JPWO2016170893A1 - Curable resin composition and electronic device such as organic electroluminescent element using the cured product - Google Patents

Abstract

The present invention is a curable resin composition comprising an aliphatic epoxy compound or an aliphatic oxetane (A) and / or an aliphatic (meth) acrylic compound (B) and a polymerization initiator compound (C). The molecular weights of A) and / or compound (B) are independently 290 or more and 500,000 or less, and the weight composition ratio when the curable resin composition is 100% by weight is the compound (A) and It is related with the curable resin composition whose compound (B) is 80 to 99.99 weight% in total, and compound (C) is 0.01 to 20 weight%. The composition eliminates damage when directly contacting the metal electrode of an organic EL element or flexible battery, and can solve the problem of peeling off of dark spots and metal electrodes on the light emitting surface.

Description

  The present invention relates to a curable resin composition useful as a sealant for an electronic device such as an organic electroluminescent element, and an electronic device using the cured product.

  An organic electroluminescent element (organic EL element) is an electronic device, and is expected as a liquid crystal backlight or a self-luminous thin flat display device. However, organic EL elements are extremely susceptible to deterioration when exposed to moisture and oxygen. In other words, the interface between the metal electrode and the organic EL layer is peeled off due to the influence of moisture, the metal is oxidized to increase the resistance, or the light emitting material contained in the light emitting layer of the organic EL element is altered by moisture. I do. For this reason, there are disadvantages that the organic EL element does not emit light or the luminance is lowered. In addition, even in an electronic device such as an inorganic LED, an electrical circuit connected to the device may be deteriorated by contact with moisture or the like.

  Therefore, many methods for protecting electronic devices such as organic EL elements from moisture and oxygen have been reported. As one of the methods, there is known a method of covering (surface sealing) an organic EL element with a sealant layer obtained by curing an epoxy resin composition (see, for example, Patent Documents 1 to 5). ). In these patent documents, resin compositions containing epoxy compounds having various structures and physical properties have been proposed as sealing agents, and the results are described that the influence on metal electrodes such as the occurrence of dark spots has been suppressed. However, it does not satisfy the requirements at a higher level than the present level, and there are actually problems that dark spots and electrodes are peeled off and the stability over time as a composition is poor.

  As another conventionally known protection method, a method of covering an organic EL element with a passivation layer made of an inorganic compound and then covering with a resin layer is also known. This is a method of forming a passivation film between them in order to suppress the influence of the resin component on the metal electrode of the organic EL element. In this method, in addition to the formation of the resin layer, the formation of the passivation film is performed. A process is required, which is not economical in terms of material cost and the number of processes.

  Therefore, a curable resin composition capable of forming a resin layer that does not require the formation of a passivation film, that is, the structure of the organic EL element, in particular, the metal electrode such as the cathode is not damaged and is more preferably stored. A resin composition having high stability is desired.

  On the other hand, in addition to organic EL elements, there are many electronic devices that use metals that can be eroded by moisture, oxygen, organic substances, etc., especially because the package edge portions of the anode and cathode used in flexible batteries are close to the outside world. A protective layer is required. However, since the protective layer itself may erode the anode and the cathode, there is a demand for a resin composition that does not cause damage even when directly in contact with a metal electrode such as the cathode, and more preferably has high storage stability.

JP 2006-179318 A International Publication No. 2006/104078 JP 2010-126699 A International Publication No. 2010/119706 JP 2013-166949 A

  The present invention has been made in view of the above situation. For example, it is a curable resin composition useful as a sealant for electronic devices such as organic EL elements and batteries (hereinafter also referred to as organic EL elements), particularly organic It is an object of the present invention to provide a curable resin composition that is not damaged even when directly contacted with an EL element or a battery structure (for example, a metal electrode such as a cathode) and more preferably has high storage stability.

  As a result of various studies to solve the above-described problems, the present inventors have found that a resin composition mainly composed of an aliphatic epoxy and / or an aliphatic oxetane compound (A) or an aliphatic (meth) acrylic compound (B). The present inventors have found that the above object can be achieved and have completed the present invention.

[1]
A curable resin composition comprising compound (A) and / or compound (B) and compound (C),
(A) Aliphatic epoxy and / or aliphatic oxetane (B) Aliphatic (meth) acrylic (C) polymerization initiator The molecular weights of the compound (A) and / or the compound (B) are independently 290 or more and 500 Less than 1,000,
The weight composition ratio when the curable resin composition is 100% by weight is that the total of the compound (A) and the compound (B) is 80% to 99.99% by weight, and the compound (C) is 0.01%. A curable resin composition that is 20% by weight to 20% by weight.

[2]
Compound (A) is a monovalent or divalent crosslinkable functional group represented by the following formula (AI), a monovalent or divalent crosslinkable functional group represented by formula (A-II), or The curable resin composition according to the above [1], which has at least one divalent crosslinkable functional group represented by the formula (A-III).
X in the above formula (AI) is 1 or 2, R ¹ is a single bond or an alkylene group having 1 to 30 carbon atoms, and at least one of the alkylene groups — (CH ₂ ) — is — May be substituted with O- or-(COO)-, R ² is an organic group represented by any one of the above formulas (R ² ), and R in * in formula (R ² ) ¹ and R ³ is hydrogen, a methyl group or an ethyl group,
X in the above formula (A-II) is 1 or 2,
One of R ⁴ in the above formula (A-III) is a single bond, and the other represents no bond,
The crosslinkable functional groups represented by the formulas (A-I) to (A-III) bind to other sites in the compound (A) at * in each formula, and the formula (A-I) or (A At least one hydrogen of the cyclohexane ring in -II) may be substituted with a methyl group, an ethyl group, a trifluoromethyl group, fluorine, chlorine, bromine or iodine.

[3]
Compound (A) is at least one of the compounds represented by the following formula (A-I-1), formula (A-I-2), formula (A-II-1) or formula (A-III-1) The curable resin composition according to the above [1] or [2].
R ⁵ in the above formula (AI-1) is a single bond or —C (R ¹⁰ ) ₂ —, and each R ¹⁰ is independently hydrogen, a methyl group or a trifluoromethyl group, R ⁶ is each independently a single bond or an alkylene group having 1 to 30 carbon atoms, and at least one — (CH ₂ ) — of the alkylene group is substituted with —O— or — (COO) —. And at least one hydrogen of the cyclohexane ring in formula (A-I-1) may be substituted with a methyl group, bromine, fluorine or chlorine,
R ⁷ in the above formula (A-I-2) is hydrogen, an alkyl group having 1 to 6 carbon atoms or a hydroxyl group, p is an integer of 1 to 100,
N in the above formula (A-II-1) is an integer of 1 to 4, R ⁸ is an n-valent alkylene group having 1 to 60 carbon atoms, and at least one of the alkylene groups — (CH ₂ ) — May be substituted with -O- or-(COO)-
R ⁹ in the above formula (A-III-1) is each independently hydrogen, an alkyl group having 1 to 6 carbon atoms or a hydroxyl group, and at least one — (CH ₂ ) — of the alkyl group is —O. -It may be substituted with a divalent oxirane group or-(COO)-, and v, w and x are each independently an integer of 1 to 50 and are repeated in v, w and x The position of the repeating unit may be interchanged. When Y is a single bond or an oxygen atom and is a single bond, it means that it is a double bond, and — (CH ₂ of the alkyl group of R ⁹ )-Is not substituted with a divalent oxirane group, at least one of Y is an oxygen atom, and z is an integer of 1-50.

[4]
[1] to [1] above, wherein the compound (B) comprises at least one of the compounds represented by the following formula (BI-1), formula (BI-2), or formula (BI-3): The curable resin composition according to any one of [3].
R ¹¹ in the above formula (BI-1), formula (BI-2), or formula (BI-3) is each independently hydrogen or a methyl group, and R ⁶ is Each independently represents a single bond or an alkylene group having 1 to 30 carbon atoms, and at least one — (CH ₂ ) — of the alkylene group may be substituted with —O— or — (COO) —;
R ⁵ in the above formula (BI-3) is a single bond or —C (R ¹⁰ ) ₂ —, and each R ¹⁰ is independently hydrogen, a methyl group or a trifluoromethyl group.

[5]
The curable resin according to any one of the above [1] to [4], wherein the compound (A) and / or the compound (B) are each independently a low molecular weight compound having a molecular weight of 290 or more and less than 2,000. Composition.

[6]
Compound (A) and / or Compound (B) each independently comprises a low molecular weight component having a molecular weight of 290 or more and less than 2,000 and a high molecular weight component having a weight average molecular weight of 2,000 or more and less than 30,000. The curable resin composition according to any one of the above [1] to [4].

[7]
Curable resin composition in any one of said [1]-[6] containing a compound (A).

[8]
The weight composition ratio when the curable resin composition is 100% by weight is 95% to 99.99% by weight of the compound (A) and 0.01% to 5% by weight of the compound (C). The curable resin composition according to the above [7].

[9]
Curable resin composition in any one of said [1]-[6] containing a compound (B).

[10]
The weight composition ratio when the curable resin composition is 100% by weight is 80% to 95% by weight of the compound (B) and 5% to 20% by weight of the compound (C). [9] The curable resin composition according to [9].

[11]
The curable resin composition according to any one of the above [1] to [10], wherein the compound (C) is a photo / thermal acid generator or a photo radical generator.

[12]
Furthermore, when a solvent is contained, curable resin composition in any one of said [1]-[11] whose solvent is a non-aromatic compound.

[13]
When the solvent is included, the curable resin composition according to any one of the above [1] to [12], wherein the weight composition ratio when the curable resin composition is 100% by weight is 1% by weight or less.

[14]
The electronic device using the hardened | cured material of the curable resin composition in any one of said [1]-[13].

[15]
The organic electroluminescent element in which the hardened | cured material of the curable resin composition in any one of said [1]-[13] is directly contacting with the electrode and / or the organic thin film.

[16]
A battery, wherein a cured product of the curable resin composition according to any one of [1] to [13] is in direct contact with an electrode and / or an electrolytic solution.

  According to a preferred embodiment of the present invention, the curable resin composition significantly suppresses or eliminates damage caused by direct contact with, for example, a structure of an organic EL element or a battery (for example, a flexible battery), particularly a metal electrode such as a cathode. Therefore, an electronic device such as an organic EL element or a battery can be sealed with a resin layer without a passivation film. As a result, the problem of peeling off of dark spots and metal electrodes on the light emitting surface can be solved, and furthermore, the formation of the passivation film can be omitted to obtain an electronic device that is extremely advantageous economically. it can. Furthermore, according to a preferred embodiment, since this curable resin composition is excellent in storage stability, an advantageous sealing step can be realized also in this respect.

It is a schematic sectional drawing which shows the organic EL element which concerns on this embodiment. It is a schematic sectional drawing which shows the organic EL element (without a passivation layer) which concerns on this embodiment. It is a schematic sectional drawing which shows the flexible battery which concerns on this embodiment.

1. Curable resin composition of the present invention The curable resin composition of the present invention is a curable resin composition comprising a compound (A) and / or a compound (B) and a compound (C),
(A) Aliphatic epoxy and / or aliphatic oxetane (B) Aliphatic (meth) acrylic (C) polymerization initiator The molecular weights of the compound (A) and / or the compound (B) are independently 290 or more and 500 Less than 1,000,
The weight composition ratio when the curable resin composition is 100% by weight is that the total of the compound (A) and the compound (B) is 80% to 99.99% by weight, and the compound (C) is 0.01%. It is a curable resin composition that is 20% by weight to 20% by weight.

  When the aliphatic epoxy compound and / or the aliphatic oxetane compound (A) and the aliphatic (meth) acrylic compound (B) are contained in the resin composition, the total amount of the compound (A) and the compound (B) is 100% by weight. The weight composition ratio of the compound (A) is 5 to 95% by weight (the compound (B) is 95 to 5% by weight), the compound (A) is 20 to 80% by weight (the compound (B) is 80 to 80%). 20 wt%), compound (A) 30 to 70 wt% (compound (B) 70 to 30 wt%), compound (A) 40 to 60 wt% (compound (B) 60 to 40 wt%) The compound (A) is 45 to 55% by weight (the compound (B) is 55 to 45% by weight), the compound (A) is 50% by weight (the compound (B) is 50% by weight), and the like.

1-1. Aliphatic epoxy compounds and aliphatic oxetane compounds (A)
The compound (A) may be an aliphatic compound having an epoxy group or oxetanyl group in the molecule, and the number of epoxy groups or oxetanyl groups and the form of the aliphatic moiety may be any. In addition to linear aliphatic groups such as linear alkyls, branched aliphatic groups such as branched alkyls, and cyclic aliphatics such as cycloalkyls, the aliphatic moiety forms include linear aliphatic structures and cyclic aliphatics. A form in which a group structure is combined and a form in which a branched chain aliphatic structure and a cycloaliphatic structure are combined are also included. Since the compound (A) is an aliphatic compound, basically, no aromatic group (aryl group or heteroaryl group) is contained in the molecule.

  The molecular weight of the compound (A) is 290 to 500,000. From the viewpoint of molecular weight, the compound (A) is a low molecular weight compound having a molecular weight of 290 or more and less than 2,000 and a high molecular weight of 2,000 or more and 500,000 or less. It is divided into molecular weight compounds.

  The molecular weight of the low molecular weight compound is preferably 290 to 1,500, more preferably 290 to 1,000, and more preferably 290 to 500. When the molecular weight of the low molecular weight compound is within these ranges, the viscosity of the resin composition can be lowered, and for example, a coating process can be advantageously performed.

  The molecular weight of the high molecular weight compound is preferably 2,000 to 300,000, more preferably 2,000 to 100,000, more preferably 2,000 to 50,000, particularly preferably 2, 000 to 30,000, most preferably 2,000 to 10,000. If the molecular weight of the high molecular weight compound is within these ranges, the handling properties are good, the process can be applied to the printing process, and the yield is also good.

  The molecular weight of the low molecular weight compound can be obtained by calculating the sum of atomic weights of atoms constituting the molecule. On the other hand, the molecular weight of the high molecular weight compound is the weight average molecular weight Mw, which is a value in terms of polystyrene determined by the GPC method (column temperature: 35 ° C., flow rate: 1 ml / min). Standard polystyrene has a molecular weight of 580 to 300,000 polystyrene (for example, Agilent S-M2-10 polystyrene calibration kit Agilent Technologies), and PLgel MIXED-D (Agilent Technology) is used for the column. And can be measured using THF as the mobile phase. In addition, the weight average molecular weight of the commercial item in this specification is a catalog publication value.

  As described above, the compound (A) is divided into a low molecular weight compound and a high molecular weight compound, which may be composed of both of them, but is preferably composed of only a low molecular weight compound. This is because the handleability is particularly good, suitable for various printing processes, and the yield is also good.

As an epoxy group or oxetanyl group which a compound (A) has, the crosslinkable functional group represented, for example by a following formula (AI), a formula (A-II), or a formula (A-III) is mentioned.

  The crosslinkable functional groups represented by the above formulas (AI) to (A-III) are bonded to other sites (that is, aliphatic sites) in the compound (A) at * in each formula. Hereinafter, each formula will be described in detail.

