JP7056314B2 - Thioepoxy resins, curable resin compositions, cured products thereof, and electronic devices - Google Patents

Description

The present invention relates to a thioepoxy resin, a curable resin composition, a cured product thereof, and an electronic device.

Functional elements made of organic materials such as organic electroluminescence (EL) elements and organic thin-film solar cells are expected to be flexible functional elements that can be bent and used by folding or winding. ..

The organic EL element has a structure in which an element portion main body made of a thin film laminate including a light emitting layer sandwiched by a cathode and an anode is formed on a substrate such as glass or a film on which a drive circuit such as a TFT is formed. ing. A layer such as a light emitting layer or an electrode of an element portion is likely to be deteriorated by moisture or oxygen, and the deterioration causes a decrease in brightness. Therefore, the organic EL element is sealed so as to block the infiltration of moisture or impurities from the outside. In order to realize a high-quality and highly reliable organic EL element, a higher-performance sealing method and sealing material are desired, and various techniques have been studied conventionally.

As a typical sealing method for an organic EL element, a method of fixing a metal or glass sealing cap into which a desiccant has been inserted to a substrate of the organic EL element using a sealing adhesive has been studied. (Patent Document 1). In this method, an adhesive is applied to the outer peripheral portion of the substrate of the organic EL element, a sealing cap is placed on the adhesive, and then the adhesive is solidified to fix the substrate and the sealing cap to fix the organic EL element. Is sealed. However, glass sealing caps are made by processing a digging to insert the desiccant into a flat glass substrate, which is costly and tends to thicken the entire device. .. Further, since the hollow structure is used, the glass substrate is liable to be distorted or bent due to the increase in size of the panel, and there is a problem in impact resistance. Further, in the sealing with the sealing cap, since the desiccant is inserted inside the sealing cap, light cannot be taken out from the sealing cap side. That is, the light emitted from the light source is taken out from the substrate side of the element, and is limited to the bottom emission type element. In the case of a bottom emission type element, there are problems that the aperture ratio is lowered by the drive circuit portion formed on the substrate and the extraction efficiency is lowered by partially blocking the light by the drive circuit portion. Therefore, it is desired to develop a sealing method applicable to a top emission type element that extracts light from the opposite side of the substrate of the organic EL element.

There is a thin film encapsulation method as a typical encapsulation method applicable to top emission type elements and flexible organic EL elements. The thin film encapsulation method is a method of laminating a thin film made of an inorganic or organic material on an organic EL element (Patent Document 2). Silicon nitride is used as an inorganic material in a typical sealing film, and is often used by laminating it with an organic material such as (meth) acrylate resin or epoxy resin. In the case of a top emission type element, there is a sealing material in the direction of extracting light. Generally, in an organic EL element, a member having a high refractive index (high refractive index member) such as an inorganic material used for an electrode or a sealing film is often used. Therefore, the organic material used for the sealing film has low moisture permeability and also reflects light generated at the interface with the high refractive index member even when it is arranged in contact with the high refractive index member. It is required to have a high refractive index in order to suppress the above.

Japanese Patent No. 487669 Japanese Unexamined Patent Publication No. 2012-059553

The present invention has been made in view of the above circumstances, and provides a curable resin composition that gives a cured product having low moisture permeability and a high refractive index, a cured product obtained from the composition, and an electronic device including the cured product. The purpose is to provide.

As a result of diligent studies to achieve the above object, the present inventors have a curability containing a thioepoxy resin obtained by polymerizing a thioepoxy group-containing fluorene derivative and a dithiol compound, a predetermined phenylsulfide derivative and a fluorene derivative. We have found that the above problems can be solved by the resin composition, and have completed the present invention.

（式中、Ｒ^A及びＲ^Bは、それぞれ独立に、ハロゲン原子、ニトロ基、シアノ基、アミノ基、アルデヒド基、ヒドロキシ基、スルホン酸基、カルボキシ基、Ｚ¹で置換されていてもよい炭素数１～２０のアルキル基、Ｚ²で置換されていてもよい炭素数６～２０のアリール基、Ｚ²で置換されていてもよい炭素数２～２０のヘテロアリール基、－ＮＨＹ¹、－ＮＹ²Ｙ³、－Ｃ(Ｏ)Ｙ⁴、－ＯＹ⁵、－ＳＹ⁶、－ＳＯ₃Ｙ⁷、－Ｃ(Ｏ)ＯＹ⁸、－ＯＣ(Ｏ)Ｙ⁹、－Ｃ(Ｏ)ＮＨＹ¹⁰、又は－Ｃ(Ｏ)ＮＹ¹¹Ｙ¹²であり、ｘ及びｙが２以上の整数のとき、各Ｒ^A及び各Ｒ^Bは、互いに同一であっても異なっていてもよく；
Ｙ¹～Ｙ¹²は、それぞれ独立に、Ｚ¹で置換されていてもよい炭素数１～２０のアルキル基、Ｚ²で置換されていてもよい炭素数６～２０のアリール基、又はＺ²で置換されていてもよい炭素数２～２０のヘテロアリール基であり；
Ｌ^A及びＬ^Bは、それぞれ独立に、Ｚ²で置換されていてもよいフェニレン基、又はＺ²で置換されていてもよいナフタレンジイル基であり；
Ｌ^C及びＬ^Dは、それぞれ独立に、炭素数１～８の２価炭化水素基であり；
Ｚ¹は、ハロゲン原子、ニトロ基、シアノ基、アミノ基、アルデヒド基、ヒドロキシ基、スルホン酸基、カルボキシ基、Ｚ³で置換されていてもよい炭素数１～２０のアルコキシ基、Ｚ³で置換されていてもよい炭素数６～２０のアリール基、又はＺ³で置換されていてもよい炭素数２～２０のヘテロアリール基であり；
Ｚ²は、ハロゲン原子、ニトロ基、シアノ基、アミノ基、アルデヒド基、ヒドロキシ基、スルホン酸基、カルボキシ基、Ｚ³で置換されていてもよい炭素数１～２０のアルキル基、又はＺ³で置換されていてもよい炭素数１～２０のアルコキシ基であり；
Ｚ³は、ハロゲン原子、ニトロ基、シアノ基、アミノ基、アルデヒド基、ヒドロキシ基、スルホン酸基、又はカルボキシ基であり；
Ｘ¹及びＸ²は、それぞれ独立に、－ＣＨ－又は－Ｎ－であり；
ｘ及びｙは、それぞれ独立に、０～４の整数である。）
２．Ｘ¹及びＸ²が、ともにＮである１のチオエポキシ樹脂。
３．ｘ及びｙが、ともに０である１又は２のチオエポキシ樹脂。
４．（Ａ）１～３のいずれかのチオエポキシ樹脂、
（Ｂ）下記式（Ｂ）で表されるフェニルスルフィド誘導体、及び
（Ｃ）下記式（Ｃ）で表されるフルオレン誘導体
を含む硬化性樹脂組成物。

