TW201920585A - Cationic polymerization curing-type ink jet resin composition for sealing organic el element - Google Patents

Abstract

The present invention addresses the problem of providing a resin composition for sealing an organic EL element, the resin composition having a viscosity that allows application by ink jet, exceptional curing characteristics, and no coloring problem. This cationic polymerization curing-type ink jet resin composition for sealing an organic EL element includes a curable resin (A) and a cationic photoinitiator (B), the cationic polymerization curing-type ink jet resin composition for sealing an organic EL element being constituted such that the curable resin (A) includes the compound represented formula (II), and the cationic photoinitiator (B) is an iodonium salt.

Description

Resin composition for cationic polymerization hardening type inkjet for sealing organic EL elements

This invention relates to the resin composition for cationic polymerization hardening type inkjet for sealing of an organic EL element.

In recent years, organic electroluminescence elements (hereinafter also referred to as "organic EL elements") have been used in electronic devices such as next-generation lighting and displays due to their high brightness and low power consumption. When the organic EL element is brought into contact with water or oxygen, problems such as deterioration, decrease in luminance, or non-light emission occur. Therefore, the organic EL element must be protected from water or oxygen intruding into the electronic device. For this purpose, a sealing structure using a metal plate or a glass plate is used, but in this structure, the device cannot be made flexible.

As a method capable of making the device flexible and protecting the organic EL element from water or oxygen, there is a method in which a plurality of inorganic layers and organic layers are alternately laminated on the organic EL element to form a barrier film. ) To seal the organic EL element. According to this method, the penetration path of water and oxygen is extended by the barrier film, and the organic EL element can be protected from water or oxygen invading into the electronic device. The method for forming the inorganic layer as the barrier film is performed by ALD, CVD, and sputtering. As a method for forming the organic layer, Patent Document 1 discloses a method by vapor deposition. However, in the method for forming an organic layer by vapor deposition, there are many problems such as the loss of the composition used and the contamination of the chamber.

On the other hand, as a general method of applying a composition to form an organic layer, there is an inkjet method. The inkjet method can solve the above-mentioned problems of the vapor deposition method. However, in order to discharge the inkjet nozzle, the composition must have a low viscosity.

Patent Document 2 discloses a composition for inkjet coating, which is used as an organic layer of a barrier film for sealing an organic EL element, and uses a curable resin containing a specific polysiloxane, Make the composition low in viscosity. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2005-522891 [Patent Document 2] WO2016 / 167347

[Problems to be Solved by the Invention]

The composition for inkjet coating disclosed in Patent Document 2 contains a resin having a high viscosity as a curable resin in addition to a specific polysiloxane, and therefore the composition has a high viscosity as a whole, which is difficult. Used for inkjet at room temperature. In addition, the composition for inkjet coating of Patent Document 2 confirms its curability at a so-called short wavelength of 365 nm, and is required to have more excellent curability even in the visible light region. Therefore, an object of the present invention is to provide a resin composition for sealing an organic EL device having a low viscosity, an excellent curability, and no coloring problem. [Means for solving problems]