The crosslinkable functional group represented by the above formula (AI) is a monovalent (formula (A-Ia)) or divalent (formula (A-Ib)) group as follows.

R ^{1 in} formula (AI) is a single bond or an alkylene group having 1 to 30 carbon atoms, and at least one — (CH ₂ ) — of the alkylene group is substituted with —O— or — (COO) —. R ² is an organic group (epoxy group or oxetanyl group) represented by any of the above formulas (R ² ), and is bonded to R ¹ in * in formula (R ² ) R ³ is hydrogen, a methyl group or an ethyl group. The “-(COO) —” means “— (C═O) —O—” or “—O— (C═O) —”.

The alkylene group having 1 to 30 carbon atoms in R ¹ in formula (AI) is preferably an alkylene group having 1 to 20 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, preferably carbon. an alkylene group having 1-5, alkylene group with at least one - (CH ₂₎ - is -O- or - (COO) - may be substituted with.

R ^{1 in} formula (AI) is preferably a single bond or an organic group represented by any ^{one of the} above formulas (R ¹ ), and n in formula (R ¹ ) is 1 to 10 An integer, which is bonded to the cyclohexane ring and R ² in formula (AI) at * in formula (R ¹ ). n is preferably an integer of 1 to 5, more preferably an integer of 1 to 3.

  At least one hydrogen of the cyclohexane ring in the formula (AI) may be substituted with a methyl group, an ethyl group, a trifluoromethyl group, fluorine, chlorine, bromine or iodine.

The crosslinkable functional group represented by the above formula (A-II) is a monovalent (formula (A-IIa)) or divalent (formula (A-IIb)) group as follows.

  At least one hydrogen of the cyclohexane ring in the formula (A-II) may be substituted with a methyl group, an ethyl group, a trifluoromethyl group, fluorine, chlorine, bromine or iodine.

The crosslinkable functional group represented by the above formula (A-III) is a divalent group.

One of R ⁴ in the formula (A-III) represents a single bond, and the other represents no bond. That is, the formula (A-III) means either the above formula (A-IIIa) or the formula (A-IIIb), and the structure of the formula (A-IIIa) has an unsaturated group branched from an aliphatic chain as an epoxy group. The structure of the formula (A-IIIb) is found when the unsaturated group contained in the aliphatic main chain is epoxidized.

Specific examples of the compound (A) include compounds represented by the following formula (AI-1) or the following formula (AI-1 ′).

R ⁵ in the above formula (AI-1) is a single bond or —C (R ¹⁰ ) ₂ —, and each R ¹⁰ is independently hydrogen, a methyl group or a trifluoromethyl group. R ⁶ in the formula (A-I-1) is each independently a single bond or an alkylene group having 1 to 30 carbon atoms, preferably an alkylene group having 1 to 20 carbon atoms, preferably carbon number. An alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 5 carbon atoms, wherein at least one — (CH ₂ ) — of the alkylene group may be substituted with —O— or — (COO) —. Good. The “-(COO) —” means “— (C═O) —O—” or “—O— (C═O) —”. At least one hydrogen of the cyclohexane ring in the formula (AI-1) may be substituted with a methyl group, bromine, fluorine or chlorine.

R ⁵ in the above formula (AI-1 ′) is a single bond or —C (R ¹⁰ ) ₂ —, and each R ¹⁰ is independently hydrogen, a methyl group or a trifluoromethyl group. . R ⁶ in the formula (AI-1 ′) is each independently a single bond, a methylene group or an organic group represented by any one of the above formulas (R ⁶ ), and n is 1 to 1 An integer of 10, which is bonded to a cyclohexane ring and an oxygen atom at * in the formula (R ⁶ ). n is preferably an integer of 1 to 5, more preferably an integer of 1 to 3. At least one hydrogen of the cyclohexane ring in the formula (AI-1 ′) may be substituted with a methyl group, bromine, fluorine or chlorine. Specific examples include the following compounds.

Specific examples of the compound (A) include a compound represented by the following formula (A-I-2).

R ⁷ in the above formula (A-I-2) is hydrogen, an alkyl group having 1 to 6 carbon atoms, or a hydroxyl group, and p is an integer of 1 to 100. R ⁷ is preferably a methyl group, hydrogen, or a hydroxyl group. Further, p is preferably an integer of 5 to 20.

Specific examples of the compound (A) include, for example, compounds represented by the following formula (A-II-1), the following formula (A-II-1 ′), or the following formula (A-II-1 ″). Can be mentioned.

N in the above formula (A-II-1) is an integer of 1 to 4. R ^{8 in} Formula (A-II-1) is an n-valent alkylene group having 1 to 60 carbon atoms, preferably an n-valent alkylene group having 1 to 50 carbon atoms, more preferably 1 to 1 carbon atom. A n-valent alkylene group having 40 to 30 carbon atoms, more preferably an n-valent alkylene group having 1 to 30 carbon atoms, and at least one — (CH ₂ ) — of the alkylene group is —O— or — (COO) —. May be substituted. The “-(COO) —” means “— (C═O) —O—” or “—O— (C═O) —”.

  P in the formula (A-II-1 ′) is an integer of 1 to 5, preferably an integer of 1 to 3.

  Q, r, s and t in the above formula (A-II-2 ″) are each independently an integer of 0 or more and satisfy q + r + s + t = 1 to 3. Preferred forms of q, r, s and t are q + r + s + t = 1 to 2, and a more preferable form is q + r + s + t = 1.

Specific examples of the compound (A) include a compound represented by the following formula (A-III-1).

R ⁹ in the above formula (A-III-1) is each independently hydrogen, an alkyl group having 1 to 6 carbon atoms or a hydroxyl group, and at least one — (CH ₂ ) — of the alkyl group is —O. -It may be substituted with a divalent oxirane group or-(COO)-. The “-(COO) —” means “— (C═O) —O—” or “—O— (C═O) —”. V, w and x in formula (A-III-1) are each independently an integer of 1 to 50, and the positions of the three types of repeating units repeated in v, w and x may be interchanged with each other. , Y is a single bond or an oxygen atom, and when it is a single bond, it means that it is a double bond. In addition, since the compound represented by Formula (A-III-1) has at least one oxirane as seen in Formula (A-III), — (CH ₂ ) — of the alkyl group of R ⁹ is When not substituted with a divalent oxirane group, at least one of Y is an oxygen atom. Z in Formula (A-III-1) is an integer of 1-50. When Y is a single bond in the repeating unit repeated at v, it means a cis-type double bond, and when Y is a single bond in the repeating unit repeated at x, it means a trans-type double bond.

R ⁹ is preferably a methyl group, hydrogen, or a hydroxyl group. V is preferably an integer of 2 to 30, more preferably an integer of 2 to 10. Moreover, w is preferably an integer of 2 to 30, more preferably an integer of 2 to 10. X is preferably an integer of 2 to 30, more preferably an integer of 2 to 10. The preferred form of v, w and x is w> v ≧ x, and the more preferred form is w> 2v ≧ 2x. Z is preferably an integer of 2 to 30, more preferably an integer of 2 to 10.

  Other specific examples of the compound (A) include hydantoin-based epoxy compounds derived from 5,5-dimethylhydantoin and the like; 2,2-bis [4- (2,3-epoxypropyl) cyclohexyl] propane (molecular weight 320 ), Aliphatic epoxy resins such as 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (molecular weight 367); aliphatics obtained by oxidizing double bonds in unsaturated hydrocarbon compounds such as polybutadiene An epoxy resin etc. are mentioned.

  Another specific example of the aliphatic epoxy resin is a polyglycidyl ether of a polyhydric alcohol having at least one cycloaliphatic structure, or cyclohexane oxide obtained by epoxidizing a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. And an epoxy resin obtained from a cyclopentene oxide-containing compound.

  For example, 2,3,14,15-diepoxy-7,11,18,21-tetraoxatrispiro [5.2.2.5.2.2] henicosane (molecular weight 324), ethylene bis (3,4- Epoxycyclohexanecarboxylate (molecular weight 310), methylenebis (3,4-epoxycyclohexane) (molecular weight 324), diethylene glycol (3,4-epoxycyclohexylmethyl ether) (molecular weight 326), hydrogenated bisphenol A diglycidyl ether (molecular weight 352) ), Hydrogenated tetramethylbiphenyl diglycidyl ether (molecular weight 366), hydrogenated bisphenol F diglycidyl ether (molecular weight 324), hydrogenated bisphenol E diglycidyl ether (molecular weight 338), bis (3,4-epoxycyclohexylmethyl) Adipate (molecular weight 366), dicyclopentadienedimethanol diglycidyl ether (molecular weight 306), bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate (molecular weight 394), dioctyl epoxyhexahydrophthalate (molecular weight 410), Epoxy hexahydrophthalate di-2-ethylhexyl (molecular weight 410), epoxidized 3-cyclohexene-1,2-dicarboxylic acid bis (3-cyclohexenylmethyl) modified ε-caprolactone (molecular weight 520) (trade name: Epolide GT301, Daicel Chemical Co., Ltd.), epoxidized butanetetracarboxylic acid tetrakis- (3-cyclohexenylmethyl) modified ε-caprolactone (molecular weight 789) (trade name: Epolide GT401, Daicel Chemical Co., Ltd.), 2,2-bis ( 1,2-epoxy-4- (2-oxiranyl) cyclosexane adduct of droxymethyl) -1-butanol (weight average molecular weight 2400) (trade name: EHPE3150, Daicel Chemical Co., Ltd.), epoxidized polybutadiene (weight average molecular weight 5900) ) (Trade name: Epolide PB3600, Daicel Chemical Co., Ltd.), epoxidized polybutadiene (number average molecular weight 2800) (trade name: R-45EPT, Nagase ChemteX Corporation), and the like.

  Further, examples of the epoxy resin include an epoxy resin obtained from a polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof; an epoxy resin obtained from a polyglycidyl ester of an aliphatic long-chain polybasic acid; glycidyl acrylate or Examples include homopolymers synthesized by vinyl polymerization of glycidyl methacrylate; glycidyl acrylate, or copolymers synthesized by vinyl polymerization of glycidyl methacrylate and other vinyl monomers. Specific examples of the polyglycidyl ether include triglycidyl ether of trimethylolpropane (molecular weight 302), tetraglycidyl ether of sorbitol (molecular weight 518), hexaglycidyl ether of dipentaerythritol (molecular weight 591), diglycidyl ether of polyethylene glycol, Polyglycol glycidyl ethers such as polypropylene glycol diglycidyl ether are included.

  In addition, specific examples of the polyglycidyl ester include a polyether polyol polyglycidyl obtained by adding one or more alkylene oxides to an aliphatic polyhydric alcohol such as propylene glycol, trimethylolpropane, and glycerin. Ethers, diglycidyl esters of long aliphatic dibasic acids are included.

  Further, examples of the epoxy resin include an epoxy resin obtained from a monoglycidyl ether of an aliphatic higher alcohol or a polyether alcohol obtained by adding an alkylene oxide thereto; a glycidyl ester of a higher fatty acid. Epoxy resins; epoxy resins obtained from epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized linseed oil, epoxidized polybutadiene and the like are included.

  About content of a compound (A), when curable resin composition is 100 weight%, the sum total of a compound (A) and the compound (B) mentioned later is 80 weight%-99.99 weight%, and is the remainder. Is basically occupied by the compound (C) described later. Since the resin composition contains “compound (A) and / or compound (B)”, only the epoxy and / or oxetane component of compound (A) is the part occupied by compounds (A) and (B) in the composition. This may be prepared in particular by an epoxy-oxetane curable resin composition. In the epoxy / oxetane curable resin composition, the compound (A) is contained in an amount of 80 to 99.99% by weight, preferably 85 to 99.99% by weight, more preferably 90 to 99% by weight. It is contained in an amount of .99 wt%, more preferably 95 wt% to 99.99 wt%. The remaining part in the resin composition is basically occupied by the compound (C) described later, and when the solvent is included, it is occupied by the compound (C) and the solvent. The epoxy and / or oxetane compound (A) requires a relatively small amount of a polymerization initiator, for example, a photo / thermal acid generator, for curing the epoxy and / or oxetane compound (A). The content can be increased. As a result, since the content of the compound (A) having a relatively large molecular weight is increased, the influence on the organic EL element is reduced. For example, the organic EL element can suppress the generation of dark spots and extend the lifetime of the electronic device. can do.

1-2. Aliphatic (meth) acrylic compound (B)
(Meth) acryl is a term representing both an acrylic group and a methacryl group.
The compound (B) may be an aliphatic compound having a (meth) acryl group in the molecule, and the number of (meth) acryl groups and the form of the aliphatic moiety may be any. In addition to linear aliphatic groups such as linear alkyls, branched aliphatic groups such as branched alkyls, and cyclic aliphatics such as cycloalkyls, the aliphatic moiety forms include linear aliphatic structures and cyclic aliphatics. A form in which a group structure is combined and a form in which a branched chain aliphatic structure and a cycloaliphatic structure are combined are also included. Since the compound (B) is an aliphatic compound, basically, no aromatic group (aryl group or heteroaryl group) is contained in the molecule.

  The molecular weight of the compound (B) is 290 to 500,000. From the viewpoint of molecular weight, the compound (B) is a low molecular weight compound having a molecular weight of 290 or more and less than 2,000 and a high molecular weight of 2,000 or more and 500,000 or less. It is divided into molecular weight compounds.

  The molecular weight of the low molecular weight compound is preferably 290 to 1,500, more preferably 290 to 1,000, and more preferably 290 to 500. When the molecular weight of the low molecular weight compound is within these ranges, the viscosity of the resin composition can be lowered, and for example, a coating process can be advantageously performed.

  The molecular weight of the high molecular weight compound is preferably 2,000 to 300,000, more preferably 2,000 to 100,000, more preferably 2,000 to 50,000, particularly preferably 2, 000 to 30,000, most preferably 2,000 to 10,000. If the molecular weight of the high molecular weight compound is within these ranges, it is likely to be a liquid having a viscosity suitable for mixing / coating operations at normal temperature and pressure, so that an improvement in process efficiency can be expected.

  The molecular weight of the low molecular weight compound can be obtained by calculating the sum of atomic weights of atoms constituting the molecule. On the other hand, the molecular weight of the high molecular weight compound is the weight average molecular weight Mw, which is a value in terms of polystyrene determined by the GPC method (column temperature: 35 ° C., flow rate: 1 ml / min). Standard polystyrene has a molecular weight of 580 to 300,000 polystyrene (for example, Agilent S-M2-10 polystyrene calibration kit Agilent Technologies), and PLgel MIXED-D (Agilent Technology) is used for the column. And can be measured using THF as the mobile phase. In addition, the weight average molecular weight of the commercial item in this specification is a catalog publication value.

  As described above, the compound (B) is divided into a low molecular weight compound and a high molecular weight compound, which may be composed of both of them, but is preferably composed of only the low molecular weight compound. This is because low molecular weight compounds have a wide range of viscosity depending on the material and are relatively easy to adjust the viscosity, so that they can be applied to various coating methods.

Specific examples of the compound (B) include compounds represented by the following formula (B-I-1) or formula (B-I-1 ′).

