JP7155576B2 - Curable composition, cured product thereof, and electronic device - Google Patents

Description

The present invention relates to a curable 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, folded, and wound. .

An organic EL element has a structure in which an element body composed of a thin film laminate including a light-emitting layer sandwiched between a cathode and an anode is formed on a substrate such as glass or film on which a drive circuit such as a TFT is formed. ing. A layer such as a light-emitting layer or an electrode in an element portion is easily deteriorated by moisture or oxygen, and luminance is lowered due to the deterioration. Therefore, the organic EL element is sealed so as to block entry of moisture or impurities from the outside. Toward the realization of high-quality and highly-reliable organic EL devices, there is a demand for higher performance encapsulation methods and encapsulation materials, and various techniques have been studied in the past.

As a representative sealing method for organic EL elements, a method of fixing a metal or glass sealing cap into which a desiccant is inserted in advance to the 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 periphery of the substrate of the organic EL element, a sealing cap is placed thereon, and the adhesive is solidified to fix the substrate and the sealing cap, and the organic EL element is produced. is sealed. However, since the glass sealing cap is made by processing a groove for inserting a desiccant into a flat glass substrate, it is expensive and tends to increase the thickness of the entire device. . In addition, due to the hollow structure, the glass substrate tends to warp or bend as the size of the panel increases, and there is also a problem in impact resistance. Furthermore, sealing with a sealing cap means that a desiccant is inserted inside the sealing cap, so light cannot be extracted from the side of the sealing cap. That is, the light emitted from the light source is taken out from the substrate side of the element, which is limited to bottom emission type elements. In the case of a bottom emission type element, there are problems such as a decrease in aperture ratio due to the drive circuit formed on the substrate and a decrease in extraction efficiency due to partial light blocking by the drive circuit. Therefore, it is desired to develop a sealing method that can be applied to a top emission type device in which light is extracted from the opposite side of the substrate of the organic EL device.

A thin film encapsulation method is a representative encapsulation method applicable to top emission type elements and flexible organic EL elements. The thin film encapsulation method is a method of laminating a multilayer of thin films made of inorganic or organic materials on an organic EL element (Patent Document 2). Silicon nitride is used as an inorganic material for a typical sealing film, and it is often used by being laminated with an organic material such as (meth)acrylate resin or epoxy resin. In the case of a top-emission type device, the encapsulant exists in the direction in which light is extracted. In general, organic EL elements often use members with a high refractive index (high refractive index members) such as inorganic materials used for electrodes and sealing films. For this reason, the organic material used for the sealing film should have low moisture permeability, and even if it is placed in contact with the high refractive index member, the light reflection occurring at the interface with the high refractive index member should be low. In order to suppress this, it is required to have a high refractive index.

On the other hand, for example, a method of introducing sulfur atoms into the material to improve the refractive index is known. However, molecules having a sulfur atom often have a strong odor, and thiols and the like have a particularly strong odor. Therefore, it was necessary to suppress the odor while introducing the sulfur atom. In addition, when sulfur atoms are introduced into the material, the strength of the film may decrease at the same time, so it is necessary to achieve both the refractive index and the strength of the film.

Japanese Patent No. 4876609 JP 2012-059553 A

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

The present inventors have made intensive studies to achieve the above objects, and as a result, have found that the above problems can be solved by a curable composition containing a given phenyl sulfide derivative and a fluorene derivative, and have completed the present invention. .

（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、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、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、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、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；
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；
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、チオール基、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、チオール基、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、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。）
２．（Ａ）成分が、下記式（１'）で表される化合物である１の硬化性組成物。

３．（Ｂ）成分が、下記式（２'）で表される化合物である１又は２の硬化性組成物。

（式中、Ｒ¹¹及びＲ¹²は、水素原子又はメチル基である。）
４．更に、（Ｃ）ラジカル重合開始剤を含む１～３のいずれかの硬化性組成物。
５．溶媒を含まない１～４のいずれかの硬化性組成物。
６．電子デバイス用封止材料である１～５のいずれかの硬化性組成物。
７．有機ＥＬ素子用封止材料である６の硬化性組成物。
８．１～７のいずれかの硬化性組成物から得られる硬化物。
９．（Ａ）下記式（１）で表されるフェニルスルフィド誘導体及び（Ｂ）下記式（２）で表されるフルオレン誘導体から得られる共重合体を含む硬化物。

（式中、Ｒ^P1～Ｒ^P4、Ｒ¹～Ｒ⁶、Ｌ、Ｌ¹～Ｌ⁴、ａ～ｆ、ｐ、ｑ及びｒは、前記と同じ。）
１０．８又は９の硬化物を備える電子デバイス。
１１．８又は９の硬化物を備える有機ＥＬ素子。 That is, the present invention provides the following curable composition, its cured product, and electronic device.
1. A curable composition comprising (A) a phenyl sulfide derivative represented by the following formula (1) and (B) a fluorene derivative represented by the following formula (2).

(Wherein, R ^P1 and R ^P2 are each independently a hydrogen atom or a polymerizable unsaturated bond-containing group;
R ^P3 and R ^P4 are each independently a polymerizable unsaturated bond-containing group;
R ¹ to R ⁶ each 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 the number of carbon atoms optionally substituted by Z ¹ an alkyl group of 1 to 20, an aryl group of 6 to 20 carbon atoms optionally substituted by Z ² , a heteroaryl group of 2 to 20 carbon atoms optionally substituted by 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 , and when a to f are integers of 2 or more, each R ¹ to each R ⁶ may be the same or different;
Y ¹ to Y ¹² are each independently an alkyl group having 1 to 20 carbon atoms optionally substituted by Z ¹ , an aryl group having 6 to 20 carbon atoms optionally substituted by Z ² , or Z ² A heteroaryl group having 2 to 20 carbon atoms which may be substituted with;
L is a single bond or a divalent linking group;
L ¹ and L ² are each independently a phenylene group optionally substituted with Z ² or a naphthalene diyl group optionally substituted with Z ² ;
L ³ and L ⁴ are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms;
Z ¹ 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 optionally substituted by Z ³ ; an aryl group having 6 to 20 carbon atoms optionally substituted by Z ³ or a heteroaryl group having 2 to 20 carbon atoms optionally 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 thiol group, a sulfonic acid group, a carboxy group, an alkyl group having 1 to 20 carbon atoms optionally substituted by Z ³ ; or an alkoxy group having 1 to 20 carbon atoms optionally substituted by Z ³ ;
Z ³ 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 each independently an integer of 0 to 4;
p is an integer from 0 to 10;
q and r are each independently an integer of 0-10. )
2. The curable composition of 1, wherein the component (A) is a compound represented by the following formula (1′).

3. The curable composition of 1 or 2, wherein component (B) is a compound represented by the following formula (2′).

(In the formula, R ¹¹ and R ¹² are hydrogen atoms or methyl groups.)
4. 3. The curable composition according to any one of 1 to 3, further comprising (C) a radical polymerization initiator.
5. The curable composition of any one of 1 to 4 that does not contain solvent.
6. The curable composition according to any one of 1 to 5, which is a sealing material for electronic devices.
7. The curable composition of 6, which is a sealing material for organic EL elements.
8. A cured product obtained from the curable composition according to any one of 1 to 7.
9. A cured product containing a copolymer obtained from (A) a phenyl sulfide derivative represented by the following formula (1) and (B) a fluorene derivative represented by the following formula (2).

(Wherein, 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 above.)
10. An electronic device comprising the cured product of 8 or 9.
11. An organic EL device comprising the cured product of 8 or 9.

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

[Curable composition]
The curable composition of the present invention contains (A) a phenyl sulfide derivative represented by the following formula (1) and (B) a fluorene derivative represented by the following formula (2).

In formula (1), R ^P1 and R ^P2 are each independently a hydrogen atom or a polymerizable unsaturated bond-containing group. In formula (2), R ^P3 and R ^P4 are each independently a polymerizable unsaturated bond-containing group.

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, R ^P1 and R ^P2 are preferably vinyl groups or allyl groups, and R ^P3 and R ^P4 are preferably (meth)acryloyl groups.

In formulas (1) and (2), R ¹ to R ⁶ each independently represent a halogen atom, nitro group, cyano group, amino group, aldehyde group, hydroxy group, thiol group, sulfonic acid group, carboxy group, Z an alkyl group having 1 to 20 carbon atoms which may be substituted with ¹ ; an aryl group having 6 to ^{20 carbon atoms which may be substituted with Z 2 ;} heteroaryl groups, —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 R ⁶ may be the same or different.

Y ¹ to Y ¹² are each independently an alkyl group having 1 to 20 carbon atoms optionally substituted by Z ¹ , an aryl group having 6 to 20 carbon atoms optionally substituted by Z ² , or Z ² A heteroaryl group having 2 to 20 carbon atoms which may be substituted with .

In Formula (1), L is a single bond or a divalent linking group.

In formula (2), L ¹ and L ² are each independently a phenylene group optionally substituted with Z ² or a naphthalenediyl group optionally substituted with Z ² .

In formula (2), L ³ and L ⁴ are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms.

Z ¹ 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 optionally substituted by Z ³ ; It is an aryl group having 6 to 20 carbon atoms which may be substituted with Z ³ or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z ³ .

Z ² 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 alkyl group having 1 to 20 carbon atoms optionally substituted by Z ³ ; or an alkoxy group having 1 to 20 carbon atoms which may be substituted with Z ³ .

^Z3 is a halogen atom, nitro group, cyano group, amino group, aldehyde group, hydroxy group, thiol group, sulfonic acid group, or carboxy group.

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

The alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl. straight groups having 1 to 20 carbon atoms such as group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group; 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 , a bicyclooctyl group, a bicyclononyl group, a bicyclodecyl group, and other cyclic alkyl groups having 3 to 20 carbon atoms.

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

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, 3- isoxazolyl group, 4-isoxazolyl group, 5-isoxazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 2-imidazolyl group, 4- imidazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group and the like.

Among these, R ¹ to R ⁶ are a halogen atom, an alkyl group having 1 to 10 carbon atoms optionally substituted by Z ¹ , or an aryl group having 6 to 14 carbon atoms optionally substituted by Z ² is preferred, and an alkyl group having 1 to 10 carbon atoms is more preferred.

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 linked. and the like. 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, 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.

Among these, L is preferably a single bond, a divalent hydrocarbon group having 1 to 2 carbon atoms, a thioether bond, a carbonate bond or an amide bond, more preferably a single bond.

The phenylene groups optionally substituted by Z ² represented by L ¹ and L ² include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 2-methylbenzene- 1,4-diyl group, 2-aminobenzene-1,4-diyl group, 2,4-dibromobenzene-1,3-diyl group, 2,6-dibromobenzene-1,4-diyl group and the like. . The naphthalene diyl group optionally substituted by Z ² includes 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 and naphthalene-2,6-diyl group.

Among these, L ¹ and L ² are 1,4-phenylene group, 1,3-phenylene group, 2-methylbenzene-1,4-diyl group, naphthalene-1,4-diyl group, naphthalene-1 ,5-diyl group is preferred, and 1,4-phenylene group and naphthalene-1,5-diyl group are more preferred.

The divalent hydrocarbon group having 1 to 6 carbon atoms represented by L ³ and L ⁴ may be linear, branched or cyclic. 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 -diyl group, alkanediyl group such as cyclohexane-1,4-diyl group, and the like.

Among these, L ³ and L ⁴ are preferably a methylene group, an ethane-1,2-diyl group and a propane-1,2-diyl group, more preferably an ethane-1,2-diyl group.

In formulas (1) and (2), a to f are each independently an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1, and most preferably 0.

In formula (1), p is an integer of 0 to 10, preferably 0 to 4, more preferably 0 or 1, and most preferably 0. In formula (2), q and r are each independently an integer of 0 to 10, preferably 0 to 4, more preferably 0 to 2, and most preferably 0 or 1.

As the component (A), a compound represented by the following formula (1′) 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 (B), a compound represented by the following formula (2′) is preferable from the viewpoint of film curability, refractive index and water vapor barrier properties.

(In the formula, R ¹¹ and R ¹² are each independently a hydrogen atom or a methyl group.)

The content of component (A) in the composition of the present invention is preferably 50 to 99.9% by mass, more preferably 60 to 95% by mass, and even more preferably 65 to 85% by mass. The content of component (B) is preferably 0.1 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 15 to 35% by mass.

The (A) component and the (B) component may each be used singly or in combination of two or more. In addition, a commercial item can be used for the (A) component and the (B) component.

The composition of the present invention may further contain (C) a radical polymerization initiator. The radical polymerization initiator may be a photo-radical polymerization initiator or a thermal radical polymerization initiator, but is preferably one that does not decompose (generate radicals) and generate gas at the same time. The radical polymerization initiator enables photo-curing treatment or low-temperature curing treatment.

Examples of photoradical polymerization initiators include benzophenone derivatives, imidazole derivatives, bisimidazole derivatives, N-arylglycine derivatives, organic azide compounds, titanocene compounds, aluminate complexes, organic peroxides, N-alkoxypyridinium salts, thioxanthone derivatives, and the like. is mentioned. More specifically, benzophenone, 1,3-di(tert-butyldioxycarbonyl)benzophenone, 3,3′,4,4′-tetrakis(tert-butyldioxycarbonyl)benzophenone, 3-phenyl-5- isoxazolone, 2-mercaptobenzimidazole, bis(2,4,5-triphenyl)imidazole, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-benzyl- 2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, bis(η ⁵ -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole- 1-yl)phenyl)titanium and the like, but are not limited to these.

Commercially available products can also be used as the radical photopolymerization initiator, and examples thereof include IRGACURE (registered trademark) 651, 184, 369, 784 manufactured by BASF. In addition, commercially available products other than the above can also be used. Lambson Speedcure (registered trademark) MBB, PBZ, ITX, CTX, EDB; Lamberti Esacure (registered trademark) ONE, KIP150, KTO46; Nippon Kayaku Co., Ltd. KAYACURE (registered trademark) DETX -S, CTX, BMS, DMBI and the like.

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-butyl 2-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'-azobisisobutyrate, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(1-cyclohexanecarbonitrile), 2-(carbamoylazo)isobutyro Nitriles, 2,2'-azobis(2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis(2-methylpropane) and other azo system compounds; persulfates such as ammonium persulfate, sodium persulfate, potassium persulfate, etc., but not limited thereto. Moreover, a commercial item can be used as said thermal radical polymerization initiator.

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

The content of the radical polymerization initiator is 0 to 10% by mass in the composition of the present invention. .

The composition of the present invention may be a solvent-type composition containing a solvent or may be a solvent-free composition containing no solvent. A mold is preferred. When a solvent is used, the solvent should be compatible with other components and should not remain after curing, or even if it does remain, it should not degrade the organic film used in the electronic device. If there is, it is not particularly limited.

The viscosity of the composition of the present invention is preferably from 0.1 to 1,000 mPa·s, more preferably from 1 to 200 mPa·s at 25° C. from the viewpoints of applicability and handling. In addition, in this invention, a viscosity is a measured value by an E-type viscometer.

The composition of the present invention further optionally contains polymerizable compounds other than components (A) and (B) (e.g., epoxy compounds, acrylic compounds, olefin compounds, etc.), polymerization inhibitors, and antioxidants. , Light stabilizers, plasticizers, leveling agents, antifoaming agents, pigments, ultraviolet absorbers, ion adsorbents, pigments, phosphors, release agents, organic fillers such as cellulose, etc. may be contained within a 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. Examples of the electronic device include, but are not limited to, an organic EL element, an organic thin film solar cell, a light emitting diode element, and the like. Among these, the composition of the present invention is suitable as a sealing material for organic EL elements, and particularly suitable as a sealing material for top emission type organic EL elements.

The method for sealing the electronic device is not particularly limited, and conventionally known methods 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, the coating method includes a spin coating method, a cast coating method, a blade coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, a spray coating method, an inkjet method, a printing method (letterpress, intaglio, lithography). , screen printing, etc.).

Alternatively, the composition of the present invention may be formed into a film, and the resulting film may be placed on a substrate or element for sealing.

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

[1] Preparation of curable composition [Example 1-1] Preparation of curable composition A 5.0 g of MPV, 1.0 g of A-BPEF and 0.06 g of Irg. TPO are uniformly mixed in a mix rotor at room temperature. and a curable composition A was prepared.

[Example 1-2] Preparation of curable composition B A curable composition was prepared in the same manner as in Example 1-1, except that the amounts of MVP and A-BPEF were changed to 4.5 g and 1.5 g, respectively. B was prepared.

[Example 1-3] Preparation of curable composition C A curable composition was prepared in the same manner as in Example 1-1, except that the amounts of MVP and A-BPEF were changed to 4.3 g and 1.7 g, respectively. C was prepared.

[Example 1-4] Preparation of curable composition D A curable composition was prepared in the same manner as in Example 1-1, except that the amounts of MVP and A-BPEF were changed to 4.0 g and 2.0 g, respectively. D was prepared.

[Comparative Example 1-1] Preparation of Composition E 6.0 g of MPV and 0.06 g of Irg.TPO were uniformly mixed in a mix rotor at room temperature to prepare composition E.

[Comparative Example 1-2]
An attempt was made to prepare a composition by stirring 6.0 g of A-BPEF and 0.06 g of Irg.TPO in a mix rotor at room temperature, but a uniform composition could not be prepared.

[2] Production of Cured Film and Evaluation of Optical Properties [Example 2-1] Production of Cured Film A A silicon rubber spacer having a thickness of 100 μm was sandwiched between a quartz substrate and a release glass substrate. , curable composition A was cast. This was irradiated with UV light from the quartz substrate side (Fusion UV Systems CV-110QC-G H bulb) so that the cumulative irradiation dose at the UV-A wavelength was 3,000 mJ/cm ² . This was further heated in a constant temperature blower oven at 100° C. for 30 minutes, and after cooling, the release glass substrate was removed to form a cured film A having a thickness of 100 μm on the quartz substrate.

[Example 2-2] Preparation of cured film B A 100 μm-thick film was formed on a quartz substrate in the same manner as in Example 2-1, except that the curable composition B was used instead of the curable composition A. A cured film B was formed.

[Example 2-3] Preparation of cured film C A 100 µm-thick film was formed on a quartz substrate in the same manner as in Example 2-1, except that the curable composition C was used instead of the curable composition A. A cured film C was formed.

[Example 2-4] Production of cured film D A film having a thickness of 100 µm was formed on a quartz substrate in the same manner as in Example 2-1, except that curable composition D was used instead of curable composition A. A cured film D was formed.

[Comparative Example 2-1]
An attempt was made to form a cured film in the same manner as in Example 2-1, except that composition E was used instead of curable composition A, but no cured film could be formed.

<Measurement of transmittance and refractive index>
The transmittance of the cured films A to D was measured with an ultraviolet-visible spectrophotometer (UV-2600 manufactured by Shimadzu Corporation), and the average transmittance of 400 to 800 nm was calculated. A prism coupler (Model 2010 manufactured by Metricon) was used to measure the refractive index (25° C.) of light with a wavelength of 589 nm. Table 1 shows the results.