The present invention has the following constitution. [1]. A cationic polymerization hardening type inkjet resin composition for sealing an organic EL element, comprising a hardening resin (A) and a photocationic polymerization initiator (B), wherein the hardening resin (A) contains In the compound represented by the formula (II), the photocationic polymerization initiator (B) is an iodonium salt. [2]. The resin composition for cationic polymerization hardening type inkjet for sealing of the organic EL element according to [1], wherein the curable resin (A) further contains a polysiloxane. [3]. The cationic polymerization hardening type inkjet resin composition for sealing an organic EL element according to [2], wherein the polysiloxane compound is a compound having a cation-curable functional group. [4]. The cationic polymerization hardening type inkjet composition for sealing an organic EL element according to [2] or [3], wherein the polysiloxane compound contains a compound selected from the following formula (IV), (V ) And at least one of the groups formed by the compounds represented by (IX). (In formula (IV), R ¹ is independently C ₁ to C ₆ alkyl, X ¹ is a group represented by -R ^{2 to} R ³ , and R ² is independently a single bond or C ₁ to C ₃ Alkyl, R ³ is independently 3,4-epoxycyclohexyl or 3,4-epoxycyclopentyl, m is an integer of 0 to 3, n is an integer of 0 to 3, in formula (V) , R ⁴ is independently C ₁ to C ₆ alkyl, and R ⁵ is independently C ₁ to C ₆ alkyl or 2- (3,4-epoxycyclohexyl) ethyl. In formula (IX), R ¹⁰ , R ¹¹ , and R ¹² are each independently methyl, methoxy, or ethoxy, and at least one of R ¹⁰ , R ^11, and R ¹² is methoxy or ethoxy. R ¹³ is under Any one of the structures represented by the formula, a is an integer of 1 to 4) [5]. The cation polymerization hardening type inkjet composition for sealing an organic EL element according to any one of [1] to [4], wherein the curable resin ( A) It further contains at least 1 sort (s) chosen from the group which consists of the compound represented by following formula (I), (III), and (VI). [6]. The cationic polymerization hardening type inkjet resin composition for sealing the organic EL element according to any one of [1] to [5], further comprising a thioxanthone sensitizer (C). [7]. The cationic polymerization hardening type inkjet resin composition for sealing an organic EL element according to any one of [1] to [6], wherein the viscosity at 25 ° C is 20 mPams or less. [8] An organic EL element comprising: a substrate; and an organic electroluminescent layer formed on the substrate by a first electrode layer and a second electrode layer, and between the first electrode layer and the second electrode layer. A formed element body portion; a barrier film formed on the element body portion by laminating an organic layer and an inorganic layer alternately, the organic layer in the barrier film is any one of [1] to [7] The cured product of the resin composition for cationic polymerization hardening type inkjet for sealing of the organic EL element of one item. [9]. The organic EL device according to [8], wherein in the barrier film, the organic layer and the inorganic layer are alternately laminated such that the first layer on the element body side becomes an organic layer. . [10]. The organic EL device according to [8], wherein in the barrier film, the organic layer and the inorganic layer are alternately laminated so that the first layer on the element body side becomes an inorganic layer. . [11]. A method for manufacturing an organic EL device according to any one of [8] to [10], which comprises forming the barrier film in the foregoing barrier film by the following steps (i) and (ii). Organic layer, step (i): coating the resin composition for sealing cation polymerization hardening type inkjet of the organic EL element according to any one of [1] to [7] by inkjet; step (ii) : The coated cation polymerization hardening type inkjet composition for an organic EL element is hardened by light irradiation and / or heating. [12]. A display comprising the organic EL element according to any one of [8] to [10]. [Effect of the invention]

The sealing resin composition of the organic EL element of the present invention has a low viscosity, is excellent in hardenability, and does not have a problem of coloring.

[Best Mode for Implementing Invention]

1. Resin composition for cationic polymerization hardening type inkjet resin composition for cationic polymerization hardening type inkjet resin (hereinafter also referred to as "resin composition"), which contains a curable resin (A) and a photocationic polymerization initiator (B) A cationic polymerization-curable resin composition for sealing an organic EL element, wherein the curable resin (A) includes a compound represented by the following formula (II) and the photocationic polymerization initiator (B ) Is a resin composition for cation polymerization hardening type inkjet for sealing organic EL elements that are iodonium salts. Here, the "cationic hardening composition" refers to a hardening composition which is polymerized using an acid as an initiator.

(1) Curable resin (A) The curable resin (A) is a resin that is cured by light or heat, and is preferably a resin that is cured by light. The sclerosing | hardenable resin (A) contains the compound represented by the said Formula (II).使用 By using the compound represented by the above formula (II), the balance between surface tension and viscosity can be improved, it is suitable for coating by inkjet, and a thin film can be formed.

The hardening resin (A) is represented by the above formula (II) from the viewpoint that the hardening property is good, the surface tension can be adjusted to a value suitable for inkjet coating, and the viscosity can be further reduced. The proportion of the compound is preferably 10 to 60% by mass, and more preferably 10 to 40% by mass.

The curable resin (A) is preferably further containing a polysiloxane. Polysiloxanes improve wetting. The polysiloxane is preferably a polysiloxane having a cation-curable functional group. The cation-curable functional group refers to a functional group that can be polymerized by an acid, and examples include a vinyl group having a high electron density containing a heterocyclic group and an electron donating group, and more specifically, an epoxy group. Group, oxetanyl, vinyl ether group (CH ₂ = CH-O-), and the like, particularly preferably an epoxy group. Among polysiloxanes having a cation-curable functional group, an alicyclic epoxy polysiloxane is more preferred.

The polysiloxane compound having a cation-curable functional group is preferably at least one selected from the group consisting of the following formulae (IV), (V), and (IX). (In formula (IV), R ¹ is independently C ₁ to C ₆ alkyl, X ¹ is a group represented by -R ^{2 to} R ³ , and R ² is independently a single bond or C ₁ to C ₃ Alkyl, R ³ is independently 3,4-epoxycyclohexyl or 3,4-epoxycyclopentyl, m is an integer of 0 to 3, n is an integer of 0 to 3, in formula (V) , R ⁴ is independently C ₁ to C ₆ alkyl, and R ⁵ is independently C ₁ to C ₆ alkyl or 2- (3,4-epoxycyclohexyl) ethyl. In formula (IX), R ¹⁰ , R ¹¹ , and R ¹² are each independently methyl, methoxy, or ethoxy, and at least one of R ¹⁰ , R ^11, and R ¹² is methoxy or ethoxy. R ¹³ is under Any one of the structures represented by the formula, a is an integer from 1 to 4).