（式中、Ｒ^P1及びＲ^P2は、それぞれ独立に、水素原子又は重合性不飽和結合含有基であり；
Ｒ^P3及びＲ^P4は、それぞれ独立に、重合性不飽和結合含有基であり；
Ｒ¹～Ｒ⁶は、それぞれ独立に、ハロゲン原子、ニトロ基、シアノ基、アミノ基、アルデヒド基、ヒドロキシ基、チオール基、スルホン酸基、カルボキシ基、Ｚ¹¹で置換されていてもよい炭素数１～２０のアルキル基、Ｚ¹²で置換されていてもよい炭素数６～２０のアリール基、Ｚ¹²で置換されていてもよい炭素数２～２０のヘテロアリール基、－ＮＨＹ¹、－ＮＹ²Ｙ³、－Ｃ(Ｏ)Ｙ⁴、－ＯＹ⁵、－ＳＹ⁶、－ＳＯ₃Ｙ⁷、－Ｃ(Ｏ)ＯＹ⁸、－ＯＣ(Ｏ)Ｙ⁹、－Ｃ(Ｏ)ＮＨＹ¹⁰、又は－Ｃ(Ｏ)ＮＹ¹¹Ｙ¹²であり、ａ～ｆが２以上の整数のとき、各Ｒ¹～各Ｒ⁶は、互いに同一であっても異なっていてもよく；
Ｙ¹～Ｙ¹²は、それぞれ独立に、Ｚ¹¹で置換されていてもよい炭素数１～２０のアルキル基、Ｚ¹²で置換されていてもよい炭素数６～２０のアリール基、又はＺ¹²で置換されていてもよい炭素数２～２０のヘテロアリール基であり；
Ｌは、単結合又は２価の連結基であり；
Ｌ¹及びＬ²は、それぞれ独立に、Ｚ¹²で置換されていてもよいフェニレン基、又はＺ¹²で置換されていてもよいナフタレンジイル基であり；
Ｌ³及びＬ⁴は、それぞれ独立に、炭素数１～６の２価炭化水素基であり；
Ｚ¹¹は、ハロゲン原子、ニトロ基、シアノ基、アミノ基、アルデヒド基、ヒドロキシ基、チオール基、スルホン酸基、カルボキシ基、Ｚ¹³で置換されていてもよい炭素数１～２０のアルコキシ基、Ｚ¹³で置換されていてもよい炭素数６～２０のアリール基、又はＺ¹³で置換されていてもよい炭素数２～２０のヘテロアリール基であり；
Ｚ¹²は、ハロゲン原子、ニトロ基、シアノ基、アミノ基、アルデヒド基、ヒドロキシ基、チオール基、スルホン酸基、カルボキシ基、Ｚ¹³で置換されていてもよい炭素数１～２０のアルキル基、又はＺ¹³で置換されていてもよい炭素数１～２０のアルコキシ基であり；
Ｚ¹³は、ハロゲン原子、ニトロ基、シアノ基、アミノ基、アルデヒド基、ヒドロキシ基、チオール基、スルホン酸基、又はカルボキシ基であり；
ａ～ｆは、それぞれ独立に、０～４の整数であり；
ｐは、０～１０の整数であり；
ｑ及びｒは、それぞれ独立に、０～１０の整数である。）
５．（Ｂ）成分が、下記式（Ｂ'）で表される化合物である４の硬化性樹脂組成物。

６．（Ｃ）成分が、下記式（Ｃ'）で表される化合物である４又は５の硬化性樹脂組成物。

（式中、Ｒ¹¹及びＲ¹²は、水素原子又はメチル基である。）
７．更に、（Ｄ）ラジカル重合開始剤を含む４～６のいずれかの硬化性樹脂組成物。
８．溶媒を含まない４～７のいずれかの硬化性樹脂組成物。
９．電子デバイス用封止材料である４～８のいずれかの硬化性樹脂組成物。
１０．有機ＥＬ素子用封止材料である９の硬化性樹脂組成物。
１１．４～１０のいずれかの硬化性樹脂組成物から得られる硬化物。
１２．（Ａ）１～３のいずれかのポリマー、（Ｂ）下記式（Ｂ）で表されるフェニルスルフィド誘導体、及び（Ｃ）下記式（Ｃ）で表されるフルオレン誘導体の反応物を含む硬化物。

（式中、Ｒ^P1～Ｒ^P4、Ｒ¹～Ｒ⁶、Ｌ、Ｌ¹～Ｌ⁴、ａ～ｆ、ｐ、ｑ及びｒは、前記と同じ。）
１３．１１又は１２の硬化物を備える電子デバイス。
１４．１１又は１２の硬化物を備える有機エレクトロルミネッセンス素子。
１５．下記式（Ａ－１）で表されるチオエポキシ基含有フルオレン誘導体及び下記式（Ａ－２）で表されるジチオール化合物を有機溶媒中で重合させる、チオエポキシ樹脂の製造方法。

（式中、Ｒ^A、Ｒ^B、Ｌ^A～Ｌ^D、Ｘ¹、Ｘ²、ｘ及びｙは、前記と同じ。） That is, the present invention provides the following thioepoxy resin, curable resin composition, cured product thereof, and electronic device.
1. 1. A thioepoxy resin obtained by polymerizing a thioepoxy group-containing fluorene derivative represented by the following formula (A-1) and a dithiol compound represented by the following formula (A-2).

(In the formula, ^RA and ^RB are independently substituted with a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a sulfonic acid group, a carboxy group, and Z ¹ carbon. An alkyl group of number 1 to 20, an aryl group having 6 to 20 carbon atoms which may be substituted with Z ² , a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z ² , -NHY ¹ ,- NY ² Y ³ , -C (O) Y ⁴ , -OY ⁵ , -SY ⁶ , -SO ₃ Y ⁷ , -C (O) OY ⁸ , -OC (O) Y ⁹ , -C (O) NHY ¹⁰ , Or -C (O) NY ¹¹ Y ¹² , where x and y are integers greater than or equal to 2, each ^RA and each ^RB may be the same or different from each other;
Y ¹ to Y ¹² are independently an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹ , an aryl group having 6 to 20 carbon atoms which may be substituted with Z ² , or Z ² It is a heteroaryl group having 2 to 20 carbon atoms which may be substituted with;
^LA and ^LB are independently phenylene groups optionally substituted with Z ² or naphthalenediyl groups optionally substituted with Z ² ;
LC and ^LD are each independently a divalent hydrocarbon group having 1 to 8 carbon ^atoms ;
Z ¹ is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a sulfonic acid group, a carboxy group, an alkoxy group having 1 to 20 carbon atoms which may be substituted with Z ³ , and Z ³ . An aryl group having 6 to 20 carbon atoms which may be substituted, or a heteroaryl group having 2 to 20 carbon atoms which may be substituted by Z ³ ;
Z ² is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a sulfonic acid group, a carboxy group, an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ³ , or Z ³ It is an alkoxy group having 1 to 20 carbon atoms which may be substituted with;
Z ³ is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a sulfonic acid group, or a carboxy group;
X ¹ and X ² are independently -CH- or -N-;
x and y are each independently an integer of 0 to 4. )
2. 2. A thioepoxy resin of 1 in which both X ¹ and X ² are N.
3. 3. A thioepoxy resin having 1 or 2 in which both x and y are 0.
4. (A) The thioepoxy resin according to any one of 1 to 3.
(B) A curable resin composition containing a phenylsulfide derivative represented by the following formula (B) and (C) a fluorene derivative represented by the following formula (C).

