μm was prepared, and 100 g of this zeolite powder and 100 g of ion-exchanged water were mixed to prepare a slurry. The zeolite powder in this slurry was pulverized with a bead mill using zirconia beads, and then the slurry was left at a temperature of 180 ° C. for 2 to 3 hours to obtain finely pulverized zeolite powder. This zeolite powder was crushed in a mortar, and then passed through a mesh to adjust the particle size, thereby obtaining a hygroscopic agent 1.

The pH of the desiccant was measured by the following method. After putting 0.05 g of the moisture absorbent and 99.95 g of ion-exchanged water into a polyethylene bottle, the bottle was placed in a thermostat and heated at 90 ° C. for 24 hours. Subsequently, the pH of the supernatant of the liquid in the bottle was measured using a compact pH meter <LAQUAAtwin> B-711 manufactured by Horiba, Ltd.
・ Hygroscopic agent 2:
The hygroscopic agent 2 is manufactured by the following method, and is a zeolite particle having a D50 of 150 nm, a D90 of 250 nm, and a pH of 10.

  As a starting material zeolite powder, sodium 4A zeolite having an average particle size of 5 μm was prepared, and 100 g of this zeolite powder and 100 g of ion-exchanged water were mixed to prepare a slurry. The zeolite powder in this slurry was pulverized by a method similar to that for zeolite particles 1 so that the average particle size became 150 nm.

  Subsequently, the slurry was left at a temperature of 180 ° C. for 2 to 3 hours to obtain finely pulverized zeolite powder. This zeolite powder was crushed in a mortar, and then passed through a mesh to adjust the particle size, thereby obtaining a hygroscopic agent 2.

2. Evaluation Test The following evaluation tests were performed on the examples and comparative examples. The results are shown in the table.

(1) Viscosity The viscosity of the composition was measured using a rheometer (manufactured by Anton Paar Japan, model number DHR-2) at a temperature of 25 ° C. and a shear rate of 1000 s ⁻¹ .

(2) Adhesion The composition was applied on an alkali-free glass (“AN100”, manufactured by Asahi Glass Co., Ltd.) to a thickness of 10 μm using a spin coater, and an LED-UV irradiator (peak wavelength) manufactured by Panasonic Electric Works, Ltd. (365 nm) and cured by irradiating ultraviolet rays under the condition of an integrated light quantity of 3000 mJ / cm ² to obtain a cured product. The cured product was subjected to a cross-cut test at a cutting interval of 1 mm in accordance with JIS K 5600-5-6. "A" when the peeling was 0%, "B" when the peeling was more than 0% and 10% or less, and "B" when the peeling was more than 10% in the cross cut test. C ".

(3) Outgas evaluation Outgas when a cured product of the composition was heated was sampled by a headspace method and measured by gas chromatography. 100 mg of the composition was placed in a vial for head space, and the composition was irradiated with ultraviolet rays using an LED-UV irradiator (peak wavelength: 365 nm) manufactured by Panasonic Electric Works Co., Ltd. under the condition of an integrated light amount of 1500 mJ / cm ² . After curing, the vial was sealed and heated at 100 ° C. for 100 hours, and then the gas phase in the vial was introduced into a gas chromatograph for analysis. As a result, with respect to the cured product, the case where the mass parts per million of the gas generated from the cured product was 300 ppm or less was “A”, and the case where it was more than 300 ppm and less than 500 ppm was “B”, it was 500 ppm or more. The case was rated "C".

(4) Luminescent Performance of Organic EL Element An ITO layer having a thickness of 1000 mm was formed on a glass substrate (length: 25 mm, width: 25 mm, thickness: 0.7 mm). The ITO layer was washed and then subjected to an ozone treatment. Subsequently, a 60 nm thick layer of α-NPD, a 60 nm thick layer of Alq3, a 0.5 nm thick layer of lithium fluoride, and a thickness of 10 mm × 10 mm of the ITO layer were formed by vacuum evaporation. Layers of 100 nm aluminum were made sequentially. Thus, an organic EL device was manufactured on a glass substrate. A silicon nitride layer (first passivation layer) having a thickness of about 1 μm covering the organic EL element was formed by a plasma CVD method. After discharging the composition on the first passivation layer using an ink jet printer (manufactured by MicroJet, “NanoPrinter300”), using an LED-UV irradiator (peak wavelength 365 nm) manufactured by Panasonic Electric Works, Ltd. Ultraviolet rays were irradiated under the condition of an integrated light quantity of 3000 mJ / cm ² to produce a sealing material. A silicon nitride layer (second passivation layer) having a thickness of about 1 μm and covering the sealing material was formed by a plasma CVD method. Thus, a sample was manufactured.

