WO2020218065A1 - Composition - Google Patents

Abstract

A composition which contains a cationically polymerizable compound having a cationically ring-opening polymerizable group, a vinyl ether compound having a vinyloxy group, and a cationic photopolymerization initiator, wherein the content of the vinyl ether compound is more than 50 parts by mass but not more than 95 parts by mass relative to a total of 100 parts by mass of the cationically polymerizable compound and the vinyl ether compound.

Description

Composition

The present invention relates to a composition.

In recent years, research on organic optical devices using organic thin film devices such as organic electroluminescence (organic EL) display devices has been promoted.

Since the light emitting layer, electrodes, etc. of an organic EL display element deteriorate in its light emitting characteristics when exposed to the outside air, a sealing technology for blocking from the outside air is indispensable, and one of the sealing technologies. Photocurable sealants are known as (for example, Patent Documents 1 to 5).

Japanese Unexamined Patent Publication No. 2001-357973 Japanese Patent No. 5919574 Japanese Patent No. 4800247 Japanese Unexamined Patent Publication No. 2016-058273 Japanese Patent No. 4384509

By the way, when a photocurable sealant is applied to a member, workability is improved if the sealant has a low viscosity. For this reason, in order to improve workability, for example, a method of adjusting the viscosity by adding an organic solvent to the sealant has been adopted, but there is a problem that the remaining organic solvent increases the generation of outgas. there were.

Therefore, an object of the present invention is to provide a composition having a low viscosity and excellent reliability after curing. Further, the present invention relates to a sealing agent for an organic EL display element containing the above composition, a cured product of the sealing agent for the organic EL display element, a sealing material containing the cured body, and an organic EL containing the sealing material. An object of the present invention is to provide a display device and a method for manufacturing the organic EL display device.

One aspect of the present invention contains a cationically polymerizable compound having a cationic ring-opening polymerizable group, a vinyl ether-based compound having a vinyloxy group, and a photocationic polymerization initiator, and the content of the vinyl ether-based compound is high. The present invention relates to a composition which is larger than 50 parts by mass and 95 parts by mass or less with respect to 100 parts by mass of the total of the cationically polymerizable compound and the vinyl ether compound.

The above composition is a combination of a vinyl ether compound having a vinyl oxy group and a cationically polymerizable compound, and the content of the vinyl ether compound is a certain amount or more. With this particular composition, the composition can achieve both low viscosity and excellent moisture resistance and transparency after curing. From this, the organic electroluminescence display sealing agent containing the above composition can be easily applied uniformly to the members and is excellent in workability. Further, since the composition is excellent in moisture resistance and transparency after curing, an organic electroluminescence display device having excellent reliability can be realized by using the composition as a sealing agent for displaying organic electroluminescence.

In one embodiment, the viscosity of the vinyl ether compound at 25 ° C. may be lower than the viscosity of the cationically polymerizable compound at 25 ° C.

In one embodiment, the cationic ring-opening polymerizable group may be selected from the group consisting of an epoxy group and an oxetane group.

In one embodiment, the content of the photocationic polymerization initiator may be 0.1 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass in total of the cationically polymerizable compound and the vinyl ether compound.

The composition according to one embodiment may further contain a curing retarder.

In one aspect, the viscosity when measured using an E-type viscometer under the conditions of 25 ° C. and 10 rpm may be 2 to 200 cps.

In one embodiment, the vinyl ether compound may have two vinyl oxy groups and further have a cyclic group.

Another aspect of the present invention relates to a sealing agent for an organic electroluminescence display element containing the above-mentioned composition.

Yet another aspect of the present invention relates to a cured product of the above-mentioned sealant for an organic electroluminescence display element.

In one embodiment, the total light transmittance at a wavelength of 380 to 800 nm per 10 μm thickness may be 80% or more.

Yet another aspect of the present invention relates to a sealing material for an organic electroluminescence display element, which contains the above-mentioned cured product.

Yet another aspect of the present invention relates to an organic electroluminescence display device including the organic electroluminescence display device and the above-mentioned sealing material for the organic electroluminescence display device.

Still another aspect of the present invention is a bonding step of attaching the above-mentioned sealing agent for an organic electroluminescence display element to the first member, and light is applied to the above-mentioned sealing agent for an organic electroluminescence display element. An organic electroluminescence display comprising an irradiation step of irradiating and a bonding step of bonding the first member and the second member via the light-irradiated sealant for the organic electroluminescence display element. Regarding the manufacturing method of the device.

According to the present invention, there is provided a composition having a low viscosity and excellent reliability after curing. Further, according to the present invention, a sealing agent for an organic EL display element containing the above composition, a cured product of the sealing agent for the organic EL display element, a sealing material containing the cured body, and the sealing material are included. An organic EL display device and a method for manufacturing the organic EL display device are provided.

Hereinafter, one embodiment of the present invention will be described in detail.

The composition according to this embodiment can be used as a resin composition. The resin composition according to the present embodiment contains a cationically polymerizable compound (component (A)), a vinyl ether compound (component (B)), and a photocationic polymerization initiator (component (C)).

In the present embodiment, the cationically polymerizable compound (component (A)) has a cationic ring-opening polymerizable group.

In the present embodiment, the vinyl ether compound (component (B)) has a vinyl oxy group. The content of the vinyl ether compound is more than 50 parts by mass and 95 parts by mass or less with respect to 100 parts by mass in total of the cationically polymerizable compound and the vinyl ether compound.

The resin composition according to the present embodiment is a combination of a vinyl ether compound having a vinyl oxy group and a cationically polymerizable compound, and the content of the vinyl ether compound is a certain amount or more. With this particular composition, the resin composition can achieve both low viscosity and excellent moisture resistance and transparency after curing. Therefore, the encapsulant for an organic electroluminescence (EL) display device (hereinafter, also simply referred to as a encapsulant) containing the resin composition according to the present embodiment can form a highly reliable encapsulant and is reliable. An organic EL display device having excellent properties can be realized.

(Component (A): cationically polymerizable compound)
The component (A) is a compound having a cationic ring-opening polymerizable property, and can also be said to be a compound having a cationic ring-opening polymerizable group. Examples of the cationic ring-opening polymerizable group include a cyclic ether group (for example, an epoxy group (oxylan ring)) and an oxetane group (oxetane ring), which are composed of an epoxy group and an oxetane group from the viewpoint of adhesiveness and moisture resistance. At least one selected from the group is preferred.

The component (A) may be a compound having one cationic ring-opening polymerizable group, or may be a compound having two or more. The component (A) preferably has two or more cationic ring-opening polymerizable groups, and more preferably two cationic ring-opening polymerizable groups.

Examples of the compound having an epoxy group include a compound having an epoxy group and an alicyclic group (hereinafter, also referred to as an alicyclic epoxy compound) and a compound having an epoxy group and an aromatic group (hereinafter, may be referred to as an alicyclic epoxy compound) from the viewpoint of adhesiveness and moisture resistance. Hereinafter, at least one selected from the group consisting of aromatic epoxy compounds) is preferable.

<(A1) component: alicyclic compound having an epoxy group>
The component (A1) may be a compound having one epoxy group or a compound having two or more epoxy groups. The component (A1) preferably has two or more epoxy groups, and more preferably has two epoxy groups. The component (A1) may be a compound having no aromatic ring. The component (A1) may be used alone or in combination of two or more.

The component (A1) may be, for example, a compound obtained by epoxidizing a compound having a cycloalkene ring or a derivative thereof. Examples of the cycloalkene ring include a cyclohexene ring, a cyclopentene ring, a pinene ring and the like. Epoxylation can be carried out using, for example, an oxidizing agent. Examples of the oxidizing agent include hydrogen peroxide and peracid. Examples of such (A1) components include 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxycyclohexylalkyl (meth) acrylate (eg, 3,4-epoxy). Cyclohexylmethyl (meth) acrylate and the like), (3,3', 4,4'-diepoxy) bicyclohexyl and the like.

