JP7440498B2 - Composition - Google Patents

Description

The present invention relates to compositions.

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

Organic EL display elements deteriorate their luminescent properties when their light-emitting layers, electrodes, etc. are exposed to the outside air, so sealing technology to isolate them from the outside air is essential, and one type of sealing technology is Photocurable sealants are known as (eg, Patent Documents 1 to 5).

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

By the way, when applying a photocurable sealant to a member, workability is improved if the sealant has a low viscosity. For this reason, in order to improve workability, methods have been adopted to adjust the viscosity, for example by adding an organic solvent to the sealant, but this has led to problems such as the remaining organic solvent increasing the generation of outgas. there were.

Therefore, an object of the present invention is to provide a composition that has low viscosity and excellent reliability after curing. The present invention also provides a sealant for an organic EL display element containing the above composition, a cured body of the sealant for an organic EL display element, a sealant containing the cured body, and an organic EL display element containing the sealant. The present invention aims to provide a display device and a method for manufacturing the organic EL display device.

One aspect of the present invention includes a cationic polymerizable compound having a cationic 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 The present invention relates to a composition in which the amount is more than 50 parts by mass and not more than 95 parts by mass based on 100 parts by mass of the cationically polymerizable compound and the vinyl ether compound.

The above composition is a combination of a vinyl ether compound having a vinyloxy group and a cationically polymerizable compound, and the content of the vinyl ether compound is a certain amount or more. This specific composition allows the composition to have both low viscosity and excellent moisture resistance and transparency after curing. Therefore, the organic electroluminescent display encapsulant containing the above composition can be easily applied uniformly to a member, and has excellent workability. Moreover, since the above composition has excellent moisture resistance and transparency after curing, an organic electroluminescence display device with excellent reliability can be realized by using the above composition as a sealant for organic electroluminescence display.

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 epoxy groups and oxetane groups.

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 based on 100 parts by mass of the cationically polymerizable compound and the vinyl ether compound.

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

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

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

Another aspect of the present invention relates to an encapsulant for organic electroluminescent display elements, which includes the composition described above.

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

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

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

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

Still another aspect of the present invention includes an adhesion step of attaching the above-mentioned sealant for an organic electroluminescent display element to the first member, and a step of applying light to the attached sealant for an organic electroluminescent display element. An organic electroluminescent display comprising: an irradiation step of irradiating light; and a bonding step of bonding the first member and the second member together via the light-irradiated sealant for organic electroluminescent display elements. The present invention relates to a method for manufacturing a device.

According to the present invention, a composition having low viscosity and excellent reliability after curing is provided. Further, according to the present invention, there is provided a sealant for an organic EL display element containing the above composition, a cured product of the sealant for an organic EL display element, a sealant containing the cured product, and a sealant containing the sealant. 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 cationic polymerizable compound (component (A)), a vinyl ether compound (component (B)), and a photocationic polymerization initiator (component (C)).

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

In this embodiment, the vinyl ether compound (component (B)) has a vinyloxy group. Further, the content of the vinyl ether compound is greater than 50 parts by mass and 95 parts by mass or less based on 100 parts by mass 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 vinyloxy group and a cationically polymerizable compound, and the content of the vinyl ether compound is a certain amount or more. This specific composition allows the resin composition to have both low viscosity and excellent moisture resistance and transparency after curing. Therefore, the encapsulant for organic electroluminescence (EL) display elements (hereinafter also simply referred to as encapsulant) containing the resin composition according to the present embodiment can form a highly reliable encapsulant and is highly reliable. An organic EL display device with excellent properties can be realized.

((A) component: cationic polymerizable compound)
Component (A) is a compound having cationic ring-opening polymerizability, and can also be referred to as 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 (oxirane ring)), an oxetane group (oxetane ring), etc. At least one selected from the group is preferred.

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

From the viewpoint of adhesiveness and moisture resistance, compounds having an epoxy group include compounds having an epoxy group and an alicyclic group (hereinafter sometimes referred to as alicyclic epoxy compounds), and compounds having an epoxy group and an aromatic group ( At least one selected from the group consisting of aromatic epoxy compounds (hereinafter also referred to as aromatic epoxy compounds) is preferred.

<Component (A1): Alicyclic compound having an epoxy group>
Component (A1) may be a compound having one epoxy group, or may be a compound having two or more epoxy groups. The component (A1) preferably has two or more epoxy groups, more preferably two epoxy groups. Component (A1) may be a compound that does not have an aromatic ring. Component (A1) can be used alone or in combination of two or more.

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, and a pinene ring. Epoxidation can be carried out using, for example, an oxidizing agent. Examples of the oxidizing agent include hydrogen peroxide and peracid. Examples of such component (A1) include 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyl alkyl (meth)acrylate (for example, 3,4-epoxy (cyclohexylmethyl (meth)acrylate, etc.), (3,3',4,4'-diepoxy)bicyclohexyl, and the like.

