JP5422872B2 - Method for curing photocurable composition - Google Patents

Description

The present invention is useful as a photosensitizer such as a photopolymerizable composition, a photosensitizer comprising a combination of an anthracene derivative compound and a naphthalene derivative compound or a benzene derivative compound , a photocationic polymerization initiator, and a cationic polymerizable compound. The present invention relates to a method for curing a photocurable composition containing a monomer .

  Conventionally, iodonium salts and sulfonium salts have been widely used as photoinitiators for cationic polymerization. Of these, the sulfonium salt is cured even without a photosensitizer by irradiation with UV light having a wavelength of 366 nm, such as a high-pressure mercury lamp, so that the necessity of a photosensitizer has not been particularly felt. On the other hand, since iodonium salts have a low absorption wavelength of around 240 nm, thioxanthone or anthracene-9,10-diether (hereinafter referred to as dialkoxyanthracene) having UV absorption around 360 to 400 nm is used for matching with UV light such as a high pressure mercury lamp. Have also been used as photosensitizers.

Further, even when a sulfonium salt is used as an initiator, dialkoxyanthracene is used as a photosensitizer because UV light around 366 nm is absorbed when a pigment is used as an additive. Furthermore, in recent years, longer wavelength ultraviolet LEDs have been developed, and dialkoxyanthracene is also preferably used in this case in order to match the 395 nm wavelength light of the sulfonium salt and the ultraviolet LED.
JP-A-10-147608 JP 2001-348497 A Special table 2000-515182

  However, dialkoxyanthracene is a high-sensitivity photosensitizer, but it is expensive, so it is required to reduce the amount added to the monomer. Furthermore, in order to increase the productivity of photopolymerization, the photocuring must be advanced faster. There is a need for photosensitizers that can be used.

  As a result of intensive studies on the use of anthracene-9,10-diether, which is an anthracene derivative compound, as a photosensitizer, the present inventors have found that in addition to anthracene-9,10-diether, naphthalene-1,4- Specific naphthalene derivative compounds such as diether, 4-alkoxy-naphthol or naphthalene-1,4-diol, or specific benzene derivatives such as hydroquinone (1,4-dihydroxybenzene) and catechol (1,2-dihydroxybenzene) It was found that the sensitizing effect of anthracene-9,10-diether can be remarkably enhanced by using the compound in combination, and the present invention has been completed.

That is, this invention has the summary characterized by the following.
(1) A photosensitizer containing an anthracene derivative compound represented by the formula (1) and a naphthalene derivative compound represented by the formula (2) or a benzene derivative compound represented by the formula (3) , light A curing method for a photocurable composition, comprising curing a photocurable composition containing a cationic polymerization initiator and a cationic polymerizable monomer by irradiating with light contained in a wavelength range of 360 to 450 nm.

（式（１）中、Ｒ_１はアルキル基を示す。また、ｎ、ｍは０、１〜４から選ばれる整数である。なお、ｎ、ｍが０の場合は、無置換の水素原子を表す。Ｘ_１及びＹ_１はそれぞれ独立して、水素原子、アルキル基、アルコキシ基、ハロゲン原子、ニトロ基、スルホン酸基、水酸基、アミノ基又はカルボアルコキシ基を示し、ｎ、ｍが２以上の場合は、Ｘ_１同士あるいはＹ_１同士が同一でも異なっていてもよい。）

(In formula (1), R ₁ represents an alkyl group . N and m are integers selected from 0 and 1 to 4. When n and m are 0, an unsubstituted hydrogen atom is X ₁ and Y ₁ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group, a sulfonic acid group, a hydroxyl group, an amino group, or a carboalkoxy group, and n and m are 2 or more. In this case, X ₁ or Y ₁ may be the same or different.)

（式（２）中、Ｒ₂，Ｒ₃はそれぞれ独立して、水素原子又はアルキル基を示す。また、ｐは０、１又は２の整数であり、ｑは０、１〜４から選ばれる整数である。なお、ｐ、ｑが０の場合は、無置換の水素原子を表す。Ｘ₂及びＹ₂はそれぞれ独立して、水素原子、アルキル基、アルコキシ基、ハロゲン原子、ニトロ基、スルホン酸基、水酸基、アミノ基又はカルボアルコキシ基を示し、ｐ、ｑが２以上の場合は、Ｘ₂同士あるいはＹ₂同士が同一でも異なっていてもよい。）

(In the formula (2), R ₂ and R ₃ each independently represent a hydrogen atom or an alkyl group . Further, p is an integer of 0, 1 or 2 , and q is selected from 0 and 1-4. In addition, when p and q are 0, it represents an unsubstituted hydrogen atom, X ₂ and Y ₂ are each independently a hydrogen atom, alkyl group, alkoxy group, halogen atom, nitro group, sulfone. An acid group, a hydroxyl group, an amino group or a carboalkoxy group, and when p and q are 2 or more, X _{2 s} or Y _{2 s} may be the same or different.

（式（３）中、Ｒ_４，Ｒ_５はそれぞれ独立して、水素原子又はアルキル基を示し、置換基ＯＲ_４とＯＲ_５は互いにオルト又はパラ位に位置する。また、ｒは０、１〜４から選ばれる整数である。Ｘ_３は水素原子、アルキル基、アルコキシ基、ハロゲン原子、ニトロ基、スルホン酸基、水酸基、アミノ基又はカルボアルコキシ基を示し、ｒが２以上の場合は、Ｘ_３同士が同一でも異なっていてもよい。）

(In Formula (3), R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group, and the substituents OR ₄ and OR ₅ are located in the ortho or para position with respect to each other. X ₃ is an integer selected from 4. X ₃ represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group, a sulfonic acid group, a hydroxyl group, an amino group, or a carboalkoxy group, and when r is 2 or more, X ₃ may be the same or different.)

(2) The curing method of the photocurable composition according to the above (1), wherein in formula (1), R ₁ is a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or a 2-ethylhexyl group. .
(3) In Formula (2), all of R ₂ , R ₃ , X ₂ and Y ₂ are hydrogen atoms ; R ₂ , R ₃ and Y ₂ are hydrogen atoms and X ₂ is a methyl group ; R ₂ , X ₂ And Y ₂ is a hydrogen atom and R ₃ is a methyl group ; R ₂ and R ₃ are ethyl groups and X ₂ and Y ₂ are hydrogen atoms ; R ₂ and R ₃ are ethyl groups, X ₂ is a methyl group, and Y ₂ is The method for curing a photocurable composition according to (1) above, wherein R ₂ is an ethyl group, R ₃ is a methyl group, and X ₂ and Y ₂ are hydrogen atoms .
(4) In formula (3), all of R ₄ , R ₅ and X ₃ are hydrogen atoms ; R ₄ and X ₃ are hydrogen atoms and R ₅ is a methyl group; R ₄ and R ₅ are hydrogen atoms and X ₃ is The method for curing a photocurable composition according to the above (1), wherein R ₄ and R ₅ are hydrogen atoms and X ₃ is a t-butyl group .
(5) In the formula (1), R ₁ is a methyl group, an ethyl group, an n-propyl group, an n-butyl group or a 2-ethylhexyl group, and in the formula (2), R ₂ and R ₃ are an ethyl group. X ₂ and Y ₂ are hydrogen atoms ; R ₂ and R ₃ are ethyl groups and X ₂ is a methyl group and Y ₂ is a hydrogen atom ; or R ₂ is an ethyl group and R ₃ is a methyl group and X ₂ and Y _The method for curing a photocurable composition according to the above (1), wherein ₂ is a hydrogen atom .
(6) R ₁ in formula (1) is a methyl group, ethyl group, n-propyl group, n-butyl group or 2-ethylhexyl group, and R ₂ , X ₂ , Y ₂ in formula (2) The method for curing a photocurable composition according to the above (1), wherein is a hydrogen atom and R ₃ is a methyl group.
(7) In the formula (1), R ₁ is a methyl group, an ethyl group, an n-propyl group, an n-butyl group or a 2-ethylhexyl group, and R ₂ , R ₃ , X ₂ in the formula (2) , Y ₂ are all hydrogen atoms ; or R ₂ , R ₃ , Y ₂ are hydrogen atoms and X ₂ is a methyl group . The method for curing a photocurable composition according to the above (1).
(8) In Formula (1), R ₁ is an n-butyl group, and in Formula (2), all of R ₂ , R ₃ , X ₂ and Y ₂ are hydrogen atoms ; R ₂ , X ₂ and Y ₂ Is a hydrogen atom and R ₃ is a methyl group ; or R ₂ and R ₃ are ethyl groups and X ₂ and Y ₂ are hydrogen atoms. The method for curing a photocurable composition according to the above (1).
(9) In the formula (1), R ₁ is a methyl group, an ethyl group, an n-propyl group, an n-butyl group or a 2-ethylhexyl group, and in the formula (3), R ₄ , R ₅ , X ₃ Are all hydrogen atoms ; R ₄ and X ₃ are hydrogen atoms and R ₅ is a methyl group; R ₄ and R ₅ are hydrogen atoms and X ₃ is a methyl group; or R ₄ and R ₅ are hydrogen atoms and X ₃ is t -Curing method of the photocurable composition as described in said (1) which is a butyl group .
(10) In formula (1), R ₁ is an n-butyl group, and in formula (3), all of R ₄ , R ₅ and X ₃ are hydrogen atoms ; or R ₄ and X ₃ are hydrogen atoms. The method for curing a photocurable composition according to the above (1), wherein R ₅ is a methyl group.
(11) The anthracene derivative compound represented by the formula (1) is 9,10-diethoxyanthracene or 9,10-di (n-butoxy) anthracene, and the naphthalene derivative compound represented by the formula (2) is 1,4-naphthohydroquinone, 2-methyl-1,4-naphthohydroquinone, 4-methoxy-1-naphthol , 1,4- diethoxynaphthalene, or 1-ethoxy-4-methoxynaphthalene (1) The curing method of the photocurable composition as described in 1.
(12) The anthracene derivative compound represented by the formula (1) is 9,10-diethoxyanthracene or 9,10-di (n-butoxy) anthracene, and the benzene derivative compound represented by the formula (3) is , hydroquinone, method for curing the photocurable composition according to the above (1) is 4-methoxyphenol or Kateko Le.
(13) The naphthalene derivative compound represented by the formula (2) or the benzene derivative compound represented by the formula (3) is added in an amount of 0.1 to 10 with respect to 1 part by weight of the anthracene derivative compound represented by the formula (1). The method for curing a photocurable composition according to any one of (1) to (12), wherein the photocurable composition is contained in parts by weight.
( 14) The method for curing a photocurable composition according to any one of ( 1) to (13), further including a pigment .
( 15) The method for curing a photocurable composition according to any one of ( 1) to ( 14) , wherein the cationically polymerizable monomer is an epoxy compound or vinyl ether.