R ¹¹ in the above formula (BI-1) is each independently hydrogen or a methyl group. R ⁶ in the formula (BI-1) is each independently a single bond or an alkylene group having 1 to 30 carbon atoms, and at least one — (CH ₂ ) — of the alkylene group is —O— or It may be substituted with-(COO)-. The “-(COO) —” means “— (C═O) —O—” or “—O— (C═O) —”.

The alkylene group having 1 to 30 carbon atoms in R ⁶ in the formula (BI-1) is preferably an alkylene group having 1 to 20 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, preferably Is an alkylene group having 1 to 5 carbon atoms, and at least one — (CH ₂ ) — of the alkylene group may be substituted with —O— or — (COO) —.

R ¹¹ and R ¹² in the above formula (BI-1 ′) are each independently hydrogen or a methyl group, and n is an integer of 0 to 10. n is preferably an integer of 0 to 5, more preferably 0.

Specific examples of the compound (B) include compounds represented by the following formula (B-I-2) or formula (B-I-2 ′).

R ¹¹ in the above formula (BI-2) is each independently hydrogen or a methyl group. R ^{6 in} formula (BI-2) is each independently a single bond or an alkylene group having 1 to 30 carbon atoms, and at least one — (CH ₂ ) — of the alkylene group is —O— or It may be substituted with-(COO)-. The “-(COO) —” means “— (C═O) —O—” or “—O— (C═O) —”. The formula (B-I-2) means a chemical structure in which three (meth) acryloyloxy units and one ethyl group are bonded to carbon C.

The alkylene group having 1 to 30 carbon atoms in R ⁶ in the formula (BI-2) is preferably an alkylene group having 1 to 20 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, preferably Is an alkylene group having 1 to 5 carbon atoms, and at least one — (CH ₂ ) — of the alkylene group may be substituted with —O— or — (COO) —.

R ¹¹ and R ¹² in the above formula (BI-2 ′) are each independently hydrogen or a methyl group, and n is an integer of 0 to 10. The formula (BI-2 ′) means a chemical structure in which three (meth) acryloyloxy units and one ethyl group are bonded to carbon C. n is preferably an integer of 0 to 5, more preferably 0.

Specific examples of the compound (B) include compounds represented by the following formula (BI-3) or formula (BI-3 ′).

R ¹¹ in the above formula (BI-3) is each independently hydrogen or a methyl group. R ^{6 in} formula (BI-3) is each independently a single bond or an alkylene group having 1 to 30 carbon atoms, and at least one — (CH ₂ ) — of the alkylene group is —O— or It may be substituted with-(COO)-. The “-(COO) —” means “— (C═O) —O—” or “—O— (C═O) —”. R ^{5 in} formula (BI-3) is a single bond or —C (R ¹⁰ ) ₂ —, and each R ¹⁰ is independently hydrogen, a methyl group, or a trifluoromethyl group.

The alkylene group having 1 to 30 carbon atoms in R ⁶ in the formula (BI-3) is preferably an alkylene group having 1 to 20 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, preferably Is an alkylene group having 1 to 5 carbon atoms, and at least one — (CH ₂ ) — of the alkylene group may be substituted with —O— or — (COO) —.

R ⁵ in the above formula (BI-3 ′) is a single bond or —C (R ¹⁰ ) ₂ —, and each R ¹⁰ is independently hydrogen, a methyl group or a trifluoromethyl group. . R ⁶ in the formula (BI-3 ′) is each independently a single bond, a methylene group or an organic group represented by any one of the above formulas (R ⁶ ), and the formula (R ⁶ N is an integer of 0 to 10, and is bonded to the cyclohexane ring and the oxygen atom in the formula (BI-3 ′) at * in the formula (R ⁶ ). R ^{11 in} formula (BI-3 ′) is independently hydrogen or a methyl group. R ^{5 in} formula (BI-3 ′) is preferably a single bond, —CH ₂ — or —C (Me) ₂ —, and R ⁶ is preferably a single bond or a methylene group.

  Other specific examples of the compound (B) are listed below.

  Examples of the monofunctional aliphatic (meth) acrylic compound include ω-carboxypolycaprolactone mono (meth) acrylate (molecular weight 300 (molecular weight 314, the same applies when the residue is methyl)).

  Examples of the bifunctional aliphatic (meth) acrylic compound include isocyanuric acid ethylene oxide-modified di (meth) acrylate (molecular weight 397 (425)), polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, pentaerythritol di (Meth) acrylate monostearate (molecular weight 510 (538)), dipentaerythritol di (meth) acrylate (molecular weight 362 (390)) and the like.

  Examples of the trifunctional or higher polyfunctional aliphatic (meth) acrylic compound include trimethylolpropane tri (meth) acrylate (molecular weight 296 (338)), ethylene oxide-modified trimethylolpropane tri (meth) acrylate (molecular weight 296 (338) Above), propylene oxide modified trimethylolpropane tri (meth) acrylate (molecular weight 296 (338) or higher), epichlorohydrin modified trimethylolpropane tri (meth) acrylate (molecular weight 296 (338) or higher), ditrimethylolpropane tetra (meth) acrylate (Molecular weight 578 (620)), epichlorohydrin-modified glycerol tri (meth) acrylate (molecular weight 434 (476)), diglycerin tetra (meth) acrylate (molecular weight 382 (424)) Pentaerythritol tri (meth) acrylate (molecular weight 298 (340)), pentaerythritol tetra (meth) acrylate (molecular weight 352 (408)), dipentaerythritol penta (meth) acrylate (molecular weight 524 (594)), alkyl-modified dipenta Erythritol penta (meth) acrylate (molecular weight 578 (662) or more), alkyl-modified dipentaerythritol tetra (meth) acrylate (molecular weight 470 (526) or more), alkyl-modified dipentaerythritol tri (meth) acrylate (molecular weight 416 (458) Above, dipentaerythritol hexa (meth) acrylate (molecular weight 578 (662)), caprolactone-modified dipentaerythritol hexa (meth) acrylate (molecular weight 692-1262 ( 76-1346)), ethylene oxide-modified tri (meth) acrylate phosphate (molecular weight 392 (434)), tris [(meth) acryloxyethyl] isocyanurate (molecular weight 437 (479)), caprolactone-modified tris [(meth) acrylic. Roxyethyl] isocyanurate (molecular weight 551-779 (593-821)), urethane (meth) acrylate polystyrene macromonomer, polymethyl methacrylate macromonomer and the like.

  The curable resin composition of the present invention can also be used as a sealing agent for organic EL elements (hereinafter also referred to as “sealing agent for organic EL elements”). This sealing agent for organic EL elements contains a radically polymerizable monomer and a photoradical initiator. By being a radical polymerization system containing a radical polymerizable monomer and a photo radical initiator, the sealing agent for organic EL of the present invention can be inhibited from being polymerized by a substance eluted from the sealing agent. And the organic EL element can be surely sealed.

  The radical polymerizable monomer contains an aliphatic polyfunctional (meth) acrylate. The aliphatic polyfunctional (meth) acrylate does not dissolve the resin constituting the light emitting layer of the organic EL element. Moreover, since aliphatic polyfunctional (meth) acrylate is comparatively low-viscosity, it is excellent also in the handleability of the sealing agent for organic EL elements obtained.

  The aliphatic polyfunctional (meth) acrylate is not particularly limited and includes, for example, tricyclodecane dimethanol diacrylate, hydrogenated bisphenol A epoxy acrylate, hydrogenated bisphenol F epoxy acrylate, and the like. These aliphatic polyfunctional (meth) acrylates may be used alone or in combination of two or more.

  The radical polymerizable monomer preferably contains polyfunctional epoxy (meth) acrylate as long as the resin constituting the light emitting layer of the organic EL element is not dissolved. By containing polyfunctional epoxy (meth) acrylate, the sealing agent for organic EL elements obtained becomes a thing with little cure shrinkage at the time of hardening. In addition, in this specification, polyfunctional epoxy (meth) acrylate means what made acrylic acid or methacrylic acid react with the epoxy group of polyfunctional epoxy resin, and was made into (meth) acrylate.

  The polyfunctional epoxy resin used as the raw material of the said polyfunctional epoxy (meth) acrylate is not specifically limited, For example, a hydrogenated bisphenol type epoxy resin etc. are mentioned.

  In the polyfunctional epoxy (meth) acrylate, it is preferable that all epoxy groups are (meth) acrylated. The polyfunctional epoxy (meth) acrylate in which the epoxy group remains may dissolve the resin constituting the light emitting layer of the organic EL element. Moreover, the polyfunctional epoxy (meth) acrylate in which an epoxy group remains may corrode an electrode.

  The radical polymerizable monomer is a polyfunctional (meth) acrylate other than the above aliphatic polyfunctional (meth) acrylate and polyfunctional epoxy (meth) acrylate as long as the resin constituting the light emitting layer of the organic EL device is not dissolved. It is preferable to contain. By containing such a polyfunctional (meth) acrylate, the obtained sealing agent for organic EL elements improves the degree of polymerization of the cured product, reduces unreacted materials, and improves heat resistance.

  It is preferable that the sealing agent for organic EL elements of this invention contains a thermal radical initiator further. By containing a thermal radical initiator, the residual monomer after curing can be reduced by heating.

  The thermal radical initiator is not particularly limited, and examples thereof include organic oxides (manufactured by NOF Corporation, Perbutyl O, etc.), azo polymerization initiators (manufactured by Wako Pure Chemical Industries, Ltd., V-65, etc.), and the like. These thermal radical initiators may be used alone or in combination of two or more.

  About content of a compound (B), when a curable resin composition is 100 weight%, the sum total of a compound (A) and the compound (B) mentioned later is 80 weight%-99.99 weight%, and is the remainder. Is basically occupied by the compound (C) described later. Since the resin composition contains “compound (A) and / or compound (B)”, the portion occupied by the compounds (A) and (B) in the composition is only the (meth) acrylic component of the compound (B). It may be prepared, and this is particularly called a (meth) acrylic curable resin composition. In the (meth) acrylic curable resin composition, the compound (B) is contained in an amount of 80 to 99.99% by weight, preferably 80 to 99% by weight, more preferably 80 to 97% by weight. %, More preferably 80% to 95% by weight. The remaining part in the resin composition is basically occupied by the compound (C) described later, and when the solvent is included, it is occupied by the compound (C) and the solvent. The epoxy compound (B) needs to have a relatively large amount of polymerization initiator, for example, a photo radical generator, necessary for curing the epoxy compound (B), and inevitably the content in the resin composition as described above. However, the curing time is relatively short and the process is very efficient.

1-3. Polymerization initiator (C)
The polymerization initiator is for curing the above-described aliphatic epoxy compound (A) or aliphatic (meth) acrylic compound (B), and is a light / thermal acid generator, a photo radical generator, a curing catalyst, and an acid. An anhydride etc. are mentioned. In order to cure the aliphatic epoxy compound (A), among these, a light / thermal acid generator, a curing catalyst, an acid anhydride, and the like are used, and a light / thermal acid generator with relatively high curing efficiency is used. preferable. In order to cure the aliphatic (meth) acrylic compound (B), among these, a photo radical generator is particularly preferable.

  As described above, the polymer of the present invention having a crosslinkable functional group can be used in combination with a monomer that forms a matrix resin (for example, an epoxy resin) and a curing reaction initiator (for example, an acid generator).

  There is no restriction | limiting in a hardening reaction initiator, What is necessary is just a compound which can discharge | release the substance which starts cationic polymerization by active energy ray irradiation or a thermal energy. Examples of the curing reaction initiator include a carboxylic acid, an amine, an acid anhydride compound, an acid generator and the like, and preferably a double salt which is an onium salt which releases a Lewis acid or a compound thereof.

Representative examples of the curing reaction initiator include cation and anion salts represented by the following general formula.
[A] _{m +} [B] _m−

In the above formula, the cation [A] _{m +} is preferably an onium ion, and is represented by the following formula, for example.
[(Α) _a Q] _{m +}
α is an organic group having 1 to 60 carbon atoms and any number of atoms other than carbon atoms. a is an integer of 1-5. The a αs may be the same or different independently. Further, at least one α is preferably an organic group having an aromatic ring. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N = N. Further, when the valence of Q in the cation [A] _{m +} is q, m = a−q (where N = N is treated as valence 0).

On the other hand, the anion [B] _m- is preferably a halide complex, for example, represented by the following formula.
[LX _b ] _m−
L is a metal or metalloid such as B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, and halide. The central atom of the complex. X is a halogen atom or a pentafluorophenyl group, and b is an integer of 3 to 7. Further, when the valence of L in the anion [B] _m− is p, m = b−p.

Specific examples of the anion [LX _b ] _{m- represented by} the above general formula include tetrafluoroborate (BF ₄ ), hexafluorophosphate (PF ₆ ), hexafluoroantimonate (SbF ₆ ), hexafluoroarsenate. (AsF ₆ ), hexachloroantimonate (SbCl ₆ ), tetrakis (pentafluorophenyl) borate (B (C ₆ F ₅ ) ₄ ) and the like are included.

Moreover, what is shown by a following formula can also be preferably used for anion [B] _m- . L, X, and b in the following formula are the same as above.
[LX _b-1 (OH)] _m-

Examples of the anion [B] _m- further include perchlorate ion (ClO ₄ ) ⁻ , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonate ion (FSO ₃ ) ⁻ , toluenesulfonate anion Ions, trinitrobenzenesulfonic acid anions, and the like are also included.

  Among such onium salts, the curing reaction initiator in the present invention is more preferably an aromatic onium salt exemplified by the following (A) to (C). Among these, one of them can be used alone, or two or more of them can be mixed and used.

  (I) Aryl diazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate

  (B) Diaryliodonium salts such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-t-butylphenyl) iodonium hexafluorophosphate

  (C) 4-hydroxyphenylbenzylmethylsulfonium = tetrakis (pentafluorophenyl) borate, (4-acetoxyphenyl) benzyl (methyl) sulfonium = tetrakis (pentafluorophenyl) borate, (4-acetoxyphenyl) methyl (2-methyl) Benzyl) sulfonium = phosphonium salts such as tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluoroantimonate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate, diphenyl -4-thiophenoxyphenylsulfonium hexafluorophosphate, 4,4'-bis (diphenylsulfonio) fe Sulfido-bis-hexafluoroantimonate, 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluorophosphate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide -Bis-hexafluoroantimonate, 4,4'-bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexafluorophosphate, 4- [4 '-(benzoyl) phenylthio] phenyl-di- Triarylsulfonium salts such as (4-fluorophenyl) sulfonium hexafluoroantimonate and 4- [4 ′-(benzoyl) phenylthio] phenyl-di- (4-fluorophenyl) sulfonium hexafluorophosphate

Further, the curing reaction initiator in the present invention may be a mixture of an iron arene complex or an aluminum complex and silanols such as triphenylsilanol. Examples of iron arene complexes include (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron. -Hexafluorophosphate and the like, and examples of aluminum complexes include tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum and the like.

  Among these, from the viewpoint of practical use, the curing reaction initiator in the present invention is preferably an aromatic iodonium salt, an aromatic sulfonium salt, or an iron-arene complex.