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 epoxy resin, bisphenol F epoxy resin, and the like. Examples of such component (A1) include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, and the like.

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

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

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

Preferably, X is 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 connected 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 formula (A1-1), 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is particularly preferred.

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

When component (A1) has a molecular weight distribution, it is preferable that the number average molecular weight of component (A1) is within the above range. Note that in this specification, the number average molecular weight indicates a value in terms of polystyrene, which is measured by gel permeation chromatography (GPC) under the following measurement conditions.
・Solvent (mobile phase): THF
・Deaerator: ERC-3310 manufactured by ERMA
・Pump: JASCO Corporation PU-980
・Flow rate: 1.0ml/min
・Auto sampler: Tosoh AS-8020
・Column oven: Hitachi L-5030
・Set temperature: 40℃
・Column configuration: 2 TSKguardcolumn MP (xL) 6.0 mm ID x 4.0 cm manufactured by Tosoh, and 2 TSK-GELMULTIPORE HXL-M 7.8 mm ID x 30.0 cm manufactured by Tosoh, 4 in total ・Detector: RI Hitachi L-3350
・Data processing: SIC480 data station

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

(A2) Components include, for example, 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, cresol novolak Examples include type epoxy resins and modified products thereof.

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

Component (A2) includes, for example, a compound represented by formula (A2-1).

In formula (A2-1), n represents a real number from 0.1 to 30, and R ²¹ , R ²² , R ²³ and R ²⁴ are each independently a hydrogen atom or a carbon that may have a substituent. Indicates an alkyl group of numbers 1 to 5. When a plurality of R ²³ and R ²⁴ are present, these 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 preferred.

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 component (A2) is preferably 100 or more, more preferably 150 or more, and even more preferably 200 or more, from the viewpoint of moisture resistance of the cured product. Moreover, the molecular weight of the component (A2) is preferably 5,000 or less, more preferably 1,000 or less, and most preferably 450 or less, from the viewpoint of moisture resistance of the cured product.

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

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

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

As the component (A3), for example, 3-ethyl-3-hydroxymethyloxetane (manufactured by Toagosei Co., Ltd., trade name OXT-101, etc.), 1,4-bis[(3-ethyl-3-oxetanyl)methoxy Methyl]benzene (manufactured by Toagosei Co., Ltd., trade name OXT-121, etc.), 3-ethyl-3-(phenoxymethyl)oxetane (manufactured by Toagosei Co., Ltd., trade name OXT-211, etc.), di(1- Ethyl-(3-oxetanyl)) methyl ether (manufactured by Toagosei Co., Ltd., product name: OXT-221, etc.), 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (manufactured by Toagosei Co., Ltd., product name: OXT-221, etc.) (name OXT-212, etc.).

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

<(A4) component>
Component (A4) may be any compound having a cationic ring-opening polymerizable group, such as a compound having a cyclic ether group. Component (A4) may be a compound having one cationic ring-opening polymerizable group, and preferably has two or more. Component (A4) may be a compound that does not have an alicyclic group, an aromatic ring, or an oxetane group. Component (A4) can 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 (oxirane ring). As component (A4), a compound having a glycidyloxy group is preferred. 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, and di- or triglycidyl ether of glycerin or its alkylene oxide adduct. Examples of the alkylene glycol include ethylene glycol, propylene glycol, and 1,6-hexanediol. Examples of the polyalkylene glycol include polyethylene glycol or its alkylene oxide adduct, polypropylene glycol or its alkylene oxide adduct, and the like. Examples of the alkylene oxide include ethylene oxide and propylene oxide.

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

((B) Vinyl ether compound)
Component (B) is a compound having a vinyloxy group. Component (B) can be used alone or in combination of two or more.

The compound having a vinyloxy group is preferably a compound having a vinyl ether group in which the oxygen atom of the vinyloxy group (CH ₂ ═CH—O—) is bonded to a carbon atom. Such compounds include, for example, 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, cyclohexanedimethanol divinyl ether. , di- or trivinyl ether compounds such as trimethylolpropane 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 , isopropyl vinyl 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, etc. Can be mentioned.

It is preferable that component (B) has two vinyloxy groups and further has a cyclic group. Examples of such component (B) include cyclohexanedimethanol divinyl ether and 2,2-adamantanedimethanol divinyl ether.

From the viewpoint of keeping the viscosity low, the content of component (B) is preferably greater than 50 parts by mass, more preferably 51 parts by mass or more, based on a total of 100 parts by mass of components (A) and (B). , more preferably 60 parts by mass or more, and still more preferably 70 parts by mass or more. In addition, the content of component (B) is preferably 95 parts by mass or less based on a total of 100 parts by mass of components (A) and (B), from the viewpoint of easily obtaining a cured product with excellent durability. It is more preferably 85 parts by mass or less, and even more preferably 75 parts by mass or less.