The component (A1) may be, for example, a compound obtained by hydrogenating a compound having an epoxy group and an aromatic ring, or a derivative thereof. Examples of the compound having an epoxy group and an aromatic ring include bisphenol A type epoxy resin and bisphenol F type epoxy resin. Examples of such (A1) component include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin and the like.

As the component (A1), a compound having a 1,2-epoxycyclohexane structure is preferable. Examples of the compound having a 1,2-epoxycyclohexane structure include a compound represented by the formula (A1-1).

In the formula (A1-1), X represents a single bond or a linking group (a divalent group having one or more atoms).

When X is a single bond, the compound represented by the formula (A1-1) is (3,3', 4,4'-diepoxy) bicyclohexyl.

X is preferably a linking group. The linking group may be, for example, a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide bond, or a group in which a plurality of these are linked. As the linking group, a group having an ester bond is preferable, and a group in which an ester bond and a divalent hydrocarbon group are linked is more preferable.

As the divalent hydrocarbon group, an alkanediyl group is preferable, and an alkanediyl group having 1 to 3 carbon atoms is more preferable.

As the compound represented by the formula (A1-1), 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is particularly preferable.

The molecular weight of the component (A1) is preferably 450 or less, more preferably 400 or less, further preferably less than 300, still more preferably 280 or less, from the viewpoint of storage stability of the resin composition and moisture resistance of the cured product. The molecular weight of the component (A1) may be, for example, 100 or more.

When the component (A1) has a molecular weight distribution, the number average molecular weight of the component (A1) is preferably in the above range. In the present specification, the number average molecular weight indicates a polystyrene-equivalent value measured by gel permeation chromatography (GPC) under the following measurement conditions.
-Solvent (mobile phase): THF
・ Degassing device: ERC-3310 manufactured by ERMA
-Pump: PU-980 manufactured by JASCO Corporation
-Flow velocity: 1.0 ml / min
・ Autosampler: AS-8020 manufactured by Tosoh Corporation
-Column oven: L-5030 manufactured by Hitachi, Ltd.
・ Set temperature: 40 ℃
-Column configuration: TSKguardcolumMP (xL) manufactured by Tosoh Co., Ltd. 6.0 mm ID x 4.0 cm 2 pieces, and TSK-GELMULTIPORE HXL-M manufactured by Tosoh Co., Ltd. 7.8 mm ID x 30.0 cm 2 pieces, total 4 pieces-Detector: RI Hitachi L-3350
-Data processing: SIC480 data station

<Component (A2): Aromatic compound having an epoxy group>
The aromatic epoxy compound may be a compound having one epoxy group or a compound having two or more epoxy groups. The aromatic epoxy compound preferably has two or more epoxy groups, and more preferably has two epoxy groups. The aromatic epoxy compound may be a compound having no alicyclic group. The aromatic epoxy compound may be used alone or in combination of two or more.

Examples of the component (A2) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, novolac phenol type epoxy resin, and cresol novolac. Examples include type epoxy resins and modified products thereof.

As the component (A2), a compound having a bisphenol structure (for example, bisphenol A structure, bisphenol F structure, bisphenol S structure, etc.) is preferable, and at least selected from the group consisting of bisphenol A type epoxy resin and bisphenol F type epoxy resin. One type is more preferable.

Examples of the component (A2) include a compound represented by the formula (A2-1).

In formula (A2-1), n represents a real number of 0.1 to 30, and R ²¹ , R ²² , R ²³ and R ²⁴ are carbons that may independently have a hydrogen atom or a substituent. It shows an alkyl group of the number 1-5. When there are a plurality of R ^23s and R ^24s , they may be the same or different from each other.

Examples of the substituent that the alkyl group may have include a fluorine atom and an oxyalkyl group, and among these, a fluorine atom is preferable.

R ²¹ , R ²² , R ²³ and R ²⁴ are preferably hydrogen atoms or methyl groups. Further, it is preferable that R ²¹ , R ²² , R ²³ and R ²⁴ are all the same group.

The molecular weight of the component (A2) is preferably 100 or more, more preferably 150 or more, still more preferably 200 or more, from the viewpoint of moisture resistance of the cured product. The molecular weight of the component (A2) is preferably 5000 or less, more preferably 1000 or less, and most preferably 450 or less from the viewpoint of moisture resistance of the cured product.

When the component (A2) has a molecular weight distribution, it is preferable that the number average molecular weight of the component (A2) is in the above range. In the present specification, the number average molecular weight indicates a polystyrene-equivalent value measured by gel permeation chromatography (GPC) under the above-mentioned measurement conditions.

Examples of the compound having an oxetane group include the following (A3) component.

<(A3) component: compound having an oxetane group>
The component (A3) may be a compound having one oxetane group, or may be a compound having two or more oxetane groups. The component (A3) may be used alone or in combination of two or more.

Examples of the component (A3) include 3-ethyl-3-hydroxymethyloxetane (manufactured by Toa Synthetic Co., Ltd., trade name OXT-101, etc.), 1,4-bis [(3-ethyl-3-oxetanyl) methoxy). Methyl] benzene (manufactured by Toa Synthetic Co., Ltd., trade name OXT-121, etc.), 3-ethyl-3- (phenoxymethyl) oxetane (manufactured by Toa Synthetic Co., Ltd., trade name OXT-211, etc.), di (1- Ethyl- (3-oxetanyl)) methyl ether (manufactured by Toa Synthetic Co., Ltd., trade name OXT-221 etc.), 3-Ethyl-3- (2-ethylhexyloxymethyl) oxetane (manufactured by Toa Synthetic Co., Ltd., product) Name OXT-212 etc.) and the like.

The component (A) may be a compound other than the component (A1), the component (A2) and the component (A3). Examples of such a compound include the following component (A4).

<(A4) component>
The component (A4) may be a compound having a cationic ring-opening polymerizable group, and may be, for example, a compound having a cyclic ether group. The component (A4) may be a compound having one cationic ring-opening polymerizable group, and preferably has two or more. The component (A4) may be a compound having no alicyclic group, aromatic ring and oxetane group. The component (A4) may be used alone or in combination of two or more.

Among the components (A4), examples of the compound having a cyclic ether group include compounds having an epoxy group (oxylan ring). As the component (A4), a compound having a glycidyloxy group is preferable. The compound having a glycidyloxy group is preferably a compound having two or more glycidyloxy groups.

Examples of the compound having a glycidyloxy group include diglycidyl ether of alkylene glycol, diglycidyl ether of polyalkylene glycol, di or triglycidyl ether of glycerin or its alkylene oxide adduct. Examples of the alkylene glycol include ethylene glycol, propylene glycol, 1,6-hexanediol and the like. Examples of the polyalkylene glycol include polyethylene glycol or an alkylene oxide adduct thereof, polypropylene glycol or an alkylene oxide adduct thereof. Examples of the alkylene oxide include ethylene oxide and propylene oxide.

The content of the component (A) may be, for example, 5 parts by mass or more out of a total of 100 parts by mass of the components (A) and (B), and 10 parts by mass from the viewpoint of further improving the durability after curing. It is preferably 20 parts by mass or more, and more preferably 20 parts by mass or more. Further, the content of the component (A) may be, for example, 49.9 parts by mass or less in a total of 100 parts by mass of the components (A) and (B), from the viewpoint of further improving the durability after curing. Is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less.

((B) Vinyl ether compound)
The component (B) is a compound having a vinyloxy group. As the component (B), one type can be used alone or two or more types can be used in combination.

The compound having a vinyloxy group is preferably a compound having a vinyl ether group in which an oxygen atom of a vinyloxy group (CH ₂ = CH—O—) is bonded to a carbon atom. Examples of such compounds include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, and cyclohexanedimethanol divinyl ether. , Di or trivinyl ether compounds such as trimethylpropan trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether. , Isopropenyl ether, isopropenyl ether-o-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether, ethylene glycol monovinyl ether, triethylene glycol monovinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether and other monovinyl ether compounds. Can be mentioned.

The component (B) preferably has two vinyloxy groups and further has a cyclic group. Examples of such component (B) include cyclohexanedimethanol divinyl ether, 2,2-adamantane dimethanol divinyl ether and the like.

From the viewpoint of keeping the viscosity low, the content of the component (B) is preferably larger than 50 parts by mass, more preferably 51 parts by mass or more, based on 100 parts by mass of the total of the components (A) and (B). , 60 parts by mass or more is more preferable, and 70 parts by mass or more is further preferable. Further, the content of the component (B) is preferably 95 parts by mass or less with respect to 100 parts by mass in total of the components (A) and (B) from the viewpoint that a cured product having excellent durability can be easily obtained. It is more preferably 85 parts by mass or less, and further preferably 75 parts by mass or less.

The viscosity (initial viscosity) of the component (B) at 25 ° C. is not particularly limited, but is preferably lower than the viscosity of the component (A) at 25 ° C. from the viewpoint of keeping the viscosity low.

((C) Photocationic polymerization initiator)
The component (C) may be any component that can be activated by light to initiate cationic polymerization of the component (A). As the component (C), one type can be used alone or two or more types can be used in combination.

Examples of the component (C) include aryl sulfonium salt derivatives (for example, Cyracure UVI-6990 and Cyracure UVI-6974 manufactured by Dow Chemical Co., Ltd., Adekaoptomer SP-150 manufactured by Asahi Denka Kogyo Co., Ltd., and Adekaoptomer SP-152. , Adekaoptomer SP-170, Adekaoptomer SP-172, CPI-100P, CPI-101A, CPI-200K, CPI-210S, LW-S1, Double Bond CibaCure-1190, etc.), Aryliodonium salt derivatives (for example, Irgacure 250 manufactured by Tivas Specialty Chemicals, RP-2074 manufactured by Rhodia Japan, etc.), allen-ion complex derivatives, diazonium salt derivatives, triazine initiators, other halides, etc. Examples include acid generators.

As the component (C), an onium salt compound is preferable from the viewpoint of obtaining the above-mentioned effects more remarkably.

Examples of the onium salt compound of the component (C) include an onium salt compound represented by the formula (C-1).

In the formula (C-1), A represents an element having a valence m of the genus VIA to VIIA, and m represents 1 or 2. p represents an integer of 0 to 3. R represents an organic group attached to A. X ^- represents the counterion of onium, the number of which is (p + 1) per molecule. D represents a divalent group represented by the following formula (C-1-1). The plurality of Rs may be the same or different from each other. A plurality of X ^-s may be the same as or different from each other. When there are multiple A's, they may be the same or different from each other. When there are multiple D's, they may be the same or different from each other.

In formula (C-1-1), E represents a divalent group, G is -O-, -S-, -SO-, -SO _2- , -NH-, -NR'-, -CO-. , -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group (R'is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms). a indicates an integer from 0 to 5. The a + 1 E and the a G may be the same or different from each other.

R is an organic group bonded to A, which is an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and the like. Alternatively, it represents an alkynyl group having 2 to 30 carbon atoms, which are an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, or an arylthio group. , Alkylthio group, aryl group, heterocyclic group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, alkyleneoxy group, amino group, cyano group, nitro group, and halogen group. It may be replaced with one or more selected more.

The number of Rs is (m + p (m-1) + 1), and a plurality of Rs may be the same or different from each other. Also, two or more R are directly or, -O -, - S -, - SO -, - SO 2 -, - NH -, - NR '-, - CO -, - COO -, - CONH- , It may be bonded via an alkylene or phenylene group having 1 to 3 carbon atoms to form a ring structure containing the element A. Here, R'represents an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

Examples of the aryl group having 6 to 30 carbon atoms include a monocyclic aryl group such as a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a chrysenyl group, a naphthacenyl group, a benzanthrasenyl group and an anthraquinolyl group. Examples thereof include a fused polycyclic aryl group such as a fluorenyl group, a naphthoquinone group and an anthraquinone group.

An aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 30 carbon atoms is one or more. It may have a substituent. As a substituent, for example,
Linear alkyl groups with 1 to 18 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group and octadecyl group;
Branched alkyl groups having 1 to 18 carbon atoms such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group and isohexyl group;
Cycloalkyl group having 3 to 18 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group;
Hydroxy group;
Linear group with 1 to 18 carbon atoms such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, hexyloxy group, decyloxy group, dodecyloxy group, etc. Branched alkoxy group;
Acetyl group, propionyl group, butanoyl group, 2-methylpropionyl group, heptanoil group, 2-methylbutanoyl group, 3-methylbutanoyl group, octanoyl group, decanoyl group, dodecanoyl group, octadecanoyl group, etc. ~ 18 linear or branched alkylcarbonyl groups;
Arylcarbonyl groups having 7 to 11 carbon atoms such as benzoyl groups and naphthoyl groups;
Methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, octyloxycarbonyl group, tetradecyloxycarbonyl group, octa A linear or branched alkoxycarbonyl group having 2 to 19 carbon atoms such as a decyloxycarbonyl group;
Aryloxycarbonyl groups having 7 to 11 carbon atoms such as phenoxycarbonyl groups and naphthoxycarbonyl groups;
An arylthiocarbonyl group having 7 to 11 carbon atoms such as a phenylthiocarbonyl group and a naphthoxythiocarbonyl group;
Acetoxy group, ethylcarbonyloxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group, isobutylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group, octylcarbonyloxy group, tetradecylcarbonyl A linear or branched asyloxy group having 2 to 19 carbon atoms such as an oxy group and an octadecylcarbonyloxy group;
Phenylthio group, 2-methylphenylthio group, 3-methylphenylthio group, 4-methylphenylthio group, 2-chlorophenylthio group, 3-chlorophenylthio group, 4-chlorophenylthio group, 2-bromophenylthio group, 3 -Bromophenylthio group, 4-bromophenylthio group, 2-fluorophenylthio group, 3-fluorophenylthio group, 4-fluorophenylthio group, 2-hydroxyphenylthio group, 4-hydroxyphenylthio group, 2- Methoxyphenylthio group, 4-methoxyphenylthio group, 1-naphthylthio group, 2-naphthylthio group, 4- [4- (phenylthio) benzoyl] phenylthio group, 4- [4- (phenylthio) phenoxy] phenylthio group, 4- [4- (Phenylthio) phenyl] phenylthio group, 4- (phenylthio) phenylthio group, 4-benzoylphenylthio group, 4-benzoyl-2-chlorophenylthio group, 4-benzoyl-3-chlorophenylthio group, 4-benzoyl- 3-Methylthiophenylthio group, 4-benzoyl-2-methylthiophenylthio group, 4- (4-methylthiobenzoyl) phenylthio group, 4- (2-methylthiobenzoyl) phenylthio group, 4- (p-methylbenzoyl) phenylthio group , 4- (p-ethylbenzoyl) phenylthio group 4- (p-isopropylbenzoyl) phenylthio group, 4- (p-tert-butylbenzoyl) phenylthio group and other arylthio groups having 6 to 20 carbon atoms;
Methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, pentylthio group, isopentylthio group, neopentylthio group, tert-pentylthio group, octylthio group. , A linear or branched alkylthio group having 1 to 18 carbon atoms such as a decylthio group and a dodecylthio group;
Aryl groups having 6 to 10 carbon atoms such as phenyl group, tolyl group, dimethylphenyl group and naphthyl group;
Thienyl group, furanyl group, pyranyl group, pyrrolyl group, oxazolyl group, thiazolyl group, pyridyl group, pyrimidyl group, pyrazinyl group, indolyl group, benzofuranyl group, benzothienyl group, quinolyl group, isoquinolyl group, quinoxalinyl group, quinazolinyl group, carbazolyl Number of carbon atoms of group, acridinyl group, phenothiazinyl group, phenazinyl group, xanthenyl group, thianthrenyl group, phenoxadinyl group, phenoxatinyl group, chromanyl group, isochromanyl group, dibenzothienyl group, xanthonyl group, thioxanthonyl group, dibenzofuranyl, etc. 4 to 20 heterocyclic groups;
Aryloxy groups having 6 to 10 carbon atoms such as phenoxy groups and naphthyloxy groups;
Methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, isobutylsulfinyl group, sec-butylsulfinyl group, tert-butylsulfinyl group, pentylsulfinyl group, isopentylsulfinyl group, neopentylsulfinyl group, A linear or branched alkylsulfinyl group having 1 to 18 carbon atoms such as a tert-pentylsulfinyl group and an octylsulfinyl group;
Arylsulfinyl groups having 6 to 10 carbon atoms such as phenylsulfinyl group, trillsulfinyl group, and naphthylsulfinyl group;
Methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group, tert-butylsulfonyl group, pentylsulfonyl group, isopentylsulfonyl group, neopentylsulfonyl group, A linear or branched alkylsulfonyl group having 1 to 18 carbon atoms such as a tert-pentylsulfonyl group and an octylsulfonyl group;
Arylsulfonyl groups having 6 to 10 carbon atoms such as phenylsulfonyl groups, trillsulfonyl groups (tosyl groups), and naphthylsulfonyl groups;
An alkyleneoxy group represented by the following formula (C-1-2);
An unsubstituted amino group and an amino group mono-substituted or di-substituted with an alkyl having 1 to 5 carbon atoms and / or an aryl having 6 to 10 carbon atoms;
Cyano group;
Nitro group;
Halogen groups such as fluorine, chlorine, bromine and iodine can be mentioned.

In the formula (C-1-2), Q represents a hydrogen atom or a methyl group, and k represents an integer of 1 to 5. The k Qs may be the same or different from each other.

As the onium ion (A ⁺ ) in the formula (C-1), a sulfonium ion, an iodonium ion, and a selenium ion are preferable. Representative examples of these are shown below.

Examples of the sulfonium ion include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris (4-methoxyphenyl) sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, and tris (4-). Fluorophenyl) sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris (4-hydroxyphenyl) sulfonium, 4- (phenylthio) phenyldiphenylsulfonium, 4- (p-tolylthio) phenyldi-p-tolylsulfonium , 4- (4-methoxyphenylthio) phenylbis (4-methoxyphenyl) sulfonium, 4- (phenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (phenylthio) phenylbis (4-methoxyphenyl) sulfonium, 4- (Phenylthio) phenyldi-p-tolylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, bis [4- {bis [4- (2-hydroxyethoxy) phenyl] sulfonio} phenyl] sulfide, bis { 4- [Bis (4-fluorophenyl) Sulfonio] phenyl} sulfide, bis {4- [bis (4-methylphenyl) sulfonio] phenyl} sulfide, bis {4- [bis (4-methoxyphenyl) sulfonio] phenyl} Sulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenyldiphenylsulfonium, 4- (4-benzoylphenylthio) phenyl Bis (4-fluorophenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-Isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl) sulfonio] thioxanthone, 2-[(diphenyl) sulfonio] thioxanthone, 4 -[4- (4-tert-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldiphenylsulfonium, 4- [4- (benzoylphenyl) (Lucio)] Phenyldi-p-tolylsulfonium, 4- [4- (benzoylphenylthio)] phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiaanthrenium, 5-phenylthiaanthrenium, 5-triluciaanthrenium , 5- (4-ethoxyphenyl) thiaanthrenium, triarylsulfoniums such as 5- (2,4,6-trimethylphenyl) thiaanthrenium;
Diarylsulfoniums such as diphenylphenacil sulfonium, diphenyl4-nitrophenacil sulfonium, diphenylbenzyl sulfonium, diphenylmethyl sulfonium;
Phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetcarbonyloxyphenylmethylbenzylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium , Phenylmethylphenacil sulfonium, 4-hydroxyphenylmethylphenacil sulfonium, 4-methoxyphenylmethylphenacil sulfonium, 4-acetocarbonyloxyphenylmethylphenacil sulfonium, 2-naphthylmethylphenacil sulfonium, 2-naphthyloctadecylphenacil Monoaryl sulfonium such as sulfonium, 9-anthrasenyl methylphenacil sulfonium;
Examples thereof include trialkyl sulfoniums such as dimethylphenacil sulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium and octadecylmethylphenacilsulfonium.

Among these, triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, bis [4- {bis [4- (2-hydroxy) Ethoxy) phenyl] sulfonio} phenyl] sulfide, bis {4- [bis (4-fluorophenyl) sulfonio] phenyl} sulfide, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10 -Chia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl) sulfonio] thioxanthone, 2-[(diphenyl) sulfonio] thioxanthone, 4- [4- (4-tert-) Butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- [4- (benzoylphenylthio)] phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiaanthrenium, 5-phenylthiaanthrenium, diphenylphenacil sulfonium , 4-Hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, 4-hydroxyphenylmethylphenacilsulfonium and octadecylmethylphenacilsulfonium are preferably one or more selected from the group.

In formula (C-1), X ^- is a counterion. The number of counterions is (p + 1) per molecule. Although counter ion is not particularly limited, for ^{example, F -, Cl -, Br} -, I - halogen ions such _{^{as; OH -; ClO 4 -;}} FSO 3 -, ClSO 3 -, CH 3 SO 3 -, C 6 _{^{H 5 SO 3 -, CF 3}} SO 3 - sulfonate ion such _as; ^HSO 4 -, sulfate ions of _SO ^{4 _{2-like; HCO 3 -, CO 3 2-}} , carbonate ions and the _like; H 2 PO ^4-, _HPO ⁴ 2-, phosphate ions of _PO ^{4 3-} and the _{^{like; PF 6 -, PF 5 OH}} -, fluorophosphate ions such as fluorinated alkyl fluorophosphate _ion; ^BF 4 -, B (C _{^{6 F 5) 4 -, B}} (C 6 H 4 CF 3) 4 - borate ions such _{^{as; AlCl 4 -; BiF 6 -}} , SBF 6 -, SBF 5 OH - fluoro antimonate ion such as; AsF ₆ ^-, _AsF 5 OH ^- fluoroarsenate periodate ions such as and the like.

Examples of the fluorinated alkylfluorophosphate ion include a fluorinated alkylfluorophosphate ion represented by the formula (C-1-3) and the like.

In formula (C-1-3), R ^f represents an alkyl fluoride group. b is the number of R ^f and indicates an integer of 1 to 5. The b R ^fs may be the same or different from each other.

B is preferably 2 to 4, more preferably 2 to 3.

The alkyl fluoride group of R ^f represents a group in which a part or all of the hydrogen atom of the alkyl group is substituted with a fluorine atom. The number of carbon atoms of the alkyl group is preferably 1 to 8, and more preferably 1 to 4. Examples of the alkyl group include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group and octyl group; branched alkyl such as isopropyl group, isobutyl group, sec-butyl group and tert-butyl group. Group: Cycloalkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.

Specific examples of alkyl fluoride groups include CF _3- , CF ₃ CF _2- , (CF ₃ ) ₂ CF-, CF ₃ CF ₂ CF _2- , CF ₃ CF ₂ CF ₂ CF _2- , (CF ₃ ). ₂ CFCF _2- , CF ₃ CF ₂ (CF ₃ ) CF-, (CF ₃ ) ₃ C- and the like can be mentioned.

Specific examples of preferred fluorinated alkylfluorophosphate ions include [(CF ₃ CF ₂ ) ₂ PF ₄ ] ^- , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ] ^- , [ _{(CF 3 CF 2 CF 2 CF} 2) 3 PF 3] - , and the like.

In the present embodiment, as the component (C), diphenyl4-thiophenoxyphenylsulfonium tris (pentafluoroethyl) trifluorophosphate represented by the formula (C-2) and the formula (C-3) are represented. The triarylsulfonium salt hexafluoroantimonate can be particularly preferably used, and among these, the triarylsulfonium salt hexafluoroantimonate represented by the formula (C-3) is more preferable.

The component (C) may be previously dissolved in a solvent in order to facilitate mixing with other components such as the component (A). The solvent is not particularly limited, and examples thereof include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, and diethyl carbonate.