Here, the alkyl group may be arbitrarily linear or branched, and examples thereof include methyl, ethyl, propyl, i-propyl, n-butyl, t-butyl, n-pentyl, and n -Hexy etc.

In formula (IV), R ¹ is preferably the same methyl or ethyl group. R ² is preferably the same C ₂ to C ₃ alkylene. The R ³ system is preferably the same 3,4-epoxycyclohexyl group. In formula (V), R ⁴ is preferably the same methyl or ethyl group, and R ⁵ is preferably the same methyl, ethyl or 2- (3,4-epoxyhexyl) ethyl group.

Examples of the compound represented by the formula (IX) include: These are commercially available as KBM-403, KBM-402, KBE-403, KBE-402, KBM-303 as Shinetsu silicone Co., Ltd.

In formula (IX), R ¹⁰ , R ^11, and R ¹² are each preferably a methoxy group or an ethoxy group, and R ^{13 is} preferably a structure represented by the following formula.

As the compound represented by formula (IV), the following compounds are particularly preferred. As the compound represented by formula (V), the following compounds are particularly preferred. As the compound represented by formula (IX), the following compounds are particularly preferred.

The compound represented by the formula (IV), the compound represented by the formula (V), and the compound represented by the formula (IX) may be used alone or in a combination of two or more. Among the compound represented by formula (IV), the compound represented by formula (V), and the compound represented by formula (IX), it is preferably selected from the compound represented by formula (V) and the compound represented by formula (IX) At least one compound in a group of compounds.化合物 The compounds represented by the above formulae (IV), (V), and (IX) can improve the hardenability, and the molecular weight is substantially low, so the volatility can be reduced.

When the compounds represented by the above formulae (IV), (V), and (IX) are included, the above formula (in the curable resin (A)) is from the viewpoint of good curability and low viscosity. The proportion of the compound represented by IV) is preferably 10 to 80% by mass, more preferably 10 to 40% by mass, and even more preferably 10 to 30% by mass. The above formula (V) in the curable resin (A) The proportion of the compound represented is preferably 10 to 50% by mass, and more preferably 10 to 40% by mass. The proportion of the compound represented by the formula (IX) in the curable resin (A) is preferably 10 ~ 60% by mass, and more preferably 20 ~ 50% by mass.

The curable resin (A) preferably further contains at least one selected from the group consisting of compounds represented by the following formulae (I), (III), and (VI).

In the case where the compounds represented by the formulae (I), (III), and (VI) are included, the formula (I) in the curable resin (A) is in terms of good curability and low viscosity. The proportion of the compound represented by I) is preferably from 10 to 50% by mass, and more preferably from 10 to 40% by mass. The proportion of the compound represented by the formula (III) in the curable resin (A) is more preferred. It is 10 to 40% by mass, and more preferably 10 to 30% by mass. The proportion of the compound represented by the formula (VI) in the curable resin (A) is preferably 5 to 40% by mass, and more preferably 5 to 30% by mass.

The curable resin (A) may include the following curable resins in addition to the compounds described above. The other curable resin is not particularly limited as long as it has at least one cationically polymerizable functional group in the molecule, and examples thereof include epoxy, oxetanyl, and ethylene having at least one in the molecule. Ether group (CH ₂ = CH-O-) and the like.

Examples of the compound having an epoxy group in the molecule include an aromatic epoxy compound, an aliphatic epoxy compound, an alicyclic epoxy compound, and other epoxy resins. An alicyclic epoxy compound is preferable because it has higher cationic polymerizability and can effectively perform light curing.

Examples of the aromatic epoxy compound include compounds such as phenyl glycidyl ether, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol AD type epoxy compounds, and bisphenol S type Bisphenol epoxy compounds such as epoxy compounds; naphthalene epoxy compounds; novolac epoxy compounds such as phenol novolac epoxy compounds, cresol novolac epoxy compounds; hydrogenated bisphenol A epoxy Alcohol-type epoxy compounds such as compounds; halogenated epoxy compounds such as brominated epoxy compounds; polyfunctional epoxy compounds. Specific examples thereof include EPICLON850, 850-S, and EXA-850CPR manufactured by DIC Corporation. Bisphenol A epoxy compounds; bisphenol F epoxy compounds such as EPICLON830-S, EXA-830LVP manufactured by DIC; naphthalene epoxy compounds such as HP-4032D and HP-7200H of EPICLON manufactured by DIC ; Phenol novolac type epoxy compounds such as EPICLON N-740, N-770 manufactured by DIC; cresol novolac types such as EPICLON N-660, N-670, N-655-EXP-S manufactured by DIC Epoxy compound; glycidyl ether of tetra (hydroxyphenyl) alkane, tetra Polyfunctional epoxy compounds such as glycidyl ether of hydroxydiphenyl ketone, epoxidized polyvinyl phenol and the like.