(In the formula, ^RP1 and ^RP2 are each independently a hydrogen atom or a polymerizable unsaturated bond-containing group;
^RP3 and ^RP4 are independently polymerizable unsaturated bond-containing groups;
R ¹ to R ⁶ each independently have a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a thiol group, a sulfonic acid group, a carboxy group, and the number of carbon atoms which may be substituted with Z ¹¹ . An alkyl group of 1 to 20, an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹² , a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z ¹² , -NHY ¹ , -NY. ² Y ³ , -C (O) Y ⁴ , -OY ⁵ , -SY ⁶ , -SO ₃ Y ⁷ , -C (O) OY ⁸ , -OC (O) Y ⁹ , -C (O) NHY ¹⁰ , Or -C (O) NY ¹¹ Y ¹² , and when a to f are integers of 2 or more, each R ¹ to each R ⁶ may be the same or different from each other;
Y ¹ to Y ¹² are independently an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹¹ , an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹² , or Z ¹² . It is a heteroaryl group having 2 to 20 carbon atoms which may be substituted with;
L is a single bond or divalent linking group;
L ¹ and L ² are independently phenylene groups optionally substituted with Z ¹² or naphthalenediyl groups optionally substituted with Z ¹² ;
L ³ and L ⁴ are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms;
Z ¹¹ is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a thiol group, a sulfonic acid group, a carboxy group, an alkoxy group having 1 to 20 carbon atoms which may be substituted with Z ¹³ . An aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹³ or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z ¹³ ;
Z ¹² includes a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a thiol group, a sulfonic acid group, a carboxy group, and an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹³ . Alternatively, it is an alkoxy group having 1 to 20 carbon atoms which may be substituted with Z ¹³ ;
Z ¹³ is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a thiol group, a sulfonic acid group, or a carboxy group;
a to f are independently integers of 0 to 4;
p is an integer from 0 to 10;
q and r are independently integers from 0 to 10. )
5. The curable resin composition of 4 in which the component (B) is a compound represented by the following formula (B').

6. The curable resin composition of 4 or 5 in which the component (C) is a compound represented by the following formula (C').

(In the formula, R ¹¹ and R ¹² are hydrogen atoms or methyl groups.)
7. Further, the curable resin composition according to any one of 4 to 6, which comprises (D) a radical polymerization initiator.
8. The curable resin composition according to any one of 4 to 7 containing no solvent.
9. The curable resin composition according to any one of 4 to 8, which is a sealing material for electronic devices.
10. 9. Curable resin composition of 9 which is a sealing material for an organic EL element.
A cured product obtained from any of the curable resin compositions of 11.4 to 10.
12. A cured product containing (A) a polymer according to any one of 1 to 3, (B) a phenylsulfide derivative represented by the following formula (B), and (C) a reaction product of a fluorene derivative represented by the following formula (C). ..

(In the formula, R ^P1 to R ^P4 , R ¹ to R ⁶ , L, L ¹ to L ⁴ , a to f, p, q and r are the same as described above.)
An electronic device comprising a cure of 13.11 or 12.
An organic electroluminescent device comprising a cured product of 14.11 or 12.
15. A method for producing a thioepoxy resin, wherein a thioepoxy group-containing fluorene derivative represented by the following formula (A-1) and a dithiol compound represented by the following formula (A-2) are polymerized in an organic solvent.

(In the formula, ^RA , ^RB , ^LA to ^LD , X ¹ , X ² , x and y are the same as above.)

The curable resin composition containing the thioepoxy resin of the present invention can give a cured product having low moisture permeability and a high refractive index, and is suitable as a sealing material for electronic devices such as organic EL elements.

[Thioepoxy resin]
The thioepoxy resin of the present invention is obtained by polymerizing a fluorene derivative represented by the following formula (A-1) and a dithiol compound represented by the following formula (A-2). That is, the thioepoxy resin of the present invention is a copolymer obtained from these compounds.

In formula ( ^A -1), ^RA and RB are independently substituted with a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a sulfonic acid group, a carboxy group and Z ¹ . An alkyl group having 1 to 20 carbon atoms may be substituted, an aryl group having 6 to 20 carbon atoms may be substituted with Z ² , a heteroaryl group having 2 to 20 carbon atoms may be substituted with Z ² , and-. NHY ¹ , -NY ² Y ³ , -C (O) Y ⁴ , -OY ⁵ , -SY ⁶ , -SO ₃ Y ⁷ , -C (O) OY ⁸ , -OC (O) Y ⁹ , -C ( When O) ^{NHY 10} or -C (O) NY ¹¹ Y ¹² and x and y are integers of 2 or more, each ^RA and each RB may be the same or different from each other.

Y ¹ to Y ¹² are independently an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹ , an aryl group having 6 to 20 carbon atoms which may be substituted with Z ² , or Z ² It is a heteroaryl group having 2 to 20 carbon atoms which may be substituted with.

In formula ( ^{A -} 1), LA and LB are phenylene groups which may be substituted with Z ² or naphthalenediyl groups which may be substituted with Z ² , respectively.

In the formula ( ^{A -} 1), LC and LD are each independently a divalent hydrocarbon group having 1 to 8 carbon atoms.

Z ¹ is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a sulfonic acid group, a carboxy group, an alkoxy group having 1 to 20 carbon atoms which may be substituted with Z ³ , and Z ³ . It is an aryl group having 6 to 20 carbon atoms which may be substituted, or a heteroaryl group having 2 to 20 carbon atoms which may be substituted by Z ³ .

Z ² is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a sulfonic acid group, a carboxy group, an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ³ , or Z ³ It is an alkoxy group having 1 to 20 carbon atoms which may be substituted with.

Z ³ is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a sulfonic acid group, or a carboxy group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl. Group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc. Chain or branched alkyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group. , Bicyclooctyl group, bicyclononyl group, bicyclodecyl group and the like, cyclic alkyl groups having 3 to 20 carbon atoms can be mentioned.

Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group and a 2-phenanthryl group. Examples thereof include a 3-phenanthryl group, a 4-phenanthryl group and a 9-phenanthril group.

Examples of the heteroaryl group having 2 to 20 carbon atoms include 2-thienyl group, 3-thienyl group, 2-furanyl group, 3-furanyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group and 3-. Isooxazolyl group, 4-isoxazolyl group, 5-isooxazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 2-imidazolyl group, 4- Examples thereof include an imidazolyl group, a 2-pyridyl group, a 3-pyridyl group, and a 4-pyridyl group.