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

((C) Photocationic polymerization initiator)
Component (C) may be any component as long as it can be activated by light to initiate cationic polymerization of component (A). Component (C) can be used alone or in combination of two or more.

Component (C) includes, for example, arylsulfonium salt derivatives (for example, Cylacure UVI-6990, Cylacure UVI-6974 manufactured by Dow Chemical Co., Ltd., Adeka Optomer SP-150, Adeka Optomer SP-152 manufactured by Asahi Denka Kogyo Co., Ltd. , ADEKA OPTOMER SP-170, ADEKA OPTOMER SP-172, CPI-100P, CPI-101A, CPI-200K, CPI-210S, LW-S1 manufactured by Sun-Apro, Cibacure-1190 manufactured by Double Bond, etc.), Aryl iodonium salt derivatives (for example, Irgacure 250 manufactured by Ciba Specialty Chemicals, RP-2074 manufactured by Rhodia Japan, etc.), arene-ion complex derivatives, diazonium salt derivatives, triazine initiators, other halides, etc. Examples include acid generators.

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

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

In formula (C-1), A represents an element of valence m from group VIA to group VIIA, and m represents 1 or 2. p represents an integer from 0 to 3. R represents an organic group bonded to A. X ⁻ represents an onium counter ion, the number of which is (p+1) per molecule. D represents a divalent group represented by the following formula (C-1-1). A plurality of R's may be the same or different from each other. A plurality of X ^−s may be the same or different. When a plurality of A's exist, they may be the same or different from each other. When a plurality of Ds exist, they may be the same or different from each other.

In formula (C-1-1), E represents a divalent group, and G represents -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 represents an integer from 0 to 5. a+1 E's and a G's may be the same or different from each other.

R is an organic group bonded to A, such as 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; these 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, 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 may be substituted with one or more selected from.

The number of R's is (m+p(m-1)+1), and a plurality of R's may be the same or different. In addition, two or more R are directly or -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR'-, -CO-, -COO-, -CONH- , may be bonded via an alkylene group having 1 to 3 carbon atoms or a phenylene group 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 benzanthracenyl group, an anthraquinolyl group, Examples include fused polycyclic aryl groups 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. Examples of substituents include:
Straight chain alkyl groups having 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, ocdadecyl 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, isohexyl group;
Cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group;
Hydroxy group;
A straight chain 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, Branched alkoxy group;
2 carbon atoms such as acetyl group, propionyl group, butanoyl group, 2-methylpropionyl group, heptanoyl group, 2-methylbutanoyl group, 3-methylbutanoyl group, octanoyl group, decanoyl group, dodecanoyl group, octadecanoyl group, etc. ~18 linear or branched alkylcarbonyl groups;
Arylcarbonyl group having 7 to 11 carbon atoms such as benzoyl group and naphthoyl group;
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;
Arylthiocarbonyl groups having 7 to 11 carbon atoms such as phenylthiocarbonyl groups and naphthoxythiocarbonyl groups;
Acetoxy group, ethylcarbonyloxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group, isobutylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group, octylcarbonyloxy group, tetradecylcarbonyl group A linear or branched acyloxy group having 2 to 19 carbon atoms such as an oxy group or 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 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 straight or branched alkylthio group having 1 to 18 carbon atoms, such as a decylthio group or a dodecylthio group;
Aryl groups having 6 to 10 carbon atoms such as phenyl group, tolyl group, dimethylphenyl group, 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 group carbon number of the group, acridinyl group, phenothiazinyl group, phenazinyl group, xanthenyl group, thianthrenyl group, phenoxazinyl group, phenoxathiinyl group, chromanyl group, isochromanyl group, dibenzothienyl group, xanthonyl group, thioxanthonyl group, dibenzofuranyl group, 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, Straight-chain or branched alkylsulfinyl groups having 1 to 18 carbon atoms, such as tert-pentylsulfinyl groups and octylsulfinyl groups;
Arylsulfinyl groups having 6 to 10 carbon atoms, such as phenylsulfinyl groups, tolylsulfinyl groups, naphthylsulfinyl groups;
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 straight or branched alkylsulfonyl group having 1 to 18 carbon atoms, such as a tert-pentylsulfonyl group or an octylsulfonyl group;
Arylsulfonyl groups having 6 to 10 carbon atoms such as phenylsulfonyl groups, tolylsulfonyl groups (tosyl groups), and naphthylsulfonyl groups;
an alkyleneoxy group represented by the following formula (C-1-2);
Unsubstituted amino groups, and amino groups mono- or di-substituted with alkyl having 1 to 5 carbon atoms and/or aryl having 6 to 10 carbon atoms;
Cyano group;
Nitro group;
Examples include halogen groups such as fluorine, chlorine, bromine, and iodine.

In 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.