Examples of the aliphatic epoxy compound include polyglycidyl ether of a polyhydric alcohol or an alkylene oxide adduct thereof, and specific examples thereof include ethylene glycol diglycidyl ether and diethylene glycol diglycidyl ether , Propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,9-nonanediol diglycidyl ether Ether, 1,12-dodecanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether (Epolite 100MF manufactured by Kyoeisha Chemical Co., Ltd.), polyethylene glycol diglycidyl Ether, etc.

Examples of the alicyclic epoxy compound include a hydride of the aforementioned aromatic epoxy compound, a cyclohexane system, a cyclohexyl methyl ester system, a cyclohexyl methyl ether system, a spiro ring system, and a tricyclodecane system ring. Examples of the oxygen compound include hydrogenated bisphenol A type epoxy compounds such as KRM-2408 manufactured by ADEKA Corporation and YX-8034 manufactured by JER Corporation; 3 ', 4'-epoxycyclohexylmethyl 3 1,4-epoxycyclohexane carboxylic acid ester, 1, 2: 8,9-diepoxy limonene, 1,2-epoxy-4-vinylcyclohexane, 2,2-bis (hydroxymethyl An alicyclic epoxy compound such as 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 1-butanol (EHPE3150 manufactured by Daicel).

Examples of other compounds having an epoxy group in the molecule include a heterocyclic epoxy compound, a glycidyl ether epoxy compound, a glycidyl ester epoxy compound, a glycidylamine epoxy compound, and rubber modification. Epoxy compound, urethane modified epoxy compound, epoxidized polybutadiene, epoxidized styrene-butadiene-styrene block copolymer, epoxy-containing polyester compound, epoxy-containing Based polyurethane compounds, epoxy-containing acrylic compounds, and the like.

Specific examples of the compound having an oxetanyl group in the molecule include 3-ethyl-3-hydroxymethyloxetane (oxetanol) (for example, OXT manufactured by Toa Synthesis Corporation) -101), 2-ethylhexyloxetane (e.g., OXT-212 manufactured by Toa Synthesis), xylylene dioxetane (XDO / e.g., OXT-121 manufactured by Toa Synthesis), 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane (for example, OXT-221 manufactured by Toa Synthetic Corporation), oxetan Butylsilsesquioxane (e.g., OXT-191 manufactured by Toa Synthesis), phenol novolac oxetane (e.g., PHOX manufactured by Toa Synthesis) and 3-ethyl-3-phenoxymethyl Oxetane (POX: For example, OXT-211 manufactured by Toa Synthesis Corporation).

Specific examples of the compound having a vinyl ether group in the molecule include hydroxybutyl vinyl ether (for example, HBVE manufactured by Nippon Carbide Industries), and vinyl ether of 1,4-cyclohexanedimethanol (for example, Nippon Carveide Industries (CHVE), triethylene glycol divinyl ether (for example, DVE-3 manufactured by ISP), dodecyl vinyl ether (for example, DVE manufactured by Nippon Carbide Industries), and cyclohexyl vinyl ether (For example, CVE manufactured by Nippon Carbide Industries).

When the above compounds are combined with the compounds represented by the formulae (I) to (VI) and (IX), the viscosity and surface tension are selected in a manner suitable for inkjet coating. Decide how much to deploy. Therefore, in the curable resin (A), the curable resin other than the compounds represented by the formulae (I) to (VI) and (IX) is preferably less than 10% by mass, and more preferably 5% by mass or less. It is more preferable that curable resins other than the compounds represented by the formulae (I) to (VI) and (IX) are not included.

(2) Photocationic polymerization initiator (B) The photocationic polymerization initiator (B) is an iodonium salt. Since an iodonium salt can be used in a small amount to obtain excellent curability, it does not have problems such as coloring. Examples of the iodonium salt include compounds represented by the following formula (VII). In formula (VII), Ar ¹ and Ar ² are independently a substituted or unsubstituted aryl group, and an X ^- based anion.

Here, the "aryl group" in the formula (VII) means an aromatic hydrocarbon group having 6 to 18 carbon atoms, and is preferably a phenyl group or a naphthyl group. The aryl group may be unsubstituted or substituted with one or more optional substituents. Examples of such a substituent include a linear or branched alkyl group having 1 to 18 carbon atoms and a carbon number of 1 to 18 Straight or branched alkoxy group of 18, straight or branched alkoxycarbonyl group of 2 to 18 carbon atoms, straight or branched alkoxy group of 2 to 18 carbon atoms, halogen atom , Cyano, nitro, hydroxyl, etc.