Of these, ^RA and ^RB include a halogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted with Z ¹ , and an aryl having 6 to 14 carbon atoms which may be substituted with Z ² . A group is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable.

The phenylene groups represented by LA and LB, which may be substituted with Z ² , include 1,2 ^- phenylene group, 1,3 ^- phenylene group, 1,4-phenylene group, and 2-methylbenzene-. Examples thereof include a 1,4-diyl group, a 2-aminobenzene-1,4-diyl group, a 2,4-dibromobenzene-1,3-diyl group, and a 2,6-dibromobenzene-1,4-diyl group. .. Examples of the naphthalene diyl group optionally substituted with Z ² include naphthalene-1,2-diyl group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group and naphthalene-1,8-diyl group. , Naphthalene-2,3-diyl group, naphthalene-2,6-diyl group and the like.

Of these, as LA and LB, a 1,4 ^- phenylene group, a naphthalene ^- 1,4-diyl group and a naphthalene-1,5-diyl group are preferable, and a 1,4-phenylene group and a naphthalene-1, A 5-diyl group is more preferred.

The divalent hydrocarbon group having 1 to 8 carbon atoms represented by LC and LD may be linear, branched or cyclic, and specific examples thereof include a methylene group and ethane ^{- 1,1-} . Diyl group, ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, propane-2,2-diyl group, cyclopentane-1,2-diyl group, cyclo Examples thereof include an alkanediyl group such as a pentane-1,3-diyl group, a cyclohexane-1,2-diyl group, a cyclohexane-1,3-diyl group and a cyclohexane-1,4-diyl group.

Of these, as L ^C and ^LD , a methylene group, an ethane-1,2-diyl group and a propane-1,2-diyl group are preferable, and a methylene group is more preferable.

In the formula (A-1), x and y are independently integers of 0 to 4, but 0 to 2 are preferable, 0 or 1 is more preferable, and 0 is the most suitable.

In formula (A-2), X ¹ and X ² are independently -CH- or -N-, but both are preferably -N-.

The weight average molecular weight (Mw) of the thioepoxy resin is preferably 2,000 to 10,000, more preferably 3,000 to 6,000, from the viewpoint of solubility and viscosity. In the present invention, Mw is a polystyrene-equivalent measured value by gel permeation chromatography (GPC).

[Manufacturing method of thioepoxy resin]
The thioepoxy resin can be produced by polymerizing a thioepoxy group-containing fluorene derivative represented by the formula (A-1) and a dithiol compound represented by the formula (A-2) in an organic solvent.

Examples of the organic solvent include tetrahydrofuran (THF), cyclohexanone (CHN), dioxane, N-methyl-2-pyrrolidone (NMP) and the like. Of these, THF and CHN are particularly preferable. These organic solvents may be used alone or in combination of two or more. The amount of the organic solvent used is 300 to 600 parts by mass with respect to 100 parts by mass in total of the thioepoxy group-containing fluorene derivative represented by the formula (A-1) and the dithiol compound represented by the formula (A-2). It is preferably 400 to 500 parts by mass, more preferably 400 to 500 parts by mass.

In the polymerization reaction, the amount of the dithiol compound represented by the formula (A-2) is preferably 1.1 to 1.5 mol with respect to 1 mol of the thioepoxy group-containing fluorene derivative represented by the formula (A-1). 1.1 to 1.3 mol is more preferable.

In the polymerization reaction, a catalyst may be used to accelerate the reaction. Examples of the catalyst include quaternary phosphonium salts such as tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, ethyltriphenylphosphonium chloride, and ethyltriphenylphosphonium bromide; benzyltrimethylammonium chloride, Tertiary ammonium such as benzyltrimethylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltripropylammonium chloride, benzyltripropylammonium bromide, tetramethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide, etc. Examples include salt.

The amount of the catalyst used is preferably 1.5 to 3.0% by mass, more preferably 1.9 to 2.5% by mass, based on the thioepoxy group-containing fluorene derivative represented by the formula (A-1).

In the polymerization reaction, the reaction temperature may be appropriately set in the range from the melting point of the solvent to be used to the boiling point of the solvent, and is usually about 40 to 90 ° C., preferably about 40 to 60 ° C. The reaction time is appropriately set depending on the reaction temperature, but is usually about 30 minutes to 50 hours.

After the completion of the polymerization reaction, post-treatment is carried out according to a conventional method, and if necessary, purification such as reprecipitation can be performed to obtain the desired thioepoxy resin.

（式中、Ｒ^A、Ｒ^B、Ｌ^A、Ｌ^B、Ｌ^C、Ｌ^D、ｘ及びｙは、前記と同じ。） The fluorene derivative represented by the formula (A-1) is obtained by reacting the epoxy group-containing fluorene derivative represented by the following formula (A-1-1) with a cheating agent such as thiourea or thiocyanate. Obtainable. The conditions for the cheerleading reaction may be those conventionally known.

(In the ^formula , ^RA , ^RB , ^LA , ^LB , LC, ^LD , x and y are the same as above.)

[Curable resin composition]
The curable resin composition of the present invention comprises (A) the above-mentioned thioepoxy resin, (B) a phenylsulfide derivative represented by the following formula (B), and (C) a fluorene derivative represented by the following formula (C). It includes.

In formula (B), ^RP1 and ^RP2 are independently hydrogen atoms or polymerizable unsaturated bond-containing groups. In formula (C), ^RP3 and ^RP4 are independently polymerizable unsaturated bond-containing groups.

The polymerizable unsaturated bond-containing group is preferably a group having a polymerizable carbon-carbon double bond, and examples thereof include a vinyl group, an allyl group, and a (meth) acryloyl group. Of these, a vinyl group or an allyl group is particularly preferable as ^RP1 and ^RP2 , and a (meth) acryloyl group is preferable as ^RP3 and ^RP4 .

In formulas (B) and (C), R ¹ to R ⁶ independently represent a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a thiol group, a sulfonic acid group, a carboxy group, and Z. An alkyl group having 1 to 20 carbon atoms which may be substituted with ¹¹ , an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹² , and an alkyl group having 2 to 20 carbon atoms which may be substituted with Z ¹² . Heteroaryl group, -NHY ¹ , -NY ² Y ³ , -C (O) Y ⁴ , -OY ⁵ , -SY ⁶ , -SO ₃ Y ⁷ , -C (O) OY ⁸ , -OC (O) Y ⁹ , -C (O) NHY ¹⁰ , or -C (O) NY ¹¹ Y ¹² . When a to f are integers of 2 or more, each R ¹ to each R ⁶ may be the same as or different from each other.

Y ¹ to Y ¹² are independently an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹¹ , an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹² , or Z ¹² . It is a heteroaryl group having 2 to 20 carbon atoms which may be substituted with.

In formula (B), L is a single bond or a divalent linking group.

In formula (C), L ¹ and L ² are phenylene groups which may be substituted with Z ¹² or naphthalenediyl groups which may be substituted with Z ¹² , respectively.