  For example, when the matrix resin is an epoxy resin, the content of the curing reaction initiator (preferably an acid generator) is 10 to 500 mol of the epoxy group of the polymer of the present invention and the epoxy resin monomer. It is preferably 1 mole.

  The photo radical generator is not particularly limited as long as it is a compound that generates a radical or an acid upon irradiation with ultraviolet rays or visible light. However, the acyl phosphine oxide initiator, the oxyphenyl acetate ester initiator, the benzoylformate initiator, and Hydroxyphenyl ketone-based initiators are preferable, and among these, hydroxyphenyl ketone-based initiators are particularly preferable from the viewpoints of photocurability of the composition and light transmittance of a cured film to be obtained.

Specific examples of the photo radical generator include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy- 2-methyl-4'-isopropylpropiophenone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 4-dimethylaminobenzoic acid Ethyl acetate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4,4′-tri (t-butylperoxycarbonyl) Benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3′-di (methoxy) Carbonyl) -4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4′-di (methoxycarbonyl) -4,3′-di (t-butylperoxycarbonyl) benzophenone, 4,4′-di (Methoxycarbonyl) -3,3′-di (t-butylperoxycarbonyl) benzophenone, 2- (4′-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ′, 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ', 4'-dimethoxystyryl) -4,6-bi (Trichloromethyl) -s-triazine, 2- (2′-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4′-pentyloxystyryl) -4,6-bis ( Trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5 -(2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (P-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3′-carbonylbis (7-diethylaminocoumarin), 2- (o -Chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (4 -Ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, , 2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) ) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-) Morpholinopropionyl) -9-n-dodecylcarbazole, bis (Η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy 2-methyl-1-phenyl-1-propanone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propanone, 2-hydroxy-1- {4- [ 4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-1-propanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2- (Dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone, 2- (dimethylamino) -2-[(4-methylpheny L) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester, oxy-phenyl- Acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, methyl benzoylformate, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4 , 6-Trimethylbenzoyldiphenylphosphinate, 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzoyloxime)], 1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl] -ethanone-1- (O-acetyloxy) Beam), and the like.

  Among these, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl- 1-propanone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-1-propanone, 2,2-dimethoxy-2-phenyl Acetophenone, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester, oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, methyl benzoylformate, bis ( 2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethyl Diphenylphosphine oxide, and 2,4,6-trimethylbenzoyl diphenylphosphine acid esters are preferred.

  Examples of commercially available photo radical generators include Irgacure 184, Irgacure 651, Irgacure 127, Irgacure 1173, Irgacure 500, Irgacure 2959, Irgacure 754, Irgacure MBF, and Irgacure TPO (manufactured by BASF).

  Among these, Irgacure 1173 and Irgacure 184 are more preferable because of high reactivity and high curability of the (meth) acrylate monomer.

  The photo radical generator used in the composition of the present invention may be a single compound or a mixture of two or more compounds. The content of the photo radical generator is preferably 1 to 20% by weight of the total amount of the composition, and particularly preferably 5 to 15% by weight of the total amount of the ink composition in consideration of balance with other materials. A cured film having excellent light-curing property and high light transmittance can be obtained.

  As the photoradical initiator, a high molecular weight polymer photoradical polymer is suitable. After radical polymerization is initiated by irradiating a normal photoradical initiator with light, the residue may be outgassed to deteriorate the organic EL element or the like. However, it has been found that outgassing can be suppressed by using a polymer-type photoradical polymer. Examples of the polymer type photoradical polymer that are commercially available include KIP-150 and KIP EM (Lamberti).

  The curing catalyst has a function of starting the curing of the epoxy resin and promoting the curing. The curing catalyst may be a Lewis base compound. Examples of Lewis base compounds include tertiary amine compounds such as benzyldimethylamine and 2,4,6-tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2. -Imidazole compounds such as methylimidazole can be used, but other Lewis base compounds can also be used.

  The curing catalyst is not limited to the above, and a compound containing at least one oxetanyl group in the molecule can also be used. This compound includes 3-ethyl-3-hydroxymethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, [1- (3-ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, 2-ethylhexyl ( Monofunctional oxetane compounds such as 3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether; (3-ethyl-3-methyloxetane) ether, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) Methyl] benzene, dicyclopentenylbis (3-ethyl-3-oxeta) Rumethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, bisphenol F bis (3-ethyl-3-oxetanylmethyl) ether, etc. Bifunctional oxetane compounds of the above; polyfunctional oxetane compounds such as (3-ethyl-3-oxetanylmethyl) etherification product of phenol novolak resin, (3-ethyl-3-oxetanylmethyl) etherification product of cresol novolak resin It is done.

  The molecular weight of the curing catalyst is preferably 290 to 800, more preferably 290 to 500, and further preferably 290 to 400. When the molecular weight of the curing catalyst is less than 290, the influence on the organic EL element and the like is increased. On the other hand, if the molecular weight exceeds 800, the viscosity of the composition increases, which may be undesirable in the process.

  It is desirable to use an acid anhydride curing agent that can be cured at a temperature of 80 to 120 ° C. or lower, which is a heat resistant temperature of an organic EL element or the like. Specific examples include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, and the like.

  Furthermore, a polymer having an acid anhydride group can also be used. Examples of a method for introducing an acid anhydride group into the polymer include a method in which a vinyl monomer having an acid anhydride group is polymerized to form a polymer. Is mentioned. Examples of vinyl monomers having an acid anhydride group include compounds having an acid anhydride group and a vinyl group in the molecule such as itaconic anhydride, maleic anhydride, and 4-methacrylic acid ethyl trimellitic anhydride. It is done. Further, it may be a copolymer of a vinyl monomer having an acid anhydride group and other vinyl monomers. Examples of other vinyl monomers include (meth) acrylates. Examples of the ester group of (meth) acrylates include methyl group, ethyl group, isopropyl group, normal butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, benzyl group, isobornyl group, lauryl group, Regardless of a linear or branched structure such as a myristyl group, a group having a non-functional alkyl ester is preferable. In addition, monomers such as styrene, α-methylstyrene, and vinyl acetate that can be copolymerized with vinyl monomers having an acid anhydride group should be used as monomers constituting an acid anhydride group-containing polymer. Can do.

  By subjecting the vinyl monomers having the acid anhydride groups mentioned above and other vinyl monomers to radical polymerization in an organic solvent using an organic peroxide or an azo compound as a radical polymerization initiator, an acid anhydride group is obtained. A polymer containing is obtained. Although it may be used as it is after the polymerization, it is also possible to remove the organic solvent from the resin solution containing this polymer.

  Other methods for obtaining an acid anhydride group-containing polymer include a method of chemically modifying the main chain, side chain or terminal of a polymer having no acid anhydride group to form an epoxy group, And a method of polymerizing a polymer using a polymerization initiator or a chain transfer agent. The weight average molecular weight (polystyrene conversion) of the acid anhydride group-containing polymer by GPC is not particularly limited as long as it is compatible with other components forming the organic EL device sealing agent, and preferably the weight average molecular weight. 500 to 50,000. A polymer containing at least one acid anhydride in the molecule can be used in combination with other acid anhydrides.

  The content of the compound (C) is 0.01% by weight to 20% by weight when the curable resin composition is 100% by weight. However, there are many compounds containing aromatics in the polymerization initiator, and such aromatic compounds often cause problems by affecting the organic layers and metal electrodes of electronic devices such as organic EL elements. Is preferably as small as possible. From this viewpoint, the content of the compound (C) is preferably 0.01 to 15% by weight, more preferably 0.01 to 12.5% by weight, still more preferably 0.01 to 10% by weight. %, Particularly preferably 0.01 to 7.5% by weight, even more preferably 0.01 to 5% by weight, and most preferably 0.01 to 2.5% by weight.

  Further, the content of the polymerization initiator varies depending on whether the compound to be cured is an epoxy / oxetane type or a (meth) acrylic type, and a polymerization initiator necessary for curing the epoxy / oxetane compound (A), for example, light The amount of the thermal acid generator may be relatively small, and the amount of the polymerization initiator required for curing the (meth) acryl compound (B), for example, the photo radical generator, needs to be relatively large.

  The content of the polymerization initiator necessary for curing the epoxy-oxetane compound (A) is 0.01 to 20% by weight, preferably 0.01 to 15% by weight, more preferably 0.00. 01 to 12.5% by weight, more preferably 0.01 to 10% by weight, particularly preferably 0.01 to 7.5% by weight, and still more preferably 0.01 to 5% by weight. Most preferably, it is 0.01 to 2.5% by weight. However, when the resin composition contains a solvent, the content is reduced according to the content of the solvent.

  The content of the polymerization initiator necessary for curing the (meth) acrylic compound (B) is 0.01 to 20% by weight, preferably 0.1 to 20% by weight, more preferably 1 -20% by weight, more preferably 5-20% by weight. However, when the resin composition contains a solvent, the content is reduced according to the content of the solvent.

  If it is necessary to contain a large amount of a polymerization initiator, whether it is an epoxy / oxetane compound (A) or a (meth) acrylic compound (B), it is not an aromatic compound polymerization initiator. It is preferable to use a polymerization initiator of an aromatic compound. The compound (C) may be a mixed system of an aromatic compound and a non-aromatic compound, and the weight composition ratio when the compound (C) is 100% by weight is preferably 1 to 50 wt. % (Non-aromatic system is 50 to 99% by weight), more preferably aromatic system is 1 to 30% by weight (non-aromatic system is 70 to 99% by weight), more preferably aromatic system is 1 to 20% by weight (non-aromatic system is 80 to 99% by weight), particularly preferably aromatic system is 1 to 15% by weight (non-aromatic system is 85 to 99% by weight), most preferably Aromatic is 1 to 10% by weight (non-aromatic is 90 to 99% by weight).

  Further, when the resin composition contains the epoxy / oxetane compound (A) and the (meth) acrylic compound (B), the polymerization suitable for the epoxy / oxetane compound (A) depending on the weight composition ratio thereof. What is necessary is just to distribute the quantity of an initiator, and the quantity of the polymerization initiator suitable for a (meth) acrylic compound (B).

1-4. The solvent curable resin composition may contain a solvent, but as explained in the column of the polymerization initiator, the aromatic solvent affects the organic layer and the metal electrode of an electronic device such as an organic EL element. This often causes problems. Further, many solvents have a small molecular weight, and there is a high possibility that the solvent will penetrate into an organic layer constituting the organic EL element. Therefore, when using a solvent, it is preferable to use a non-aromatic solvent or to reduce the content as much as possible.

  From this viewpoint, the content of the solvent is preferably 0.01 to 15% by weight, more preferably 0.01 to 10% by weight, based on 100% by weight of the curable resin composition. Preferably it is 0.01-7 weight%, Especially preferably, it is 0.01-4 weight%, More preferably, it is 0.01-2 weight%, Most preferably, it is 0.01-1 weight% .

  Specific examples of solvents that can be used include ethyl lactate, water, methanol, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, glycerin, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl 3-methoxypropionate, 3-ethoxypropionic acid Ethyl, butyrate , Butyl propionate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy-2-methylpropyl Methyl pionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, cyclohexanone, cyclo Pentanone, toluene, xylene, anisole, 1,3-dioxolane, ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, dipropylene glycol dimethyl ether, Diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol Nomethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ether, triethylene glycol divinyl ether , Tripropylene glycol monomethyl ether, tetramethylene glycol monovinyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol Monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, methyl benzoate, ethyl benzoate, 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1- ( 2-hydroxyethyl) -2-pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylpropion Amide, N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, α-acetyl-γ-butyrolactone, ε-caprolactone, γ-hexanolactone, δ-hexanolactone, Methyl ethyl sul Examples include hydroxide and dimethyl sulfoxide. Also, Examide (trade name) manufactured by Idemitsu Kosan Co., Ltd., propylene carbonate, ethylene carbonate, hydrochlorofluorocarbon solvents (HCFC-141b, HCFC-225), hydrofluorocarbon (HFCs) solvents (2 to 4, 5 carbon atoms) And 6 or more HFCs), perfluorocarbon solvents (perfluoropentane, perfluorohexane), aliphatic hydrofluorocarbon solvents (fluorocyclopentane, fluorocyclobutane), oxygen-containing fluorine solvents (fluoroether, fluoropolyether, fluoro) Ketone, fluoroalcohol), aromatic fluorine solvent (α, α, α-trifluorotoluene, hexafluorobenzene) and the like.

  Among these, from the viewpoint of solubility, methyl ethyl ketone, cyclohexanone, isopropanol, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy Preference is given to methyl propionate, γ-butyrolactone, dimethyl sulfoxide and equamide (trade name) manufactured by Idemitsu Kosan Co., Ltd., propylene carbonate, ethylene carbonate and the like.

  In addition, when the curable resin composition of the present invention is applied to a substrate or the like with a slit coater (preferably used for application to a large substrate), propylene glycol monomethyl ether is improved in that application uniformity is improved. It is preferable to use a mixed solvent of acetate and diethylene glycol methyl ethyl ether, a mixed solvent of methyl 3-methoxypropionate and diethylene glycol methyl ethyl ether, a mixed solvent of propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate and diethylene glycol methyl ethyl ether. .

  As described above, a chlorofluorocarbon organic solvent can be used as the solvent, but in view of environmental considerations, a non-fluorocarbon organic solvent is preferable. In general, for example, a mixed solvent such as MEK (methyl ethyl ketone), CHN (cyclohexanone), MMP (methyl 3-methoxypropionate), IPA (isopropanol) and the like can be preferably used. Specifically, MEK, MMP and A mixed solvent of IPA or a mixed solvent of MEK, CHN, MMP and IPA can be mentioned. It is preferable that the blending ratio thereof is appropriately adjusted as necessary, for example, the kind of the epoxy resin, the kind of the copolymer, and improvement of leveling properties.

  In the above mixed solvent, further in terms of improving coating uniformity, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol Monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethyl lactate and the like are preferably blended. Among these, in consideration of safety to the human body, preferable examples of the solvent include propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether, ethyl lactate and the like. Is preferred.

  Specific examples of the solvent include these solvents, but a mixed solvent obtained by mixing another solvent other than the solvent may be used as long as the ratio is 30% by weight or less with respect to the total amount of these solvents. it can. Only 1 type may be used for a solvent and 2 or more types may be mixed and used for it.

1-6. Other Additives The composition of the present invention may contain additives depending on the intended properties. Examples of the additive include an epoxy resin other than the compound (A), a (meth) acrylic monomer / polymer other than the compound (B), a polyimide resin, an antistatic agent, a coupling agent, a pH adjuster, a rust inhibitor, and an antiseptic. Agents, antifungal agents, antioxidants, surfactants, fillers, anti-reduction agents, evaporation accelerators, chelating agents, and water-soluble polymers. Moreover, you may contain a pigment or dye according to a desired use. Only one type of additive may be used, or two or more types may be mixed and used.

<Epoxy resin other than compound (A)>
As the epoxy resin other than the compound (A), a compound having two or more oxirane rings is preferably used, and the epoxy resin other than the compound (A) may be used alone or in combination of two or more. It may be used.

  Examples of the epoxy resin other than the compound (A) include bisphenol A type epoxy resins such as aromatic epoxy resins, glycidyl ester type epoxy resins, aliphatic epoxy resins having a molecular weight of less than 290, and oxirane rings having a molecular weight of less than 290. And a copolymer of a monomer having a monomer and another monomer, and a polysilsesquioxane-modified epoxy resin.

  Examples of the monomer having an oxirane ring having a molecular weight of less than 290 include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.

  Specific examples of the epoxy resin other than the compound (A) include epoxy resins “807”, “815”, “825”, “827”, “828”, “190P”, “191P”, “1004”, “1256”. "JERYL6800" (manufactured by Mitsubishi Chemical Corporation), "Araldite CY177", "Araldite CY184" (trade name, manufactured by BASF), trade name "TECHMORE VG3101L" (manufactured by Printec Co., Ltd.), N, N, N ′, N′-tetraglycidyl-m-xylenediamine, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, trade name “XQ1247” (JNC Corporation) , TEPIC-VL, TEPIC-UC (Nissan Chemical Industry Co., Ltd.), epoxidized thermoplastic elastomer (number average molecular weight 2900) (Trade name: EPOFRIEND, Daicel Chemical Co., Ltd.), and ion fluid-type epoxy.

  In addition, a specific example of the epoxy resin other than the compound (A) may be a cycloaliphatic epoxy resin. Specific examples thereof include a polyglycidyl ether of a polyhydric alcohol having at least one cycloaliphatic, or a cyclohexane oxide or cyclopentene oxide-containing compound obtained by epoxidizing a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. Among the obtained epoxy resins, the molecular weight is less than 290.

  For example, “Celoxide 2021P”, “Celoxide 3000” (trade name, manufactured by Daicel Chemical Industries, Ltd.), 2,2-bis (3,4-epoxycyclohexyl) propane (molecular weight 224), vinylcyclohexene dioxide ( Molecular weight 140), 4-vinyl epoxycyclohexane (molecular weight 124), vinyl cyclohexene dioxide (molecular weight 140), dicyclopentadiene diepoxide (molecular weight 164), 1,2,8,9 diepoxy limonene (molecular weight 168) (trade name) : CEL3000, Daicel Chemical Co., Ltd.), 3,4-epoxy-6-methylcyclohexylcarboxylate (molecular weight 168), bis (2,3-epoxycyclopentyl) ether (molecular weight 182), 2- (3,4-epoxycyclohexyl) -5,5-spi -3,4-epoxy) cyclohexane-metadioxane (molecular weight 266), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (molecular weight 252), 3,4-epoxy-1-methylcyclohexylmethyl-3 , 4-epoxy-1-methylcyclohexanecarboxylate (molecular weight 278), 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate (molecular weight 278), 3,4-epoxy -3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate (molecular weight 278), 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate (molecular weight 78), ethylene glycol bis (3,4-epoxycyclohexyl methyl ether) (molecular weight 282), 1,2-epoxy-4- (2-oxiranyl) cyclosoxane of 2,2-bis (hydroxymethyl) -1-butanol Mixture of adduct and 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (trade name: EHPE3150CE, Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (molecular weight 182) ( Trade name: Cyclomer A400, Daicel Chemical Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (molecular weight 196) (trade name: Cyclomer M100, Daicel Chemical Co., Ltd.).

  Further, examples of the epoxy resin include an epoxy resin obtained from a polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof; an epoxy resin obtained from a polyglycidyl ester of an aliphatic long-chain polybasic acid; glycidyl acrylate or Examples include homopolymers synthesized by vinyl polymerization of glycidyl methacrylate; glycidyl acrylate, or copolymers synthesized by vinyl polymerization of glycidyl methacrylate and other vinyl monomers. Specific examples of the polyglycidyl ether include 1,4-butanediol diglycidyl ether (molecular weight 202), 1,6-hexanediol diglycidyl ether (molecular weight 230), glycerin triglycidyl ether (molecular weight 260), Among them, a composition containing the trade name “Araldite CY184”, the trade name “Celoxide 2021P”, the trade name “TECHMORE VG3101L”, the epoxy resin “828”, and the trade name “XQ1247” obtains a cured film with particularly good flatness. This is preferable.

  The concentration of the epoxy resin other than the compound (A) in the composition is preferably 0 to 5% by weight from the viewpoint that transparency and a cured film having excellent balance of adhesion to glass and ITO and electrodes are obtained. 0 to 3% by weight is more preferable.

<Polyimide resin>
The polyimide resin is not particularly limited as long as it has an imide group. A polyimide resin may use only 1 type and may mix and use 2 or more types. The polyimide resin can be obtained, for example, by imidizing an amic acid obtained by reacting an acid dianhydride and a diamine. The acid dianhydride and diamine are not particularly limited. The concentration of the polyimide resin in the composition is not particularly limited, but is preferably 0 to 5% by weight, more preferably 0 to 3% by weight from the viewpoint of obtaining a cured film having better heat resistance and chemical resistance. preferable.

<(Meth) acrylic monomer other than compound (B)>
Examples of the (meth) acrylic monomer other than the compound (B) include an aromatic monofunctional polymerizable monomer, an aromatic bifunctional (meth) acrylate, an aromatic trifunctional or higher polyfunctional (meth) acrylate, and a molecular weight of 290. Examples thereof include monofunctional polymerizable monomers that are less than 2, bifunctional (meth) acrylates having a molecular weight of less than 290, and trifunctional or more polyfunctional (meth) acrylates having a molecular weight of less than 290. Only 1 type may be used for (meth) acrylic monomers other than a compound (B), and 2 or more types may be mixed and used for it.

  The concentration of the (meth) acrylic monomer other than the compound (B) in the composition is not particularly limited, but is preferably from 0 to 20% by weight from the viewpoint of obtaining a cured film having better chemical resistance. 10 to 10% by weight is more preferable.

As the (meth) acrylic monomer other than the compound (B), for example, as a functional polymerizable monomer, 2-hydroxyethyl (meth) acrylate (molecular weight 116 (molecular weight 130, the same applies when the residue is methyl)), 2-hydroxypropyl (meth) acrylate (molecular weight 130 (144)), 4-hydroxybutyl (meth) acrylate (molecular weight 144 (158)), 1,4-cyclohexanedimethanol mono (meth) acrylate (molecular weight 198 (212) ), Methyl (meth) acrylate (molecular weight 88 (100)), ethyl (meth) acrylate (molecular weight 100 (114)), isopropyl (meth) acrylate (molecular weight 114 (128)), butyl (meth) acrylate (molecular weight 114 ( 128)), isobutyl (meth) acrylate Molecular weight 114 (128)), t-butyl (meth) acrylate (molecular weight 114 (128)), cyclohexyl (meth) acrylate (molecular weight 152 (168)), phenyl (meth) acrylate (molecular weight 148 (162)), benzyl ( (Meth) acrylate (molecular weight 162 (176)), isobornyl (meth) acrylate (molecular weight 208 (222)), dicyclopentenyl (meth) acrylate (molecular weight 204 (218)), dicyclopentenyloxyethyl (meth) acrylate (molecular weight) 248 (262)), dicyclopentanyl (meth) acrylate (molecular weight 206 (220)), tricyclo [5.2.1.0 ^2,6 ] decanyl (meth) acrylate (molecular weight 206 (220)), glycerol mono (Meth) acrylate (molecular weight 1 46 (160)), 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, (meth) acrylate of ethylene oxide adduct of lauryl alcohol, glycidyl (meth) acrylate (molecular weight 128 (142)), methyl glycidyl (meth) acrylate (Molecular weight 142 (156)), 3,4-epoxycyclohexyl (meth) acrylate (molecular weight 142 (156)), 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3- (meth) acryl Roxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-ethyl-3- (meth) acryloxyethyl oxetane, p-vinylphenyl-3-ethyloxeta-3-ylmethyl ether, 2-phenyl -3- (Meta) Ac Roxymethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxymethyl oxetane, 4-trifluoromethyl-2- (meth) acryloxymethyl oxetane, (3-ethyl-3-oxetanyl) methyl (meth) acrylate Styrene (molecular weight 104), methylstyrene (molecular weight 119), chloromethylstyrene (molecular weight 152), vinyltoluene (molecular weight 119), N-cyclohexylmaleimide (molecular weight 179), N-phenylmaleimide (molecular weight 173), (meth) Acrylamide (molecular weight 71 (85)), N- (meth) acryloylmorpholine (molecular weight 141 (155)), (meth) acrylic acid (molecular weight 72 (86)), crotonic acid (molecular weight 86), α-chloroacrylic acid ( Molecular weight 106), cinnamic acid (molecular weight 148), Maleic acid (molecular weight 116), fumaric acid (molecular weight 116), itaconic acid (molecular weight 130), citraconic acid (molecular weight 130), mesaconic acid (molecular weight 130), succinic acid mono [2- (meth) acryloyloxyethyl] ( Molecular weight 216 (230)), mono [2- (meth) acryloyloxyethyl maleate] (molecular weight 228 (242)), mono [2- (meth) acryloyloxyethyl] cyclohexene-3,4-dicarboxylate ( Molecular weight 268 (282)).

  Examples of the bifunctional (meth) acrylate other than the compound (B) include bisphenol F ethylene oxide modified di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, and pentaerythritol di. (Meth) acrylate (molecular weight 244 (272)), 1,4-butanediol di (meth) acrylate (molecular weight 198 (226)), 1,6-hexanediol di (meth) acrylate (molecular weight 226 (254)), 1,9-nonanediol di (meth) acrylate (molecular weight 240 (268)), 1,4-cyclohexanedimethanol di (meth) acrylate (molecular weight 252 (280)), 2-n-butyl-2-ethyl-1 , 3-propanediol di Meth) acrylate (molecular weight 226 (254)), trimethylolpropane di (meth) acrylate (molecular weight 242 (260)), and the like.

  Examples of the trifunctional or higher polyfunctional (meth) acrylate other than the compound (B) include glycerol tri (meth) acrylate (molecular weight 254 (286)).

<Antistatic agent>
The antistatic agent can be used to prevent the composition from being charged, and is preferably used in an amount of 0 to 20% by weight in the composition. A known antistatic agent can be used as the antistatic agent. Specific examples include metal oxides such as tin oxide, tin oxide / antimony oxide composite oxide, tin oxide / indium oxide composite oxide; and quaternary ammonium salts. Only one type of antistatic agent may be used, or a mixture of two or more types may be used.

<Coupling agent>
The coupling agent is not particularly limited, and a known coupling agent such as a silane coupling agent can be used for the purpose of improving adhesion to glass or ITO. The silane coupling agent mainly has a role as an adhesion aid for favorably bonding the organic EL element sealing agent of the present invention to the organic EL panel and the protective substrate. The coupling agent is preferably added and used so that the solid content of the composition (residue obtained by removing the solvent from the composition) is 100 parts by weight. A coupling agent may use only 1 type and may mix and use 2 or more types.

  Examples of the silane coupling agent include trialkoxysilane compounds and dialkoxysilane compounds. Preferably, for example, γ-vinylpropyltrimethoxysilane, γ-vinylpropyltriethoxysilane, γ-acryloylpropylmethyldimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropylmethyldiethoxysilane, γ-acryloylpropyl Triethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ-methacryloylpropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycyl Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropylmethyl Rudimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-aminoethyl-γ-iminopropylmethyldimethoxysilane, N-aminoethyl-γ-amino Propyltrimethoxysilane, N-aminoethyl-γ-aminopropyltodiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyl Methyldimethoxysilane, N-phenyl-γ-aminopropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltriethoxysilane, γ-isocyana DOO propyl methyl diethoxy silane, include γ- isocyanato propyl triethoxysilane.

  Among these, γ-vinylpropyltrimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-isocyanatopropyltriethoxysilane are particularly preferable.

  Moreover, you may use the polycondensation product of these compounds. Specifically, Coatosil MP200 (product name: MOMENTIVE) is mentioned.

  The blending amount of the silane coupling agent is not particularly limited, but a preferred lower limit is 0.1 parts by weight and a preferred upper limit is 10 parts by weight with respect to 100 parts by weight of the radical polymerizable monomer. If the amount of the silane coupling agent is less than 0.1 parts by weight, the effect of adding the silane coupling agent may be hardly obtained. If the amount exceeds 10 parts by weight, the excess of the silane coupling agent Since the alkoxy group is decomposed to generate alcohol, the organic EL element or the like may be deteriorated. A more preferred lower limit of the amount of the silane coupling agent is 0.5 parts by weight, and a more preferred upper limit is 5 parts by weight.

<Antioxidant>
When the composition contains an antioxidant, it is possible to prevent deterioration when a cured film obtained from the composition is exposed to high temperature or light. The antioxidant is preferably added in an amount of 0 to 3 parts by weight with respect to 100 parts by weight of the solid content of the composition excluding the antioxidant (residue obtained by removing the solvent from the composition). Only 1 type may be used for antioxidant and 2 or more types may be mixed and used for it.

  Examples of the antioxidant include hindered amine compounds and hindered phenol compounds. Specifically, IRGAFOS XP40, IRGAFOS XP60, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 1520L (above trade names, manufactured by BASF) and the like can be mentioned.

<Surfactant>
When the composition contains a surfactant, it is possible to obtain a composition with improved wettability, leveling property, and coating property to the base substrate. The surfactant is preferably used in an amount of 0.01 to 1% by weight based on the total weight of the composition. Only one surfactant may be used, or two or more surfactants may be mixed and used.

  As the surfactant, for example, trade names “BYK-300”, “BYK-306”, “BYK-335”, “BYK-310”, “BYK-” can be used from the viewpoint of improving the coating property of the composition. Silicone surfactants such as “341”, “BYK-344”, “BYK-370” (manufactured by BYK Japan Japan); trade names “BYK-354”, “BYK-358”, “BYK-361” Acrylic surfactants (such as Big Chemie Japan Co., Ltd.) and the like; Fluorosurfactants such as trade names “DFX-18”, “Fargent 250”, “Furgent 251” (manufactured by Neos) Is mentioned.

<Pigment or dye>
Examples of the pigment include boron nitride, aluminum nitride, silicon carbide, alumina, magnesia, silica, rutile titanium oxide, zinc oxide, low-order titanium oxide, and graphite. Rutile titanium oxide refers to white titanium oxide represented by TiO ₂ . Low-order titanium oxide refers to black titanium oxide such as Ti ₃ O ₅ , Ti ₂ O ₃ and TiO. For example, a low-order titanium oxide (black) known as titanium black includes Tirac D (trade name) manufactured by Ako Kasei Co., Ltd. Examples of the dye include azo dyes, azomethine dyes, xanthene dyes, and quinone dyes. Each of the pigment and the dye may be used alone or in combination of two or more.

<Filler>
The sealing agent for organic EL elements of this invention may contain the filler in the range which does not inhibit transparency. The filler is not particularly limited, for example, talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, diatomaceous earth, magnesium oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, Examples include inorganic fillers such as glass beads, barium sulfate, gypsum, calcium silicate, talc, glass beads, sericite activated clay, bentonite, and organic fillers such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles. .