From the viewpoint of photocurability of the resin composition, the content of the component (C) is preferably 0.1 part by mass or more with respect to 100 parts by mass in total of the components (A) and (B), and 0. More preferably, 15 parts by mass or more. Further, the content of the component (C) is preferably 5.0 parts by mass or less with respect to 100 parts by mass in total of the components (A) and (B) from the viewpoint of the adhesive durability of the cured product. More preferably, it is 0.0 parts by mass or less.

The resin composition may further contain other components other than the component (A), the component (B) and the component (C).

Examples of other components include a curing retarder (component (X)). The curing retarder is a compound that suppresses an increase in viscosity after light irradiation and prolongs the pot life by temporarily capturing active species involved in the reaction.

(Component (X): Curing retarder)
The curing retarder is preferably a curing retarder selected from the group consisting of a phosphoric acid-based curing retarder (component (D)) and an ether-based curing retarder (component (E)). The curing retarder may be used alone or in combination of two or more.

<Component (D): Phosphoric acid-based curing retarder>
The phosphoric acid-based curing retarder is a curing retarder selected from the group consisting of a phosphoric acid ester (component (D1)) and a phosphite ester (component (D2)). The component (D) may be used alone or in combination of two or more.

Examples of the component (D1) include diethylbenzyl phosphate, trimethylphosphate, triethyl phosphate, tri-n-butyl phosphate, tris (butoxyethyl) phosphate, tris (2-ethylhexyl) phosphate, and (RO) ₃ P = O (R). , Octyl group, lauryl group, cetyl group, stearyl group or oleyl group), tris (2-chloroethyl) phosphate, tris (2-dichloropropyl) phosphate, triphenyl phosphate, butylpyrrophosphate, tricresyl phosphate, trixylenyl Examples thereof include phosphate, octyldiphenyl phosphate, cresildiphenyl phosphate, xylenyldiphosphate, monobutyl phosphate, dibutyl phosphate, di-2-ethylhexyl phosphate, monoisodecyl phosphate, ammonium ethyl acid phosphate, 2-ethylhexyl acid phosphate salt and the like. .. The component (D1) may be used alone or in combination of two or more.

The component (D1) is a compound represented by the formula (D1-1), a compound represented by the formula (D1-2), and a compound represented by the formula (D1-3) from the viewpoint of appropriate reactivity with cations and reduction of outgas. It is preferable to contain at least one selected from the group consisting of the compounds represented by, and it is more preferable to contain the compound represented by the formula (D1-2).

Formula (D1-1), wherein (D1-2) and the formula ^(D1-3), have ^{R 1, R 2, R 3} , R 4, R 5 and ^{R 6} each independently represent a substituent Shows good hydrocarbon groups.

^R 2 in the formula (D1-2), ^{R 3} and ^{R 4,} and, ^{R 5} and ^{R 6} in the formula (D1-3) is preferably in the formula of the same group.

Examples of the substituent that the hydrocarbon group in R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may have include an oxyalkyl group and the like. The hydrocarbon groups in R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are preferably unsubstituted hydrocarbon groups.

The hydrocarbon group in R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is preferably an alkyl group or an aryl group, more preferably an alkyl group or a phenyl group, and is an alkyl group. Is even more preferable. The number of carbon atoms of the alkyl group may be, for example, 1 to 18, preferably 4 to 13.

The compound represented by the formula (D1-1) may be, for example, monoalkyl phosphate (that is, a compound in which R ¹ is an alkyl group), and specific examples thereof include monoethyl phosphate and mono n-butyl. Examples thereof include phosphate, mono (butoxyethyl) phosphate, mono (2-ethylhexyl) phosphate and the like.

Examples of the compound represented by the formula (D1-2), trialkyl phosphates ^(i.e., compound R 2, ^{R 3} and ^{R 4} is an alkyl group) are preferred. At this time, the number of carbon atoms of the alkyl groups of R ² , R ³ and R ⁴ is preferably 1 to 18, more preferably 4 to 12, and even more preferably 8.

Specific examples of the trialkyl phosphate include triethyl phosphate, tri-n-butyl phosphate, tris (butoxyethyl) phosphate, tris (2-ethylhexyl) phosphate, (RO) ₃ P = O (R is a lauryl group, a cetyl group, Stearyl group or oleyl group) and the like.

Examples of the compound represented by the formula (D1-3) include dialkyl phosphates (that is, compounds in which R ⁵ and R ⁶ are alkyl groups) and the like. Specific examples of the dialkyl phosphate include dibutyl phthalate and bis (2-ethylhexyl) phosphate.

The (D2) component is a phosphite ester. Examples of the component (D2) include trimethylphosphite, triethylphosphite, trin-butylphosphite, tris (2-ethylhexyl) phosphite, triisooctylphosphite, tridecylphosphite, triisodecylphosphite, and the like. Tris (tridecyl) phosphite, trioleyl phosphite, tristearyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, phenyldiisooctyl Phosphite, phenyldiisodecylphosphite, diphenylmono (2-ethylhexyl) phosphite, diphenylisooctylphosphite, diphenylmonodecylphosphite, diphenylmonoisodecylphosphite, diphenylmono (tridecyl) phosphite, bis (nonylphenyl) Dinonylphenylphosphite, tetraphenyldipropylene glycol diphosphite, poly (dipropylene glycol) phenylphosphite, diisodecylpentaerythritol diphosphite, bis (tridecyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, Bis (nonylphenyl) pentaerythritol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, tetra (tridecyl) -4,4'-isopropyridendiphenylphosphite, trilauryltrithiophosphite, dimethylhydrodienephosphite , Dibutylhydrodienephosphite, di (2-ethylhexyl) hydrodienephosphite, dilaurylhydrodienphosphite, diolayl hydrodienephosphite, diphenylhydrodienphosphite, diphenylmono (2-ethylhexyl) phosphite, diphenylmono Examples thereof include decylphosphite and diphenylmono (tridecyl) phosphite. The component (D2) may be used alone or in combination of two or more.

The component (D2) is represented by a compound represented by the formula (D2-1), a compound represented by the formula (D2-2), and a compound represented by the formula (D2-3) from the viewpoint of appropriate reactivity with a cation. It contains at least one selected from the group consisting of a compound, a compound represented by the formula (D2-4), a compound represented by the formula (D2-5) and a compound represented by the formula (D2-6). Is preferable.

In equations (D2-1) to (D2-6), R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are independent of each other. Indicates a hydrocarbon group which may have a substituent.

Substituents that the hydrocarbon groups in R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ may have include, for example, Examples thereof include an oxyalkyl group. The hydrocarbon groups in R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are preferably unsubstituted hydrocarbon groups.

The hydrocarbon groups in R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are preferably alkyl or aryl groups. It is more preferably a group or a phenyl group, and even more preferably an alkyl group. The number of carbon atoms of the alkyl group may be, for example, 1 to 30, preferably 1 to 18.

R ⁸ and R ^{9 in} formula (D2-2), R ¹⁰ , R ¹¹ and R ¹² in formula (D2-3), R ¹³ and R ^{14 in} formula (D2-4), and formula (D2). It is preferable that R ¹⁵ and R ^{16 in} -5) are the same in each formula.

Examples of the compound represented by the formula (D2-1) include monoalkyl phosphite (that is, a compound in which R ⁷ is an alkyl group) and the like.

Examples of the compound represented by the formula (D2-2) include dialkyl phosphite (that is, a compound in which R ⁸ and R ⁹ are alkyl groups) and the like.

Examples of the compound represented by the formula (D2-3) include trialkylphosphite (that is, a compound in which R ¹⁰ , R ¹¹ and R ¹² are alkyl groups) and the like. Specific examples of the compound represented by the formula (D2-3) include triethyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite, and trio. Examples include rail phosphite.

Examples of the compound represented by the formula (C2-4) include bis (alkyl) pentaerythritol diphosphite (that is, a compound in which R ¹³ and R ¹⁴ are alkyl groups) and the like. Specific examples of the compound represented by the formula (D2-4) include bis (decyl) pentaerythritol diphosphite, bis (tridecylic) pentaerythritol diphosphite, and distearyl pentaerythritol diphosphite. ..

Examples of the compound represented by the formula (D2-5) include dialkylhydrogen phosphite (that is, a compound in which R ¹⁵ and R ¹⁶ are alkyl groups) and the like. Specific examples of the compound represented by the formula (D2-5) include diethylhydrogen phosphite, bis (2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, diolayl hydrogen phosphite and the like.

Examples of the compound represented by the formula (D2-6) include monoalkylhydrogen phosphite (that is, a compound in which R ¹⁷ is an alkyl group) and the like. Specific examples of the compound represented by the formula (D2-6) include monoethylhydrogen phosphite, mono (2-ethylhexyl) hydrogen phosphite, monolauryl hydrogen phosphite, monooleyl hydrogen phosphite and the like. ..

The components (D2) include trimethylphosphite, triethylphosphite, tri-n-butylphosphite, tris (2-ethylhexyl) phosphite, triisooctylphosphite, tridecylphosphite, triisodecylphosphite, and tris (D2). Tridecyl) phosphite, trioleyl phosphite, tristearyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol di Phosphite, bis (nonylphenyl) pentaerythritol diphosphite, dimethylhydrodienephosphite, dibutylhydrodienephosphite, di (2-ethylhexyl) hydrodienephosphite, dilaurylhydrodienephosphite, dioleylhydrodienphosphite It is preferable to contain at least one selected from the group consisting of trimethylphosphite, triethylphosphite, tri-n-butylphosphite, tris (2-ethylhexyl) phosphite, triisooctylphosphite, tridecylphosphite. , Triisodecyl phosphite, tris (tridecyl) phosphite, trioleyl phosphite, tristearyl phosphite, triphenyl phosphite and tris (nonylphenyl) phosphite may contain at least one selected from the group. More preferable.

When the resin composition contains the component (D), the content of the component (D) is based on 100 parts by mass of the total of the components (A) and (B) from the viewpoint of obtaining a longer pot life. 0.01 parts by mass or more is preferable, and 0.02 parts by mass or more is more preferable. The content of the component (D) is preferably 2 parts by mass or less, preferably 1 part by mass, based on 100 parts by mass of the total of the components (A) and (B) from the viewpoint of moisture resistance and adhesive strength of the cured product. Less than a part is more preferable.

When the resin composition contains the component (D), the content of the component (D) is preferably 5 parts by mass or more from the viewpoint of obtaining a longer pot life with respect to 100 parts by mass of the component (C). More than 10 parts by mass is more preferable. The content of the component (D) is preferably 2000 parts by mass or less, more preferably 1000 parts by mass or less, with respect to 100 parts by mass of the component (C) from the viewpoint of photocurability.

<Component (E): Ether-based curing retarder>
The component (E) is a curing retarder having an ether bond. As the component (E), one type can be used alone or two or more types can be used in combination.

The component (E) may be a chain ether or a cyclic ether. Examples of the chain ether include polyalkylene oxides such as polyethylene glycol, polypropylene glycol, and polyoxytetramethylene glycol. Examples of the cyclic ether include crown ether and the like.

The component (E) is preferably a cyclic ether, more preferably a crown ether, from the viewpoint of appropriate reactivity with cations.

When the resin composition contains the component (E), the content of the component (E) is such that a longer pot life can be obtained with respect to a total of 100 parts by mass of the components (A) and (B). 0.1 part by mass or more is preferable, and 0.3 part by mass or more is more preferable. The content of the component (E) is preferably 5 parts by mass or less, preferably 3 parts by mass, based on 100 parts by mass of the total of the components (A) and (B) from the viewpoint of moisture resistance and adhesive strength of the cured product. Less than a part is more preferable.

When the resin composition contains the component (E), the content of the component (E) is preferably 5 parts by mass or more from the viewpoint of obtaining a longer pot life with respect to 100 parts by mass of the component (C). More than 10 parts by mass is more preferable. The content of the component (E) is preferably 2000 parts by mass or less, more preferably 1000 parts by mass or less, with respect to 100 parts by mass of the component (C) from the viewpoint of photocurability.

The resin composition may further contain other components other than the component (A), the component (B), the component (C) and the component (X).

Examples of other components include a photosensitizer. The photosensitizer is a compound that absorbs energy rays and efficiently generates cations from the photocationic polymerization initiator.

The photosensitizer is not particularly limited, but benzophenone derivative, phenothiazine derivative, phenylketone derivative, naphthalene derivative, anthracene derivative, phenanthrene derivative, naphthacene derivative, chrysene derivative, perylene derivative, pentacene derivative, aclysine derivative, benzothiazole derivative, Benzoin derivative, fluorene derivative, naphthoquinone derivative, anthraquinone derivative, xanthene derivative, xantone derivative, thioxanthene derivative, thioxanthone derivative, coumarin derivative, ketocoumarin derivative, cyanine derivative, azine derivative, thiazine derivative, oxazine derivative, indolin derivative, azulene derivative, tri Examples thereof include allylmethane derivatives, phthalocyanine derivatives, spiropirane derivatives, spiroxazine derivatives, thiospiropirane derivatives, and organic ruthenium complexes. Among these, at least one selected from the group consisting of anthracene derivatives such as 9,10-dibutoxyanthracene and phenylketone derivatives such as 2-hydroxy-2-methyl-1-phenyl-propane-1-one is preferable. , 9,10-Dibutoxyanthracene and other anthracene derivatives are more preferred. The photosensitizer may be used alone or in combination of two or more.

When the resin composition contains a photosensitizer, the content of the photosensitizer is preferably 0.01 part by mass or more, preferably 0.02 parts by mass or more, based on 100 parts by mass of the total of the components (A) and (B). More than parts by mass is more preferable. The content of the photosensitizer is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the total of the components (A) and (B). Within such a range, better curability and storage stability can be obtained.

Examples of other components include silane coupling agents. The inclusion of the silane coupling agent tends to improve the adhesiveness and adhesive durability of the resin composition.

The silane coupling agent is not particularly limited, but is γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltricrolsilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ- (meth). Acryloxipropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-Aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane And so on. Among these, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane and γ- (meth) acryloxipropyltrimethoxy At least one selected from the group consisting of silane is preferred. The silane coupling agent may be used alone or in combination of two or more.

When the resin composition contains a silane coupling agent, the content of the silane coupling agent is preferably 0.1 part by mass or more with respect to 100 parts by mass in total of the components (A) and (B). More than 2 parts by mass is more preferable. The content of the silane coupling agent is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the total of the components (A) and (B). With such a content range, higher adhesiveness and adhesive durability can be obtained.

In the present embodiment, the method for producing the resin composition is not particularly limited, and for example, the above-mentioned components may be mixed. The mixing method is not particularly limited as long as each of the above-mentioned components can be sufficiently mixed. Examples of the mixing method include a stirring method using a stirring force accompanying the rotation of the propeller, a method using a normal disperser such as a planetary stirrer by rotation and revolution, and the like. These mixing methods are preferable in that stable mixing can be performed at low cost.

The resin composition according to this embodiment may be used, for example, so as to contribute to the sealing of the organic EL display element. For example, the resin composition may be used for forming a coating material for coating the organic EL display element, or may be used as an adhesive for adhering the members constituting the organic EL display device to each other.

The viscosity of the resin composition according to this embodiment appropriately increases after light irradiation, and then cures as the polymerization reaction of the cationically polymerizable compound progresses. The resin composition after light irradiation can also be rapidly cured by heating.

The light source for irradiating the resin composition is not particularly limited, and for example, a halogen lamp, a metal halide lamp, a high power metal halide lamp (containing indium, etc.), a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, and a xenon lamp. , Xenon excimer lamp, xenon flash lamp, light-emitting diode (hereinafter referred to as LED) and the like. These light sources are preferable in that they can efficiently irradiate energy rays corresponding to the reaction wavelength of the photocationic polymerization initiator.

The above light sources have different radiation wavelengths and energy distributions. Therefore, the light source can be appropriately selected depending on the reaction wavelength of the photocationic polymerization initiator and the like. Natural light (sunlight) can also be a reaction initiation light source for the resin composition.