In the formula (C), L ³ and L ⁴ are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms.

Z ¹¹ is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a thiol group, a sulfonic acid group, a carboxy group, an alkoxy group having 1 to 20 carbon atoms which may be substituted with Z ¹³ . It is an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹³ , or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z ¹³ .

Z ¹² includes a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a thiol group, a sulfonic acid group, a carboxy group, and an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹³ . Alternatively, it is an alkoxy group having 1 to 20 carbon atoms which may be substituted with Z ¹³ .

Z ¹³ is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a thiol group, a sulfonic acid group, or a carboxy group.

The halogen atom, the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms and the heteroaryl group having 2 to 20 carbon atoms are the same as those described in the description of ^RA and ^RB . Can be mentioned.

Of these, R ¹ to R ⁶ include a halogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted with Z ¹¹ , or an aryl having 6 to 14 carbon atoms which may be substituted with Z ¹² . A group is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable.

The divalent linking group represented by L includes a divalent hydrocarbon group having 1 to 6 carbon atoms, a carbonyl group, an ether bond, a thioether bond, an ester bond, a carbonate bond, an amide bond, or a plurality of these. The group etc. can be mentioned. The divalent hydrocarbon group may be linear, branched or cyclic, and specific examples thereof include a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group and a propane-. 1,2-diyl group, propane-1,3-diyl group, propane-2,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, cyclopentane-1,2- Diyl group, cyclopentane-1,3-diyl group, hexane-1,6-diyl group, cyclohexane-1,2-diyl group, cyclohexane-1,3-diyl group, cyclohexane-1,4-diyl group, etc. An alkanediyl group and the like can be mentioned.

Of these, as L, a single bond, a divalent hydrocarbon group having 1 to 2 carbon atoms, a thioether bond, a carbonate bond, and an amide bond are preferable, and a single bond is more preferable.

Examples of the phenylene group represented by L ¹ and L ² which may be substituted with Z ¹² include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, and 2-methylbenzene-. Examples thereof include a 1,4-diyl group, a 2-aminobenzene-1,4-diyl group, a 2,4-dibromobenzene-1,3-diyl group, and a 2,6-dibromobenzene-1,4-diyl group. .. Examples of the naphthalene diyl group optionally substituted with Z ¹² include naphthalene-1,2-diyl group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group and naphthalene-1,8-diyl group. , Naphthalene-2,3-diyl group, naphthalene-2,6-diyl group and the like.

Of these, L ¹ and L ² include 1,4-phenylene group, 1,3-phenylene group, 2-methylbenzene-1,4-diyl group, naphthalene-1,4-diyl group, and naphthalene-1. , 5-Diyl group is preferable, 1,4-phenylene group and naphthalene-1,5-diyl group are more preferable.

The divalent hydrocarbon group having 1 to 6 carbon atoms represented by L ³ and L ⁴ may be linear, branched or cyclic, and specific examples thereof include a methylene group and ethane-1,1-. Diyl group, ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, propane-2,2-diyl group, butane-1,4-diyl group, pentane- 1,5-Diyl group, cyclopentane-1,2-diyl group, cyclopentane-1,3-diyl group, hexane-1,6-diyl group, cyclohexane-1,2-diyl group, cyclohexane-1,3 -Alkanediyl groups such as diyl group and cyclohexane-1,4-diyl group can be mentioned.

Of these, as L ³ and L ⁴ , a methylene group, an ethane-1,2-diyl group and a propane-1,2-diyl group are preferable, and an ethane-1,2-diyl group is more preferable.

In the formulas (B) and (C), a to f are independently integers of 0 to 4, but 0 to 2 are preferable, 0 or 1 is more preferable, and 0 is optimal.

In the formula (B), p is an integer of 0 to 10, but 0 to 4 is preferable, 0 or 1 is more preferable, and 0 is the most suitable. In the formula (C), q and r are independently integers of 0 to 10, but 0 to 4 are preferable, 0 to 2 are more preferable, and 0 or 1 is the most suitable.

As the component (B), a compound represented by the following formula (B') is preferable from the viewpoint of refractive index, viscosity and production.

（式中、Ｒ¹¹及びＲ¹²は、それぞれ独立に、水素原子又はメチル基である。） As the component (C), a compound represented by the following formula (C') is preferable from the viewpoint of film curability, refractive index and water vapor barrier property.

(In the formula, R ¹¹ and R ¹² are independently hydrogen atoms or methyl groups, respectively.)

In the composition of the present invention, the content of the component (A) is preferably 10 to 60% by mass, more preferably 20 to 50% by mass. The content of the component (B) is preferably 35 to 70% by mass, more preferably 40 to 60% by mass. The content of the component (C) is preferably 5 to 20% by mass, more preferably 10 to 20% by mass.

Each of the components (A) to (C) may be used alone or in combination of two or more. Commercially available products can be used as the component (B) and the component (C).

The composition of the present invention may further contain (D) a radical polymerization initiator. The radical polymerization initiator may be a photoradical polymerization initiator or a thermal radical polymerization initiator, but those that do not generate gas at the same time as decomposition (radical generation) are preferable. The radical polymerization initiator enables a photocuring treatment or a low temperature curing treatment.

Examples of the photoradical polymerization initiator include benzophenone derivatives, imidazole derivatives, bisimidazole derivatives, N-arylglycine derivatives, organic azido compounds, titanosen compounds, aluminate complexes, organic peroxides, N-alkoxypyridinium salts, thioxanthone derivatives and the like. Can be mentioned. More specifically, benzophenone, 1,3-di (tert-butyldioxycarbonyl) benzophenone, 3,3', 4,4'-tetrakis (tert-butyldioxycarbonyl) benzophenone, 3-phenyl-5- Isooxazolone, 2-mercaptobenzimidazole, bis (2,4,5-triphenyl) imidazole, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenylketone, 2-benzyl- 2-Dimethylamino-1- (4-morpholinophenyl) butane-1-one, bis (η ^5-2,4 -cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-) 1-Il) Phenyl) Titanium and the like can be mentioned, but the present invention is not limited thereto.

Commercially available products can also be used as the photoradical polymerization initiator, and examples thereof include IRGACURE (registered trademark) 651, 184, 369, and 784 manufactured by BASF. In addition, commercially available products other than the above can also be used. Specifically, BASF's IRGACURE (registered trademark) 500, 907, 379, 819, 127, 500, 754, 250, 1800, 1870, OXE01, TPO, DAROCUR ( 1173; Lambson Speedcure (registered trademark) MBB, PBZ, ITX, CTX, EDB; Lamberti Esacure (registered trademark) ONE, KIP150, KTO46; KAYACURE (registered trademark) DETX manufactured by Nippon Kayaku Co., Ltd. -S, CTX, BMS, DMBI, etc. can be mentioned.