The onium ion (A ⁺ ) in formula (C-1) is preferably a sulfonium ion, an iodonium ion, or a selenium ion. 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, 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} Sulfide, 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-dihydroanthracen-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-(benzoylphenylthio) ] Phenyldi-p-tolylsulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thianthrenium, 5-phenylthianthrenium, 5-tolylthianthrenium, 5 - triarylsulfonium such as (4-ethoxyphenyl) thianthrenium, 5-(2,4,6-trimethylphenyl) thianthrenium;
Diarylsulfoniums such as diphenyl phenacylsulfonium, diphenyl 4-nitrophenacylsulfonium, diphenylbenzylsulfonium, diphenylmethylsulfonium;
Phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium , phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium, 4-acetocarbonyloxyphenylmethylphenacylsulfonium, 2-naphthylmethylphenacylsulfonium, 2-naphthyloctadecylphenacyl Monoarylsulfonium such as sulfonium, 9-anthracenylmethylphenacylsulfonium;
Trialkylsulfoniums such as dimethylphenacylsulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, and octadecylmethylphenacylsulfonium are included.

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-dihydroanthracen-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-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thianthrenium, 5-phenylthianthrenium, diphenylphenacylsulfonium , 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, and octadecylmethylphenacylsulfonium.

In formula (C-1), X ⁻ is a counter ion. The number of counterions is (p+1) per molecule. Counter ions are not particularly limited, but include, for example, halogen ions such as F ^- , Cl ^- , Br ^- , I ^- ; OH ^- ; ClO ₄ ^- ; FSO ₃ ^- , ClSO ₃ ^- , CH ₃ SO ₃ ^- , C ₆ Sulfonic acid ions such as H ₅ SO ₃ ^- , CF ₃ SO ₃ ^- ; Sulfuric acid ions such as HSO ₄ ^- , SO ₄ ^2- ; Carbonate ions such as HCO ₃ ^- , CO ₃ ^2- ; H ₂ PO Phosphate ions such as ^4- , HPO ₄ ^2- , PO ₄ ^3- ; Fluorophosphate ions such as PF ₆ ^- , PF ₅ OH ^- , fluorinated alkylfluorophosphate ions; BF ₄ ^- , B(C Boric acid ions such as ₆ F ₅ ) ₄ ^- and B(C ₆ H ₄ CF ₃ ) ₄ ^- ; AlCl ₄ ^- ; fluoroantimonate ions such as BiF ₆ ^- , SBF ₆ ^- , SBF ₅ OH ^- ; AsF Examples include fluoroarsenate ions such as ₆ ⁻ , AsF ₅ OH ^−, and the like.

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

In formula (C-1-3), R ^f represents a fluorinated alkyl group. b is the number of R ^f and represents an integer from 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 fluorinated alkyl group of R ^f indicates a group in which some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. The number of carbon atoms in the alkyl group is preferably 1 to 8, more preferably 1 to 4. Examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched alkyl such as isopropyl, isobutyl, sec-butyl, and tert-butyl. Group; Examples include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group.

Specific examples of the fluorinated alkyl group 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.

Specific examples of preferable 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 this embodiment, as component (C), diphenyl 4-thiophenoxyphenylsulfonium tris(pentafluoroethyl) trifluorophosphate represented by formula (C-2) and formula (C-3) are used. Triarylsulfonium salt hexafluoroantimonate can be particularly preferably used, and among these, triarylsulfonium salt hexafluoroantimonate represented by formula (C-3) is more preferred.

Component (C) may be dissolved in a solvent in advance to facilitate mixing with other components such as 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 component (C) is preferably 0.1 part by mass or more, and 0.1 part by mass or more, based on a total of 100 parts by mass of components (A) and (B). More preferably 15 parts by mass or more. In addition, from the viewpoint of adhesive durability of the cured product, the content of component (C) is preferably 5.0 parts by mass or less, and 1.0 parts by mass or less per 100 parts by mass of components (A) and (B). More preferably, the amount is .0 part by mass or less.

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

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

((X) component: curing retarder)
The curing retarder is preferably selected from the group consisting of phosphoric acid curing retarders (component (D)) and ether curing retarders (component (E)). The curing retarder can be used alone or in combination of two or more.

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

As the component (D1), for example, diethylbenzyl phosphate, trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, tris(butoxyethyl) phosphate, tris(2-ethylhexyl) phosphate, (RO) ₃ P=O (R is , octyl group, lauryl group, cetyl group, stearyl group or oleyl group), tris (2-chloroethyl) phosphate, tris (2-dichloropropyl) phosphate, triphenyl phosphate, butyl pyrophosphate, tricresyl phosphate, tricylenyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, xylenyl diphosphate, monobutyl phosphate, dibutyl phosphate, di-2-ethylhexyl phosphate, monoisodecyl phosphate, ammonium ethyl acid phosphate, 2-ethylhexyl acid phosphate salt, etc. . Component (D1) can be used alone or in combination of two or more.