The anionic portion X of the formula (VII) ^-, include _{^{C1 -, Br -, SbF 6}} -, PF 6 -, BF 4 -, by the following formula (VIII) represented by the anion portion, PF ₄ (CF _{3 ^{CF 2) 2 -, PF 5}} (CF 3 CF 2) -, (C 6 F 5) 4 B -, ((CF 3) 2 C 6 H 3) 4 B -, (C 6 F 5) 4 Ga - _{, ((CF 3) 2 C} 6 H 3) 4 Ga - like, preferably by the following formula (VIII) or of the anionic portion represented by _{(C 6 F 5) 4 B} -, and is preferably represented by the following formula ( VIII). In formula (VIII), n is an integer of 3 to 5, and p is an integer of 1 to 3. In formula (VIII), since 6-n is 1 or more, the anion has a fluorinated carbon chain and can act as a relatively strong acid. Therefore, the cationic polymerization performance becomes higher, and the UV curability becomes better. As the anion moiety of formula (VIII) represented by the, preferably _{[P (C 2 F 5)} 3 F 3] -. As the iodonium salt, a fluoroalkylfluorophosphonium iodonium salt is preferred, and in particular, Ar ¹ in the formula (VII) is 4-methylphenyl, Ar ² is 4-isopropylphenyl, X ^- is _{[P (C 2 F 5)} 3 F 3] - compounds are preferred. As a commercial item of a photocationic polymerization initiator (B), IK-1 (made by San-apro company) is mentioned.

(3) Thiotanone-type sensitizer (C) The photocationic polymerization initiator (B) is preferably used together with thioxanthone-type sensitizer (C). Examples of the thioxanthone-based sensitizer include isopropylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2- Chloroxanthones, thioxanthone ammonium salts, and the like, among these, 2,4-diethylthioxanthone is preferred.

(4) Other components 树脂 As long as the effects of the present invention can be exhibited, the resin composition may contain further components. Examples of the further components include a storage stabilizer, an antioxidant, a plasticizer, a viscoelasticity adjusting agent, an interfacial activity adjusting agent (wetting agent or antifoaming agent), and a filler. The other components in the resin composition are preferably less than 10% by mass, and more preferably less than 3% by mass. As the storage stabilizer, a hindered phenol-based antioxidant can be used, and for example, Irganox 1010, Irganox 565, and Irganox 1035FF (all manufactured by BASF) can be used.

(5) Resin composition The resin composition is used for coating by inkjet. In order to discharge from a nozzle suitable for inkjet, the viscosity of the resin composition at 25 ° C is preferably 20 mPa ･ s or less, and more preferably 5 to 20 mPa ･ s. The viscosity was measured according to the method described in the examples. The composition for sealing the organic EL element is preferably reduced in viscosity without heating. With such a viscosity, the resin composition is suitable for coating by inkjet without heating.

The resin composition preferably does not contain an organic solvent. In order to reduce the viscosity of the composition, an organic solvent is generally used. However, if an organic solvent is contained in the composition for sealing the organic EL element, the organic solvent will penetrate into the interfaces of the organic EL element of the laminate and vaporize, thereby becoming The reason for interfacial peeling or because the remaining organic solvents cause the carriers of electrons and holes to be quenched and become a cause of hindering the function of the organic EL element, it is not appropriate to dilute the composition with an organic solvent to reduce the viscosity. Here, the term “does not include organic solvents” means that organic solvents are not included in an amount that affects the viscosity of the composition or the function of the organic EL element, but it does not exclude that it will not affect them. A very small amount of organic solvents. Examples of the organic solvent include organic compounds having a viscosity of less than 1 mPa ･ s at 25 ° C, and particularly alcohols, ethers, and lactones having a viscosity of less than 1 mPa ･ s at 25 ° C. Since it affects the organic EL element, it is preferable that the resin composition does not include water as a solvent, but the inclusion of moisture in the atmosphere is not excluded. Resin compositions are used for sealing organic EL devices.

The ratio of the photocationic polymerization initiator (B) to 100 parts by mass of the curable resin (A) in the resin composition is preferably 0.5 to 2 parts by mass, and more preferably 0.5 to 1 part by mass; thioxanthone The ratio of the system sensitizer (C) is preferably 0.01 to 1 part by mass, and more preferably 0.01 to 0.05 part by mass. In such a range, the hardening properties can be fully exhibited without coloring. The proportion of the storage stabilizer (including the antioxidant used as the storage stabilizer) is preferably 0.01 to 1.0 parts by mass, and more preferably 0.01 to 100 parts by mass of the curable resin (A) in the resin composition. 0.50 parts by mass.树脂 A resin composition can be produced by a method including a step of mixing the aforementioned components.