Examples of the thermal radical polymerization initiator include acetyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, and dilauroyl. Peroxides such as peroxides, tert-butylperoxyacetate, tert-butylperoxypivalate, tert-butylperoxy-2-ethylhexanoate (tert-butyl2-ethylhexaneperoxoate); 2,2'-azobis Isobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), (1-phenylethyl) azodiphenylmethane, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), Dimethyl 2,2'-azobis isobutyrate, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) isobutyro Azo such as nitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane) System compounds: Examples thereof include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate, but the present invention is not limited thereto. Further, as the thermal radical polymerization initiator, a commercially available product can be used.

Among the radical polymerization initiators, a photoradical polymerization initiator is preferable from the viewpoint of convenience and stability. Among the photoradical polymerization initiators, those having absorption in the UV-A (315 to 400 nm) region are preferable, and those having absorption at 350 nm or more are particularly preferable in order to avoid absorption by the component (A) and the component (B). Is more preferable

The content of the radical polymerization initiator is 0 to 2% by mass in the composition of the present invention, but when it is contained, it is preferably 0.5 to 1.5% by mass, preferably 0.7 to 1% by mass. More preferred.

The composition of the present invention may be a solvent-type composition containing a solvent or a solvent-free composition containing no solvent, but is a solvent-free type in order to prevent deterioration of the organic film used in the electronic device. Is preferable. When a solvent is used, the solvent that can be used is one that is compatible with other components and does not remain after curing, or even if it remains, it does not deteriorate the organic film used for the electronic device. However, it is not particularly limited.

Further, the composition of the present invention further comprises a polymerizable compound other than the components (B) and (C) (for example, an epoxy-based compound, an acrylic-based compound, an olefin-based compound, etc.), a polymerization inhibitor, and an antioxidant. The present invention provides conventionally known additives such as light stabilizers, plasticizers, leveling agents, defoaming agents, pigments, ultraviolet absorbers, ion adsorbents, pigments, phosphors, mold release agents, and organic fillers such as cellulose. It may be included within the range that does not impair the effect of.

[Electronic device]
The composition of the present invention can be suitably used as a sealing material for electronic devices. The electronic device is not particularly limited, and examples thereof include an organic EL element, an organic thin film solar cell, and a light emitting diode element. Among these, the composition of the present invention is suitable as a sealing material for an organic EL element, and particularly suitable as a sealing material for a top emission type organic EL element.

The method for sealing the electronic device is not particularly limited, and a conventionally known method may be used. For example, an electronic device can be sealed by applying the composition of the present invention onto a substrate or an element and then curing the composition. At this time, as the coating method, the spin coating method, the cast coating method, the blade coating method, the dip coating method, the roll coating method, the bar coating method, the die coating method, the spray coating method, the inkjet method, and the printing method (letter plate, intaglio, lithographic plate). , Screen printing, etc.).

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The reagents used are as follows.
(1) BGPF: 9,9-bis [4-glycidyloxyphenyl] fluorene (manufactured by Tokyo Chemical Industry Co., Ltd.)
(2) BMT: Bismthiol (manufactured by Tokyo Chemical Industry Co., Ltd.)
(3) MPV: Bis (4-vinylthiophenyl) sulfide (manufactured by Sumitomo Seika Chemical Co., Ltd.)
(4) A-BPEF: 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (NK ester A-BPEF, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
(5) Irg. TPO: Irgacure TPO (manufactured by BASF)

The GPC measuring device and conditions are as follows.
Equipment: SCL-10Avp series manufactured by Shimadzu Corporation Column: Shodex KF-804L + KF-803L
Eluent: THF
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detector: UV (254nm)
Calibration curve: Standard polystyrene

[1] Synthesis of thioepoxy resin [Example 1-1] Synthesis of SBGPF

420 mL of THF was added to 50.85 g (109.9 mmol) of BGPF, and the mixture was stirred and dissolved at room temperature for 1 hour, then 25.10 g (329.7 mmol) of thiourea and 200 mL of methanol were added and reacted at room temperature for 3 days. Then, 250 mL of chloroform and 250 mL of water were added to the obtained reaction solution, and the mixture was extracted with a separating funnel. The chloroform layer was washed 3 times with 250 mL of water and then concentrated to obtain 55.79 g of a crude product.
This crude product was bottom-cut and concentrated on a short column (silica gel 60N (spherical, neutral), manufactured by Kanto Chemical Co., Inc., chloroform) to obtain the target SBGPF as a white solid (52.05 g, yield). 95.7%).

[Example 1-2] Synthesis of thioepoxy resin 1

7.90 g of SBGPF and 2.65 g of BMT were added to 40 mL of THF, and the mixture was stirred at room temperature for 1 hour under a nitrogen atmosphere. After dissolving the substrate, 155 mg of ethyltriphenylphosphonium bromide was added, and the mixture was reacted at 60 ° C. for 21 hours. This was added dropwise to 700 mL of methanol, and the precipitated solid was collected by filtration, washed with 50 mL of methanol, and dried under reduced pressure to obtain 10.29 g of thioepoxy resin 1 (acquisition rate: 96.1%). As a result of GPC measurement, the Mw of the thioepoxy resin 1 was 6,022 and the dispersity was 2.42.

[2] Preparation of curable resin composition [Example 2-1]
Put 30 parts by mass of thioepoxy resin, 60 parts by mass of MPV, and 10 parts by mass of A-BPEF in a sample bottle, heat at 60 ° C, and then rotate / revolve mixer (Awatori Rentaro ARE-310, manufactured by Shinky Co., Ltd.). , Stirred, mixed and dissolved sufficiently. Subsequently, 1 part by mass of a photoradical polymerization initiator Irgacre TPO (manufactured by BASF) was added, and the mixture was stirred, mixed and dissolved with a rotation / revolution mixer to prepare a curable resin composition A.

[Example 2-2]
The curable resin composition B was prepared in the same manner as in Example 1 except that the MPV was 50 parts by mass and the A-BPEF was 20 parts by mass.

[Example 2-3]
The curable resin composition C was prepared by the same method as in Example 1 except that the thioepoxy resin 1 was 40 parts by mass, the MPV was 50 parts by mass, and the A-BPEF was 10 parts by mass.

[Comparative Example 1-1]
60 parts by mass of MPV and 10 parts by mass of A-BPEF were placed in a sample bottle and sufficiently mixed with a hot mix rotor heated to 50 ° C. to prepare a curable resin composition D.

[Comparative Example 1-2]
The curable resin composition E was prepared in the same manner as in Comparative Example 1-1 except that the MPV was 50 parts by mass and the A-BPEF was 20 parts by mass.

[Comparative Example 1-3]
The curable resin composition F was prepared in the same manner as in Comparative Example 1-1 except that the MPV was 50 parts by mass.

[3] Preparation of cured film and evaluation of moisture permeability [Example 2-1] Preparation of cured product A An acetate film in which the curable resin composition A is attached onto a substrate with a spin coater (Brewer CEE100 Programmable Spin Coater). Apply on (HOLBEIN ART MATERIAL INC.), Under a nitrogen atmosphere, expose at 3,000 mJ / cm ² with an ultraviolet irradiation device (FUSION UV RAMP SYSTEM), and then heat in a clean oven at 100 ° C for 30 minutes. It was cured and peeled off from the acetate film to obtain a cured product A.