Component (D1) is a compound represented by formula (D1-1), a compound represented by formula (D1-2), and a compound represented by 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 compounds represented by formula (D1-2), and more preferably to contain a compound represented by formula (D1-2).

In formula (D1-1), formula (D1-2) and formula (D1-3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently have a substituent; Indicates a good hydrocarbon group.

R ² , R ³ and R ⁴ in formula (D1-2) and R ⁵ and R ⁶ in formula (D1-3) are preferably the same group in each formula.

Examples of substituents that the hydrocarbon groups in R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may have include oxyalkyl groups. 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 an alkyl group. More preferably. The number of carbon atoms in the alkyl group may be, for example, 1 to 18, preferably 4 to 13.

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

The compound represented by formula (D1-2) is preferably a trialkyl phosphate (ie, a compound in which R ² , R ³ and R ⁴ are alkyl groups). At this time, the number of carbon atoms in 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 trialkyl phosphates 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).

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

Component (D2) is a phosphite ester. Component (D2) includes, for example, trimethyl phosphite, triethyl phosphite, tri-n-butyl phosphite, tris(2-ethylhexyl) phosphite, triisooctyl phosphite, tridecyl phosphite, triisodecyl phosphite, Tris (tridecyl) phosphite, trioleylphosphite, tristearyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, phenyldiisooctyl Phosphite, phenyl diisodecyl phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenylisooctyl phosphite, diphenyl monodecyl phosphite, diphenyl monoisodecyl phosphite, diphenyl mono(tridecyl) phosphite, bis(nonylphenyl) dinonylphenyl phosphite, tetraphenyldipropylene glycol diphosphite, poly(dipropylene glycol) phenyl phosphite, diisodecyl pentaerythritol diphosphite, bis(tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, Bis(nonylphenyl)pentaerythritol diphosphite, tetraphenyltetra(tridecyl)pentaerythritol tetraphosphite, tetra(tridecyl)-4,4'-isopropylidene diphenylphosphite, trilauryl trithiophosphite, dimethylhydrodiene phosphite , dibutyl hydrogen phosphite, di(2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl mono Examples include decyl phosphite and diphenyl mono(tridecyl) phosphite. Component (D2) can be used alone or in combination of two or more.

Component (D2) is a compound represented by formula (D2-1), a compound represented by formula (D2-2), or a compound represented by formula (D2-3) from the viewpoint of appropriate reactivity toward cations. Containing at least one selected from the group consisting of a compound, a compound represented by formula (D2-4), a compound represented by formula (D2-5), and a compound represented by formula (D2-6). is preferred.

In formulas (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 each independent represents a hydrocarbon group which may have a substituent.

Examples of 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: Examples include oxyalkyl 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 unsubstituted hydrocarbon groups.

The hydrocarbon group in R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ is preferably an alkyl group or an aryl group; or a phenyl group, and even more preferably an alkyl group. The number of carbon atoms in 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 R ¹⁵ and R ¹⁶ in -5) are preferably the same as each other in each formula.

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

Examples of the compound represented by formula (D2-2) include dialkyl phosphites (ie, compounds in which R ⁸ and R ⁹ are alkyl groups).

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

Examples of the compound represented by formula (C2-4) include bis(alkyl)pentaerythritol diphosphite (ie, a compound in which R ¹³ and R ¹⁴ are alkyl groups). Further, specific examples of the compound represented by formula (D2-4) include bis(decyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, etc. .

Examples of the compound represented by formula (D2-5) include dialkyl hydrogen phosphite (ie, a compound in which R ¹⁵ and R ¹⁶ are alkyl groups). Specific examples of the compound represented by formula (D2-5) include diethyl hydrogen phosphite, bis(2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, and the like.

Examples of the compound represented by formula (D2-6) include monoalkyl hydrogen phosphite (ie, a compound in which R ¹⁷ is an alkyl group). Further, specific examples of the compound represented by formula (D2-6) include monoethyl hydrogen phosphite, mono(2-ethylhexyl) hydrogen phosphite, monolauryl hydrogen phosphite, monooleyl hydrogen phosphite, etc. .

Component (D2) includes trimethyl phosphite, triethyl phosphite, tri-n-butyl phosphite, tris(2-ethylhexyl) phosphite, triisooctyl phosphite, tridecyl phosphite, triisodecyl phosphite, tris( tridecyl) phosphite, trioleyl phosphite, tristearyl phosphite, triphenyl phosphite, tris(nonylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite Phosphite, bis(nonylphenyl)pentaerythritol diphosphite, dimethylhydrodiene phosphite, dibutylhydrodiene phosphite, di(2-ethylhexyl)hydrodiene phosphite, dilaurylhydrodiene phosphite, dioleylhydrodiene phosphite It is preferable to contain at least one selected from the group consisting of trimethyl phosphite, triethyl phosphite, tri-n-butyl phosphite, tris(2-ethylhexyl) phosphite, triisooctyl phosphite, and tridecyl phosphite. , triisodecylphosphite, tris(tridecyl)phosphite, trioleylphosphite, tristearylphosphite, triphenylphosphite, and tris(nonylphenyl)phosphite. More preferred.