2. Organic EL element and manufacturing method thereof The organic EL element includes a substrate, an element body portion, and a barrier film. The element body portion is formed on the substrate by a first electrode layer and a second electrode layer, and the first electrode layer. The barrier film is formed of an organic electroluminescence layer between an electrode layer and a second electrode layer. The barrier film is formed on the element body, and an organic layer and an inorganic layer are alternately laminated.

The organic EL device may further include a vapor-deposited film of an ionic inorganic compound such as lithium fluoride, or a protective film made of an organic substance such as parylene between the element body and the barrier film. Functional film. The substrate is not particularly limited, and examples thereof include glass substrates, polysiloxane polymers such as polydimethylsiloxane and diphenylsiloxane, polysiloxane resin / polysiloxane rubber, and poly (siloxane). (Meth) acrylate, polyethylene terephthalate, polymethyl methacrylate A, polycarbonate, polyethylene, polypropylene, etc. polyolefin, polyurethane, polystyrene, fluorine Polymers (PTFE (polytetrafluoroethylene), PVdF (polyvinylidene fluoride), etc.), polyvinyl chloride, polymethylhydrosiloxane, and dimethylsiloxane and methylhydrosiloxane units A substrate formed of a copolymer or the like; an organic or inorganic light-emitting element; and an organic or inorganic semiconductor substrate, preferably a transparent and flexible material, and more preferably a polymer material.

The first and second electrodes are not particularly limited, and examples include zinc oxide, tin oxide, zinc aluminum oxide, tantalum oxide, and metal thin films (such as Ag with a thickness of 10 to 20 nm, ITO, ZnO, or IZO). A well-known transparent electrode material such as a metal film such as MgAg. As the organic electroluminescent layer, a layered structure composed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer is generally set as a basic structure, but these layers may be omitted. A few layers in the structure. As a material of each layer, a well-known material can be suitably selected and used.

The barrier film covers a surface of the element main body portion that is in contact with the substrate on the opposite side, and the side surface of the element main body portion and the substrate around the element main body portion may be covered as required. In addition to the above, a barrier film may be further provided between the element body and the substrate. The organic layer and the inorganic layer in the barrier film can be alternately laminated in such a manner that the first layer on the element body side becomes an organic layer, or the first layer in the body portion side can be interactively laminated. The lamination is performed, but the lamination is preferably performed alternately such that the first layer on the element body portion side becomes an organic layer. This is because at the same time that the bending of the organic EL element can be strengthened, the barrier film can be flattened, and further, foreign matter on the element body can be embedded.

The organic layer included in the barrier film is a cured product of the aforementioned cationic polymerization-curable resin composition for inkjet, and can be formed by the following steps (i) and (ii). Step (i): by spraying The above-mentioned resin composition for cation polymerization-curable inkjet is coated with ink; step (ii): the applied cation polymerization-curable resin composition for inkjet is cured by light irradiation and / or heating. Compared with the case where the organic layer is formed by the vapor deposition method, the resin composition is less lost when the organic layer is formed by using inkjet, so the amount of the resin composition can be reduced while not contaminating. Reaction chamber.

(Step i) As the inkjet device, a known device can be used. Examples of the coating method in coating by inkjet include a piezoelectric inkjet method, a thermal inkjet method, a valve inkjet method, and a continuous inkjet method. However, as a method of sealing an organic EL element, The unheated one is preferable, so the piezoelectric inkjet method and the valve inkjet method are preferable. The discharge temperature of the resin composition in the inkjet device is preferably 23 to 55 ° C, and more preferably 23 to 50 ° C. The above resin composition can be discharged without being heated, and the production of the organic EL element is desirably carried out without being heated, so it is particularly preferably 23 to 27 ° C.

(Step ii) The light source in step ii is not particularly limited as long as it is an energy ray, and examples thereof include active energy rays such as visible rays, ultraviolet rays, X-rays, and electron rays. Examples of the light source of the energy line include metal halogen lamps, ultra-high pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, xenon lamps, mercury-xenon lamps, halogen lamps, pulsed xenon lamps, and LEDs. Irradiation of energy rays can be performed in such a manner that the accumulated light amount of the energy rays becomes 100 to 15,000 mJ / cm ² . The cumulative light amount is preferably 500 to 10,000 mJ / cm ² , and more preferably 1,000 to 6,000 mJ / cm ² . The resin composition has a wavelength from the visible light region to a shorter wavelength from the viewpoint of the curability of the wavelength of the light irradiated by the light source. From the viewpoint of preventing damage to the organic EL element, Since the wavelength from the visible light region to a longer wavelength is suitable, the wavelength in the visible light region is more suitable in terms of both the hardening property and the prevention of damage to the organic EL element. Specifically, the peak wavelength of the LED includes 365 nm, 405 nm, 375 nm, 385 nm, 395 nm, and 405 nm, and is preferably 395 nm and 405 nm.