As the irradiation method, direct irradiation, focused irradiation with a reflecting mirror or the like, or focused irradiation with a fiber or the like may be performed. Irradiation using a low wavelength cut filter, a heat ray cut filter, a cold mirror, or the like can also be performed.

The amount of light irradiation is not particularly limited, and may be appropriately adjusted depending on the thickness of the coating film of the resin composition and the like. The irradiation amount of light may be, for example, 50 to 20000 mJ / cm ² , preferably 100 to 10000 mJ / cm ² .

When heating after light irradiation (also referred to as post-heating), the heating temperature is preferably 150 ° C. or lower, more preferably 80 ° C. or lower, from the viewpoint of avoiding damage to the organic EL display element. When post-heating is performed, the heating temperature is preferably 50 ° C. or higher.

The viscosity of the resin composition according to the present embodiment when measured using an E-type viscometer under the conditions of 25 ° C. and 10 rpm prevents unintentional dripping from a device used for ejection such as a dispenser or an inkjet device. From the viewpoint of the above, 2 cps or more is preferable, and 5 cps or more is more preferable. Further, the viscosity is preferably 200 cps or less, more preferably 50 cps or less, still more preferably 30 cps or less, from the viewpoint of ease of coating / discharging. When the viscosity is 30 cps or less, ejection by an inkjet type device is easy at 25 ° C.

The resin composition according to the present embodiment preferably has a viscosity 20 minutes after irradiation with light, which is 1.2 times or more and less than 10 times the viscosity before light irradiation. For example, 20 minutes after irradiating the resin composition coated so that the coating amount per unit area is 10 mg / cm ² with ultraviolet rays at an irradiation amount of 100 mW / cm ² for 10 seconds with a high-pressure mercury lamp. It is preferable that the viscosity is 1.2 times or more and less than 10 times the viscosity before ultraviolet irradiation.

The resin composition according to the present embodiment preferably has a viscosity after curing for 10 minutes in a high temperature atmosphere after irradiation with light, which is 3 times or more the viscosity before curing. For example, when cured in an atmosphere of 80 ° C., the viscosity 10 minutes after curing is preferably three times or more the viscosity before curing.

The resin composition according to this embodiment can have a sufficiently long pot life after light irradiation. Further, since the viscosity of the resin composition according to the present embodiment appropriately increases after light irradiation, the members can be easily bonded and the workability is excellent. Further, the resin composition according to the present embodiment is excellent in moisture resistance and adhesiveness after curing. Therefore, according to the resin composition according to the present embodiment, a sealing material having excellent sealing characteristics can be formed, and an organic electroluminescence display device having excellent reliability can be manufactured.

In the present embodiment, the encapsulant may contain a resin composition.

It cured product of the sealing agent according to the present embodiment, the moisture permeability of at 0.1m thickness is preferably not more than ^{250g / (m 2 · 24hr)} , is 200g ^/ (m 2 · 24hr) or less Is more preferable. In the present specification, the moisture permeability of the cured product is based on JIS Z0208 "Moisture Permeability Test Method for Moisture-Proof Packaging Material (Cup Method)", using calcium chloride (anhydrous) as a moisture absorbent, and having an atmospheric temperature of 60 ° C. and relative humidity. The value measured under the condition of humidity 90% is shown.

It is preferable that the cured product of the encapsulant according to the present embodiment has excellent transparency. Specifically, the cured product has a total light transmittance of 60% or more, more preferably 80% or more, and 95% or more at a wavelength of 380 to 800 nm per 10 μm thickness. Is more preferable.

The method of using the sealant according to the present embodiment is not particularly limited. For example, by applying a sealant to an object (for example, a member constituting an organic EL display device) and curing the sealant on the object, a sealant made of a cured body of the sealant is formed. it can.

Further, the sealing agent may be cured into a predetermined shape (for example, a film shape, a sheet shape, etc.) to form a sealing material having a predetermined shape. In this case, for example, when assembling the organic EL display device, the organic EL display element can be sealed by arranging the sealing material on the organic EL display element.

In the present embodiment, the encapsulant may be made of a cured product of the encapsulant, or may contain a cured product of the encapsulant and other constituent materials. Examples of other constituent materials include an inorganic layer such as a silicon nitride film, a silicon oxide film, and silicon nitride, and an inorganic filler such as silica, mica, kaolin, talc, and aluminum oxide.

According to the sealant according to the present embodiment, an organic EL display device including an organic EL display element and a sealing material can be easily manufactured.

The method for manufacturing the organic EL display device is, for example, an attachment step of attaching the above-mentioned sealing agent to the first member, an irradiation step of irradiating the attached sealing agent with light, and a light-irradiated sealing. It may include a bonding step of bonding the first member and the second member via an agent. According to such a manufacturing method, the joint surface between the first member and the second member constituting the organic EL display device can be sealed with a sealing material.

The sealant placed on the first member in the adhesion process thickens by light irradiation. In the bonding step, the first member and the second member are bonded to each other until the light-irradiated sealant is cured, so that the first member and the second member are bonded to each other. Is glued by. The sealant interposed between the first member and the second member is cured by post-heating, if necessary, to form a sealant.

In the above manufacturing method, the process after the irradiation step may be carried out by blocking light. As a result, the second member can be adhered to the first member without being exposed to light.

The method of attaching the sealant is not particularly limited, and may be, for example, an inkjet method, a method using a dispenser, or the like.

The first member and the second member may be any members constituting the organic EL display device, and are not particularly limited.

In one aspect, the first member may be an organic EL display element and the second member may be a substrate.

Further, in another aspect, the first member may be a substrate, and the second member may be an organic EL display element.

The type of substrate is not particularly limited, and examples thereof include a glass substrate, a silicon substrate, and a plastic substrate. Of these, a glass substrate and a plastic substrate are preferable, and a glass substrate is more preferable.

Although the preferred embodiment of the present invention has been described above, the present invention is not limited to the above embodiment.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the Examples. Unless otherwise specified, it was carried out at 25 ° C.

(Examples 1 to 13 and Comparative Examples 1 to 3)
<Preparation of sealant>
Each component shown in Table 1 was mixed at the composition ratio (part by mass) shown in Table 1 to prepare the encapsulant of the example. With respect to the obtained sealant, the viscosity of the sealant and the ejection property in an inkjet device were evaluated by the following evaluation methods. Further, the obtained encapsulant was cured under the following photocuring conditions to form a cured product, and the moisture permeability, yellowness, transmittance and organic EL evaluation of the cured product were measured by the evaluation methods shown below. ..

Each component shown in Table 1 means the following.

(Component (A): cationically polymerizable compound)
(A-1) 3', 4'-Epoxy Cyclohexyl Methyl-3,4-Epoxy Cyclohexane Carboxylate ("Ceroxide 2021P" manufactured by Daicel Chemical Industries, Ltd., viscosity: 200 cps)
(A-2) Hydrogenated bisphenol A type epoxy resin ("YX8000" manufactured by Mitsubishi Chemical Corporation, viscosity: 18,500 cps))
(A-3) 3,4-Epoxycyclohexylmethylmethacrylate ("Cyclomer M100" manufactured by Daicel Corporation, viscosity: 100 cps)
(A-4) Di (1-ethyl- (3-oxetanyl)) methyl ether ("Aron Oxetane OXT-221" manufactured by Toagosei Co., Ltd., viscosity: 9 to 14 cps)

(Component (B): Vinyl ether compound)
(B-1) Cyclohexanedimethanol divinyl ether (“CHDVE” manufactured by Nippon Carbide Co., Ltd., viscosity: 4.5 cps)
(B-2) 1,4-Butanediol divinyl ether (“BDVE” manufactured by Nippon Carbide Co., Ltd., viscosity: 1.2 cps)
(B-3) Triethylene glycol divinyl ether (“TEGDVE” manufactured by Nippon Carbide, Inc., viscosity: 3.4 cps)
(B-4) Cyclohexyl vinyl ether (“CHVE” manufactured by Nippon Carbide Co., Ltd., viscosity: 1.3 cps)
(B-5) 4-Hydroxybromo vinyl ether (“HBVE” manufactured by Nippon Carbide Co., Ltd., viscosity: 5.2 cps)
(Component (C): Photocationic polymerization initiator)
(C-1) Diphenyl [4- (Phenylthio) phenyl] Sulfonium Hexafluoroantimonate (“CPI-110A” manufactured by San-Apro)

(Component (X): Curing retarder)
(X-1) Trioctyl phosphate (manufactured by Daihachi Chemical Co., Ltd.)
(X-2) 18-Crown-6-Ether ("Crown Ether O-18" manufactured by Nippon Soda Corporation)

[Viscosity measurement method]
The viscosity was measured using an E-type viscometer (cone rotor: 1 ° 34'x R24, "DV3T" manufactured by BROOKFIELD) under the conditions of a temperature of 25 ° C. and a rotation speed of 10 rpm.

[Ejectability with an inkjet device]
An inkjet ejection device (MID500B manufactured by Musashi Engineering Co., Ltd., solvent-based head "MID head") is placed on a 70 mm × 70 mm × 0.7 mmt base material (non-alkali glass (Eagle XG manufactured by Corning Inc.)) of the obtained composition. Discharged using. Dischargeability was evaluated according to the following criteria.
A: The nozzle can be discharged without clogging.
B: The nozzle is clogged and cannot be discharged.

[Curing conditions]
The sealant was photocured under the conditions of a wavelength of 365 nm and an integrated light intensity of 1,000 mJ / cm ² using a UV curing device (manufactured by Fusion) equipped with an electrodeless discharge metal halide lamp. Then, heat treatment was carried out for 30 minutes in an oven at 80 ° C. to prepare a cured product.

[Humidity permeability]
A sheet-shaped cured product having a thickness of 0.1 mm was produced under the above curing conditions. According to JIS Z0208 "Moisture Permeability Test Method for Moisture-Proof Packaging Material (Cup Method)", calcium chloride (anhydrous) is used as a moisture absorbent, and the moisture permeability of the cured product is measured under the conditions of an ambient temperature of 60 ° C. and a relative humidity of 90%. did. The moisture permeability is 250g ^/ (m 2 · 24hr) or less.

[Transmittance and yellowness]
Two borosilicate glass test pieces (length 25 mm × width 25 mm × thickness 2.0 mm, Tempax (registered trademark) glass” were used, and the resin composition was cured under the above photocuring conditions with an adhesive thickness of 10 μm. After curing, using a test piece bonded with an adhesive made of this resin composition, using an ultraviolet-visible spectrophotometer (UV2550 manufactured by Shimadzu Corporation), the total light transmittance of light with a wavelength of 300 to 800 nm and JIS K 7373: 2006 Plastic-Yellowness (b value) was measured according to the method for determining yellowness and yellowing.

[Manufacturing of organic EL display element substrate]
The glass substrate with ITO electrode was washed with acetone and isopropanol, respectively. Then, the following compounds were sequentially vapor-deposited into a thin film by a vacuum vapor deposition method to obtain an organic EL element substrate composed of an anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode. The structure of each layer is as follows.
・ Anode ITO, anode film thickness 250 nm
・ Hole injection layer Copper phthalocyanine Thickness 30 nm
-Hole transport layer N, N'-diphenyl-N, N'-dinaphthylbenzidine (α-NPD) 20 nm thick
-Light emitting layer Tris (8-hydroxyquinolinato) aluminum (metal complex material), light emitting layer film thickness 1000Å
・ Electron injection layer Lithium fluoride Thickness 1 nm
・ Cathode aluminum, anode film thickness 250 nm

[Manufacturing of organic EL display element]
The resin compositions obtained in Examples and Comparative Examples were applied to glass with a coating device under a nitrogen atmosphere, and the resin composition was coated with an ultraviolet irradiation device (HOYA ultra-high pressure mercury lamp irradiation device, "UL-750". ”) Is irradiated with ultraviolet rays having a wavelength of 365 nm and 100 mW / cm ² for 10 seconds, and after 20 minutes, the resin composition is bonded to an organic EL display element substrate with an adhesive thickness of 10 μm and cured in an atmosphere of 80 ° C. for 30 minutes. An organic EL display element was produced by curing an adhesive made of. The cathode side of the organic EL element substrate was bonded to glass via a sealant. The obtained organic EL display element was evaluated for organic EL by the evaluation method shown below.

[Evaluation of organic EL: Evaluation of initial light emission state]
A voltage of 6 V was applied to the organic EL display element immediately after production for 10 seconds, and the light emitting state of the organic EL display element was visually and microscopically observed, and the diameter of the dark spot was measured.

[Evaluation of organic EL: Evaluation of light emission state after high temperature and high humidity test]
The organic EL display element immediately after production is exposed for 1000 hours under the conditions of 60 ° C. and 90% by mass relative humidity, then a voltage of 6 V is applied for 10 seconds, and the light emitting state of the organic EL display element is visually and microscopically observed. It was observed and the diameter of the dark spot was measured. The diameter of the dark spot is preferably 300 μm or less, more preferably 50 μm or less, and further preferably no dark spot.

Table 1 shows the results of each of the above evaluations. According to the encapsulant of the example, it was shown that the viscosity was low and the reliability after curing was excellent. Further, when the content of the component (A) is less than 50 parts by mass out of a total of 100 parts by mass of the components (A) and (B), the viscosity of the sealant becomes high and the coating / discharging property deteriorates. It was shown (Comparative Examples 1 and 2). Furthermore, it was shown that the encapsulant did not cure when the component (C) was not used (Comparative Example 3).

The resin composition according to the present embodiment includes, for example, a sealing agent for an organic electroluminescence (EL) display element containing the resin composition, a sealing material for an organic EL display element containing a cured product of the sealing agent, and a sealing material for an organic EL display element. , Can be used as an organic EL display device containing the sealing material.

Claims (13)

1. A cationically polymerizable compound having a cationic ring-opening polymerizable group and
   Vinyl ether compounds with vinyl oxy groups and
   Photocationic polymerization initiator and
   Contains,
   A composition in which the content of the vinyl ether compound is greater than 50 parts by mass and 95 parts by mass or less with respect to a total of 100 parts by mass of the cationically polymerizable compound and the vinyl ether compound.
2. The composition according to claim 1, wherein the viscosity of the vinyl ether compound at 25 ° C. is lower than the viscosity of the cationically polymerizable compound at 25 ° C.
3. The composition according to claim 1 or 2, wherein the cation ring-opening polymerizable group is selected from the group consisting of an epoxy group and an oxetane group.
4. Claims 1 to 3 wherein the content of the photocationic polymerization initiator is 0.1 part by mass or more and 5.0 part by mass or less with respect to 100 parts by mass in total of the cationically polymerizable compound and the vinyl ether compound. The composition according to any one item.
5. The composition according to any one of claims 1 to 4, further containing a curing retarder.
6. The composition according to any one of claims 1 to 5, wherein the viscosity when measured using an E-type viscometer under the conditions of 25 ° C. and 10 rpm is 2 to 200 cps.
7. The composition according to any one of claims 1 to 6, wherein the vinyl ether compound has two vinyl oxy groups and further has a cyclic group.
8. A sealant for an organic electroluminescence display element containing the composition according to any one of claims 1 to 7.
9. A cured product of the sealant for an organic electroluminescence display element according to claim 8.
10. The cured product according to claim 9, wherein the total light transmittance at a wavelength of 380 to 800 nm per 10 μm thickness is 80% or more.
11. A sealing material for an organic electroluminescence display element, which comprises the cured product according to claim 9 or 10.
12. Organic electroluminescence display element and
    An organic electroluminescence display device including the sealing material for an organic electroluminescence display element according to claim 11.
13. An attachment step of attaching the sealing agent for an organic electroluminescence display element according to claim 8 to the first member,
    An irradiation step of irradiating the attached sealing agent for an organic electroluminescence display element with light, and
    A bonding step of bonding the first member and the second member via the light-irradiated sealing agent for the organic electroluminescence display element.
    A method for manufacturing an organic electroluminescence display device.