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

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

<Component (E): Ether curing retardant>
Component (E) is a curing retarder having an ether bond. Component (E) can be used alone or in combination of two or more.

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

Component (E) is preferably a cyclic ether, more preferably a crown ether, from the viewpoint of appropriate reactivity toward cations.

When the resin composition contains component (E), the content of component (E) is determined from the viewpoint of obtaining a longer pot life with respect to the total of 100 parts by mass of components (A) and (B). The amount is preferably 0.1 parts by mass or more, and more preferably 0.3 parts by mass or more. In addition, the content of component (E) is preferably 5 parts by mass or less, and 3 parts by mass or less, from the viewpoint of moisture resistance and adhesive strength of the cured product, based on a total of 100 parts by mass of components (A) and (B). Part or less is more preferable.

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

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

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

Examples of photosensitizers include, but are not limited to, benzophenone derivatives, phenothiazine derivatives, phenylketone derivatives, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, naphthacene derivatives, chrysene derivatives, perylene derivatives, pentacene derivatives, acridine derivatives, benzothiazole derivatives, Benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, xanthone derivatives, thioxanthene derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, Examples include allylmethane derivatives, phthalocyanine derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran 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-propan-1-one is preferred. , 9,10-dibutoxyanthracene and the like are more preferred. The photosensitizers can 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 parts by mass or more, and 0.02 parts by mass based on the total of 100 parts by mass of components (A) and (B). Parts by mass or more are more preferable. Moreover, the content of the photosensitizer is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, based on a total of 100 parts by mass of components (A) and (B). By setting it as such a range, better curability and storage stability can be obtained.

Other components include a silane coupling agent. Containing a silane coupling agent tends to improve the adhesiveness and adhesive durability of the resin composition.

Examples of the silane coupling agent include, but are not limited to, γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris(β-methoxyethoxy)silane, γ-(meth) Acryloxypropyltrimethoxysilane, 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 etc. Among these are β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane and γ-(meth)acryloxypropyltrimethoxysilane. At least one selected from the group consisting of silanes is preferred. The silane coupling agents can 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, and 0.1 part by mass or more, based on a total of 100 parts by mass of components (A) and (B). More preferably 2 parts by mass or more. 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 a total of 100 parts by mass of components (A) and (B). By setting it as such a content range, higher adhesiveness and adhesive durability can be obtained.

In this 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 the above-mentioned components can be sufficiently mixed. Examples of the mixing method include a stirring method using the stirring force caused by the rotation of a propeller, and a method using a normal disperser such as a planetary stirrer using rotation and revolution. These mixing methods are preferable because stable mixing can be performed at low cost.

The resin composition according to this embodiment may be used, for example, to contribute to sealing of an organic EL display element. For example, the resin composition may be used to form a coating material that covers an organic EL display element, or may be used as an adhesive for bonding members that constitute an organic EL display device.

The resin composition according to the present embodiment has a moderate increase in viscosity after being irradiated with light, and is then cured 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 examples include halogen lamps, metal halide lamps, high-power metal halide lamps (containing indium, etc.), low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and xenon lamps. , xenon excimer lamps, xenon flash lamps, light emitting diodes (hereinafter referred to as LEDs), 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 light sources have different emission wavelengths and energy distributions. Therefore, the above-mentioned light source can be appropriately selected depending on the reaction wavelength of the photocationic polymerization initiator, etc. Furthermore, natural light (sunlight) can also serve as a light source for initiating the reaction of the resin composition.

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

The amount of light irradiation is not particularly limited, and may be adjusted as appropriate depending on the thickness of the coating film of the resin composition. The amount of light irradiation may be, for example, 50 to 20,000 mJ/cm ² , preferably 100 to 10,000 mJ/cm ² .

When heating after light irradiation (also referred to as post-heating) is performed, 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 performing post-heating, 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 at 25°C and 10 rpm prevents unintentional dripping from devices used for ejection such as dispensers and inkjet devices. From the viewpoint of this, 2 cps or more is preferable, and 5 cps or more is more preferable. Further, from the viewpoint of ease of coating and discharging, the viscosity is preferably 200 cps or less, more preferably 50 cps or less, and even more preferably 30 cps or less. If the viscosity is 30 cps or less, it can be easily ejected by an inkjet type device at 25°C.

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

It is preferable that the viscosity of the resin composition according to the present embodiment after curing in a high temperature atmosphere for 10 minutes after irradiation with light is three times or more as compared to the viscosity before curing. For example, when curing in an atmosphere of 80° C., the viscosity 10 minutes after curing is preferably three times or more as compared to the viscosity before curing.