The inorganic layer included in the barrier film can be formed by ALD, CVD, sputtering, or the like. Examples of the inorganic material used include, but are not limited to, metal nitride compounds, metal oxide compounds, and metal halide compounds.

When a barrier film formed by laminating an organic layer and an inorganic layer alternately on the element body portion, the penetration path of water and oxygen can be extended, and the element body portion can be protected from water invading into the electronic device. Or oxygen. The organic EL element may have further layers. Examples of further layers include films of organic materials, inorganic materials, and combinations thereof, and inorganic material films are preferred. As an organic material, the organic material mentioned in the material of a base material is mentioned, for example. Examples of the inorganic material include metal oxides such as A1 ₂ O ₃ , SiO ₂ , TiO ₂ , ZrO ₂ , and ITO, metals such as Cu, Au, Mg, and Ag, BN, Si ₃ N ₄ , GaN, and TiN. Metal nitride and so on. The method for forming a further layer is not particularly limited, and in the case of an inorganic material film, the method is not particularly limited, and examples thereof include a sputtering method and an electron cyclotron resonance plasma CVD method. The thickness of the further layer is not particularly limited, but is preferably 0.01 to 1,000 μm, and more preferably 0.1 to 0.2 μm.

A preferred method for manufacturing an organic EL element is as follows: a method for manufacturing an organic EL element, which includes the following steps (1) and (2), (1): forming the element body on the substrate; (1) step ( 2): An organic layer and an inorganic layer are alternately laminated on the element body to form a barrier film. The organic layer in the step (2) is formed by the following steps (i) and (ii). ， Step (i): coating the aforementioned cationic polymerization-curable inkjet resin composition by inkjet; (ii) step (ii): curing the coated inkjet composition by light irradiation and / or heating. [Example]

Each composition of the Example and the comparative example was manufactured using the following raw materials. Formula (I): The compound represented by the above formula (I) Formula (II): The compound represented by the above formula (II) Formula (III): The compound represented by the above formula (III) Formula (IV): As the above formula (IV) One of the following compounds Formula (V): The following compound is one of the compounds represented by the formula (V). Formula (VI): The compound represented by the above formula (VI) Formula (IX): The following compound as one of the compounds represented by the above formula (IX) AL-OX: EX-141: Phenyl glycidyl ether (manufactured by Nagase chemtex Co., Ltd.) POX: phenyloxetane (manufactured by Toa Synthetic Corporation). It has the following structure. IK-1: 4-methylphenyl-4- (1-methylethyl) phenyliodonium tris (pentafluoroethyl) trifluorophosphate (manufactured by San-apro) DETXs: 2,4- Diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.) CPI-410S: 鋶 -type photoacid generator manufactured by San-apro Co. SI auxiliary: 4-hydroxyphenyldimethyl sulfonium methyl sulfite (Sanshin Industries (Production company) Storage stabilizer Irganox 1010: Hindered phenolic antioxidant (manufactured by BASF) used as a storage stabilizer

<Measurement method and evaluation criteria> (Viscosity) Measured at 25 ° C, No. 1 ° 34 '× R24 rotor, and 100 rpm using a viscometer (RC-215 manufactured by Toki Sangyo).

(Film hardenability) Each resin composition of the examples and comparative examples was applied on a glass substrate by a spin coating method to a thickness of 10 μm, and the coating films were each performed: (1) at 100 mW / cm ² , 10 seconds (1000mJ / cm ²⁾ to illuminate an LED 395nm case; (2) at 100mW / cm ^2, 30 seconds (3000mJ / cm ²⁾ to illuminate an LED 395nm situation; (3) passing through the metal halide lamp (the MHL) is irradiated 2 times to 3000mJ / cm ² of the case; by finger touch and evaluated according to the following basis of a hardened state immediately after the light irradiation. ：: The surface of the film is dry, so it is judged that the curing is sufficiently completed. (Triangle | delta): The stickiness of the residual part on a film, it is judged that hardening will continue as time progresses, but the current hardening after the said irradiation is insufficient. ×: The integrity of the film was not dried, so the hardenability was judged to be insufficient.

(Coloring) Each resin composition of the Examples and Comparative Examples was sandwiched by a glass slide so that the thickness was 100 μm, and 395 nm LEDs were irradiated at 100 mW / cm ² for 10 seconds (1000 mJ / cm ² ), The appearance of the coloring state immediately after light irradiation was visually observed, and evaluated based on the following criteria. ○: almost colorless ×: with yellow

[Examples 1 to 8, Comparative Examples 1 to 5] According to the preparations described in Table 1, each component was placed in a NANKO container with a capacity of 160 m1, and a three-one-motor (Shinto) was used at room temperature (25 ° C). (Manufactured by Scientific Corporation), and about 50 g of a resin composition was obtained.