  After exposing this sample under the conditions of 85 ° C. and 85% RH for 100 hours, a voltage of 3 V was applied to the organic EL device in the sample to emit light. The emitting organic EL device was visually observed. As a result, “A” indicates that the organic EL element emits light uniformly without dark spots and peripheral extinction, and “B” indicates that at least one of dark spots and peripheral extinction is recognized. A case where a portion that did not emit light was remarkably observed was evaluated as “C”.

(5) Light transmittance The composition was applied to form a coating film, and this coating film was applied to a condition of about 200 mW / cm ² using an LED-UV irradiator (peak wavelength 365 nm) manufactured by Panasonic Electric Works, Ltd. Irradiated with UV light for 7 seconds to cure the film, thereby producing a film having a thickness of 10 μm. The transmittance of the film at a wavelength of 400 nm was measured.

Claims (12)

It contains a polymerizable compound (A), a photopolymerization initiator (B) and a hygroscopic agent (E) having an average particle diameter of 200 nm or less,
The polymerizable compound (A) is
A polyfunctional acrylic compound (A1) having a polyoxyalkylene skeleton and having two or more (meth) acryloyloxy groups in one molecule;
A monofunctional acrylic compound (A2) having one (meth) acryloyloxy group and at least one cationically polymerizable group in one molecule;
An ultraviolet curable resin composition for sealing an organic EL element. The viscosity at 25 ° C. is 5 mPa · s or more and 20 mPa · s or less;
The ultraviolet curable resin composition for sealing an organic EL element according to claim 1. The viscosity at 40 ° C. is 5 mPa · s or more and 20 mPa · s or less;
The ultraviolet curable resin composition for sealing an organic EL element according to claim 1. The glass transition temperature of the cured product obtained by curing is 100 ° C. or higher,
The ultraviolet curable resin composition for sealing an organic EL device according to claim 1. Outgas when the cured product obtained by curing is heated is 1.0% or less.
The ultraviolet curable resin composition for sealing an organic EL device according to claim 1. The mass ratio of the polyfunctional acrylic compound (A1) to the monofunctional acrylic compound (A2) is from 8: 2 to 5: 5,
The ultraviolet curable resin composition for sealing an organic EL device according to claim 1. The percentage of the amount of the photopolymerization initiator (B) to the polymerizable compound (A) is 3% by mass or more and 15% by mass or less.
The ultraviolet curable resin composition for sealing an organic EL device according to claim 1. The moisture absorbent (E) contains zeolite particles,
The ultraviolet curable resin composition for sealing an organic EL device according to claim 1. Molded by the inkjet method,
The ultraviolet curable resin composition for sealing an organic EL element according to claim 1. When the cured product obtained by curing has a thickness of 20 μm, the transmittance of light having a wavelength of 400 nm is 95% or more.
The ultraviolet curable resin composition for sealing an organic EL device according to claim 1. A method for manufacturing an organic EL light emitting device including an organic EL element and a sealing material covering the organic EL element,
The ultraviolet curable resin composition for sealing an organic EL element according to any one of claims 1 to 10, which is formed by an inkjet method, and then the ultraviolet curable resin composition for sealing an organic EL element is irradiated with ultraviolet rays. Including producing the sealing material by irradiating and curing,
A method for manufacturing an organic EL light emitting device. An organic EL element and a sealing material covering the organic EL element, wherein the sealing material is the ultraviolet curable resin composition for sealing an organic EL element according to any one of claims 1 to 10. A cured product,
Organic EL light emitting device.