The resin composition according to this embodiment can have a sufficiently long pot life after irradiation with light. Moreover, since the resin composition according to the present embodiment has a moderate increase in viscosity after being irradiated with light, it is easy to bond members together, and the workability is excellent. Furthermore, the resin composition according to this embodiment has excellent moisture proofing properties and adhesive properties after curing. Therefore, according to the resin composition of this embodiment, a sealing material with excellent sealing properties can be formed, and an organic electroluminescent display device with excellent reliability can be manufactured.

In this embodiment, the sealant may include a resin composition.

The cured product of the sealant according to the present embodiment preferably has a moisture permeability of 250 g/(m ²・24 hr) or less, and preferably 200 g/(m ²・24 hr) or less at a thickness of 0.1 m. is more preferable. In this specification, the moisture permeability of the cured product is determined in accordance with JIS Z0208 "Moisture permeability test method for moisture-proof packaging materials (cup method)" using calcium chloride (anhydrous) as a moisture absorbent, at an ambient temperature of 60°C, and at a relative temperature of 60°C. Values measured under conditions of 90% humidity are shown.

The cured product of the sealant according to this embodiment preferably has excellent transparency. Specifically, the cured product preferably 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 even more preferable.

The method of using the sealant according to this 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 product of the sealant is formed. can.

Alternatively, a sealant having a predetermined shape may be formed by curing the sealant into a predetermined shape (for example, a film shape, a sheet shape, etc.). In this case, for example, when assembling the organic EL display device, the organic EL display device can be sealed by placing the sealing material over the organic EL display device.

In this embodiment, the sealant may be made of a cured sealant, or may include a cured sealant and other constituent materials. Examples of other constituent materials include silicon nitride films, silicon oxide films, inorganic layers such as silicon nitride oxide, and inorganic fillers such as silica, mica, kaolin, talc, and aluminum oxide.

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

The method for manufacturing an organic EL display device includes, for example, an adhesion step of adhering the above-mentioned encapsulant to a first member, an irradiation step of irradiating the attached encapsulant with light, and a step of irradiating the encapsulant with light. The method may include a bonding step of bonding the first member and the second member together 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 the sealing material.

The encapsulant placed on the first member in the adhesion process becomes thickened by light irradiation. In the bonding process, the first member and the second member are bonded together until the light-irradiated sealant hardens, so that the first member and the second member are coated with the sealant. 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 steps after the irradiation step may be performed while blocking light. Thereby, the second member can be bonded to the first member without exposing it to light.

The method of applying 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 are not particularly limited as long as they are members that each constitute an organic EL display device.

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

In another embodiment, 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 glass substrates, silicon substrates, plastic substrates, and the like. Among these, glass substrates and plastic substrates are preferred, and glass substrates are more preferred.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the Examples. Unless otherwise specified, experiments were 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 (parts by mass) shown in Table 1 to prepare a sealant of an example. The obtained sealant was evaluated for its viscosity and ejection properties with an inkjet device using the evaluation method shown below. In addition, the obtained sealant was cured under the photocuring conditions shown below to form a cured product, and the moisture permeability, yellowness, transmittance, and organic EL evaluation of the cured product were measured using the evaluation methods shown below. .

Each component shown in Table 1 means the following.

((A) component: cationic polymerizable compound)
(a-1) 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate ("Celoxide 2021P" manufactured by Daicel Chemical Co., Ltd., viscosity: 200 cps)
(a-2) Hydrogenated bisphenol A epoxy resin (“YX8000” manufactured by Mitsubishi Chemical Corporation, viscosity: 18,500 cps))
(a-3) 3,4-epoxycyclohexylmethyl methacrylate (“Cyclomer M100” manufactured by Daicel, viscosity: 100 cps)
(a-4) Di(1-ethyl-(3-oxetanyl)) methyl ether (“Aronoxetane OXT-221” manufactured by Toagosei Co., Ltd., viscosity: 9 to 14 cps)

((B) component: vinyl ether compound)
(b-1) Cyclohexane dimethanol 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 Co., Ltd., 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)
((C) component: photocationic polymerization initiator)
(c-1) Diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonate (“CPI-110A” manufactured by San-Apro)

((X) component: curing retarder)
(x-1) Trioctyl phosphate (manufactured by Daihachi Kagaku Co., Ltd.)
(x-2) 18-crown-6-ether (“Crown Ether O-18” manufactured by Nippon Soda Co., Ltd.)

[Method of measuring viscosity]
The viscosity was measured using an E-type viscometer (cone rotor: 1°34'×R24, "DV3T" manufactured by BROOKFIELD) at a temperature of 25° C. and a rotation speed of 10 rpm.

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

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

[Moisture permeability]
A sheet-like 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 materials (cup method)", the moisture permeability of the cured product was measured using calcium chloride (anhydrous) as the moisture absorbent at an ambient temperature of 60°C and relative humidity of 90%. did. Note that the moisture permeability is preferably 250 g/(m ² ·24 hr) or less.