When comparing Examples 1 to 3 and Comparative Examples 1 and 2, it can be seen that if AL-OX of another oxetane compound is used instead of the compound represented by the formula (II), the hardenability is poor. . When comparing Examples 1 to 3 and Comparative Example 3, it was found that if a large amount of EX-141 of a glycidyl compound is used instead of the compound represented by the formula (II), the hardenability is poor. It can be seen from Examples 4 to 8 that the compound represented by the above formula (II) can exhibit good hardenability without coloring even if it is not combined with the compound of the above formula (I). When comparing the Examples with Comparative Examples 4 and 5, it can be seen that, as a photopolymerization initiator, if CPI-410S of a sulfonium salt is used instead of the iodonium salt, the curability is poor when the amount is small. On the other hand, when the amount is large, although the hardenability is somewhat poor, coloring problems occur. [Industrial availability]

The resin composition of the present invention can be suitably used for sealing an organic EL device.

This patent application claims the priority of Japanese Patent Application No. 2017-129703 for a patent application filed on June 30, 2017, and refers to the entire disclosure of Japanese Patent Application No. 2017-129703 for reference in this specification.

Claims (12)

A resin composition for a cationic polymerization-curable inkjet for sealing an organic EL element, comprising a curable resin (A) and a photocationic polymerization initiator (B), wherein the curable resin (A) includes the following formula (II) ), Wherein the photocationic polymerization initiator (B) is an iodonium salt, . The resin composition for cationic polymerization hardening type inkjet for sealing the organic EL element according to claim 1, wherein the curable resin (A) further contains a polysiloxane. The resin composition for cationic polymerization hardening type inkjet for sealing an organic EL element according to claim 2, wherein the polysiloxane compound is a compound having a cation-curable functional group. The cationic polymerization hardening type inkjet composition for sealing an organic EL element according to claim 2 or 3, wherein the polysiloxane compound is selected from the group consisting of the following formulae (IV), (V), and (IX) At least one of the group of compounds, (In formula (IV), R ¹ is independently C ₁ to C ₆ alkyl, X ¹ is a group represented by -R ^{2 to} R ³ , and R ² is independently a single bond or C ₁ to C ₃ Alkyl, R ³ is independently 3,4-epoxycyclohexyl or 3,4-epoxycyclopentyl, m is an integer of 0 to 3, n is an integer of 0 to 3, in formula (V) , R ⁴ is independently C ₁ to C ₆ alkyl, and R ⁵ is independently C ₁ to C ₆ alkyl or 2- (3,4-epoxycyclohexyl) ethyl. In formula (IX), R ¹⁰ , R ¹¹ , and R ¹² are each independently methyl, methoxy, or ethoxy, and at least one of R ¹⁰ , R ^11, and R ¹² is methoxy or ethoxy. R ¹³ is under Any one of the structures represented by the formula, a is an integer from 1 to 4). The cation polymerization-curable inkjet composition for sealing an organic EL element according to any one of claims 1 to 4, wherein the curable resin (A) further contains a component selected from the following formulae (I) and (III): And at least one of the groups of compounds represented by (VI), . The cationic polymerization hardening type inkjet resin composition for sealing an organic EL element according to any one of claims 1 to 5, further comprising a thioxanthone-based sensitizer (C). The resin composition for cationic polymerization hardening type inkjet for sealing organic EL elements according to any one of claims 1 to 6, wherein the viscosity at 25 ° C is 20 mPa ･ s or less. An organic EL element comprising: a substrate; and an element formed on the substrate, the organic EL layer including a first electrode layer and a second electrode layer, and an organic electroluminescent layer between the first electrode layer and the second electrode layer. A body portion; a barrier film formed on the element body portion by laminating an organic layer and an inorganic layer alternately; the organic layer in the barrier film is an organic EL device according to any one of claims 1 to 7 A cured product of a resin composition for cationic polymerization-curable inkjet for sealing. The organic EL element according to claim 8, wherein the barrier film is configured such that the first layer on the element body side becomes an organic layer, and the organic layer and the inorganic layer are alternately laminated. The organic EL device according to claim 8, wherein the barrier film is configured such that the organic layer and the inorganic layer are alternately laminated so that the first layer on the device body side becomes an inorganic layer. A method for manufacturing an organic EL device according to any one of claims 8 to 10, which comprises forming the organic layer in the foregoing barrier film through the following steps (i) and (ii), (i) step (i): A cationic polymerization hardening type inkjet resin composition for sealing an organic EL element according to any one of claims 1 to 7 is applied by inkjet; Step (ii): The coated organic EL element is used for sealing The composition for a cationic polymerization hardening type inkjet is hardened by light irradiation and / or heating. A display having the organic EL element according to any one of claims 8 to 10.