[Example 2-2] Preparation of cured product B A cured product B was obtained by the same method as in Example 2-1 except that the curable resin composition B was used instead of the curable resin composition A. ..

[Example 2-3] Preparation of cured product C A cured product C was obtained by the same method as in Example 2-1 except that the curable resin composition C was used instead of the curable resin composition A. ..

[Comparative Example 2-1] Preparation of Cured Product D The curable resin composition D is sandwiched between an acetate film attached on a substrate, a mold release-treated substrate, and a 100 μm silicon spacer, and is subjected to ultraviolet rays under a nitrogen atmosphere. After exposure at 3,000 mJ / cm ² with an irradiation device (FUSION UV RAMP SYSTEM), heat it in a clean oven at 100 ° C for 30 minutes to cure it, peel it off from the acetate film and substrate, and cure it with a film thickness of 118 μm. I got D.

[Comparative Example 2-2] Preparation of Cured Product E A cured product having a film thickness of 98 μm by the same method as in Comparative Example 2-1 except that the curable resin composition E was used instead of the curable resin composition D. I got E.

[Comparative Example 2-3] Preparation of Cured Product F A cured product having a film thickness of 110 μm was used in the same manner as in Comparative Example 2-1 except that the curable resin composition F was used instead of the curable resin composition D. I got F.

<Measurement of water vapor permeability>
The cured products A to F are attached to the moisture permeable cups, respectively, and the water vapor permeability (WVTR) of the cured product is measured under the conditions of 60 ° C. and 90% RH according to JIS L 1099, and the water vapor permeability of each film thickness is measured. A WVTR of 100 μm was calculated from the approximate formula. The results are shown in Table 1.

It was found that all of the cured products A to C had a small water vapor transmittance and could be applied as a sealing material.

[4] Preparation of cured film and evaluation of optical characteristics [Example 3-1] Preparation of cured product A'The curable resin composition A was applied onto a quartz substrate with a spin coater (Brewer CEE100 Programmable Spin Coater), and nitrogen was applied. After exposure at 3,000 mJ / cm ² with an ultraviolet irradiation device (FUSION UV RAMP SYSTEM) under an atmosphere, it is cured by heating in a clean oven at 100 ° C. for 30 minutes, and a cured product having a thickness of 43 μm is placed on a quartz substrate. A'was made.

[Example 3-2] Preparation of cured product B'Curing with a film thickness of 108 μm by the same method as in Example 3-1 except that the curable resin composition B was used instead of the curable resin composition A. The thing B'was made.

[Example 3-3] Preparation of cured product C'Curing with a film thickness of 58 μm by the same method as in Example 3-1 except that the curable resin composition C was used instead of the curable resin composition A. The thing C'was made.

[Comparative Example 3-1] Preparation of Cured Product D'The curable resin composition D is poured into a material in which a 100 μm silicon spacer is sandwiched between a quartz substrate and a mold-released substrate, and is irradiated with ultraviolet rays in a nitrogen atmosphere. After exposure at 3,000 mJ / cm ² with a device (FUSION UV RAMP SYSTEM), it is heated in a clean oven at 100 ° C. for 30 minutes to cure, and the mold release-treated substrate is peeled off to form a film on a quartz substrate. A 96 μm cured product D'was produced.

[Comparative Example 3-2] Preparation of Cured Product E'Curing with a film thickness of 100 μm by the same method as in Comparative Example 3-1 except that the curable resin composition E was used instead of the curable resin composition D. The thing E'was made.

[Comparative Example 3-3] Preparation of Cured Product F'Curing with a film thickness of 99 μm by the same method as in Comparative Example 3-1 except that the curable resin composition F was used instead of the curable resin composition D. The thing F'was made.

<Measurement of transmittance and refractive index>
The transmittance of the cured products A'to F'was measured with an ultraviolet visible spectrophotometer (UV-2600 manufactured by Shimadzu Corporation), and the average transmittance at 400 to 800 nm was calculated. In addition, the refractive index (25 ° C.) for light having a wavelength of 589 nm was measured using a prism coupler (Model 2010 manufactured by Metricon). Table 2 shows the film thickness and the results of each characteristic.

From the results of Tables 1 and 2, the cured products obtained from the curable resin composition of the present invention are both transparent in the visible light region, have a high refractive index, have a low water vapor transmittance, and are sealed. It turned out to be applicable as a material. That is, the curable resin composition of the present invention can be applied to electronic devices and the like as a sealing material having high transparency and high refractive index.

Claims (15)

A thioepoxy resin obtained by polymerizing a thioepoxy group-containing fluorene derivative represented by the following formula (A-1) and a dithiol compound represented by the following formula (A-2).

(In the formula, ^RA and ^RB are independently substituted with a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a sulfonic acid group, a carboxy group, and Z ¹ carbon. An alkyl group of number 1 to 20, an aryl group having 6 to 20 carbon atoms which may be substituted with Z ² , a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z ² , -NHY ¹ ,- NY ² Y ³ , -C (O) Y ⁴ , -OY ⁵ , -SY ⁶ , -SO ₃ Y ⁷ , -C (O) OY ⁸ , -OC (O) Y ⁹ , -C (O) NHY ¹⁰ , Or -C (O) NY ¹¹ Y ¹² , where x and y are integers greater than or equal to 2, each ^RA and each ^RB may be the same or different from each other;
Y ¹ to Y ¹² are independently an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹ , an aryl group having 6 to 20 carbon atoms which may be substituted with Z ² , or Z ² It is a heteroaryl group having 2 to 20 carbon atoms which may be substituted with;
^LA and ^LB are independently phenylene groups optionally substituted with Z ² or naphthalenediyl groups optionally substituted with Z ² ;
LC and ^LD are each independently a divalent hydrocarbon group having 1 to 8 carbon ^atoms ;
Z ¹ is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a sulfonic acid group, a carboxy group, an alkoxy group having 1 to 20 carbon atoms which may be substituted with Z ³ , and Z ³ . An aryl group having 6 to 20 carbon atoms which may be substituted, or a heteroaryl group having 2 to 20 carbon atoms which may be substituted by Z ³ ;
Z ² is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a sulfonic acid group, a carboxy group, an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ³ , or Z ³ It is an alkoxy group having 1 to 20 carbon atoms which may be substituted with;
Z ³ is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a sulfonic acid group, or a carboxy group;
X ¹ and X ² are independently -CH- or -N-;
x and y are each independently an integer of 0 to 4. ) The thioepoxy resin according to claim 1, wherein both X ¹ and X ² are N. The thioepoxy resin according to claim 1 or 2, wherein both x and y are 0. (A) The thioepoxy resin according to any one of claims 1 to 3.
(B) A curable resin composition containing a phenylsulfide derivative represented by the following formula (B) and (C) a fluorene derivative represented by the following formula (C).

(In the formula, ^RP1 and ^RP2 are each independently a hydrogen atom or a polymerizable unsaturated bond-containing group;
^RP3 and ^RP4 are independently polymerizable unsaturated bond-containing groups;
R ¹ to R ⁶ each independently have a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a thiol group, a sulfonic acid group, a carboxy group, and the number of carbon atoms which may be substituted with Z ¹¹ . An alkyl group of 1 to 20, an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹² , a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z ¹² , -NHY ¹ , -NY. ² Y ³ , -C (O) Y ⁴ , -OY ⁵ , -SY ⁶ , -SO ₃ Y ⁷ , -C (O) OY ⁸ , -OC (O) Y ⁹ , -C (O) NHY ¹⁰ , Or -C (O) NY ¹¹ Y ¹² , and when a to f are integers of 2 or more, each R ¹ to each R ⁶ may be the same or different from each other;
Y ¹ to Y ¹² are independently an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹¹ , an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹² , or Z ¹² . It is a heteroaryl group having 2 to 20 carbon atoms which may be substituted with;
L is a single bond or divalent linking group;
L ¹ and L ² are independently phenylene groups optionally substituted with Z ¹² or naphthalenediyl groups optionally substituted with Z ¹² ;
L ³ and L ⁴ are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms;
Z ¹¹ is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a thiol group, a sulfonic acid group, a carboxy group, an alkoxy group having 1 to 20 carbon atoms which may be substituted with Z ¹³ . An aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹³ or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z ¹³ ;
Z ¹² includes a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a thiol group, a sulfonic acid group, a carboxy group, and an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹³ . Alternatively, it is an alkoxy group having 1 to 20 carbon atoms which may be substituted with Z ¹³ ;
Z ¹³ is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a thiol group, a sulfonic acid group, or a carboxy group;
a to f are independently integers of 0 to 4;
p is an integer from 0 to 10;
q and r are independently integers from 0 to 10. ) The curable resin composition according to claim 4, wherein the component (B) is a compound represented by the following formula (B').

The curable resin composition according to claim 4 or 5, wherein the component (C) is a compound represented by the following formula (C').

(In the formula, R ¹¹ and R ¹² are hydrogen atoms or methyl groups.) The curable resin composition according to any one of claims 4 to 6, further comprising (D) a radical polymerization initiator. The curable resin composition according to any one of claims 4 to 7, which does not contain a solvent. The curable resin composition according to any one of claims 4 to 8, which is a sealing material for electronic devices. The curable resin composition according to claim 9, which is a sealing material for an organic electroluminescence device. A cured product obtained from the curable resin composition according to any one of claims 4 to 10. (A) The thioepoxy resin according to any one of claims 1 to 3, (B) a phenylsulfide derivative represented by the following formula (B), and (C) a fluorene derivative represented by the following formula (C). A cured product containing a reactant.

(In the formula, ^RP1 and ^RP2 are each independently a hydrogen atom or a polymerizable unsaturated bond-containing group;
^RP3 and ^RP4 are independently polymerizable unsaturated bond-containing groups;
R ¹ to R ⁶ each independently have a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a thiol group, a sulfonic acid group, a carboxy group, and the number of carbon atoms which may be substituted with Z ¹¹ . An alkyl group of 1 to 20, an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹² , a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z ¹² , -NHY ¹ , -NY. ² Y ³ , -C (O) Y ⁴ , -OY ⁵ , -SY ⁶ , -SO ₃ Y ⁷ , -C (O) OY ⁸ , -OC (O) Y ⁹ , -C (O) NHY ¹⁰ , Or -C (O) NY ¹¹ Y ¹² , and when a to f are integers of 2 or more, each R ¹ to each R ⁶ may be the same or different from each other;
Y ¹ to Y ¹² are independently an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹¹ , an aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹² , or Z ¹² . It is a heteroaryl group having 2 to 20 carbon atoms which may be substituted with;
L is a single bond or divalent linking group;
L ¹ and L ² are independently phenylene groups optionally substituted with Z ¹² or naphthalenediyl groups optionally substituted with Z ¹² ;
L ³ and L ⁴ are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms;
Z ¹¹ is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a thiol group, a sulfonic acid group, a carboxy group, an alkoxy group having 1 to 20 carbon atoms which may be substituted with Z ¹³ . An aryl group having 6 to 20 carbon atoms which may be substituted with Z ¹³ or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z ¹³ ;
Z ¹² includes a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a thiol group, a sulfonic acid group, a carboxy group, and an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹³ . Alternatively, it is an alkoxy group having 1 to 20 carbon atoms which may be substituted with Z ¹³ ;
Z ¹³ is a halogen atom, nitro group, cyano group, amino group, aldehyde group, hydroxy group, thiol group, sulfonic acid group, or carboxy group;
a to f are independently integers of 0 to 4;
p is an integer from 0 to 10;
q and r are independently integers from 0 to 10. ) An electronic device comprising the cured product according to claim 11 or 12. An organic electroluminescence device comprising the cured product according to claim 11 or 12. A method for producing a thioepoxy resin, wherein a thioepoxy group-containing fluorene derivative represented by the following formula (A-1) and a dithiol compound represented by the following formula (A-2) are polymerized in an organic solvent.

(In the formula, ^RA and ^RB are independently substituted with a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a sulfonic acid group, a carboxy group, and Z ¹ carbon. An alkyl group of number 1 to 20, an aryl group having 6 to 20 carbon atoms which may be substituted with Z ² , a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z ² , -NHY ¹ ,- NY ² Y ³ , -C (O) Y ⁴ , -OY ⁵ , -SY ⁶ , -SO ₃ Y ⁷ , -C (O) OY ⁸ , -OC (O) Y ⁹ , -C (O) NHY ¹⁰ , Or -C (O) NY ¹¹ Y ¹² , where x and y are integers greater than or equal to 2, each ^RA and each ^RB may be the same or different from each other;
Y ¹ to Y ¹² are independently an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹ , an aryl group having 6 to 20 carbon atoms which may be substituted with Z ² , or Z ² It is a heteroaryl group having 2 to 20 carbon atoms which may be substituted with;
^LA and ^LB are independently phenylene groups optionally substituted with Z ² or naphthalenediyl groups optionally substituted with Z ² ;
LC and ^LD are each independently a divalent hydrocarbon group having 1 to 8 carbon ^atoms ;
Z ¹ is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a sulfonic acid group, a carboxy group, an alkoxy group having 1 to 20 carbon atoms which may be substituted with Z ³ , and Z ³ . An aryl group having 6 to 20 carbon atoms which may be substituted, or a heteroaryl group having 2 to 20 carbon atoms which may be substituted by Z ³ ;
Z ² is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a sulfonic acid group, a carboxy group, an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ³ , or Z ³ It is an alkoxy group having 1 to 20 carbon atoms which may be substituted with;
Z ³ is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxy group, a sulfonic acid group, or a carboxy group;
X ¹ and X ² are independently -CH- or -N-;
x and y are each independently an integer of 0 to 4. )