[Transmittance and yellowness]
Using two borosilicate glass test pieces (length 25 mm x width 25 mm x thickness 2.0 mm, Tempax (registered trademark) glass), 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, the total light transmittance of light with a wavelength of 300 to 800 nm and JIS K were measured using a UV-visible spectrophotometer (UV2550 manufactured by Shimadzu Corporation). 7373:2006 Plastics - The yellowness (b value) was measured in accordance with the method for determining yellowness and yellowness.

[Preparation of organic EL display element substrate]
A glass substrate with an ITO electrode was cleaned using acetone and isopropanol. Thereafter, the following compounds were sequentially deposited to form a thin film using a vacuum evaporation method to obtain an organic EL element substrate consisting 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 250nm
・Hole injection layer Copper phthalocyanine thickness 30nm
・Hole transport layer N,N'-diphenyl-N,N'-dinaphthylbenzidine (α-NPD) thickness 20 nm
・Light-emitting layer Tris(8-hydroxyquinolinato)aluminum (metal complex material), thickness of light-emitting layer 1000 Å
・Electron injection layer: Lithium fluoride, thickness: 1 nm
・Cathode aluminum, anode film thickness 250nm

[Production of organic EL display element]
The resin compositions obtained in the Examples and Comparative Examples were applied to glass using a coating device under a nitrogen atmosphere, and the resin composition was coated with an ultraviolet irradiation device (an ultra-high pressure mercury lamp irradiation device manufactured by HOYA Co., Ltd., "UL-750"). '') was used to irradiate ultraviolet rays with a wavelength of 365 nm and 100 mW/ ^cm2 for 10 seconds, and after 20 minutes, the resin composition was bonded to an organic EL display element substrate with an adhesive thickness of 10 μm, and cured for 30 minutes in an atmosphere of 80°C. An organic EL display element was produced by curing the adhesive. The cathode side of the organic EL element substrate was bonded to glass via a sealant. Organic EL evaluation was performed on the obtained organic EL display element using the evaluation method shown below.

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

[Evaluation of organic EL: Evaluation of luminescence state after high temperature and high humidity test]
Immediately after the organic EL display element was produced, it was exposed for 1000 hours under the conditions of 60°C and relative humidity of 90% by mass, and then a voltage of 6V was applied for 10 seconds, and the luminescence state of the organic EL display element was observed visually and with a microscope. Observation was made 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 even more preferably no dark spot.

Table 1 shows the above evaluation results. The sealants of Examples were shown to have low viscosity and excellent reliability after curing. In addition, if the content of component (A) is less than 50 parts by mass out of the total of 100 parts by mass of components (A) and (B), the viscosity of the sealant increases and the coating/discharging properties decrease. This was shown (Comparative Examples 1 and 2). Furthermore, it was shown that the sealant did not harden when component (C) was not used (Comparative Example 3).

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

Claims (10)

A cationically polymerizable compound having a 1,2-epoxycyclohexane structure;
A vinyl ether compound having a vinyloxy group,
a photocationic polymerization initiator;
one or more curing retarders selected from the group consisting of phosphoric acid esters and phosphite esters ;
Contains
A sealant for an organic electroluminescent display element, wherein the content of the vinyl ether compound is greater than 50 parts by mass and not more than 95 parts by mass based on 100 parts by mass of the cationically polymerizable compound and the vinyl ether compound. The sealant for an organic electroluminescent display element according to claim 1, wherein the vinyl ether compound has a lower viscosity at 25°C than the cationically polymerizable compound at 25°C. According to claim 1 or 2, the content of the photocationic polymerization initiator is 0.1 parts by mass or more and 5.0 parts by mass or less based on a total of 100 parts by mass of the cationically polymerizable compound and the vinyl ether compound. The encapsulant for organic electroluminescent display elements described above. The sealant for an organic electroluminescent display element according to any one of claims 1 to 3, which has a viscosity of 2 to 200 cps when measured using an E-type viscometer at 25° C. and 10 rpm. The encapsulant for an organic electroluminescent display element according to any one of claims 1 to 4, wherein the vinyl ether compound has two of the vinyloxy groups and further has a cyclic group. A cured product of the sealant for organic electroluminescent display elements according to any one of claims 1 to 5. The cured product according to claim 6, which has a total light transmittance of 80% or more in a wavelength range of 380 to 800 nm per 10 μm thickness. A sealing material for an organic electroluminescent display element, comprising the cured product according to claim 6 or 7. an organic electroluminescent display element,
An organic electroluminescent display device comprising the sealing material for an organic electroluminescent display element according to claim 8. An adhesion step of adhering the sealant for an organic electroluminescent display element according to any one of claims 1 to 5 to the first member;
an irradiation step of irradiating the attached organic electroluminescent display element sealant with light;
a bonding step of bonding the first member and the second member via the light-irradiated sealant for organic electroluminescent display elements;
A method for manufacturing an organic electroluminescent display device, comprising: