JP6114107B2 - Photocurable resin composition for liquid crystal sealant - Google Patents

Description

  The present invention relates to a compound obtained by reacting dialkylaminobenzoic acid and / or hydroxy-9H-thioxanthen-9-one with a polyglycidyl ether compound of an alkane polyol which may be interrupted by an ether bond, The present invention relates to a photopolymerization initiator and a photocurable resin composition using the compound.

  In recent years, many liquid crystal display panels having features of light weight, high definition, and low power consumption have been produced by a liquid crystal dropping method as display panels for various devices such as large liquid crystal televisions and mobile phones. The liquid crystal dropping method is a method in which a light and heat combined curable liquid crystal sealing agent is applied onto a substrate on which an electrode pattern and an alignment film are applied, and the substrate on which the liquid crystal sealing agent is applied, or a pair of substrates. After the liquid crystal is dropped on the substrate, the opposite substrate is bonded, and the substrate is quickly fixed by photo-curing by ultraviolet irradiation or the like, so that the substrate is quickly fixed, that is, the cell gap is formed. This is a method for manufacturing a liquid crystal display panel by completely curing a sealant by heat curing. In such a liquid crystal dropping method, photocuring and thermosetting reactions proceed in a state where the uncured sealant and the liquid crystal are in contact with each other. Therefore, the liquid crystal sealant is used during the curing process, that is, before and after photocuring. Reduction of the contamination to the liquid crystal derived from the liquid crystal sealant before and after curing is required. Similarly, a sealing agent such as an airtight sealant for electronic components is also required to reduce contamination of the electronic component derived from the sealing agent during the curing process.

  In addition, due to the recent improvement in performance of liquid crystal panels, characteristics may change due to the influence of ultraviolet light in the alignment direction, type of alignment film, and liquid crystal material, and a sealant that can be cured in the visible light region with low energy Is required.

  Under such circumstances, as a compound suitable for a photoinitiator used in a photocurable resin composition used in the field of electronic materials such as a liquid crystal sealant, Patent Document 1 discloses an organic acid compound and / or A compound obtained by reacting a hydroxy compound with a compound containing at least two epoxy groups in the molecule, wherein the compound is a compound in which the organic acid compound is dimethylaminobenzoic acid, or the hydroxy compound A compound in which is a hydroxythioxanthone has been proposed. Here, in Examples of Patent Document 1, diethylene glycol diglycidyl ether and bisphenol A diglycidyl ether are disclosed as compounds containing at least two epoxy groups in the molecule.

International Publication No. 2012/0777720 Pamphlet

  However, the present inventors have found that there is room for improvement in terms of further reducing liquid crystal contamination in a compound suitable for a photoinitiator of the prior art.

  Therefore, the subject of this invention is providing the compound which can be used for a photoinitiator with a liquid-crystal contamination property lower than the photoinitiator of a prior art suitable for sealing agents, such as an electronic component.

  The present inventors have obtained by reacting a polyglycidyl ether compound of an alkane polyol, which may be interrupted with a specific ether bond, with a dialkylaminobenzoic acid and / or hydroxy-9H-thioxanthen-9-one. And the present invention has been found to solve the above-mentioned problems, leading to the present invention.

〔式中、
Ｘ^１は、炭素原子数１〜２０のアルキレン基、
−Ｙ^１−（Ｏ−Ｙ^１）_ｍ１−
（式中、
Ｙ^１は、炭素原子数１〜８のアルキレン基であり、
ｍ１は、１〜５０であるが、
但し、Ｙ^１が直鎖である炭素原子数２のアルキレン基であり、ｍ１が１である場合を除く）
で示される基、
−ＣＨ_２−ＣＲ^ａ１Ｒ^ａ２−ＣＨ_２−
（式中、
Ｒ^ａ１及びＲ^ａ２は、それぞれ独立して、水素、炭素原子数１〜４のアルキル基、式（２ａ）の基又は式（２ｂ）の基：

であるが、Ｒ^ａ１及びＲ^ａ２の少なくとも一つは、式（２ａ）の基又は式（２ｂ）の基である）
で示される基、又は
−ＣＨ_２−ＣＲ^ａ３Ｒ^ａ４−ＣＨ_２−Ｏ−ＣＨ_２−ＣＲ^ａ５Ｒ^ａ６−ＣＨ_２−
（式中、Ｒ^ａ３、Ｒ^ａ４、Ｒ^ａ５及びＲ^ａ６は、それぞれ独立して、水素、炭素原子数１〜４のアルキル基、式（２ａ）の基又は式（２ｂ）の基であるが、Ｒ^ａ３、Ｒ^ａ４、Ｒ^ａ５及びＲ^ａ６の少なくとも一つは、式（２ａ）の基又は式（２ｂ）の基である）
で示される基であり、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、それぞれ独立して、９−オキソ−９Ｈ−チオキサンテン−イル基、ジアルキルアミノベンゾイル基、水素、アルキル基、アリール基、ヘテロアリール基、アラルキル基、アシル基、シリル基、アセタール基又は−ＣＯ−ＮＨ−Ｚ^１（式中、Ｚ^１は、アルキル基、アリール基又はヘテロアリール基である）であるが、
但し、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８のうちの少なくとも１つは、９−オキソ−９Ｈ−チオキサンテン−イル基又はジアルキルアミノベンゾイル基である〕で示される化合物。
［２］Ｒ^１及びＲ^３が、同一であって、９−オキソ−９Ｈ−チオキサンテン−イル基又はジアルキルアミノベンゾイル基であり、Ｒ^２及びＲ^４が、それぞれ独立して、９−オキソ−９Ｈ−チオキサンテン−イル基、ジアルキルアミノベンゾイル基、水素、アルキル基、アリール基、ヘテロアリール基、アラルキル基、アシル基、シリル基、アセタール基又は−ＣＯ−ＮＨ−Ｚ^１（式中、Ｚ^１は、アルキル基、アリール基又はヘテロアリール基である）であり、Ｘ^１が、−Ｙ^１−（Ｏ−Ｙ^１）_ｍ１−（式中、Ｙ^１及びｍ１は、［１］で定義されたとおりである）で示される基である、［１］記載の化合物。
［３］式（１Ａ−１）：

（式中、ｎ１は、２〜５０である）
で示される化合物である、［１］又は［２］記載の化合物。
［４］式（１Ｂ−１）：

（式中、ｎ２は、２〜５０である）
で示される化合物である、［１］又は［２］記載の化合物。
［５］Ｘ^１が、−ＣＨ_２−ＣＲ^ａ１Ｒ^ａ２−ＣＨ_２−（式中、Ｒ^ａ１及びＲ^ａ２は、［１］で定義されたとおりである）で示される基であり、Ｒ^１、Ｒ^３、Ｒ^５及びＲ^７が、同一であって、９−オキソ−９Ｈ−チオキサンテン−イル基又はジアルキルアミノベンゾイル基であり、Ｒ^２、Ｒ^４、Ｒ^６及びＲ^８が、それぞれ独立して、９−オキソ−９Ｈ−チオキサンテン−イル基、ジアルキルアミノベンゾイル基、水素、アルキル基、アリール基、ヘテロアリール基、アラルキル基、アシル基、シリル基、アセタール基又は−ＣＯ−ＮＨ−Ｚ^１（式中、Ｚ^１は、アルキル基、アリール基又はヘテロアリール基である）である、［１］記載の化合物。
［６］［１］記載の式（１）で示される化合物の製造方法であって、工程（ａ）〜（ｄ）：
（ａ）ジアルキルアミノ安息香酸及び／又はヒドロキシ−９Ｈ−チオキサンテン−９−オンと、式（３）：

〔式中、
Ｘ^２は、炭素原子数１〜２０のアルキレン基、
−Ｙ^１−（Ｏ−Ｙ^１）_ｍ１−
（式中、Ｙ^１及びｍ１は、［１］で定義されたとおりである）
で示される基、
−ＣＨ_２−ＣＲ^ｂ１Ｒ^ｂ２−ＣＨ_２−
（式中、Ｒ^ｂ１及びＲ^ｂ２は、それぞれ独立して、水素、炭素原子数１〜４のアルキル基、グリシジルオキシ基又はグリシジルオキシメチル基であるが、Ｒ^ｂ１及びＲ^ｂ２の少なくとも１つは、グリシジルオキシ基又はグリシジルオキシメチル基である）
で示される基、又は
−ＣＨ_２−ＣＲ^ｂ３Ｒ^ｂ４−ＣＨ_２−Ｏ−ＣＨ_２−ＣＲ^ｂ５Ｒ^ｂ６−ＣＨ_２−
（式中、Ｒ^ｂ３、Ｒ^ｂ４、Ｒ^ｂ５及びＲ^ｂ６は、それぞれ独立して、水素、炭素原子数１〜４のアルキル基、グリシジルオキシ基又はグリシジルオキシメチル基であるが、Ｒ^ｂ３、Ｒ^ｂ４、Ｒ^ｂ５及びＲ^ｂ６の少なくとも１つは、グリシジルオキシ基又はグリシジルオキシメチル基である）
で示される基である〕
で示される、ポリグリシジルエーテル化合物とを反応させて、式（３）で示される化合物の少なくとも１つのグリシジル基を、式（４）：

（式中、Ｒ^９及びＲ^１０の一方は、９−オキソ−９Ｈ−チオキサンテン−イル基又はジアルキルアミノベンゾイル基であり、他方は水素である）
で示される基とする工程、
（ｂ）場合により、さらに、酸又はアルカリと反応させて、式（３）で示される化合物の少なくとも１つのグリシジル基を、式（５）：

で示される基とする工程、
（ｃ）場合により、さらに、ジアルキルアミノ安息香酸、ヒドロキシ−９Ｈ−チオキサンテン−９−オン、Ｒ^１１−ＯＨ（式中、Ｒ^１１は、アルキル基、アリール基、ヘテロアリール基又はアラルキル基である）で示される化合物及び／又はＲ^１２−ＣＯＯＨ（式中、Ｒ^１２は、アルキル基、アリール基、ヘテロアリール基又はアラルキル基である）で示される化合物と反応させることにより、式（３）で示される化合物の少なくとも１つのグリシジル基を、式（６）：

（式中、Ｒ^１３及びＲ^１４の一方は、９−オキソ−９Ｈ−チオキサンテン−イル基、ジアルキルアミノベンゾイル基、Ｒ^１１又はＲ^１２−ＣＯ−であり、他方は水素である）
で示される基とする工程、
により、式（１ａ）：

〔式中、
Ｘ^３は、炭素原子数１〜２０のアルキレン基、
−Ｙ^１−（Ｏ−Ｙ^１）_ｍ１−
（式中、Ｙ^１及びｍ１は、前記で定義されたとおりである）
で示される基、
−ＣＨ_２−ＣＲ^ｃ１Ｒ^ｃ２−ＣＨ_２−
（式中、Ｒ^ｃ１及びＲ^ｃ２は、それぞれ独立して、水素、炭素原子数１〜４のアルキル基、式（７ａ）の基、式（７ｂ）の基、式（７ｃ）の基又は式（７ｄ）の基：

であるが、Ｒ^ｃ１及びＲ^ｃ２の少なくとも１つは、式（７ａ）の基、式（７ｂ）の基、式（７ｃ）の基又は式（７ｄ）の基である）
で示される基、又は
−ＣＨ_２−ＣＲ^ｃ３Ｒ^ｃ４−ＣＨ_２−Ｏ−ＣＨ_２−ＣＲ^ｃ５Ｒ^ｃ６−ＣＨ_２−
（式中、Ｒ^ｃ３、Ｒ^ｃ４、Ｒ^ｃ５及びＲ^ｃ６は、それぞれ独立して、水素、炭素原子数１〜４のアルキル基、式（７ａ）の基、式（７ｂ）の基、式（７ｃ）の基又は式（７ｄ）の基であるが、Ｒ^ｃ３、Ｒ^ｃ４、Ｒ^ｃ５及びＲ^ｃ６の少なくとも１つは、式（７ａ）の基、式（７ｂ）の基、式（７ｃ）の基又は式（７ｄ）の基である）
で示される基であり、
Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９及びＲ^２０は、それぞれ独立して、９−オキソ−９Ｈ−チオキサンテン−イル基、ジアルキルアミノベンゾイル基、水素、Ｒ^１１又はＲ^１２−ＣＯ−であるが、但し、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９及びＲ^２０のうちの少なくとも一つは、９−オキソ−９Ｈ−チオキサンテン−イル基又はジアルキルアミノベンゾイル基である〕
で示される化合物を得る工程、及び
（ｄ）場合により、式（７ａ）の基又は式（７ｃ）の基におけるＯＨ基の少なくとも１つの水素、或いは、水素であるＲ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９又はＲ^２０を、９−オキソ−９Ｈ−チオキサンテン−イル基、ジアルキルアミノベンゾイル基、アルキル基、アリール基、ヘテロアリール基、アラルキル基、アシル基、シリル基、アセタール基又は−ＣＯ−ＮＨ−Ｚ^１（式中、Ｚ^１は、［１］で定義されたとおりである）に変換する工程
を含む、製造方法。
［７］光開始性化合物と可視光増感性化合物とからなる光重合開始剤であって、光開始性化合物は、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８の少なくとも１つがジアルキルアミノベンゾイル基である［１］記載の式（１）で示される化合物であり、可視光増感性化合物は、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８の少なくとも１つが９−オキソ−９Ｈ−チオキサンテン−イル基である［１］記載の式（１）で示される化合物である、光重合開始剤。
［８］光重合性モノマー及び／又は光重合性オリゴマーと［７］記載の光重合開始剤とを含む、光硬化性樹脂組成物。 That is, the present invention has the following configuration.
[1] General formula (1):

[Where,
X ¹ is an alkylene group having 1 to 20 carbon atoms,
-Y ^1- (O-Y ¹ ) _m1-
(Where
Y ¹ is an alkylene group having 1 to 8 carbon atoms,
m1 is 1 to 50,
However, Y ¹ is an alkylene group having 2 carbon atoms is a straight chain, except where m1 is 1)
A group represented by
—CH ₂ —CR ^a1 R ^a2 —CH ₂ —
(Where
R ^a1 and R ^a2 each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms, a group of formula (2a) or a group of formula (2b):

Wherein at least one of R ^a1 and R ^a2 is a group of formula (2a) or a group of formula (2b))
A group represented by or _{^{-CH 2 -CR a3 R a4 -CH 2}} -O-CH 2 -CR a5 R a6 -CH 2 -
Wherein R ^a3 , R ^a4 , R ^a5 and R ^a6 are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, a group of formula (2a) or a group of formula (2b). , R ^a3 , R ^a4 , R ^a5 and R ^a6 are a group of the formula (2a) or a group of the formula (2b))
A group represented by
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a 9-oxo-9H-thioxanthen-yl group, dialkylaminobenzoyl group, hydrogen, alkyl A group, an aryl group, a heteroaryl group, an aralkyl group, an acyl group, a silyl group, an acetal group or —CO—NH—Z ¹ (wherein Z ¹ is an alkyl group, an aryl group or a heteroaryl group). But,
Provided that at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is a 9-oxo-9H-thioxanthen-yl group or a dialkylaminobenzoyl group. A compound represented by
[2] R ¹ and R ³ are the same and are a 9-oxo-9H-thioxanthen-yl group or a dialkylaminobenzoyl group, and R ² and R ⁴ are each independently 9-oxo- 9H-thioxanthen-yl group, dialkylaminobenzoyl group, hydrogen, alkyl group, aryl group, heteroaryl group, aralkyl group, acyl group, silyl group, acetal group or —CO—NH—Z ¹ (wherein Z ¹ Is an alkyl group, an aryl group or a heteroaryl group, and X ¹ is —Y ¹ — (O—Y ¹ ) _m1 — (wherein Y ¹ and m1 are defined in [1]. The compound according to [1], which is a group represented by:
[3] Formula (1A-1):

(Where n1 is 2 to 50)
The compound of [1] or [2] which is a compound shown by these.
[4] Formula (1B-1):

(Wherein n2 is 2 to 50)
The compound of [1] or [2] which is a compound shown by these.
[5] X ¹ is a group represented by —CH ₂ —CR ^a1 R ^a2 —CH ₂ — (wherein R ^a1 and R ^a2 are as defined in [1]), and R ¹ , R ³ , R ⁵ and R ⁷ are the same and are a 9-oxo-9H-thioxanthen-yl group or a dialkylaminobenzoyl group, and R ² , R ⁴ , R ⁶ and R ⁸ are each independently 9-oxo-9H-thioxanthen-yl group, dialkylaminobenzoyl group, hydrogen, alkyl group, aryl group, heteroaryl group, aralkyl group, acyl group, silyl group, acetal group or -CO-NH-Z ^1. The compound according to [1], wherein Z ¹ is an alkyl group, an aryl group or a heteroaryl group.
[6] A method for producing a compound represented by the formula (1) according to [1], wherein steps (a) to (d):
(A) dialkylaminobenzoic acid and / or hydroxy-9H-thioxanthen-9-one and the formula (3):

[Where,
X ² is an alkylene group having 1 to 20 carbon atoms,
-Y ^1- (O-Y ¹ ) _m1-
(Wherein Y ¹ and m1 are as defined in [1])
A group represented by
—CH ₂ —CR ^b1 R ^b2 —CH ₂ —
(Wherein R ^b1 and R ^b2 are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, a glycidyloxy group, or a glycidyloxymethyl group, but at least one of R ^b1 and R ^b2 is , Glycidyloxy group or glycidyloxymethyl group)
A group represented by or _{^{-CH 2 -CR b3 R b4 -CH 2}} -O-CH 2 -CR b5 R b6 -CH 2 -
^{(Wherein, R b3, R b4, R} b5 and ^{R b6} are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, is a glycidyloxy group or glycidyloxy ^{methyl, R} b3, R ^At least one of ^b4 , R ^b5 and R ^b6 is a glycidyloxy group or a glycidyloxymethyl group)
Is a group represented by
And at least one glycidyl group of the compound represented by the formula (3) is reacted with a polyglycidyl ether compound represented by the formula (4):

(In the formula, one of R ⁹ and R ¹⁰ is a 9-oxo-9H-thioxanthen-yl group or a dialkylaminobenzoyl group, and the other is hydrogen)
A process based on
(B) optionally further reacting with an acid or alkali to convert at least one glycidyl group of the compound of formula (3) to formula (5):

A process based on
Optionally (c), further, dialkylamino benzoic acid, hydroxy -9H- ^{thioxanthene-9-one,} R 11 -OH ^{(wherein, R 11} is an alkyl group, an aryl group, a heteroaryl group or an aralkyl group ) And / or R ¹² —COOH (wherein R ¹² is an alkyl group, an aryl group, a heteroaryl group, or an aralkyl group). At least one glycidyl group of the compound shown is represented by formula (6):

(Wherein one of R ¹³ and R ¹⁴ is a 9-oxo-9H-thioxanthen-yl group, a dialkylaminobenzoyl group, R ¹¹ or R ¹² —CO—, and the other is hydrogen)
A process based on
According to the formula (1a):

[Where,
X ³ is an alkylene group having 1 to 20 carbon atoms,
-Y ^1- (O-Y ¹ ) _m1-
Wherein Y ¹ and m1 are as defined above.
A group represented by
—CH ₂ —CR ^c1 R ^c2 —CH ₂ —
Wherein R ^c1 and R ^c2 are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, a group of formula (7a), a group of formula (7b), a group of formula (7c) or a formula Group (7d):

Wherein at least one of R ^c1 and R ^c2 is a group of formula (7a), a group of formula (7b), a group of formula (7c) or a group of formula (7d))
A group represented by or _{^{-CH 2 -CR c3 R c4 -CH 2}} -O-CH 2 -CR c5 R c6 -CH 2 -
(Wherein R ^c3 , R ^c4 , R ^c5 and R ^c6 each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms, a group of formula (7a), a group of formula (7b), a formula ( 7c) or a group of formula (7d), wherein at least one of R ^c3 , R ^c4 , R ^c5 and R ^c6 is a group of formula (7a), a group of formula (7b), a formula (7c) Or a group of formula (7d))
A group represented by
R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a 9-oxo-9H-thioxanthen-yl group, a dialkylaminobenzoyl group, hydrogen, R ¹¹ or R ¹² -CO. -Provided that at least one of R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ is a 9-oxo-9H-thioxanthenyl group or a dialkylaminobenzoyl group. ]
And (d) optionally, at least one hydrogen of the OH group in the group of formula (7a) or the group of formula (7c), or R ¹⁵ , R ¹⁶ , R ¹⁷ which is hydrogen. , R ¹⁸ , R ¹⁹ or R ²⁰ are substituted with 9-oxo-9H-thioxanthen-yl group, dialkylaminobenzoyl group, alkyl group, aryl group, heteroaryl group, aralkyl group, acyl group, silyl group, acetal group or A production method comprising a step of converting to —CO—NH—Z ¹ (wherein Z ¹ is as defined in [1]).
[7] A photopolymerization initiator comprising a photoinitiating compound and a visible light sensitizing compound, wherein the photoinitiating compound is R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ^7. And R ⁸ is a compound represented by the formula (1) described in [1], wherein at least one of them is a dialkylaminobenzoyl group, and the visible light sensitizing compound is R ¹ , R ² , R ³ , R ⁴ , R ^5. , R ⁶ , R ^7, and R ⁸ are 9-oxo-9H-thioxanthen-yl groups [1], which is a compound represented by the formula (1).
[8] A photocurable resin composition comprising a photopolymerizable monomer and / or photopolymerizable oligomer and the photopolymerization initiator according to [7].

  The present invention provides a compound that can be used in a photoinitiator having a lower liquid crystal contamination property than a conventional photopolymerization initiator suitable for a sealant for electronic parts and the like.

〔Compound〕
The compound of the present invention is represented by the formula (1).

  The alkylene group having 1 to 20 carbon atoms is linear or branched, and includes, for example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, an octamethylene group, a decamethylene group, a dodecamethylene group, and an icon. Linear alkylene groups such as a silmethylene group; and branched alkylene groups such as a 2-methylethylene group, a 2-methylpropylene group, a 2-methylhexylene group and a 1,1,2,2-tetramethylethylene group Groups.

  The alkylene group having 1 to 8 carbon atoms is linear or branched, for example, a linear alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group and an octamethylene group; And branched alkylene groups such as 2-methylethylene group, 2-methylpropylene group, 2-methylhexylene group and 1,1,2,2-tetramethylethylene group.

  The alkyl group is a linear or branched alkyl group having 1 to 8 carbon atoms, and is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, n -Hexyl group, n-heptyl group, n-octyl group, isooctyl group and the like.

The aryl group is a monocyclic or polycyclic aromatic group having 6 to 20 carbon atoms, and examples thereof include a phenyl group, a naphthalenyl group, an anthracenyl group, and a pyrenyl group. The aryl group may have a substituent such as an amino group, monoalkylamino group, dialkylamino group, cyano group, alkoxy group, alkyl group, acyl group, nitro group, alkoxycarbonyl group, and silyl group. Here, the alkoxy group is a linear or branched alkoxy group having 1 to 8 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a t-butoxy group.
The heteroaryl group is a monocyclic or polycyclic heterocyclic group having a total number of 5 to 20 atoms including at least one heteroatom selected from the group consisting of O, S and N in addition to the carbon atom. , Imidazolyl, xanthenyl, thioxanthenyl, thienyl, dibenzofuryl, chromenyl, isothiochromenyl, phenoxathiinyl, pyrrolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl Group, indolyl group, indazolyl group, prynyl group, quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group Group, acridinyl group, pe Mijiniru group, phenanthrolinyl group, phenazinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, and furazanyl and the like. The heteroaryl group may have a substituent. Examples of the substituent include the groups exemplified as the substituent for the aryl group. Note that the heteroaryl group does not include a 9-oxo-9H-thioxanthen-yl group described later.

  The aralkyl group is a group represented by an aryl group-alkyl group. Examples of the aralkyl group include a benzyl group and a phenylethyl group.

The acyl group is a group represented by Z ³ —C (═O) — (wherein Z ³ is an alkyl group, an aryl group, or a heteroaryl group). Examples of the acyl group include an acetyl group, a propionyl group, and a benzoyl group. The acyl group does not include a dialkylaminobenzoyl group described later.

A silyl group is a group represented by —Si (Z ⁴ ) ₃ (wherein Z ⁴ is each independently an alkyl group, an alkoxy group, an aryl group or a heteroaryl group). Examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, a monomethyldimethoxysilyl group, a diethylmonoethoxysilyl group, and a monomethyldiethoxysilyl group.

The acetal group is —C (Z ⁵ ) (Z ⁶ ) (OZ ⁷ ) (wherein Z ⁵ and Z ⁶ are each independently hydrogen, an alkyl group, an aryl group, or a heteroaryl group; Z ⁷ Is an alkyl group, an aryl group or a heteroaryl group). Examples of the acetal group include —CH ₂ OCH ₃ , —CH (CH ₃ ) OCH ₃ and —CH (CH ₃ ) OC ₂ H ₅ .

Examples of —CO—NH—Z ¹ (wherein Z ¹ is an alkyl group, an aryl group, or a heteroaryl group) include a phenylaminocarbonyl group, a methylaminocarbonyl group, and an ethylaminocarbonyl group.

（式中、Ｚ^２ａ及びＺ^２ｂは、それぞれ独立して、アルキル基である）で示される。Ｚ^２ａ及びＺ^２ｂにおけるアルキル基の炭素原子数は、同一であっても、異なっていてもよい。ジアルキルアミノベンゾイル基として、２−ジアルキルアミノベンゾイル基、３−ジアルキルアミノベンゾイル基、４−ジアルキルアミノベンゾイル基が挙げられる。ジアルキルアミノベンゾイル基として、ジメチルアミノベンゾイル基、ジエチルアミノベンゾイル基、ジプロピルアミノベンゾイル基、ジブチルアミノベンゾイル基、ジヘキシルアミノベンゾイル基、ジオクチルアミノベンゾイル基、メチルエチルアミノベンゾイル基、メチルプロピルアミノベンゾイル基、メチルブチルアミノベンゾイル基、メチルヘキシルアミノベンゾイル基、エチルプロピルアミノベンゾイル基、エチルブチルアミノベンゾイル基、エチルヘキシルアミノベンゾイル基、ブチルオクチルアミノベンゾイル基及びヘキシルオクチルアミノベンゾイル基等が挙げられ、光硬化性の点からジメチルアミノベンゾイル基が好ましく、４−ジメチルアミノベンゾイル基がより好ましい。 A dialkylaminobenzoyl group is a benzoyl group substituted with a dialkylamino group and has the formula (8a):

( ^Wherein Z ^2a and Z ^2b are each independently an alkyl group). The number of carbon atoms of the alkyl group in Z ^2a and Z ^2b may be the same or different. Examples of the dialkylaminobenzoyl group include a 2-dialkylaminobenzoyl group, a 3-dialkylaminobenzoyl group, and a 4-dialkylaminobenzoyl group. Dialkylaminobenzoyl group includes dimethylaminobenzoyl group, diethylaminobenzoyl group, dipropylaminobenzoyl group, dibutylaminobenzoyl group, dihexylaminobenzoyl group, dioctylaminobenzoyl group, methylethylaminobenzoyl group, methylpropylaminobenzoyl group, methylbutyl Examples include aminobenzoyl group, methylhexylaminobenzoyl group, ethylpropylaminobenzoyl group, ethylbutylaminobenzoyl group, ethylhexylaminobenzoyl group, butyloctylaminobenzoyl group, and hexyloctylaminobenzoyl group. An aminobenzoyl group is preferred, and a 4-dimethylaminobenzoyl group is more preferred.

で示される。９−オキソ−９Ｈ−チオキサンテン−イル基として、９−オキソ−９Ｈ−チオキサンテン−１−イル基、９−オキソ−９Ｈ−チオキサンテン−２−イル基、９−オキソ−９Ｈ−チオキサンテン−３−イル基、９−オキソ−９Ｈ−チオキサンテン−４−イル基が挙げられる。 The 9-oxo-9H-thioxanthen-yl group has the formula (8b):

Indicated by The 9-oxo-9H-thioxanthen-1-yl group, 9-oxo-9H-thioxanthen-2-yl group, 9-oxo-9H-thioxanthen-yl group, A 3-yl group and a 9-oxo-9H-thioxanthen-4-yl group can be mentioned.

When X ¹ is an alkylene group having 1 to 20 carbon atoms, the number of carbon atoms is preferably 2 to 20 and more preferably 2 to 10 from the viewpoint of reducing liquid crystal contamination. When the number of carbon atoms in the alkylene group exceeds 20, the aliphaticity increases, the NI point change increases, and the liquid crystal contamination becomes high.

When X ¹ is a group represented by —Y ¹ — (O—Y ¹ ) _m1 —, Y ¹ is preferably an alkylene group having 1 to 4 carbon atoms, —CH ₂ CH (CH ₃ ) — and -CH ₂ CH ₂ - is more preferable.

When X ¹ is a group represented by —Y ¹ — (O—Y ¹ ) _m1 —, a compound in which m1 is 2 or more is more preferable. A compound in which m1 corresponding to the number of alkylene oxide repeating units — (O—Y ¹ ) — is 2 or more has liquid crystal contamination with respect to a compound having the same alkylene oxide repeating unit and m1 is 1. Since it is low and has a low viscosity, it is excellent in handleability during production of the photocurable resin composition. From the viewpoint of further reducing liquid crystal contamination, m1 is preferably 2 or more, more preferably 2 to 42, and further preferably 4 to 42. From the viewpoint of handling properties, m1 is preferably 2 to 42, more preferably 4 to 24, and even more preferably 4 to 20. In particular, if m1 is 4 or more, the viscosity is further lowered, and the handling property at the time of producing the photocurable resin composition is further improved. In addition, when the number of added parts of the compound represented by the formula (1) of the present invention is the same, from the viewpoint of improving the curability by increasing the number of moles of the structure effective for photocuring by setting the molecular weight within a predetermined range. , M1 is preferably 2 to 42, more preferably 4 to 24.

  M1 is derived from the number of alkylene oxide repeating units of the compound represented by the formula (3) described later, which is a raw material of the compound represented by the formula (1). In addition, m1 can also be measured by GPC.

When X ¹ is a group represented by —CH ₂ —CR ^a1 R ^a2 —CH ₂ —, preferred combinations of R ^a1 and R ^a2 are as follows: R ^a1 is hydrogen and R ^a2 is represented by the formula (2a R ^a1 is an alkyl group having 1 to 4 carbon atoms (more preferably an ethyl group) and R ^a2 is a group of the formula (2b); or R ^a1 and R ^a2 are A group of the formula (2b);

When X ¹ is a group represented by —CH ₂ —CR ^a3 R ^a4 —CH ₂ —O—CH ₂ —CR ^a5 R ^a6 —CH ₂ —, R ^a3 , R ^a4 , R ^a5 and R ^a6 are preferred. The combination is the following: R ^a3 , R ^a4 , R ^a5 and R ^a6 are the same and are a group of formula (2b).

At least ^{one of} R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is a 9-oxo-9H-thioxanthen-yl group or a dialkylaminobenzoyl group. In the present invention, compounds in which R ¹ and R ³ , and R ¹ , R ³ , R ⁵ and R ⁷ are the same and are 9-oxo-9H-thioxanthen-yl groups or dialkylaminobenzoyl groups are more preferred. preferable.

In the present invention, X ¹ is preferably a group represented by —Y ¹ — (O—Y ¹ ) _m1 — from the viewpoint of reducing liquid crystal contamination. The group represented by —Y ¹ — (O—Y ¹ ) _m1 — is kept highly polar by an ether bond even when the number of repeats is increased, and the aliphaticity is not greatly increased compared to the case of an alkylene chain. Therefore, it is considered that the NI point change is small and the liquid crystal contamination is reduced.

Therefore, in the present invention, R ¹ and R ³ are the same and are a 9-oxo-9H-thioxanthen-yl group or a dialkylaminobenzoyl group, and R ² and R ⁴ are each independently 9 —Oxo-9H-thioxanthen-yl group, dialkylaminobenzoyl group, hydrogen, alkyl group, aryl group, heteroaryl group, aralkyl group, acyl group, silyl group, acetal group or —CO—NH—Z ¹ (wherein , Z ¹ is an alkyl group, an aryl group or a heteroaryl group), and X ¹ is —Y ¹ — (O—Y ¹ ) _m1 — (wherein Y ¹ and m1 are as defined above). A compound represented by formula (1), which is a group represented by formula (1A-1), and a compound represented by formula (1B-1) are particularly preferred. . N1 and n2 in the compound represented by the formula (1A-1) and the compound represented by the formula (1B-1) are 2 to 50, preferably 2 to 42, and more preferably 4 to 24. Especially preferably, it is 4-20.

In the present invention, X ¹ is a group represented by —CH ₂ —CR ^a1 R ^a2 —CH ₂ —, and at least one of R ^a1 and R ^a2 is a group of formula (2a) or a group of formula (2b) And R ¹ , R ³ , R ⁵ and R ⁷ are the same and are a 9-oxo-9H-thioxanthen-yl group or a dialkylaminobenzoyl group, R ² , R ⁴ , R ⁶ And R ⁸ are each independently 9-oxo-9H-thioxanthen-yl group, dialkylaminobenzoyl group, hydrogen, alkyl group, aryl group, heteroaryl group, aralkyl group, acyl group, silyl group, acetal group or ^{-CO-NH-Z 1} (wherein, ^{Z 1} represents an alkyl group, an aryl group or a heteroaryl group) compound represented by the formula (1) is also preferably represented by the formula (1A-2) That compound, the compound represented by the formula (1A-3) a compound represented by the formula compounds represented by (1B-2) and Formula (1B-3) is more preferable.

<Method for producing compound>
The method for producing the compound of the present invention comprises a step of reacting a dialkylaminobenzoic acid and / or hydroxy-9H-thioxanthen-9-one with a polyglycidyl ether compound. In the above step, the OH group of dialkylaminobenzoic acid and the OH group of hydroxy-9H-thioxanthen-9-one react with the glycidyl group (epoxy group) of the polyglycidyl ether compound to open the glycidyl group.

Moreover, the manufacturing method of the compound of this invention can include the further process depending on the case.
The production method of the compound of the present invention can optionally include a step of reacting the compound or polyglycidyl ether compound obtained by the above step with an acid or an alkali. By this step, the glycidyl group of the compound obtained by the above step or the polyglycidyl ether compound is ring-opened to form two OH groups. In addition, the method for producing a compound of the present invention may optionally include a compound obtained by the above-described step or a polyglycidyl ether compound, a compound having a phenolic hydroxyl group, an aliphatic alcohol, an araliphatic alcohol, and a compound having a carboxyl group. A step of reacting with one or more compounds selected from the group consisting of: By this step, the glycidyl group of the compound obtained by the above step or the polyglycidyl ether compound is ring-opened to form a residue such as the compound having a carboxyl group and one OH group.
Furthermore, the production method of the present invention can include a step of converting hydrogen in the OH group generated by the above three reactions into a further group. For example, a urethane compound can be obtained by modifying hydrogen in an OH group with an alkyl group, an acyl group, a silyl group, or the like, or reacting with a compound having an isocyanato group. By combining these reactions, the compound represented by the formula (1) of the present invention is obtained. Here, the glycidyl group is a 2,3-epoxypropyl group, the glycidyloxy group is a 2,3-epoxypropyloxy group, and the glycidyloxymethyl group is a 2,3-epoxypropyloxymethyl group. .

  Specifically, in the present invention, the compound represented by the formula (1) is obtained by a production method including the steps (a) to (d):

Step (a)
In the step (a), a compound represented by the formula (3) is prepared by reacting a dialkylaminobenzoic acid and / or hydroxy-9H-thioxanthen-9-one with a polyglycidyl ether compound represented by the formula (3). In which at least one glycidyl group is a group represented by the formula (4). By step (a), at least one glycidyl group of the compound represented by formula (3) is ring-opened to obtain a compound containing one OH group and the photoinitiator moiety of the present invention. The glycidyl group in the compound represented by the formula (3) includes the glycidyl moiety in the formula (3), and the glycidyl moiety in the glycidyloxy group and the glycidyloxymethyl group in R ^{b1 to} R ^b6 .

（式中、Ｚ^２ａ及びＺ^２ｂは、前記で定義されたとおりである）で示され、２−ジアルキルアミノ安息香酸、３−ジアルキルアミノ安息香酸、４−ジアルキルアミノ安息香酸が挙げられる。ジアルキルアミノ安息香酸として、ジメチルアミノ安息香酸、ジエチルアミノ安息香酸、ジプロピルアミノ安息香酸、ジブチルアミノ安息香酸、ジヘキシルアミノ安息香酸、ジオクチルアミノ安息香酸、メチルエチルアミノ安息香酸、メチルプロピルアミノ安息香酸、メチルブチルアミノ安息香酸、メチルヘキシルアミノ安息香酸、エチルプロピルアミノ安息香酸、エチルブチルアミノ安息香酸、エチルヘキシルアミノ安息香酸、ブチルオクチルアミノ安息香酸及びヘキシルオクチルアミノ安息香酸等が挙げられ、光硬化性の観点から、ジメチルアミノ安息香酸（４−ジメチルアミノ安息香酸、２−ジメチルアミノ安息香酸、３−ジメチルアミノ安息香酸）が好ましい。 The dialkylaminobenzoic acid has the formula (9a):

Wherein Z ^2a and Z ^2b are as defined above, and include 2-dialkylaminobenzoic acid, 3-dialkylaminobenzoic acid, and 4-dialkylaminobenzoic acid. Dialkylaminobenzoic acid includes dimethylaminobenzoic acid, diethylaminobenzoic acid, dipropylaminobenzoic acid, dibutylaminobenzoic acid, dihexylaminobenzoic acid, dioctylaminobenzoic acid, methylethylaminobenzoic acid, methylpropylaminobenzoic acid, methylbutyl Aminobenzoic acid, methylhexylaminobenzoic acid, ethylpropylaminobenzoic acid, ethylbutylaminobenzoic acid, ethylhexylaminobenzoic acid, butyloctylaminobenzoic acid, hexyloctylaminobenzoic acid and the like can be mentioned from the viewpoint of photocurability, Dimethylaminobenzoic acid (4-dimethylaminobenzoic acid, 2-dimethylaminobenzoic acid, 3-dimethylaminobenzoic acid) is preferred.

で示され、１−ヒドロキシ−９Ｈ−チオキサンテン−９−オン、２−ヒドロキシ−９Ｈ−チオキサンテン−９−オン、３−ヒドロキシ−９Ｈ−チオキサンテン−９−オン、及び４−ヒドロキシ−９Ｈ−チオキサンテン−９−オンが挙げられる。 Hydroxy-9H-thioxanthen-9-one has the formula (9b):

1-hydroxy-9H-thioxanthen-9-one, 2-hydroxy-9H-thioxanthen-9-one, 3-hydroxy-9H-thioxanthen-9-one, and 4-hydroxy-9H- And thioxanthen-9-one.

The polyglycidyl ether compound in which X ² is a group represented by —Y ¹ — (O—Y ¹ ) _m1 — is a diglycidyl ether compound having a polyalkylene oxide chain. About polyethylene glycol diglycidyl ether, Nagase ChemteX Denacol EX-830 (m1 = 5-8 (actual value)) is mentioned as a commercial item. The polypropylene glycol diglycidyl ether, commercially DENACOL manufactured by Nagase ChemteX Corporation EX-911 (m1 = 0, i.e., ^{X 2} is _-CH 2 CH (CH ₃₎ - is a), 941 ^{(Y 1} is -CH ₂ CH (CH ₃ )-and m1 = 1), 920 (Y ¹ is -CH ₂ CH (CH ₃ )-and m1≈2), 931 (Y ¹ is -CH ₂ CH (CH ₃ ) — and m1≈10). Further, diglycidyl ether compounds having such polyalkylene oxide chains, ^HO-Y 1 - obtained by reacting (O-Y ¹⁾ corresponding polyalkylene glycol represented by m1 _-OH epichlorohydrin be able to.

The compound represented by the formula (3) in which X ² is an alkylene group having 1 to 20 carbon atoms is alkanediol diglycidyl ether, such as 1,3-propanediol diglycidyl ether, 1,4-butanediol. Linear alkylene diol diglycidyl ethers such as diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether and 1,12-dodecanediol diglycidyl ether; 2-methyl-1, 4-butanediol diglycidyl ether, 2-methyl-1,5-pentanediol diglycidyl ether, 2-methyl-1,7-heptanediol diglycidyl ether, 2-methyl-1,9-nonanediol diglycidyl ether, etc. Branched alkylene diol jig A lysidyl ether is mentioned.

  A commercial item can be used for the above-mentioned alkanediol diglycidyl ether. For example, for 1,4-butanediol diglycidyl ether, there is EX-214L manufactured by Nagase ChemteX, and for 1,6-hexanediol diglycidyl ether, EX-212 manufactured by Nagase ChemteX, and EX- 212L.

When X ² is a group represented by —CH ₂ —CR ^b1 R ^b2 —CH ₂ —, a preferred combination of R ^b1 and R ^b2 is the following: R ^b1 is hydrogen and R ^b2 is glycidyl R ^b1 is an alkyl group having 1 to 4 carbon atoms (more preferably, an ethyl group), and R ^b2 is a glycidyloxymethyl group; and R ^b1 and R ^b2 are each an oxy group; A combination of the same and a glycidyloxymethyl group. That is, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether are compounds represented by formula (3), wherein X ² is —CH ₂ —CR ^b1 R ^b2 —CH ₂ —. More preferred. Examples of these compounds include Denacol DLC-301 (trimethylolpropane triglycidyl ether) and Denacol DLC-402 (pentaerythritol tetraglycidyl ether) manufactured by Nagase ChemteX Corporation.

When X ² is a group represented by —CH ₂ —CR ^b3 R ^b4 —CH ₂ —O—CH ₂ —CR ^b5 R ^b6 —CH ₂ —, R ^b3 , R ^b4 , R ^b5 and R ^b6 are Preferably they are the same and are glycidyloxymethyl groups. That is, as a compound represented by the formula (3) in which X ² is —CH ₂ —CR ^b3 R ^b4 —CH ₂ —O—CH ₂ —CR ^b5 R ^b6 —CH ₂ —, dipentaerythritol hexaglycidyl ether is preferable.

As the polyglycidyl ether compound represented by the formula (3), X ² is an alkylene group having 1 to 20 carbon atoms, —Y ¹ — (O—Y ¹ ) _m1 — (wherein Y ¹ and m1 are Or a group represented by —CH ₂ —CR ^b1 R ^b2 —CH ₂ — (wherein R ^b1 and R ^b2 each independently represent hydrogen, 1 to 4 carbon atoms) In which at least one of R ^b1 and R ^b2 is a glycidyloxy group or a glycidyloxymethyl group) is preferred, and liquid crystal contamination from the viewpoint of reducing the gender, ^{X 2} is _{^{-Y 1 - (O-Y 1}} ) m1 - is more preferred compound is a group represented by - group or a _{-CH 2} ^-CR b1 ^R b2 _-CH 2 represented by

  In the step (a), the amount of the raw material compound used is such that at least one glycidyl group of the compound represented by the formula (3) reacts with an OH group of dialkylaminobenzoic acid or hydroxy-9H-thioxanthen-9-one. And if it is the quantity used as the group shown by Formula (4), it will not specifically limit. For example, the amount of dialkylaminobenzoic acid or hydroxy-9H-thioxanthen-9-one used is dialkylaminobenzoic acid or hydroxy-9H-thioxanthen-9 with respect to 1.0 mol of the epoxy group of the polyglycidyl ether compound. When the OH group contained in -one is 1.0 mol, all glycidyl groups are groups represented by the formula (4). Further, for example, by reacting 0.5 mol of dialkylaminobenzoic acid and 0.5 mol of hydroxy-9H-thioxanthen-9-one with respect to 1.0 mol of epoxy group of the polyglycidyl ether compound, All the glycidyl groups of the compound represented by (3) become groups represented by the formula (4). On the other hand, for example, by reacting 0.5 mol of dialkylaminobenzoic acid with respect to 1.0 mol of the epoxy group of the polyglycidyl ether compound, 0.5 mol of glycidyl group of the compound represented by the formula (3) is obtained. This is a group represented by the formula (4). Next, by reacting 0.5 mol of hydroxy-9H-thioxanthen-9-one, 0.5 mol of the glycidyl group of the compound represented by the formula (3) becomes a group represented by the formula (4). The glycidyl group is a group represented by the formula (4). In this way, in consideration of the amount of the glycidyl group of the compound represented by the formula (3), the starting compound and the amount thereof can be selected and reacted. Moreover, this reaction may be achieved by a method including a plurality of steps even in one pot (one step).

The reaction can be carried out in the presence of an acidic catalyst, a basic catalyst or a salt thereof. These catalysts and salts are not particularly limited as long as they are known compounds used as a catalyst for the reaction between a compound having a glycidyl group and a compound having an OH group.
Acid catalyst, an inorganic acid such as hydrochloric acid and sulfuric acid; organic acids such as p- toluenesulfonic acid; copper, zinc, iron, magnesium, silver, calcium, and metals such as _tin, ^BF 4 _{-, SiF} ^{6 2-} or PF Examples thereof include catalysts composed of anions such as ₆ ⁻ and CF ₃ SO ₂ ^— (for example, tin borofluoride).

  Examples of the basic catalyst or a salt thereof include a trivalent organic phosphorus compound, a salt of a trivalent organic phosphorus compound, an amine compound, and a quaternary ammonium salt. Quaternary ammonium salts are preferred from the standpoint of reactivity and synthesis optimization.

  Examples of the trivalent organic phosphorus compound include alkylphosphines such as triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine; triphenylphosphine, tri-m-tolylphosphine, tris (2,6-dimethoxyphenyl). ) Arylphosphines such as phosphine; and phosphorous acid triesters such as triphenyl phosphite, triethyl phosphite and tris (nonylphenyl) phosphite. As the trivalent organic phosphorus compound, triphenylphosphine is preferable.

  Examples of the salt of the trivalent organic phosphorus compound include salts of the above-mentioned trivalent organic phosphorus compound, and specifically, triphenylphosphine / ethylbromide, triphenylphosphine / butylbromide, triphenylphosphine / octylbromide. , Triphenylphosphine / decyl bromide, triphenylphosphine / isobutyl bromide, triphenylphosphine / propyl chloride, triphenylphosphine / pentyl chloride, triphenylphosphine / hexyl bromide and the like.

  Examples of the amine compound include secondary amines such as diethanolamine; tertiary amines such as triethylamine, triethanolamine, dimethylbenzylamine, trisdimethylaminomethylphenol, trisdiethylaminomethylphenol; 1,5,7-triazabicyclo [ 4.4.0] dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene (MTBD), 1,8-diazabicyclo [ 5.4.0] Undec-7-ene (DBU), 6-dibutylamino-1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] Examples include strongly basic amines such as non-5-ene (DBN) and 1,1,3,3-tetramethylguanidine.

  Examples of the quaternary ammonium salt include salts of the above-described amine compound and hydrogen halide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, and the like.

  Although the reaction temperature in a process (a) is not restrict | limited in particular, 50-130 degreeC is mentioned, It is preferable that it is 70-120 degreeC. The reaction in step (a) can be carried out in the presence or absence of an organic solvent. Examples of the organic solvent that can be used include aromatic hydrocarbons such as benzene and toluene; ketones such as cyclohexanone and methyl isobutyl ketone; dimethyl sulfoxide and the like.

  Next, the reaction product is purified by removing the catalyst by a treatment such as filtration, centrifugation and / or washing with water.

Step (b)
Step (b) is optionally further reacted with an acid or alkali to convert at least one glycidyl group of the compound represented by formula (3) to a 2,3-dihydroxypropyl group represented by formula (5). It is a process. In step (b), the glycidyl group is opened to form two OH groups.

  Step (b) is a step of ring-opening the glycidyl group that has not been reacted in step (a). If all the glycidyl groups contained in the compound represented by the formula (3) are groups represented by the formula (4) by the step (a), the compound represented by the formula (1a) is represented by the step (a). can get.

  As the acid and alkali, a known compound capable of ring-opening a glycidyl group can be used. As an acid, the inorganic acid and organic acid which were illustrated in the said acidic catalyst are mentioned. Examples of the alkali include sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, metal alkoxide (such as sodium methoxide and sodium ethoxide), and ammonia. The amount of the acid or alkali used in the step (b) is not particularly limited as long as it is an amount capable of opening a desired number of glycidyl groups.

  By the method including the step (a) and the step (b), a compound having a group represented by the formula (4) and optionally a group represented by the formula (5) is obtained.

Step (c)
Step (c) is optionally further reacted with a dialkylaminobenzoic acid, hydroxy-9H-thioxanthen-9-one, a compound represented by R ¹¹ -OH and / or a compound represented by R ¹² -COOH. In this step, at least one glycidyl group of the compound represented by the formula (3) is used as a group represented by the formula (6). In step (c), the glycidyl group is ring-opened to form one OH group, and a compound represented by dialkylaminobenzoic acid, hydroxy-9H-thioxanthen-9-one, R ¹¹ -OH or R A group derived from a compound represented by ^12- COOH is formed.

Compounds having a phenolic hydroxyl group (for example, phenol and naphthol), aliphatic alcohols (for example, methanol, ethanol and propanol) and araliphatic alcohols (for example, benzyl alcohol) as the compounds represented by R ¹¹ —OH Etc.
Examples of the compound represented by R ¹² -COOH include aromatic carboxylic acids (for example, benzoic acid), aliphatic carboxylic acids (for example, acetic acid and propionic acid), and araliphatic carboxylic acids (for example, phenylacetic acid, 3-phenylpropionic acid). On acid etc.). The compound represented by R ¹² —COOH does not include dialkylaminobenzoic acid.
Dialkylaminobenzoic acid and hydroxy-9H-thioxanthen-9-one are as described above in step (a). In the step (c), a compound represented by R ¹¹ —OH and hydroxy-9H-thioxanthen-9-one can be used simultaneously, or a compound represented by R ¹² —COOH and a dialkylaminobenzoic acid can be used simultaneously. it can.

Step (c), the dialkylamino benzoic acid, the amount of the hydroxy -9H- ^{thioxanthene-9-one,} a compound represented by R 11 -OH and / or a compound represented by ^R 12 -COOH, the step (a) Is as described above for dialkylaminobenzoic acid and hydroxy-9H-thioxanthen-9-one, and can be determined according to the amount of glycidyl group reacted in step (c). Other reaction conditions are as described in the step (a).

A method comprising a group represented by formula (4) and optionally a group represented by formula (5) and a group represented by formula (6) by a method comprising step (a), step (b) and step (c). The compound represented by (1a) is obtained. Moreover, the compound shown by Formula (1a) which has the group shown by Formula (4) and the group shown by Formula (6) by the method including a process (a) and a process (c) is obtained. That is, in the formula (1a), R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ which are hydrogen are OH groups formed in the step (a), the step (b) and the step (c). It corresponds to hydrogen in That is, in the formula (1a), R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ^{20 that} are hydrogen are represented by R ⁹ and R ¹⁰ that are hydrogen in the formula (4), and the formula (5). It corresponds to R ¹³ and R ¹⁴ which are hydrogen of the OH group in the group and hydrogen in the group represented by the formula (6). Further, the group of formula (7a) and the group of (7c) correspond to the group represented by formula (5) formed by the step (b). In the formula (1a), a dialkylaminobenzoyl group is not included as R ¹² —CO—.

Step (d)
In step (d), in the compound represented by formula (1a) obtained by step (a), step (b) and step (c), a part of hydrogen in the OH group formed by the ring-opening reaction of glycidyl group or All, 9-oxo-9H-thioxanthen-yl group, dialkylaminobenzoyl group, alkyl group, aryl group, heteroaryl group, aralkyl group, acyl group, silyl group, acetal group, or —CO—NH—Z ¹ (Wherein Z ¹ is as defined above). By the step (d), a compound represented by the formula (1) other than the compound obtained by the method including the step (a), the step (b) and the step (c) is obtained. Step (d) is obtained by reacting the compound obtained in step (a), step (b) and step (c) with a further compound. As the reaction conditions and the raw material compounds, for example, known reaction conditions for introducing a protecting group for a hydroxy group described in PROTECTIVE GROUPS IN ORGANIC SYNTHESIS Second Edition (by W. Greene and M. Wuts) can be applied.

For example, as a method for converting hydrogen to an aryl group, a method in which a compound represented by the formula (1a) and a corresponding aryl halide are reacted in the presence of a base can be mentioned. Examples of the method for converting hydrogen into an aralkyl group include a method in which a compound represented by the formula (1a) and a corresponding halogenated aralkyl are reacted in the presence of a base. Examples of the method for converting hydrogen into an acyl group include a method in which a compound represented by the formula (1a) is reacted with a corresponding acyl halide. As a method for converting hydrogen into a silyl group, a compound represented by the formula (1a) and a formula X-Si (Z ⁴ ) ₃ (wherein Z ⁴ is as defined above, X is a halogen, Examples thereof include a method in which a corresponding silyl halide represented by F, Cl, Br and I is reacted in the presence of a base. Examples of the method for converting hydrogen to acetal include a method in which a compound represented by the formula (1a) is reacted with a ketone or an aldehyde in the presence of an acid. Moreover, a urethane bond can also be introduce | transduced by making the compound which has an isocyanato group react. Examples of the compound having an isocyanato group include a compound represented by Z ¹ —N═C═O (wherein Z ¹ is as defined above). Further, the conversion from hydrogen to a heteroaryl group or 9-oxo-9H-thioxanthen-yl group can be carried out in the same manner as in the method for converting hydrogen to an aryl group. Conversion from hydrogen to a dialkylaminobenzoyl group can be carried out in the same manner as in the method for converting hydrogen to an acyl group.

  The amount of the further compound used can be used according to the number of the target OH groups in the compound represented by the formula (1a). Although the usage-amount of the further compound is not specifically limited, It can be 0.0-1.0 mol with respect to 1.0 mol of one OH group in Formula (1a).

  The reaction may be performed in the presence of a catalyst. Examples of the catalyst include the compounds mentioned in step (a).

  The reaction product thus obtained is purified by removing the catalyst by a treatment such as filtration, centrifugation and / or washing with water. Thereby, the compound shown by Formula (1) of this invention is obtained.

  In addition, as long as the compound shown by Formula (1) is obtained, the said process (a), the process (b), the process (c), and the process (d) are the process (a), the process (b), the process ( A combination of a plurality of c) and step (d) may be performed, and the order of these steps is not particularly limited. That is, in the method for producing a compound of the present invention, step (a) may be performed only once, and a method including further steps, for example, step (a), step (b) and step (d); a) and step (c); step (a), step (c) and step (d); step (a), step (b) and step (c); and step (a), step (b) and step A compound represented by the formula (1a) may be obtained by a method comprising (c) and step (d). In addition, the same type of step is performed twice or more using another compound, such as a method including a step (a) using a dialkylaminobenzoic acid and a step (a) using a hydroxy-9H-thioxanthen-9-one. You may go. This reaction combination can be designed by calculating the equivalent of the number of glycidyl groups in the raw material compound and the group that reacts with the glycidyl group in the raw material compound used in each step.

<Uses of compounds>
The compound represented by the formula (1) of the present invention is a photopolymerization initiator for a sealant such as a liquid crystal sealant, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and A compound in which at least one of R ⁸ is a dialkylaminobenzoyl group (hereinafter sometimes referred to as “compound A”) acts as a photoinitiated compound photoexcited by a visible light sensitizing compound, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ^7, and R ⁸ are 9-oxo-9H-thioxanthen-yl groups (hereinafter, may be referred to as “compound B”) Acts as a visible light sensitizing compound.

  Here, the visible light sensitizing compound refers to a compound that absorbs visible light having a wavelength of 380 nm or more, preferably 400 nm or more, and more preferably 420 nm or more. The photoinitiating compound refers to a compound that does not absorb light in the visible light, but absorbs ultraviolet light and generates a radical.

  When the compound A and the compound B act as a photoinitiating compound or a visible light sensitizing compound in the photocuring reaction, the compound itself does not cleave, so that the decomposition product does not volatilize and liquid crystal contamination does not occur. Further, since the molecular weight of the compound itself is large and hardly volatilizes, liquid crystal contamination due to the volatilization of the compound itself hardly occurs.

  Since compound A has a tertiary amino group in the dialkylaminobenzoyl group, it functions as a catalyst in the photocuring reaction and thus has excellent stability.

  Compound B acts as a visible light sensitizing compound of the so-called hydrogen abstraction type photoradical polymerization initiating compound, absorbs active energy rays, and the photoradical polymerization initiator in the triplet excited state is in an excited state with the hydrogen donor. A complex, i.e., an exciplex is formed, and a hydrogen atom is extracted from a hydrogen donor to generate an active radical to initiate radical polymerization. Therefore, there are few decomposition products and almost no outgas component is generated.

In the compound A, X ¹ is preferably an alkylene group having 1 to 20 carbon atoms or a group represented by —Y ¹ — (O—Y ¹ ) _m1 — in the formula (1) of the present invention. , R ¹ and R ³ are the same and are a dialkylaminobenzoyl group, and R ² and R ⁴ are the same and are hydrogen; or, in the formula (1) of the present invention, X ¹ Is —CH ₂ —CR ^a1 R ^a2 —CH ₂ — (wherein R ^a1 is hydrogen and R ^a2 is a group of the formula (2a); R ^a1 is an alkyl group having 1 to 4 carbon atoms; (More preferably an ethyl group) and R ^a2 is a group of the formula (2b); or R ^a1 and R ^a2 are the same and are a group of the formula (2b)) a ^{group, R 1, R 3, R} 5 and ^{R 7} are the same, dialkylamino A Nzoiru ^{group, R 2, R 4, R} 6 and ^{R 8,} the same, a compound is hydrogen, the compound B is preferably, in formula (1) of the present invention, ^{X 1} is, An alkylene group having 1 to 20 carbon atoms or a group represented by —Y ¹ — (O—Y ¹ ) _m1 —, wherein R ¹ and R ³ are the same, and 9-oxo-9H-thioxanthene- A compound in which R ² and R ⁴ are the same and are hydrogen; or, in Formula (1) of the present invention, X ¹ is —CH ₂ —CR ^a1 R ^a2 —CH ₂ — ( Wherein R ^a1 is hydrogen and R ^a2 is a group of the formula (2a); R ^a1 is an alkyl group having 1 to 4 carbon atoms (more preferably an ethyl group), and R ^a2 is is a group of the formula (2b); ^{or, R a1} and ^{R a2} are the same, the formula (2b) A group represented by a ^{group), R 1, R 3,} R 5 and ^{R 7} are the same, 9-oxo -9H- thioxanthene - a-yl ^group, R ^{2, R} 4, R ⁶ and R ⁸ are the same and are hydrogen. Compound A is more preferably a compound represented by formula (1A-1), and compound B is more preferably a compound represented by formula (1B-1).
Since these compounds have an OH group in the molecule and a high polarity, they are usually excellent in compatibility with a highly polar photopolymerizable oligomer used in a photocurable resin composition. Since the polarities of these are different, the solubility in the liquid crystal is low, so that the liquid crystal contamination can be reduced.

(Photopolymerization initiator)
The photopolymerization initiator of the present invention is a photopolymerization initiator containing a photoinitiating compound and a visible light sensitizing compound, wherein the photoinitiating compound is Compound A and / or a visible light sensitizing compound is Compound B. That is, the photopolymerization initiator of the present invention includes Compound A of the present invention, Compound B of the present invention, or Compound A and Compound B of the present invention. The photopolymerization initiator of the present invention preferably comprises Compound A and Compound B of the present invention.

  As described above, the photopolymerization initiator of the present invention uses a compound A or a compound B in at least one of a photoinitiator compound and a visible light sensitizing compound, so that the liquid crystal initiator can be compared with a conventional photopolymerization initiator. Since contamination property becomes low, a photocurable resin composition suitable for a sealant can be produced.

  When the compound A is used as the photoinitiator compound in the photopolymerization initiator of the present invention, examples of the visible light sensitizing compound include alkyldiaminobenzophenone, diaminobenzophenone, anthracene, thioxanthone, coumarin, ketocoumarin, cyanine, phthalocyanine, and naphthalocyanine. From the viewpoint of efficiency of reactivity by energy transfer, a benzophenone skeleton and / or a thioxanthone skeleton is preferable, a thioxanthone skeleton is more preferable, and a compound B is more preferable.

  In the photopolymerization initiator of the present invention, when compound B is used as the visible light sensitizing compound, the photoinitiating compound includes self-cleaving photoinitiating compounds such as benzoin compounds, acetophenones, hydroxyacetophenones, α-aminoacetophenones, α-acyloxime esters, acylphosphine oxide compounds, azo compounds, etc .; hydrogen abstraction type photoinitiating compounds such as benzophenones, benzoin ethers, benzyl ketals, dibenzosuberones, Anthraquinones, xanthones, thioxanthones, halogenoacetophenones, dialkoxyacetophenones, hydroxyacetophenones, halogenobisimidazoles, halogenotriazines and the like can be used.

  The photoinitiating compound is preferably a hydrogen abstraction type photoinitiating compound, more preferably N, N-dialkylanilines, alkylamines, N, N-dialkyl, from the viewpoint of suppressing liquid crystal contamination by outgas. Aminobenzoic acid esters, more preferably N, N-dialkylaminobenzoic acid esters, and particularly preferably Compound A.

  In the photopolymerization initiator of the present invention, the molar ratio of the photoinitiating compound to the visible light sensitizing compound (photoinitiating compound / visible light sensitizing compound) is preferably from the viewpoint of supplying a stable and sufficient radical. 1/5 to 5/1, more preferably 1/3 to 3/1, still more preferably 1/2 to 2/1.

[Photocurable resin composition]
The photocurable resin composition of the present invention contains a photopolymerizable monomer and / or a photopolymerizable oligomer and the photopolymerization initiator of the present invention.

  As the photopolymerizable monomer and / or photopolymerizable oligomer, known materials can be used. From the viewpoint of contamination due to dissolution in liquid crystal, (meth) acrylic acid ester monomers and / or oligomers thereof and bisphenol A type epoxy are used. Partial (meth) acrylated epoxy resin obtained by reacting resin and (meth) acrylic acid is preferred, and partial (meth) acrylated epoxy obtained by reacting bisphenol A type epoxy resin and (meth) acrylic acid A resin is more preferable.

  (Meth) acrylic acid ester monomers and / or oligomers thereof are preferably 2-hydroxyethyl (meth) acrylate, di, tri or tetraethylene glycol di (meth) acrylate, epoxy-modified di (meth) acrylate, urethane Modified di (meth) acrylate, more preferably epoxy-modified di (meth) acrylate and urethane-modified di (meth) acrylate, and more preferably epoxy-modified di (meth) acrylate.

  A partial (meth) acrylated epoxy resin obtained by reacting a bisphenol A type epoxy resin with (meth) acrylic acid is obtained as follows. First, bisphenol A type epoxy resin and (meth) acrylic acid are added in the presence of a basic catalyst, preferably in the presence of a trivalent organic phosphoric acid compound and / or an amine compound. ˜90 equivalent% is reacted. Next, the reaction product is purified by removing the basic catalyst by filtration, centrifugation, and / or washing with water. As a basic catalyst, the well-known basic catalyst used for reaction with an epoxy resin and (meth) acrylic acid can be used. Further, a polymer-supported basic catalyst in which a basic catalyst is supported on a polymer such as polystyrene can also be used. Here, the trivalent organic phosphorus compound and the amine compound are as described above including preferable ones.

  From the viewpoint of reducing the remaining of the uncured portion of the photopolymerizable monomer and / or photopolymerizable oligomer and suppressing the contamination of the liquid crystal, and suppressing the influence on the contamination due to the elution of the photoinitiator component to the liquid crystal, The photopolymerization initiator of the present invention is preferably 0.5 to 10.0 parts by weight, more preferably 0.5 to 5.0 parts by weight with respect to 100 parts by weight of the polymerizable monomer and / or photopolymerizable oligomer. It is.

  The photocurable resin composition containing the photopolymerization initiator of the present invention, when used as a sealant, particularly a liquid crystal sealant, greatly reduces liquid crystal contamination and hardly damages liquid crystals and alignment films. The photocurable resin can also be cured by the above. On the other hand, with the recent increase in the density of wiring of electronic components, the following problems have arisen particularly in the liquid crystal field in which the ODF method is adopted.

  The ODF method is a method in which a liquid crystal panel can be created by directly dropping, bonding, and releasing the liquid crystal in a closed loop of a sealing agent under vacuum. Compared to the conventional injection method, liquid crystal This is a mainstream method for manufacturing liquid crystal panels using a large-sized substrate.

  The sealant used for the liquid crystal substrate produced by the ODF method is composed of a resin that has both a (meth) acrylic group that is a photocurable functional group and an epoxy group that is a thermosetting functional group. They are later bonded together, irradiated with ultraviolet rays, temporarily cured, and then thermally cured. At this time, if the reaction of the (meth) acrylic group due to ultraviolet irradiation is insufficient, or if the ultraviolet ray does not hit due to the shadow of the wiring etc., the liquid crystal sealant component elutes into the liquid crystal at the time of thermal curing, This may cause display defects.

  In recent years, as described above, there is an increasing number of cases where photocuring by visible light having a lower energy than ultraviolet rays is incorporated, and further, the higher density of wiring tends to make ultraviolet rays difficult to hit. Is becoming more prominent.

  Since the photocurable resin composition of the present invention contains the photopolymerization initiator of the present invention, it is not only cured with visible light but also with a low irradiation amount of ultraviolet rays, so that it is a shadow portion. However, it can be cured and contribute to the solution of the above problems.

  The photocurable resin composition of the present invention can contain additional components other than the photoinitiator and photopolymerizable monomer and / or photopolymerizable oligomer of the present invention within the scope of the object of the present invention. That is, as the photocurable resin composition of the present invention, the photoinitiator of the present invention and a composition comprising a photopolymerizable monomer and / or a photopolymerizable oligomer, or the photoinitiator of the present invention, a photopolymerizable monomer and And / or a composition comprising a photopolymerizable oligomer and further components. When a further component is contained, the photopolymerizable monomer and / or photopolymerizable oligomer 100 of the present invention is used from the viewpoint of easy handling of the resin composition, that is, a viscosity suitable for defoaming property, coating property, and printability. The content of further components with respect to parts by weight is preferably 0.01 to 140 parts by weight.

  The photocurable resin composition of the present invention can further contain a thermosetting agent. Although it does not specifically limit as a thermosetting agent, A hydrazide compound, an amine adduct compound, and an imidazole compound are mentioned. These compounds include, for example, one hydrazide compound, a combination of one hydrazide compound and one imidazole compound, a combination of one hydrazide compound and two or more amine adduct compounds, and one hydrazide compound. Or a combination of two or more amine adduct compounds and two or more imidazole compounds, and a combination of two or more hydrazide compounds and two or more amine adduct compounds, A plurality of compounds may be used in combination.

  Examples of the hydrazide compound include adipic acid dihydrazide, 1,3-bis (hydrazinocarbonoethyl) -5-isopropylhydantoin, 7,11-octadecadien-1,18-dicarbohydrazide, and the like.

  As an amine adduct compound, Ajinomoto Fine Techno Co., Amicure PN-23, Amicure PN-30, Amicure MY-24, Amicure MY-H, etc. are mentioned as a commercial item.

  As imidazole compounds, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2- Examples include methylimidazole, 1-cyanoethyl-2-methylimidazole, and 1-cyanoethyl-2-phenylimidazole.

  As the thermosetting agent, a commercially available product can be used.

  In the photocurable resin composition of the present invention, the content of the thermosetting agent is sufficient from the viewpoint of having sufficient thermal reactivity and maintaining storage stability, and a photopolymerizable monomer and / or photopolymerizable oligomer. It is preferable that it is 5-50 weight part with respect to 100 weight part, and it is more preferable that it is 5-30 weight part.

  The photocurable resin composition of the present invention preferably contains a coupling agent such as filler particles and a silane coupling agent from the viewpoint described later, and the photopolymerizability suitable for the present invention as necessary. Monomer and / or photopolymerizable oligomer, curing agent other than thermosetting agent, initiator other than photopolymerization initiator suitable for the present invention, elastomer, chain transfer agent, ion trap agent, ion exchange agent, leveling agent, pigment And additives such as dyes, plasticizers and antifoaming agents.

  The filler particles improve the adhesive reliability of the curable resin composition by controlling the viscosity of the curable resin composition, improving the strength of the cured product obtained by curing the curable resin composition, or suppressing linear expansion. Is added for the purpose. As the filler particles, inorganic particles for fillers and / or organic resin particles for fillers can be preferably used, but inorganic particles for fillers are preferable from the viewpoint of low linear expansion coefficient and reduction of curing shrinkage due to the development of adhesive strength. .

  As inorganic particles for fillers, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titanium oxide, alumina, zinc oxide, silicon dioxide, kaolin, talc from the viewpoint of easily obtaining a particle size suitable for a sealant. At least one inorganic particle selected from the group consisting of glass beads, sericite activated clay, bentonite, aluminum nitride, and silicon nitride is preferred, and at least one selected from the group consisting of silicon dioxide, talc, alumina, and bennite The above inorganic particles are more preferable, silicon dioxide and / or talc are more preferable, and silicon dioxide is particularly preferable.

  As an organic resin particle for filler, polymethyl methacrylate, polystyrene, and a copolymer obtained by copolymerizing these monomers and other monomers from the viewpoint of developing the effect of addition as adhesive strength by stress relaxation during curing. Selected from the group consisting of polymers, polyester fine particles, polyurethane fine particles, rubber fine particles, and core-shell type fine particles composed of a shell containing a copolymer having a high glass transition temperature and a core of a copolymer having a low glass transition temperature. A core shell comprising at least one organic resin particle, preferably a polyester fine particle, polyurethane fine particle, rubber fine particle, and a shell containing a copolymer having a high glass transition temperature and a copolymer core having a low glass transition temperature At least selected from the group consisting of type fine particles More preferably seeds or organic resin particles, core-shell type fine particles composed of a core of a copolymer having a shell and a low glass transition temperature comprising a copolymer having a high glass transition temperature is more preferable. In the core-shell type fine particles, it is preferable that the copolymer having a high glass transition temperature is polymethacrylic acid and the copolymer having a low glass transition temperature is butyl acrylate.

  In the photocurable resin composition of the present invention, the content of the inorganic particles for the filler is such that the photopolymerizable monomer and / or the photopolymerizable oligomer 100 are used from the viewpoint of improvement in adhesiveness due to stress dispersion effect and improvement in linear expansion coefficient. It is preferable that it is 2-40 weight part with respect to a weight part, and it is more preferable that it is 5-30 weight part. Further, in the photocurable resin composition of the present invention, the content of the organic resin particles for the filler is a photopolymerizable monomer and / or photopolymerization from the viewpoint of expressing an addition effect as an adhesive strength due to stress relaxation during curing. The amount is preferably 2 to 40 parts by weight and more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the functional oligomer.

When the photocurable resin composition of the present invention is used as a liquid crystal sealant, the silane coupling agent is preferable as an adhesion aid for favorably bonding the liquid crystal sealant and the liquid crystal display panel.
The silane coupling agent includes at least one selected from the group consisting of γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-isocyanatopropyltrimethoxysilane. Compounds are preferred, and γ-glycidoxypropyltrimethoxysilane is more preferred.

  In the photocurable resin composition of the present invention, the content of the coupling agent is 0 with respect to 100 parts by weight of the photopolymerizable monomer and / or photopolymerizable oligomer, from the viewpoint of maintaining adhesive strength, particularly moisture resistance strength. 0.1 to 10 parts by weight is preferable, and 0.5 to 2 parts by weight is more preferable.

  The present invention is illustrated using the following examples. However, the present invention is not limited to the following examples.

Synthesis Example 1: Synthesis of Compound A (Compound represented by Formula (1A-1))

Example 1-1 Synthesis of Compound A-2 (n1 = 2-4) PEG # 200 (manufactured by Lion Corporation) 200 g (2 hydroxyl equivalents), epichlorohydrin 1110 g (6 equivalents), benzyltrimethylammonium chloride 37.14 g (0.1 eq) was placed in a 2 liter three-necked round bottom flask equipped with a mechanical stirrer, thermometer, temperature controller, condenser, Dean-Stark trap and dropping funnel. The mixture was then heated to 60-70 ° C. with stirring under a vacuum of 70 torr to vigorously reflux epichlorohydrin. 300 g (1.8 equivalents) of 48% aqueous sodium hydroxide was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. Stirring was continued for 3 hours after completion of the base addition. Next, the reaction mixture was cooled to room temperature, 500 g of chloroform was added, and the mixture was washed 6 times with 1 L of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 108 g of PEG # 200 diglycidyl ether (PEG # 200-DGE) (epoxy equivalent 160 g / eq, viscosity 35 mPa · s).
PEG # 200-DGE 8 g (0.05 epoxy equivalent), 4-dimethylaminobenzoic acid 8.26 g (1.0 equivalent), benzyltrimethylammonium chloride 1.85 g (0.2 equivalent), MIBK 50 g were placed in a flask. The mixture was stirred at ° C for 24 hours. The reaction mixture was cooled to room temperature, dissolved in 100 g of chloroform, and washed 6 times with 100 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 12.8 g of compound A-2.

Example 1-2 Synthesis of Compound A-3 (n1 = 4 to 6) Example 1-1 except that PEG # 200 was changed to 300 g (2 hydroxyl equivalents) of PEG # 300 (manufactured by Lion Corporation). Similarly, 176 g of diglycidyl ether (PEG # 300-DGE) of PEG # 300 was obtained (epoxy equivalent 209 g / eq, viscosity 55 mPa · s).
PEG # 300-DGE 15.68 g (0.075 epoxy equivalent), 4-dimethylaminobenzoic acid 12.39 g (1.0 equivalent), benzyltrimethylammonium chloride 2.78 g (0.2 equivalent), and MIBK 150 g were placed in a flask. And stirred at 110 ° C. for 24 hours. The reaction mixture was cooled to room temperature, dissolved in 150 g of chloroform and washed 6 times with 200 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 22.0 g of compound A-3.

[Example 1-3] Synthesis of compound A-4 (n1 = 6-9) Denacol EX-830 (diglycidyl ether of PEG400 (n1 = 6-9) manufactured by Nagase ChemteX Corporation) 26.8 g (0.1 Epoxy equivalent), 16.5 g (1.0 equivalent) of 4-dimethylaminobenzoic acid, 3.71 g (0.2 equivalent) of benzyltrimethylammonium chloride, and 25 g of MIBK were placed in a flask and stirred at 110 ° C. for 24 hours. The reaction mixture was cooled to room temperature, dissolved in 50 g of chloroform, and washed 6 times with 100 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 35.3 g of Compound A-4.

Example 1-4 Synthesis of Compound A-5 (n1 = 20-24) PEG # 1000 (manufactured by Lion Corporation) 300 g (0.6 hydroxyl group equivalent), epichlorohydrin 333 g (6 equivalents), benzyltrimethyl 11.1 g (0.1 equivalent) of ammonium chloride was placed in a 1 liter three-necked round bottom flask equipped with a mechanical stirrer, thermometer, temperature controller, condenser, Dean-Stark trap and dropping funnel. The mixture was then heated to 60-70 ° C. with stirring under a vacuum of 70 torr to vigorously reflux epichlorohydrin. 90 g (1.8 eq) of 48% aqueous sodium hydroxide was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. Stirring was continued for 3 hours after completion of the base addition. The reaction mixture was then cooled to room temperature, 500 g of chloroform was added, and the mixture was washed 6 times with 1 L of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 115 g of PEG # 1000 diglycidyl ether (PEG # 1000-DGE) (epoxy equivalent 551 g / eq, solid at normal temperature (wax)).
A flask is charged with 42.4 g (0.075 epoxy equivalent) of PEG # 1000-DGE, 12.39 g (1.0 equivalent) of 4-dimethylaminobenzoic acid, 2.78 g (0.2 equivalent) of benzyltrimethylammonium chloride, and 150 g of MIBK. And stirred at 110 ° C. for 24 hours.
The reaction mixture was cooled to room temperature, dissolved in 150 g of chloroform and washed 6 times with 200 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 47.0 g of Compound A-5.

Example 1-5 Synthesis of Compound A-6 (n1 = 29 to 34) PEG # 1540 (manufactured by Lion Corporation) 108 g (0.14 hydroxyl group equivalent), epichlorohydrin 77.7 g (6 equivalents), 2.60 g (0.1 eq) of benzyltrimethylammonium chloride was placed in a 500 ml three-necked round bottom flask equipped with a mechanical stirrer, thermometer, temperature controller, condenser, Dean-Stark trap and dropping funnel. The mixture was then heated to 60-70 ° C. with stirring under a vacuum of 70 torr to vigorously reflux epichlorohydrin. 21 g (1.8 eq) of 48% aqueous sodium hydroxide was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. Stirring was continued for 3 hours after completion of the base addition. The reaction mixture was then cooled to room temperature, 300 g of chloroform was added, and the mixture was washed 6 times with 500 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 65.6 g of PEG # 1540 diglycidyl ether (PEG # 1540-DGE) (epoxy equivalent 775 g / eq, solid at normal temperature (wax)).
PEG # 1540-DGE 23.3 g (0.03 epoxy equivalent), 4-dimethylaminobenzoic acid 4.96 g (1.0 equivalent), benzyltrimethylammonium chloride 1.11 g (0.2 equivalent), and MIBK 20 g were placed in a flask. And stirred at 110 ° C. for 24 hours. The reaction mixture was cooled to room temperature, dissolved in 50 g of chloroform, and washed 6 times with 100 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 23.4 g of compound A-6.

[Example 1-6] Synthesis of Compound A-7 (n1 = 37-42) PEG-2000 (manufactured by Toho Chemical Co., Ltd.) 100 g (0.1 hydroxyl group equivalent), epichlorohydrin 55.5 g (6 equivalents) ), 1.86 g (0.1 eq) of benzyltrimethylammonium chloride was placed in a 500 ml three-necked round bottom flask equipped with a mechanical stirrer, thermometer, temperature controller, condenser, Dean-Stark trap and dropping funnel. . The mixture was then heated to 60-70 ° C. with stirring under a vacuum of 70 torr to vigorously reflux epichlorohydrin. 15 g (1.8 eq) of 48% aqueous sodium hydroxide was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. Stirring was continued for 3 hours after completion of the base addition. The reaction mixture was then cooled to room temperature, 300 g of chloroform was added, and the mixture was washed 6 times with 500 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 73.5 g of PEG-2000 diglycidyl ether (PEG-2000-DGE) (epoxy equivalent 1114 g / eq, room temperature solid (wax)).
11.1 g (0.01 epoxy equivalent) of PEG-2000-DGE, 1.65 g (1.0 equivalent) of 4-dimethylaminobenzoic acid, 0.37 g (0.2 equivalent) of benzyltrimethylammonium chloride, and 20 g of MIBK were placed in a flask. And stirred at 110 ° C. for 24 hours. The reaction mixture was cooled to room temperature, dissolved in 50 g of chloroform, and washed 6 times with 100 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 8.16 g of compound A-7.

Comparative Example 1-1 Synthesis of Compound A-1 (n1 = 1) Denacol EX-850L (diethylene glycol diglycidyl ether, manufactured by Nagase ChemteX Corporation) 14.5 g (0.1 epoxy equivalent), 4-dimethylaminobenzoic acid 16.5 g (1.0 equivalent) of acid, 3.71 g (0.2 equivalent) of benzyltrimethylammonium chloride and 50 g of MIBK were placed in a flask and stirred at 110 ° C. for 24 hours. The reaction mixture was cooled to room temperature, dissolved in 50 g of chloroform, and washed 6 times with 100 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 23.3 g of compound A-1.

Synthesis Example 2: Synthesis of compound B (compound represented by formula (1B-1))

Example 1-7 Synthesis of Compound B-2 (n2 = 2-4) PEG # 200-DGE 4.98 g (0.03 epoxy equivalent), 2-hydroxy-9H-thioxanthen-9-one 6.85 g (1.0 equivalent), 1.11 g (0.2 equivalent) of benzyltrimethylammonium chloride and 50 g of MIBK were placed in a flask and stirred at 110 ° C. for 72 hours. The reaction mixture was cooled to room temperature, dissolved in 100 g of chloroform, and washed 6 times with 100 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 9.90 g of compound B-2.

Example 1-8 Synthesis of Compound B-3 (n2 = 4-6) PEG # 300-DGE 6.24 g (0.03 epoxy equivalent), 2-hydroxy-9H-thioxanthen-9-one 6.85 g (1.0 equivalent), 1.11 g (0.2 equivalent) of benzyltrimethylammonium chloride and 50 g of MIBK were placed in a flask and stirred at 110 ° C. for 72 hours. The reaction mixture was cooled to room temperature, dissolved in 100 g of chloroform, and washed 6 times with 100 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 10.68 g of compound B-3.

[Example 1-9] Synthesis of compound B-4 (n2 = 6-9) Denacol EX-830 (diglycidyl ether of PEG400 (n2 = 6-9) manufactured by Nagase ChemteX) 26.8 g (0.1 Epoxy equivalent), 22.83 g (1.0 equivalent) of 2-hydroxy-9H-thioxanthen-9-one, 3.71 g (0.2 equivalent) of benzyltrimethylammonium chloride, and 40 g of MIBK in a flask. Stir for hours. The reaction mixture was cooled to room temperature, dissolved in 50 g of chloroform, and washed 6 times with 100 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 36.2 g of compound B-4.

Example 1-10 Synthesis of Compound B-5 (n2 = 20-24) PEG # 1000-DGE 11.3 g (0.02 epoxy equivalent), 2-hydroxy-9H-thioxanthen-9-one 4.57 g (1.0 equivalent), 0.74 g (0.2 equivalent) of benzyltrimethylammonium chloride and 50 g of MIBK were placed in a flask and stirred at 110 ° C. for 72 hours. The reaction mixture was cooled to room temperature, dissolved in 100 g of chloroform, and washed 6 times with 100 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 13.54 g of compound B-5.

Example 1-11 Synthesis of Compound B-6 (n2 = 29 to 34) PEG # 1540-DGE 15.5 g (0.02 epoxy equivalent), 2-hydroxy-9H-thioxanthen-9-one 4.57 g (1.0 equivalent), 0.74 g (0.2 equivalent) of benzyltrimethylammonium chloride and 50 g of MIBK were placed in a flask and stirred at 110 ° C. for 72 hours. The reaction mixture was cooled to room temperature, dissolved in 100 g of chloroform, and washed 6 times with 100 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 16.3 g of Compound B-6.

[Example 1-12] Synthesis of compound B-7 (n2 = 37-42) PEG-2000-DGE 11.14 g (0.01 epoxy equivalent), 2-hydroxy-9H-thioxanthen-9-one 2.28 g (1.0 equivalent), 0.37 g (0.2 equivalent) of benzyltrimethylammonium chloride and 50 g of MIBK were placed in a flask and stirred at 110 ° C. for 72 hours. The reaction mixture was cooled to room temperature, dissolved in 100 g of chloroform, and washed 6 times with 100 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 4.6 g of Compound B-7.

[Comparative Example 1-2] Synthesis of Compound B-1 (n2 = 1) Denacol EX-850L (diethylene glycol diglycidyl ether, manufactured by Nagase ChemteX) 14.5 g (0.1 epoxy equivalent), 2-hydroxy-9H -22.8 g (1.0 equivalent) of thioxanthen-9-one, 3.71 g (0.2 equivalent) of benzyltrimethylammonium chloride and 50 g of MIBK were placed in a flask and stirred at 110 ° C for 24 hours. The reaction mixture was cooled to room temperature, dissolved in 50 g of chloroform, and washed 6 times with 100 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 27.8 g of compound B-1.

Synthesis Example 3: Synthesis of compound 2A (compound represented by formula (1A-2))

[Example 1-13] Synthesis of Compound 2A Denacol DLC-301 (manufactured by Nagase ChemteX Corporation) 11.80 g (0.1 epoxy equivalent), 4-dimethylaminobenzoic acid 16.52 g (1.0 equivalent), benzyl 3.71 g (0.2 equivalent) of trimethylammonium chloride and 25 g of MIBK were placed in a flask and stirred at 110 ° C. for 24 hours. The reaction mixture was cooled to room temperature, dissolved in 100 g of chloroform, and washed 6 times with 100 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 21.97 g of compound 2A.

Synthesis Example 4: Synthesis of compound 3A (compound represented by formula (1A-3))

[Example 1-14] Synthesis of compound 3A Denacol DLC-402 (manufactured by Nagase ChemteX Corporation) 9.40 g (0.1 epoxy equivalent), 4-dimethylaminobenzoic acid 16.52 g (1.0 equivalent), benzyl 3.71 g (0.2 equivalent) of trimethylammonium chloride and 25 g of MIBK were placed in a flask and stirred at 110 ° C. for 24 hours. The reaction mixture was cooled to room temperature, dissolved in 100 g of chloroform, and washed 6 times with 100 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 12.34 g of compound 3A.

Synthesis Example 5: Synthesis of compound 2B (compound represented by formula (1B-2))

[Example 1-15] Synthesis of compound 2B Denacol DLC-301 (manufactured by Nagase ChemteX) 4.72 g (0.04 epoxy equivalent), 2-hydroxy-9H-thioxanthen-9-one 9.13 g (1 0.0 eq), 1.49 g (0.2 eq) of benzyltrimethylammonium chloride and 30 g of MIBK were placed in a flask and stirred at 110 ° C. for 48 hours. The reaction mixture was cooled to room temperature, dissolved in 200 g of chloroform, and washed 6 times with 200 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 4.93 g of compound 2B.

Synthesis Example 6: Synthesis of compound 3B (compound represented by formula (1B-3))

Example 1-16 Synthesis of Compound 3B Denacol DLC-402 (manufactured by Nagase ChemteX Corp.) 3.76 g (0.04 epoxy equivalent), 2-hydroxy-9H-thioxanthen-9-one 9.13 g (1 0.0 eq), 1.49 g (0.2 eq) benzyltrimethylammonium chloride, and 25 g DMSO (dimethyl sulfoxide) were placed in a flask and stirred at 110 ° C. for 72 hours. The solvent in the reaction mixture was distilled off under reduced pressure, cooled to room temperature, dissolved in 200 g of chloroform, and washed 6 times with 200 ml of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 7.92 g of compound 3B.

Synthesis Example 7: Preparation of photocurable resin composition (a) Synthesis of photopolymerizable oligomer (compound C: partially methacrylated epoxy resin of bisphenol A type epoxy resin) Bisphenol A type epoxy resin (EXA850CRP, manufactured by DIC Corporation) 320.2 g, 90.4 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), PS-PPh ₃ (basic catalyst having triphenylphosphine (PPh ₃ ) supported on polystyrene (PS), 1.5 g of Biotage), and 100 mg of BHT (dibutylhydroxytoluene) was mixed and stirred at 100 ° C. for 6 hours. After completion of the reaction, the catalyst was removed by filtration to obtain a partially methacrylated epoxy resin (Compound C, PR-850CRP).
(B) Photopolymerization initiator [Comparative Example 1-3] Decomposed type (reactive group-containing type): EY resin, KR-2 (manufactured by KS Corporation)
[Comparative Example 1-4] Decomposition type (visible light curing type): Irgacure, I-369 (manufactured by BASF Japan)

[Example 2-1]
A photopolymerization initiator composed of 1 part by weight of photoinitiating compound A-1 and 1 part by weight of visible light sensitizing compound B-1 is dissolved in 100 parts by weight (100 g) of photopolymerizable oligomer PR-850CRP and photocured. A functional resin composition was obtained.
[Example 2-2] to [Examples 2 to 16] and [Comparative Example 2-1] to [Comparative Example 2-6] are the same as in Example 2-1 in the parts by weight shown in Tables 1 and 2. Thus, a photocurable resin composition was obtained.

[Example 1-1] to [Example 1-16], [Comparative Example 1-1], [Comparative Example 1-2], [Comparative Example 1-3], [Comparative Example 1- The following evaluation was performed on the compound of 4].
[Evaluation conditions]
(1) Viscosity measurement The viscosity was measured using an E-type viscometer (RE105U, manufactured by Toki Sangyo Co., Ltd.).
(2) Liquid crystal elution evaluation (NI point change measurement)
The elution property to the liquid crystal was evaluated by changing the NI point (nematic-isotropic point) which is the phase transition temperature of the liquid crystal. The NI point of the liquid crystal is determined by the mixed composition of each component of the liquid crystal and is a unique value for each formulation. In general, it is known that the NI point changes when some impurities (other components) are mixed in these liquid crystals, and the liquid crystal contamination can be evaluated by the amount of change of the NI point.
A liquid crystal sample for evaluation was prepared by the following procedure. 0.1 g of compound is put into an ampoule bottle, and 1 g of liquid crystal (MLC-11900-080, manufactured by Merck & Co.) is added. The bottle was placed in an oven at 120 ° C. for 1 hour, and then allowed to stand at room temperature. After returning to room temperature (25 ° C.), the liquid crystal portion was taken out and filtered through a 0.2 μm filter to obtain a liquid crystal sample for evaluation.
A differential scanning calorimeter (DSC, manufactured by PerkinElmer, Inc., Pyris 6) was used for measurement of the NI point. A 10 mg liquid crystal sample for evaluation was sealed in an aluminum sample pan, and the measurement was performed under the condition of a temperature rising rate of 5 ° C./min. The table shows NI point change values from blank.
(3) Loss on heating Using a differential thermal balance (TG-DTA, product name: Thermoplus TG8120, manufactured by Rigaku Corporation), each weighed photoinitiator is placed in an aluminum pan and measured for outgas at 120 ° C. for 60 minutes. Then, the amounts of volatile components from the compounds were compared.

The following evaluation was performed on the photocurable resin compositions of [Example 2-1] to [Example 2-16] and [Comparative Example 2-1] to [Comparative Example 2-6].
(1) Reaction rate One of the photocurable resin composition is a glass for LCD having a thickness of 25 mm × 25 mm and a thickness of 0.7 mm, and the other is a PET film having a thickness of 25 mm × 25 mm and a thickness of 0.1 mm. A thickness of 0.5 mm is sandwiched, and an irradiating device (UVX-01224S1, manufactured by Ushio Electric Co., Ltd.) is irradiated with 100 mW / cm ² of UV irradiation and light energy of 100 to 3000 mJ / cm ² to measure curability. A sample was prepared. At this time, ultraviolet rays and visible light having a wavelength of 340 nm to 450 nm were irradiated using an ultraviolet ray / heat ray cut filter. The measurement of the curing rate was measured using FT-IR (Spectrum One, manufactured by PerkinElmer), and the reaction rate of the (meth) acrylic group (conversion rate) from the peak area of the (meth) acrylic group of the obtained IR spectrum. Was calculated. Calculation of the reaction rate was calculated based on the area of absorption 1500 cm ^-1 the reduction of the area of the double bonds of the benzene ring of (meth) absorption 1630 cm ^-1 (or 945 cm ^-1) of the acryl group.

  The results are summarized in Tables 1 and 2.

As is clear from Tables 1 and 2, the compounds of Examples have a small change in NI point. Therefore, the compound of an Example has little elution amount to a liquid crystal, and its liquid-crystal contamination property is low. In particular, when n1 or n2 is 29 or more, in addition to a small change in NI point and a small change in heating loss, outgassing is greatly reduced in addition to low liquid crystal contamination. Yes. Moreover, the compound whose n1 is 2-9 and the compound whose n2 is 4-9 have a low viscosity, and its handling property is favorable. Furthermore, the compound whose n1 or n2 is 4-9 has good curability.
On the other hand, the compound of the comparative example in which n1 or n2 is 1 has a large NI point change amount and high viscosity. The compound of Comparative Example 1-3 was inferior in reactivity, and the compound of Comparative Example 1-4 had a large NI point change amount.
Therefore, it can be said that the compound of this invention is excellent in the effect as a photoinitiator for the liquid-crystal sealing compound with low liquid-contamination property with respect to the photoinitiator of a prior art.

Claims (6)

A photocurable resin composition for a liquid crystal sealant comprising a photopolymerizable monomer and / or a photopolymerizable oligomer and a photopolymerization initiator,
The photopolymerization initiator is represented by the general formula (1):

[Where,
X ¹ is an alkylene group having 1 to 20 carbon atoms,
-Y ^1- (O-Y ¹ ) _m1-
(Where
Y ¹ is an alkylene group having 1 to 8 carbon atoms,
m1 is 1 to 50,
However, Y ¹ is an alkylene group having 2 carbon atoms is a straight chain, except where m1 is 1)
A group represented by
—CH ₂ —CR ^a1 R ^a2 —CH ₂ —
(Where
R ^a1 and R ^a2 each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms, a group of formula (2a) or a group of formula (2b):

Wherein at least one of R ^a1 and R ^a2 is a group of formula (2a) or a group of formula (2b))
A group represented by or _{^{-CH 2 -CR a3 R a4 -CH 2}} -O-CH 2 -CR a5 R a6 -CH 2 -
Wherein R ^a3 , R ^a4 , R ^a5 and R ^a6 are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, a group of formula (2a) or a group of formula (2b). , R ^a3 , R ^a4 , R ^a5 and R ^a6 are a group of the formula (2a) or a group of the formula (2b))
A group represented by
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a 9-oxo-9H-thioxanthen-yl group, dialkylaminobenzoyl group, hydrogen, alkyl A group, an aryl group, a heteroaryl group, an aralkyl group, an acyl group, a silyl group, an acetal group or —CO—NH—Z ¹ (wherein Z ¹ is an alkyl group, an aryl group or a heteroaryl group). But,
Provided that at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is a 9-oxo-9H-thioxanthen-yl group or a dialkylaminobenzoyl group. A photocurable resin composition for a liquid crystal sealant comprising a compound represented by the formula: In the compound represented by the formula (1), R ¹ and R ³ are the same and are a 9-oxo-9H-thioxanthen-yl group or a dialkylaminobenzoyl group, and R ² and R ⁴ are Each independently 9-oxo-9H-thioxanthen-yl group, dialkylaminobenzoyl group, hydrogen, alkyl group, aryl group, heteroaryl group, aralkyl group, acyl group, silyl group, acetal group or -CO-NH —Z ¹ (wherein Z ¹ is an alkyl group, an aryl group, or a heteroaryl group), and X ¹ is —Y ¹ — (O—Y ¹ ) _m1 — (where Y ¹ and m1 Is as defined in claim 1), the photocurable resin composition for a liquid crystal sealant according to claim 1. The compound represented by the formula (1) is represented by the formula (1A-1):

(Where n1 is 2 to 50)
The photocurable resin composition for liquid crystal sealing agents of Claim 1 or 2 which is a compound shown by these . The compound represented by the formula (1) is represented by the formula (1B-1):

(Wherein n2 is 2 to 50)
The photocurable resin composition for liquid crystal sealing agents of Claim 1 or 2 which is a compound shown by these . In the compound represented by the formula (1), X ¹ is —CH ₂ —CR ^a1 R ^a2 —CH ₂ — (wherein R ^a1 and R ^a2 are as defined in claim 1). R ¹ , R ³ , R ⁵ and R ⁷ are the same and are a 9-oxo-9H-thioxanthen-yl group or a dialkylaminobenzoyl group, and R ² , R ⁴ , R ⁶ and R ⁸ are each independently 9-oxo-9H-thioxanthen-yl group, dialkylaminobenzoyl group, hydrogen, alkyl group, aryl group, heteroaryl group, aralkyl group, acyl group, silyl group, acetal groups or -CO-NH-Z 1 ^(wherein, Z ¹ represents an alkyl group, an aryl group or a heteroaryl group), according to claim 1 liquid crystal sealant photocurable resin composition. The photopolymerization initiator is a photopolymerization initiator composed of a photoinitiator compound and a visible light sensitizing compound, and the photoinitiator compounds are R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^The compound represented by the formula (1) according to claim 1, wherein at least one of ⁶ , R ⁷ and R ⁸ is a dialkylaminobenzoyl group, and the visible light sensitizing compound includes R ¹ , R ² , R ³ , R ^The photocurable resin composition for a liquid crystal sealant according to claim 1, wherein at least one of ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is a 9-oxo-9H-thioxanthen-yl group.