2. Characteristics of Curable Resin Composition The water content of the curable resin composition is preferably 0.1% by mass or less, more preferably 0.06% by mass or less, when the composition is 100% by weight. preferable. Since an electric circuit in which an optical semiconductor such as an organic EL element is disposed is easily deteriorated by moisture, it is preferable to reduce the water content in the composition as much as possible. The water content in the composition can be obtained by weighing about 0.1 g of a sample sample, heating to 150 ° C. using a Karl Fischer moisture meter, and measuring the amount of water generated at that time (solid vaporization). Law).

  The viscosity of the curable resin composition is measured at 25 ° C. using a viscometer TV-22 manufactured by Toki Sangyo Co., Ltd. or a rheometer MCR302 manufactured by Anton Paar Co., Ltd.

  For screen printing, the range is from 50 to 500,000 mPa · s, preferably from 100 to 300,000 mPa · s, more preferably from 100 to 100,000 mPa · s, and even more preferably from 150 to 50,000 mPa · s. · S, particularly preferably 150 to 10,000 mPa · s, most preferably 200 to 5,000 mPa · s. By setting the viscosity of the resin composition within the above range, the coating (for example, screen printing) property is enhanced, and molding into a sheet or the like is facilitated.

  For inkjet printing, the range is 2 to 120 mPa · s, preferably 5 to 120 mPa · s, more preferably 5 to 110 mPa · s, and further preferably 5 to 100 mPa · s. Especially preferably, it is 5-95 mPa * s, Most preferably, it is 5-90 mPa * s. By setting the viscosity of the resin composition within the above range, ink jet printability is enhanced and molding into a sheet or the like is facilitated.

  Further, among various printing applications, gravure offset printing, screen printing, and ink jet printing are preferable, and ink jet is more preferable. Since the inkjet printing method is a non-contact printing method, the organic EL element or the like is not in contact with the screen or the plate, and the cathode or the like is not damaged. Therefore, the life of the organic EL element or the like can be extended.

  The total light transmittance of the cured product of the curable resin composition is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. If the total light transmittance of the cured product is too low, when used as a sealing agent for an organic EL device or the like, the light extraction efficiency from the device is likely to be lowered, and the design property is also deteriorated. Generally, the upper limit of the total light transmittance of the cured product of the sealant can be about 99%.

3. Production and use of curable resin composition The curable resin composition can be produced by any method as long as the effects of the present invention are not impaired. For example, 1) a step of preparing an aliphatic epoxy / oxetane compound (A), an aliphatic (meth) acrylic compound (B), a polymerization initiator compound (C), and other optional components; 2) inertness And a step of mixing each component at about 40 ° C. in a gas environment. Mixing includes a method in which these components are charged into a flask and agitated, and a method in which the components are kneaded with three rolls.

  When the curable resin composition thus obtained is used as a sealant, for example, a gravure offset printing method, a screen printing method, a flexographic printing method, a dispensing method, an ink jet method, a spin coating method, a roll coating method, a slit Organic EL devices such as coating method, dipping method, spray coating method, gravure coating method, reverse coating method, rod coating method, bar coating method, die coating method, kiss coating method, reverse kiss coating method, air knife coating method, curtain coating method, etc. The electronic device such as an organic EL element may be surface-sealed by coating on the electronic device, curing and baking the coating layer.

4). The following organic electroluminescent element, a top emission structure, which is an example of an organic EL element according to the present embodiment will be described in detail with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an organic EL element according to this embodiment.

<Structure of organic electroluminescence device>
An organic EL element 100 shown in FIG. 1 includes a substrate 101, a bank layer 113 provided on the substrate 101, an anode 102 provided on the substrate 101, and a hole injection provided on the anode 102. Layer 103, hole transport layer 104 provided on hole injection layer 103, light-emitting layer 105 provided on hole transport layer 104, and electron transport layer provided on light-emitting layer 105 106, an electron injection layer 107 provided on the electron transport layer 106, a cathode 108 provided on the electron injection layer 107, a capping layer 109 provided on the cathode 108, and a capping layer 109 And a film 111 (hardness) of a curable resin composition provided so as to cover the cathode layer 108, the capping layer 109, and the passivation layer 110. And after), and a gas barrier layer 112 provided so as to cover the film 111 of the curable resin composition.

  The organic EL element 100 is provided on the substrate 101, the bank layer 113 provided on the substrate 101, the cathode 108 provided on the substrate 101, and the cathode 108, for example, by reversing the manufacturing order. The electron injection layer 107, the electron transport layer 106 provided on the electron injection layer 107, the light emitting layer 105 provided on the electron transport layer 106, and the holes provided on the light emitting layer 105 A transport layer 104; a hole injection layer 103 provided on the hole transport layer 104; an anode 102 provided on the hole injection layer 103; and a capping layer 109 provided on the anode 102; , A passivation layer 110 provided on the capping layer 109, and a curable resin provided so as to cover the anode 102, the capping layer 109 and the passivation layer 110. A film 111 of Narubutsu may be configured to have a gas barrier layer 112 provided so as to cover the film 111 of the curable resin composition.

A protective layer 114 is further applied on the gas barrier layer 112. By providing this protective layer 114, the fragile gas barrier layer 112 is protected, and the performance of the gas barrier can be maintained for a longer period.
Further, a member 115 made of a color filter, a circularly polarizing plate, a touch panel, or the like is bonded onto the protective layer 114, and the protective film 114 also functions as an adhesive layer with these members. These members may include a gas barrier layer.
Further, an edge seal 116 may be provided to block gas such as water vapor entering from the lateral direction of the devices stacked as described above. The edge seal is formed of an existing material, for example, a glass frit, a photocurable resin, an adhesive seal, or the like.

  Not all of the above-described layers are necessary, and the minimum structural unit is a structure of a laminated structure composed of the anode 102, the light emitting layer 105, and the cathode 108 and a film 111 of a curable resin composition covering the layer, and hole injection is performed. Layer 103, hole transport layer 104, electron transport layer 106, electron injection layer 107, capping layer 109, passivation layer 110, gas barrier layer 112, bank layer 113, protective layer 114, member 115, and edge seal 116 are optionally provided. Is a layer. Moreover, each said layer may consist of a single layer, respectively, and may consist of multiple layers.

  FIG. 2 is a schematic cross-sectional view showing an organic EL element in which a passivation layer is not formed. Even if the curable resin composition according to the present invention is in direct contact with the electrodes and / or the organic thin film constituting the organic EL device, there is almost no damage or no adverse effect on them. Therefore, as shown in FIG. 2, the passivation layer 110 can be omitted by using the film 111 of the curable resin composition of the present invention.

<Substrate in organic electroluminescence device>
The substrate 101 serves as a support for the organic EL element 100, and quartz, glass, metal, plastic, or the like is usually used. The substrate 101 is formed into a plate shape, a film shape, or a sheet shape according to the purpose. For example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like is used. Of these, glass plates and transparent synthetic resin plates such as polyester, polymethacrylate, polycarbonate, polysulfone and the like are preferable. In the case of a glass substrate, soda lime glass, non-alkali glass, or the like is used, and the thickness only needs to be sufficient to maintain the mechanical strength. The upper limit value of the thickness is, for example, 2 mm or less, preferably 1 mm or less. The glass material is preferably alkali-free glass because it is better to have less ions eluted from the glass. However, soda lime glass with a barrier coat such as SiO ₂ is also commercially available, so it can be used. it can. Further, the substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one surface in order to improve the gas barrier property, and a synthetic resin plate, film or sheet having a low gas barrier property is used as the substrate 101. When used, it is preferable to provide a gas barrier film.

  Examples of the substrate in the electronic device to which the curable resin composition of the present invention is applied include a glass epoxy substrate that conforms to various standards such as FR-1, FR-3, FR-4, CEM-3, or E668, Glass composite board, paper phenol board, paper epoxy board, green epoxy board, BT (bismaleimide triazine) resin board; copper, brass, phosphor bronze, beryllium copper, aluminum, gold, silver, nickel, tin, chromium, stainless steel, etc. A substrate made of metal (may be a substrate having a layer made of these metals on its surface); indium tin oxide (ITO), aluminum oxide (alumina), aluminum nitride, zirconium oxide (zirconia), zirconium silicate (Zircon), magnesium oxide (magnesia), aluminum titanate , Barium titanate, lead titanate (PT), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), lithium niobate, lithium tantalate, cadmium sulfide, molybdenum sulfide, beryllium oxide (beryllia) , Silicon oxide (silica), silicon carbide (silicon carbide), silicon nitride (silicon nitride), boron nitride (boron nitride), zinc oxide, mullite, ferrite, steatite, holsterite, spinel or spodumene A substrate comprising a layer containing these inorganic substances on the surface thereof; PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene terephthalate), PCT (polycyclohexylenedimethylene terephthalate) Talate), PPS (polyphenylene sulfide), polycarbonate, polyacetal, polyphenylene ether, polyamide, polyarylate, polysulfone, polyethersulfone, polyetherimide, polyamideimide, vinyl chloride resin, epoxy resin, acrylic resin, Teflon (registered trademark), A substrate made of a resin such as a thermoplastic elastomer or a liquid crystal polymer (may be a substrate having a layer containing these resins on its surface); a semiconductor substrate such as silicon, germanium or gallium arsenide; white glass, blue glass, silica-coated blue Glass substrates such as plate glass; substrates on which an electrode material (wiring) such as tin oxide, zinc oxide, ITO or ATO (antimony tin oxide) is formed; αGEL (alpha gel), βGEL (betage) Like semiconductor substrate having other ceramic plate, photoelectric conversion element;), ShitaGEL (thetagels) or GanmaGEL (Ganmageru) (or, Inc. gel sheet such as a trademark of Tayca).

  Examples of more preferred substrates are PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene terephthalate), PCT (polycyclohexylene dimethylene terephthalate), PPS (polyphenylene sulfide), polycarbonate, polyacetal, polyphenylene ether, A substrate made of a resin such as polyamide, polyarylate, polysulfone, polyethersulfone, polyetherimide, polyamideimide, vinyl chloride resin, epoxy resin, acrylic resin or liquid crystal polymer (a substrate having a layer containing these resins on the surface) Glass substrates such as white plate glass, blue plate glass and silica coated blue plate glass; electrode materials such as tin oxide, zinc oxide, ITO or ATO (antimony tin oxide) (Wiring) can be cited substrates formed on the surface.

  These substrates may be pretreated. Examples of pretreatment include chemical treatment with a silane coupling agent, sandblast treatment, corona discharge treatment, ultraviolet treatment, plasma treatment, ion plating, sputtering, gas phase. Reaction methods, vacuum deposition, etc. are included. The applied solution can be dried in an environment of room temperature to 200 ° C.

  A substrate can be protected by coating the resin composition of the present invention on the above-mentioned substrate on which an anaerobic material used for an organic EL device or a photovoltaic device is deposited and applied.

<Anode in organic electroluminescence device>
The anode 102 serves to inject holes into the light emitting layer 105. When the hole injection layer 103 and / or the hole transport layer 104 are provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through these layers. .

  Examples of the material for forming the anode 102 include inorganic compounds and organic compounds. Examples of inorganic compounds include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), indium-zinc oxide). Products (IZO), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, Nesa glass, and the like. Examples of the organic compound include polythiophene such as poly (3-methylthiophene), conductive polymer such as polypyrrole and polyaniline, and the like. In addition, it can select suitably from the substances used as an anode of an organic EL element.

  The resistance of the transparent electrode is not limited as long as it can supply a sufficient current for light emission of the light emitting element, but is preferably low resistance from the viewpoint of power consumption of the light emitting element. For example, an ITO substrate of 300Ω / □ or less functions as an element electrode. However, since it is now possible to supply a substrate of about 10Ω / □, for example, 100-5Ω / □, preferably 50-5Ω. It is particularly desirable to use a low resistance product of / □. The thickness of ITO can be arbitrarily selected according to the resistance value, but is usually used in a range of 50 to 300 nm.

<Hole injection layer and hole transport layer in organic electroluminescence device>
The hole injection layer 103 plays a role of efficiently injecting holes moving from the anode 102 into the light emitting layer 105 or the hole transport layer 104. The hole transport layer 104 plays a role of efficiently transporting holes injected from the anode 102 or holes injected from the anode 102 through the hole injection layer 103 to the light emitting layer 105. The hole injection layer 103 and the hole transport layer 104 are each formed by laminating and mixing one kind or two or more kinds of hole injection / transport materials or a mixture of the hole injection / transport material and the polymer binder. Is done. In addition, an inorganic salt such as iron (III) chloride may be added to the hole injection / transport material to form a layer.

  As a hole injection / transport material, it is necessary to efficiently inject and transport holes from the positive electrode between electrodes to which an electric field is applied. The hole injection efficiency is high, and the injected holes are transported efficiently. It is desirable to do. For this purpose, it is preferable to use a substance that has a low ionization potential, a high hole mobility, excellent stability, and is less likely to generate trapping impurities during production and use.

  As a material used as the hole injecting / transporting material, any material can be selected from known materials. Specific examples thereof include carbazole derivatives, triarylamine derivatives, stilbene derivatives, phthalocyanine derivatives, pyrazoline derivatives, hydrazone compounds, benzofuran derivatives, thiophene derivatives, and the like.

<Light emitting layer in organic electroluminescent element>
The light emitting layer 105 emits light by recombining holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied. The material for forming the light-emitting layer 105 may be a compound that emits light by being excited by recombination of holes and electrons (a light-emitting compound), can form a stable thin film shape, and is in a solid state It is preferable that the compound exhibits a strong light emission (fluorescence) efficiency.

  The light emitting layer may be either a single layer or a plurality of layers, and each is formed of a light emitting layer material (host material, dopant material). Each of the host material and the dopant material may be one kind or a plurality of combinations. The dopant material may be included in the host material as a whole, or may be included partially. As a doping method, it can be formed by a co-evaporation method with a host material, but it may be pre-mixed with the host material and then simultaneously deposited.

  The amount of the host material used varies depending on the type of the host material, and may be determined according to the characteristics of the host material. The amount of the host material used is preferably 50 to 99.999% by weight, more preferably 80 to 99.95% by weight, and still more preferably 90 to 99.9% by weight of the entire light emitting layer material. It is.

  The amount of dopant material used depends on the type of dopant material, and may be determined according to the characteristics of the dopant material. The standard of the amount of dopant used is preferably 0.001 to 50% by weight, more preferably 0.05 to 20% by weight, and further preferably 0.1 to 10% by weight of the entire material for the light emitting layer. is there. The above range is preferable in that, for example, the concentration quenching phenomenon can be prevented.

  As materials used for the light emitting layer, there are fluorescent materials and phosphorescent materials, which can be arbitrarily selected from known materials. Specific examples of the fluorescent material include a fused ring derivative such as anthracene and pyrene, a fluorene derivative, and the like as a host material, and a dopant material can be selected from various materials according to a desired emission color. Specific examples of the phosphorescent material include a carbazole derivative as the host material, and an iridium-based metal complex corresponding to the emission color as the dopant material.

<Electron injection layer and electron transport layer in organic electroluminescence device>
The electron injection layer 107 plays a role of efficiently injecting electrons moving from the cathode 108 into the light emitting layer 105 or the electron transport layer 106. The electron transport layer 106 plays a role of efficiently transporting electrons injected from the cathode 108 or electrons injected from the cathode 108 through the electron injection layer 107 to the light emitting layer 105. The electron transport layer 106 and the electron injection layer 107 are each formed by laminating and mixing one or more electron transport / injection materials or a mixture of the electron transport / injection material and the polymer binder.

  The electron injection / transport layer is a layer that is responsible for injecting electrons from the cathode and further transporting the electrons. It is desirable that the electron injection efficiency is high and the injected electrons are transported efficiently. For this purpose, it is preferable to use a substance that has a high electron affinity, a high electron mobility, excellent stability, and is unlikely to generate trapping impurities during production and use. However, considering the transport balance between holes and electrons, if the role of effectively preventing the holes from the anode from flowing to the cathode side without recombination is mainly played, the electron transport capability is much higher. Even if it is not high, the effect of improving the luminous efficiency is equivalent to that of a material having a high electron transport capability. Therefore, the electron injection / transport layer in this embodiment may include a function of a layer that can efficiently block the movement of holes.

  As a material (electron transport material) for forming the electron transport layer 106 or the electron injection layer 107, a compound conventionally used as an electron transport compound in a photoconductive material, used for an electron injection layer and an electron transport layer of an organic EL element It can be used by arbitrarily selecting from known compounds.

  Materials used for the electron transport layer or the electron injection layer include compounds composed of aromatic rings or heteroaromatic rings composed of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon and phosphorus, and pyrrole derivatives. And at least one selected from the condensed ring derivatives thereof and metal complexes having electron-accepting nitrogen. Specifically, condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives represented by 4,4′-bis (diphenylethenyl) biphenyl, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinones And quinone derivatives such as diphenoquinone, phosphorus oxide derivatives, carbazole derivatives, and indole derivatives. Examples of metal complexes having electron-accepting nitrogen include hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. These materials can be used alone or in combination with different materials.

  The electron transport layer or the electron injection layer may further contain a substance capable of reducing the material forming the electron transport layer or the electron injection layer. As this reducing substance, various substances can be used as long as they have a certain reducing ability. For example, alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkali From the group consisting of earth metal oxides, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes At least one selected can be suitably used.

  Preferred reducing substances include alkali metals such as Na (work function 2.36 eV), K (2.28 eV), Rb (2.16 eV) or Cs (1.95 eV), and Ca (2. 9eV), Sr (2.0 to 2.5 eV) or Ba (2.52 eV), and alkaline earth metals such as those having a work function of 2.9 eV or less are particularly preferable. Among these, a more preferable reducing substance is an alkali metal of K, Rb or Cs, more preferably Rb or Cs, and most preferably Cs. These alkali metals have particularly high reducing ability, and by adding a relatively small amount to the material forming the electron transport layer or the electron injection layer, the luminance of the organic EL element can be improved and the lifetime can be extended. Further, as a reducing substance having a work function of 2.9 eV or less, a combination of two or more alkali metals is also preferable. Particularly, a combination containing Cs, such as Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred. By containing Cs, the reducing ability can be efficiently exhibited, and by adding to the material for forming the electron transport layer or the electron injection layer, the luminance of the organic EL element can be improved and the lifetime can be extended.

<Cathode in organic electroluminescence device>
The cathode 108 serves to inject electrons into the light emitting layer 105 through the electron injection layer 107 and the electron transport layer 106.

  The material for forming the cathode 108 is not particularly limited as long as it can efficiently inject electrons into the organic layer, but the same material as that for forming the anode 102 can be used. Among them, metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium and magnesium or alloys thereof (magnesium-silver alloy, magnesium -Indium alloys, aluminum-lithium alloys such as lithium fluoride / aluminum) are preferred. Lithium, sodium, potassium, cesium, calcium, magnesium, or alloys containing these low work function metals are effective for increasing the electron injection efficiency and improving device characteristics. However, these low work function metals are often often unstable in the atmosphere. In order to improve this point, for example, a method is known in which an organic layer is doped with a small amount of lithium, cesium or magnesium and a highly stable electrode is used. As other dopants, inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide can also be used. However, it is not limited to these.

  Furthermore, a passivation composed of metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys using these metals, and inorganic materials such as silica, titania and silicon nitride for electrode protection. Laminate the layers. Further, in a top emission structure element, a capping layer having a refractive index is laminated on the cathode or the capping layer in order to improve the light extraction efficiency, and the curable resin composition of the present invention is further laminated. The method for producing these electrodes is not particularly limited as long as conduction can be achieved, such as resistance heating, electron beam, sputtering, ion plating, and coating. The capping layer is preferably configured using a known material.

<Binder that may be used in each layer>
The materials used for the hole injection layer, hole transport layer, light emitting layer, electron transport layer and electron injection layer can form each layer alone, but as a polymer binder, polyvinyl chloride, polycarbonate, Polystyrene, poly (N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate resin, ABS resin, polyurethane resin It can also be used by dispersing it in solvent-soluble resins such as phenol resins, xylene resins, petroleum resins, urea resins, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, silicone resins, etc. is there.

<Method for producing organic electroluminescent element>
Each layer constituting the organic EL element is a thin film formed by a method such as vapor deposition, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, printing method, spin coat method or cast method, coating method, etc. Thus, it can be formed. The thickness of each layer formed in this way is not particularly limited and can be appropriately set according to the properties of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can usually be measured with a crystal oscillation type film thickness measuring device or the like. When a thin film is formed using a vapor deposition method, the vapor deposition conditions vary depending on the type of material, the target crystal structure and association structure of the film. Deposition conditions generally include boat heating temperature +50 to + 400 ° C., vacuum degree 10 ⁻⁶ to 10 ⁻³ Pa, deposition rate 0.01 to 50 nm / sec, substrate temperature −150 to + 300 ° C., film thickness 2 nm to 5 μm. It is preferable to set appropriately within the range.

  Next, as an example of a method for producing an organic EL element, an organic EL element composed of an anode / hole injection layer / hole transport layer / a light emitting layer composed of a host material and a dopant material / electron transport layer / electron injection layer / cathode A manufacturing method of will be described. A thin film of an anode material is formed on a suitable substrate by vapor deposition or the like to produce an anode, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. A host material and a dopant material are co-evaporated to form a thin film to form a light emitting layer. An electron transport layer and an electron injection layer are formed on the light emitting layer, and a thin film made of a cathode material is formed by vapor deposition. By forming it as a cathode, a target organic EL element can be obtained. In the production of the above-mentioned organic EL device, the production order can be reversed, and the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode can be produced in this order. It is.

  After the electrode is produced as described above, the capping layer is formed by a method such as vapor deposition, the passivation layer is formed by sputtering or chemical vapor deposition, and then the curable resin composition of the present invention by printing. After coating and curing, a gas barrier layer is formed by sputtering or chemical vapor deposition. In the present invention, the curable resin composition can be directly applied on an electrode or the like without forming a passivation film.

As a material used for the capping layer, an organic material having an appropriate refractive index is selected according to the refractive index of the underlying cathode, and a material constituting the organic EL element can also be used. As a material used for the gas barrier layer, SiO ₂ , SiCN, SiNx, or the like can be used. Since the curable resin composition of the present invention has good resistance to the sputtering process or chemical vapor deposition process, which is the gas barrier layer forming process, it maintains good optical characteristics even after the gas barrier layer is formed. can do.

  When a DC voltage is applied to the organic EL device thus obtained, the anode may be applied with a positive polarity and the cathode with a negative polarity. When a voltage of about 2 to 40 V is applied, a transparent or translucent electrode is applied. Luminescence can be observed from the side (anode or cathode, and both). The organic EL element also emits light when a pulse current or an alternating current is applied. The alternating current waveform to be applied may be arbitrary.

<Application examples of organic electroluminescent devices>
Moreover, the organic EL element sealed with the curable resin composition of the present invention can also be applied to a display device or a lighting device. The display device or lighting device including the organic EL element can be manufactured by a known method such as connecting the organic EL element according to the present embodiment and a known driving device, such as DC driving, pulse driving, or AC driving. It can drive using a well-known drive method suitably.

  Examples of the display device include a panel display such as a color flat panel display, and a flexible display such as a flexible color organic electroluminescence (EL) display (for example, JP-A-10-335066 and JP-A-2003-321546). Gazette, JP-A-2004-281086, etc.). Examples of the display method of the display include a matrix and / or segment method. Note that the matrix display and the segment display may coexist in the same panel.

  A matrix means a pixel in which pixels for display are two-dimensionally arranged such as a lattice or a mosaic, and displays a character or an image with a set of pixels. The shape and size of the pixel are determined by the application. For example, a square pixel with a side of 300 μm or less is usually used for displaying images and characters on a personal computer, monitor, TV, and a pixel with a side of mm order for a large display such as a display panel. become. In monochrome display, pixels of the same color may be arranged. However, in color display, red, green, and blue pixels are displayed side by side. In this case, there are typically a delta type and a stripe type. The matrix driving method may be either a line sequential driving method or an active matrix. The line-sequential driving has an advantage that the structure is simple. However, the active matrix may be superior in consideration of the operation characteristics, so that it is necessary to properly use it depending on the application.

  In the segment system (type), a pattern is formed so as to display predetermined information, and a predetermined region is caused to emit light. For example, the time and temperature display in a digital clock or a thermometer, the operation state display of an audio device or an electromagnetic cooker, the panel display of an automobile, and the like can be mentioned.

  Examples of the illuminating device include an illuminating device such as a room illuminator, a backlight of a liquid crystal display device, and the like (for example, Japanese Patent Laid-Open Nos. 2003-257621, 2003-277741, and 2004-119211). Etc.) The backlight is used mainly for the purpose of improving the visibility of a display device that does not emit light, and is used for a liquid crystal display device, a clock, an audio device, an automobile panel, a display panel, a sign, and the like. In particular, as a backlight for liquid crystal display devices, especially personal computers for which thinning is an issue, considering that conventional methods are made of fluorescent lamps and light guide plates, it is difficult to reduce the thickness. The backlight using the light emitting element according to the embodiment is thin and lightweight.

5. The following flexible battery, will be described in detail with reference to the accompanying drawings a flexible battery that is an example of a battery according to the present embodiment. FIG. 3 is a schematic cross-sectional view showing the flexible battery according to the present embodiment. As shown in FIG. 3, the flexible battery 200 includes two substrates 201 and 205, electrodes 202 and 204 provided on these substrates, and end portions of the substrate 201, electrodes 202, electrode 204, and substrate 205. The resin composition film 206 in contact with the battery and the electrolytic solution 203 filling the inside of the battery. The curable resin composition of the present invention can be used as the resin composition film 206 by being cured.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited to these Examples. Hereinafter, names of components used in Examples and Comparative Examples are indicated by abbreviations. This abbreviation is used in the following description.

<Evaluation of resin composition>
The measurement method or evaluation method for each evaluation item was according to the following method.

(1) Measurement of viscosity The viscosity at 25 ° C. of the resin composition was measured using a viscometer TV-22 manufactured by Toki Sangyo Co., Ltd. or a rheometer MCR302 manufactured by Anton Paar Co., Ltd.

(2) Evaluation of storage stability Viscosity after preparing the resin composition, viscosity after storing for one week in a refrigerator maintained at 4 ° C., viscosity after storing for one week at room temperature of 25 ° C. And the viscosity after storage for one week in a high-temperature bath maintained at 40 ° C., and the change rate of the elapsed time of viscosity (respective viscosity / resin composition after one week at 4 ° C., 25 ° C. and 40 ° C. If the viscosity after preparation of the product × 100) was all within the range of 110 to 90%, it was evaluated as ◯, and otherwise, it was evaluated as ×. In addition, the container of the resin composition was stored in a light-shielding bag when stored for one week.

(3) Evaluation of curability After applying a resin composition on a glass substrate, UV irradiation is performed using an exposure machine (J-CURE 1500 manufactured by JATEC), and irradiation is performed so that the integrated energy is 2000 mJ / cm ^2. The time was adjusted to cure. Then, it put into an 80 degreeC hot-air circulation oven (The Yamato Scientific make, clean oven DT610) for 30 minutes, and baked (Examples 1-7, 10, 11, Comparative Examples 3-9, and Comparative Example 11).
Regarding the curing and baking conditions, in Examples 8 and 12, only the above-described curing process is not performed, and in Example 9, in addition to the above-described curing process, baking is performed in a 100 ° C. oven for 60 minutes. In No. 1, the curing step was not performed only by the above-described firing step, and in Comparative Example 10, the firing step was not performed only by the above-described curing step.
After firing, it was confirmed whether the resin was cured or whether it was rubbed with a Kimwipe soaked with acetone and ethanol.
A case where the resin was cured and did not whiten even when rubbed with Kimwipe was marked with ◯.
The resin was in a liquid state or whitened when rubbed with Kimwipe.

(4) Evaluation of optical properties Using a haze meter (haze-gard plus manufactured by BYK Co., Ltd.), the total light transmittance and HAZE of the cured film were measured. The cured film was produced using the same conditions as the curing / firing conditions in (3) Evaluation of curability with the resin composition sandwiched between glass substrates. Moreover, the film thickness of the cured resin composition was measured with the film thickness meter, and it confirmed that it existed between 200 micrometers-100 micrometers. The refractive index can be calculated using FE-3000 manufactured by Otsuka Electronics Co., Ltd. and Abbemat manufactured by Abbe refractometer Anton Paar.

(5) Evaluation of influence on OLED element The resin composition was apply | coated to the produced OLED element, and it hardened and baked using the same conditions as the hardening and baking conditions in said (3) sclerosis | hardenability evaluation. Thereafter, a direct current was passed through the electrode of the device, and the state of the light emitting surface was examined.
The case where there was no dark spot on the light emitting surface and the electrode was not peeled off was rated as ◎.
A sample having few dark spots on the light emitting surface and little peeling of the electrode was rated as “Good”.
The case where there was a dark spot on the light emitting surface or the electrode was peeled off was rated as x.

(6) Evaluation of Sputter Resistance After the resin composition applied on the glass substrate is cured under the conditions described in “(3) Evaluation of curability”, a SiO ₂ film is formed on the cured film by sputtering. It was produced with a thickness of ˜300 nm. At that time, sputtering was performed by adjusting the voltage value and the distance between the substrate and the target so that the substrate temperature did not exceed 100 ° C. Then, the total light transmittance and HAZE of the cured film were measured using a haze meter (haze-gard plus manufactured by BYK Co., Ltd.). The case where HAZE after sputtering was 0 to 25% was rated as ◯, and the case other than that was rated as ×. Unimplemented samples were marked with-.

(7) Adhesion evaluation to electrode of flexible battery Adhesion to aluminum and copper which is a kind of electrode used for flexible battery was measured as follows. First, the resin composition was applied onto a metal foil, cured under the conditions described in the above “(3) Evaluation of curability”, and then cut into a 1 cm × 5 cm rectangle. Next, a part of the metal foil was peeled off from the cured resin, and one end of the peeled metal foil and one end of the metal foil and the cured resin were attached to a tensile tester EZGraph manufactured by Shimadzu Corporation and peeled off 180 degrees. By measuring the strength, the adhesion (N / mm) was calculated.

<Example 1>
100 g of HBE100, which is a hydrogenated aliphatic epoxy low molecular weight compound, was weighed in a 200 mL eggplant-shaped flask and heated in an oil bath at 40 ° C. After heating, 0.1 g of SI-B3 which is a photo / thermal acid generator was added and stirred until dissolved, and after dissolution, the flask was removed from the oil bath and returned to room temperature. Each evaluation was performed after returning to room temperature. The results are as described in Table 2.

<Example 2>
Each evaluation was performed after preparing in the same manner as in Example 1 except that 70 g of HBE100 as an aliphatic epoxy low molecular weight compound and 30 g of EHPE3150 as an aliphatic epoxy high molecular weight compound were used in a 200 mL eggplant-shaped flask.

<Example 3>
Each evaluation was performed after preparing in the same manner as in Example 1 except that 70 g of HBE100, which is an aliphatic epoxy low molecular weight compound, and 30 g of PB3600, which is an aliphatic epoxy high molecular weight compound, were used in a 200 mL eggplant-shaped flask.

<Example 4>
Each sample was prepared in the same manner as in Example 1 except that 70 g of HBE100, an aliphatic epoxy low molecular weight compound, and 30 g of R-45EPT, an aliphatic epoxy high molecular weight compound, were used in a 200 mL eggplant-shaped flask. did.

<Example 5>
Each evaluation was performed after preparing in the same manner as in Example 1 except that YX8000, which is an aliphatic epoxy low molecular weight compound, was used in a 200 mL eggplant-shaped flask.

<Example 6>
Each evaluation was performed after preparing in the same manner as in Example 1 except that GT401 which is an aliphatic epoxy low molecular weight compound was used in a 200 mL eggplant-shaped flask.

<Example 7>
Each evaluation was performed after preparing in the same manner as in Example 1 except that CEL2081 which is an aliphatic epoxy low molecular weight compound was used in a 200 mL eggplant type flask.

<Example 8>
Prepared in the same manner as in Example 1 except that 100 g of aliphatic (meth) acrylate low molecular weight compound DCP-A was used in a 200 mL eggplant-shaped flask and 20 g of KIP150 as a photo radical generator was used as a polymerization initiator. Then, each evaluation was carried out.

<Example 9>
In a 200 mL eggplant-shaped flask, 70 g of HBE100 which is an aliphatic epoxy low molecular weight compound and 100 g of DCP-A which is an aliphatic (meth) acrylate low molecular weight compound are used, and 20 g of KIP150 which is a photo radical generator is used as a polymerization initiator. Each evaluation was carried out after preparing in the same manner as in Example 1 except that 0.2 g of SI-B3 which is a photo / thermal acid generator was used.

<Example 10>
Prepared in the same manner as in Example 1 except that 100 g of EP4088L, which is an aliphatic epoxy low molecular weight compound, and 0.1 g of SI-B3, which is a light / thermal acid generator, are used as a polymerization initiator in a 200 mL eggplant-shaped flask. Later, each evaluation was carried out.

<Example 11>
Each sample was prepared in the same manner as in Example 1 except that 100 g of an aliphatic (meth) acrylate low molecular weight compound TMPTA and 20 g of a photo radical generator KIP150 were used as a polymerization initiator in a 200 mL eggplant-shaped flask. Evaluation was performed.

  Furthermore, since the resin composition of Example 11 had a viscosity of 90 mPa * s at 25 ° C. and could be ejected by ink jetting, the ejection test and the printing test were performed using an ink jet machine (DMP-2831 manufactured by Fujifilm Dimatix). Carried out. The test conditions were a discharge temperature of 65 ° C., a discharge voltage of 20 V, a frequency of 5 kHz, and a stage temperature of 25 ° C., and the resin composition was printed on the cathode of the produced OLED element. As a result, a desired print pattern could be printed.

<Comparative Example 1>
Example 1 except that 100 g of HNA-100, which is an acid anhydride, and 5 g of 2E4MZ, which is a curing catalyst, were used as a polymerization initiator instead of SI-B3, which is a photo / thermal acid generator, in a 300 mL eggplant-shaped flask. Then, each evaluation was carried out. The results are as described in Table 3.

<Comparative example 2>
Similar to Example 1 except that 100 g of SMA 1000 as an acid anhydride and 5 g of 2E4MZ as a curing catalyst were used in a 300 mL eggplant-shaped flask instead of SI-B3 as a photo / thermal acid generator as a polymerization initiator. Then, each evaluation was carried out.

<Comparative Example 3>
Each evaluation was performed after preparing in the same manner as in Example 1 except that CEL2021P, which is an aliphatic epoxy low molecular weight compound, was used in a 200 mL eggplant-shaped flask.

<Comparative Example 4>
Each evaluation was carried out after preparing in the same manner as in Example 1 except that 70 g of HBE100 as an aliphatic epoxy low molecular weight compound and 30 g of HP7200H as an aromatic epoxy low molecular weight compound were used in a 200 mL eggplant-shaped flask.

<Comparative Example 5>
Each evaluation was performed after preparing in the same manner as in Example 1 except that EP828EL, which is an aromatic epoxy low molecular weight compound, was used in a 200 mL eggplant-shaped flask.

<Comparative Example 6>
Each sample was evaluated in the same manner as in Example 1 except that EP828EL, which is an aromatic epoxy low molecular weight compound, and SI-B3A, which is a photo / thermal acid generator, were used as a polymerization initiator in a 200 mL eggplant-shaped flask. Carried out.

<Comparative Example 7>
Each sample was evaluated in the same manner as in Example 1 except that EP828EL as an aromatic epoxy low molecular weight compound and SI-B2A as a photo / thermal acid generator were used as a polymerization initiator in a 200 mL eggplant type flask. Carried out.

<Comparative Example 8>
Example 1 with the exception that EHPE 3150, an aliphatic epoxy high molecular weight compound, 0.2 g of a photo / thermal acid generator SI-B3 as a polymerization initiator and 100 g of PGMEA as a solvent were used in a 300 mL eggplant-shaped flask. After preparing in the same manner, each evaluation was performed. In the case of evaluation requiring curing, a drying process at 80 ° C. for 5 minutes was performed before curing.

<Comparative Example 9>
Each sample was prepared in the same manner as in Example 1 except that 100 g of M208, which is an aromatic (meth) acrylate low molecular weight compound, and 20 g of KIP150, which is a photo radical generator, were used as a polymerization initiator in a 200 mL eggplant-shaped flask. Evaluation was performed.

<Comparative Example 10>
In a 300 mL eggplant-shaped flask, 100 g of HBE100, an aliphatic epoxy low molecular weight compound, 100 g of M208, an aromatic (meth) acrylate low molecular weight compound, 100 g of HNA-100, which is an acid anhydride as a polymerization initiator, a curing catalyst 2E4MZ was prepared in the same manner as in Example 1 except that 2 g of 2E4MZ and 20 g of KIP150 as a photo radical generator were used, and then each evaluation was performed.

  As can be seen from the above evaluation results, the resin compositions according to the present invention containing an aliphatic epoxy / oxetane compound or (meth) acrylic compound having a specific molecular weight in a specific amount all have good viscosity and storage stability. , Curability and optical properties were exhibited, and no adverse effect on the organic EL element was observed.

  On the other hand, the content of the aliphatic epoxy / (meth) acryl in the resin composition is small (Comparative Examples 1, 2, 4, 8 and 10), or the molecular weight of the aliphatic epoxy / (meth) acryl is small. (Comparative Example 3), containing aromatic epoxy / (meth) acrylic (Comparative Examples 4 and 10), or composed of only aromatic epoxy / (meth) acrylic (Comparative Examples 5-7 and 9) In some cases, good characteristics could not be obtained, and problems such as a bad influence on the organic EL element occurred.

  In Comparative Example 2, the polymerization initiator used was an aromatic acid anhydride, and the high oil content was considered to be the cause of this problem.

  In Comparative Example 8, the content of the solvent is large, and PGMEA is a non-aromatic solvent, but its molecular weight is low, so it is highly likely to penetrate into the organic layer constituting the organic EL element. It is thought that this was the cause. Further, it is considered that such a problem is more likely to occur with an aromatic solvent. Therefore, the resin composition of the present invention is preferably solvent-free.

  The curable resin composition of the present invention can greatly suppress or eliminate the damage when directly contacting a metal electrode such as an anode, for example, the structure of an organic EL element. In addition, it is possible to solve the problem of peeling of the film, and furthermore, it is possible to obtain an electronic device that is extremely advantageous economically by omitting the step of forming the barrier film. In addition, since the damage at the time of direct contact with the electrode of the flexible battery can be extremely suppressed or eliminated, it is possible to obtain a highly economical electronic device by omitting the film formation step. Furthermore, since this curable resin composition is excellent in storage stability, an advantageous sealing process can be realized also in this respect.

DESCRIPTION OF SYMBOLS 100 Organic electroluminescent element 101 Substrate 102 Anode 103 Hole injection layer 104 Hole transport layer 105 Light emitting layer 106 Electron transport layer 107 Electron injection layer 108 Cathode 109 Capping layer 110 Passivation layer 111 Film of curable resin composition 112 Gas barrier layer 113 Bank layer 114 Protective layer 115 Member 116 Edge seal 200 Flexible battery 201 Substrate 202 Electrode 203 Electrolytic solution 204 Electrode 205 Substrate 206 Resin composition film

Claims (16)

A curable resin composition comprising compound (A) and / or compound (B) and compound (C),
(A) Aliphatic epoxy and / or aliphatic oxetane (B) Aliphatic (meth) acrylic (C) polymerization initiator The molecular weights of the compound (A) and / or the compound (B) are independently 290 or more and 500 Less than 1,000,
The weight composition ratio when the curable resin composition is 100% by weight is that the total of the compound (A) and the compound (B) is 80% to 99.99% by weight, and the compound (C) is 0.01%. A curable resin composition that is 20% by weight to 20% by weight. Compound (A) is a monovalent or divalent crosslinkable functional group represented by the following formula (AI), a monovalent or divalent crosslinkable functional group represented by formula (A-II), or The curable resin composition of Claim 1 which has at least 1 of the bivalent crosslinkable functional group represented by Formula (A-III).
X in the above formula (AI) is 1 or 2, R ¹ is a single bond or an alkylene group having 1 to 30 carbon atoms, and at least one of the alkylene groups — (CH ₂ ) — is — May be substituted with O- or-(COO)-, R ² is an organic group represented by any one of the above formulas (R ² ), and R in * in formula (R ² ) ¹ and R ³ is hydrogen, a methyl group or an ethyl group,
X in the above formula (A-II) is 1 or 2,
One of R ⁴ in the above formula (A-III) is a single bond, and the other represents no bond,
The crosslinkable functional groups represented by the formulas (A-I) to (A-III) bind to other sites in the compound (A) at * in each formula, and the formula (A-I) or (A At least one hydrogen of the cyclohexane ring in -II) may be substituted with a methyl group, an ethyl group, a trifluoromethyl group, fluorine, chlorine, bromine or iodine. Compound (A) is at least one of the compounds represented by the following formula (A-I-1), formula (A-I-2), formula (A-II-1) or formula (A-III-1) The curable resin composition of Claim 1 or 2 containing two.
R ⁵ in the above formula (AI-1) is a single bond or —C (R ¹⁰ ) ₂ —, and each R ¹⁰ is independently hydrogen, a methyl group or a trifluoromethyl group, R ⁶ is each independently a single bond or an alkylene group having 1 to 30 carbon atoms, and at least one — (CH ₂ ) — of the alkylene group is substituted with —O— or — (COO) —. And at least one hydrogen of the cyclohexane ring in formula (A-I-1) may be substituted with a methyl group, bromine, fluorine or chlorine,
R ⁷ in the above formula (A-I-2) is hydrogen, an alkyl group having 1 to 6 carbon atoms or a hydroxyl group, p is an integer of 1 to 100,
N in the above formula (A-II-1) is an integer of 1 to 4, R ⁸ is an n-valent alkylene group having 1 to 60 carbon atoms, and at least one of the alkylene groups — (CH ₂ ) — May be substituted with -O- or-(COO)-
R ⁹ in the above formula (A-III-1) is each independently hydrogen, an alkyl group having 1 to 6 carbon atoms or a hydroxyl group, and at least one — (CH ₂ ) — of the alkyl group is —O. -It may be substituted with a divalent oxirane group or-(COO)-, and v, w and x are each independently an integer of 1 to 50 and are repeated in v, w and x The position of the repeating unit may be interchanged. When Y is a single bond or an oxygen atom and is a single bond, it means that it is a double bond, and — (CH ₂ of the alkyl group of R ⁹ )-Is not substituted with a divalent oxirane group, at least one of Y is an oxygen atom, and z is an integer of 1-50. The compound (B) contains at least one of the compounds represented by the following formula (B-I-1), formula (B-I-2) or formula (B-I-3). The curable resin composition according to any one of the above.
R ¹¹ in the above formula (BI-1), formula (BI-2), or formula (BI-3) is each independently hydrogen or a methyl group, and R ⁶ is Each independently represents a single bond or an alkylene group having 1 to 30 carbon atoms, and at least one — (CH ₂ ) — of the alkylene group may be substituted with —O— or — (COO) —;
R ⁵ in the above formula (BI-3) is a single bond or —C (R ¹⁰ ) ₂ —, and each R ¹⁰ is independently hydrogen, a methyl group or a trifluoromethyl group.   The curable resin composition according to any one of claims 1 to 4, wherein the compound (A) and / or the compound (B) are each independently a low molecular weight compound having a molecular weight of 290 or more and less than 2,000.   Compound (A) and / or Compound (B) each independently comprises a low molecular weight component having a molecular weight of 290 or more and less than 2,000 and a high molecular weight component having a weight average molecular weight of 2,000 or more and less than 30,000. The curable resin composition according to any one of claims 1 to 4, further comprising:   Curable resin composition in any one of Claims 1-6 containing a compound (A).   The weight composition ratio when the curable resin composition is 100% by weight is 95% to 99.99% by weight of the compound (A) and 0.01% to 5% by weight of the compound (C). The curable resin composition according to claim 7.   Curable resin composition in any one of Claims 1-6 containing a compound (B).   The weight composition ratio when the curable resin composition is 100% by weight is 80% to 95% by weight of the compound (B) and 5% to 20% by weight of the compound (C). 9. The curable resin composition according to 9.   The curable resin composition according to any one of claims 1 to 10, wherein the compound (C) is a light / thermal acid generator or a photo radical generator.   Furthermore, when a solvent is contained, the solvent is a non-aromatic compound, The curable resin composition in any one of Claims 1-11.   The curable resin composition according to any one of claims 1 to 12, wherein when the solvent is contained, the weight composition ratio when the curable resin composition is 100% by weight is 1% by weight or less.   The electronic device using the hardened | cured material of the curable resin composition in any one of Claims 1-13.   The organic electroluminescent element in which the hardened | cured material of the curable resin composition in any one of Claims 1-13 is directly contacting with the electrode and / or the organic thin film. The battery in which the hardened | cured material of the curable resin composition in any one of Claims 1-13 is directly contacting with the electrode and / or electrolyte solution.