Cured products A to D were all transparent in the visible light region and had a high refractive index.

[3] Preparation of cured film and evaluation of moisture permeability resistance [Example 2-1] Preparation of cured film A' Acetate film was prepared in the same manner as in Example 2-1, except that the quartz substrate was changed to an acetate film substrate. A cured film having a thickness of 100 μm was formed thereon, and the acetate film was peeled off to obtain a cured film A′.

[Example 2-2] Preparation of cured film B' Cured film B' was obtained in the same manner as in Example 2-1 except that the curable composition B was used instead of the curable composition A. .

[Example 2-3] Preparation of cured film C' Cured film C' was obtained in the same manner as in Example 2-1 except that the curable composition C was used instead of the curable composition A. .

<Measurement of water vapor transmission rate>
The cured films A' to C' were each attached to a screw-fastened moisture permeable cup (permeable part φ30 mm), and with reference to JIS Z 0208, the water vapor transmission rate (WVTR) was measured under the conditions of 40 ° C. and 90% RH. was measured. As the screw tightening type moisture permeable cup, it is possible to use a commercially available one, for example, one commercially available from Imoto Seisakusho Co., Ltd. can be used. Prepare a dried screw-tightened moisture-permeable cup, put the cured film and rubber packing on top of each other without using a sealing filler material, place the cured film and the packing in the cup so that the cured film and the cup are in close contact with each other. / A specimen was prepared by sandwiching between metal plates and sealing by tightening with a screw. The weight measurement portion after preparation of the specimen was measured according to JIS Z 0208. Table 2 shows the results.

It was found that all of the cured films have low water vapor transmission rates and are applicable as sealing materials. That is, the curable composition of the present invention can be applied to electronic devices and the like as a highly transparent and highly refractive sealing material.

Claims (10)

(A) 50 to 99.9% by mass of a phenyl sulfide derivative represented by the following formula (1), and (B) 0.1 to 50% by mass of an electron containing a fluorene derivative represented by the following formula (2) A curable composition for a device sealing material .

(Wherein, R ^P1 and R ^P2 are each independently a vinyl group, an allyl group or a (meth)acryloyl group;
R ^P3 and R ^P4 are each independently a vinyl group, an allyl group or a (meth)acryloyl group;
R ¹ to R ⁶ each independently represent a halogen atom or an alkyl group having 1 to 10 carbon atoms, and when a to f are integers of 2 or more, each R ¹ to R ⁶ are the same. may be different;
L is a single bond or a divalent linking group;
L ¹ and L ² are each independently 1,4-phenylene group, 1,3-phenylene group, 2-methylbenzene-1,4-diyl group, naphthalene-1,4-diyl group or naphthalene-1, is a 5-diyl group ;
L ³ and L ⁴ are each independently a methylene group having 1 to 6 carbon atoms, an ethane-1,2-diyl group or a propane-1,2-diyl group ;
a to f are each independently an integer of 0 to 4;
p is 0 ;
q and r are 0 or 1 ; ) 2. The curable composition according to claim 1, wherein a to f are 0. 3. The curable composition according to claim 1, wherein component (A) is a compound represented by the following formula (1').

4. The curable composition according to any one of claims 1 to 3, wherein component (B) is a compound represented by the following formula (2').

(In the formula, R ¹¹ and R ¹² are hydrogen atoms or methyl groups.) 5. The curable composition according to any one of claims 1 to 4 , further comprising (C) a radical polymerization initiator. The curable composition according to any one of claims 1 to 5 , which does not contain a solvent. The curable composition according to any one of claims 1 to 6, which is a sealing material for organic electroluminescence devices. A cured product obtained from the curable composition according to any one of claims 1 to 7. An electronic device comprising the cured product according to claim 8 . An organic electroluminescence device comprising the cured product according to claim 8 .