The photosensitizer containing the anthracene derivative compound and the naphthalene derivative compound or the benzene derivative compound of the present invention is independent for the photocationic polymerization carried out by irradiating light in the wavelength range of 360 to 450 nm . Compared to the case, the composition has a high sensitizing effect on the acid generation of the initiator and is industrially valuable.

  The anthracene derivative compound in the sensitizer of the present invention is a compound represented by the formula (1).

（式（１）中、Ｒ₁はアルキル基を示す。また、ｎ、ｍは０、１〜４から選ばれる整数であり、ｎ、ｍが０の場合は、無置換の水素原子を表す。Ｘ_１及びＹ_１はそれぞれ独立して、水素原子、アルキル基、アルコキシ基、ハロゲン原子、ニトロ基、スルホン酸基、水酸基、アミノ基又はカルボアルコキシ基を示し、ｎ、ｍが２以上の場合は、Ｘ_１同士あるいはＹ_１同士が同一でも異なっていてもよい。）

(In formula (1), R ₁ represents an alkyl group . N and m are integers selected from 0 and 1 to 4, and when n and m are 0, they represent an unsubstituted hydrogen atom. X ₁ and Y ₁ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group, a sulfonic acid group, a hydroxyl group, an amino group or a carboalkoxy group, and when n and m are 2 or more, X ₁ or Y ₁ may be the same or different.)

Examples of the alkyl group represented by R ₁ in the above formula (1) include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, n-pentyl group, n- A hexyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group, etc. are mentioned .
The alkyl group represented by the above following formula (1) Medium _{X 1} or _{Y 1,} methyl group, ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl Group, n-pentyl group, n-hexyl group, 4-methylpentyl group and the like. Examples of the alkoxy group represented by X ₁ or Y ₁ in the formula (1) include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a phenoxy group. Examples of the halogen atom represented by X ₁ or Y ₁ in Formula (1) include a chlorine atom, a bromine atom, and an iodine atom. Examples of the sulfonic acid group represented by X ₁ or Y ₁ in the formula (1) include a methanesulfonic acid group and an ethanesulfonic acid group in addition to the sulfonic acid group. In the formula (1), the amino group represented by X ₁ or Y ₁ includes, in addition to the amino group, a methylamino group, an ethylamino group, an n-propylamino group, an n-butylamino group, a dimethylamino group, and a diethylamino group. , Di (n-propyl) amino group, di (n-butyl) amino group and the like. Examples of the carboalkoxy group represented by X ₁ or Y ₁ in formula (1) include a hydroxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, and a phenoxycarbonyl group.

Typical anthracene derivative compounds in the present invention include, for example, anthracene-9,10-diether, and examples thereof include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-di ( n-propoxy) anthracene, 9,10-di (i-propoxy) anthracene, 9,10-di (n-butoxy) anthracene, 9,10-di (i-butoxy) anthracene, 9,10-di (n- Pentyloxy) anthracene, 9,10-di (n-hexyloxy) anthracene, 9,10-di (2-ethylhexyloxy) anthracene, 9,10-di (dodecyloxy) anthracene , 2 -methyl-9,10- Dimethoxyanthracene, 2-methyl-9,10-diethoxyanthracene, 2-methyl-9,1 0-di (n-propoxy) anthracene, 2-methyl-9,10-di (i-propoxy) anthracene, 2-methyl-9,10-di (n-butoxy) anthracene, 2-methyl-9,10- Di (i-butoxy) anthracene, 2-methyl-9,10-di (n-pentyloxy) anthracene, 2-methyl-9,10-di (n-hexyloxy) anthracene, 2-ethyl-9,10- Dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-ethyl-9,10-di (n-propoxy) anthracene, 2-ethyl-9,10-di (i-propoxy) anthracene, 2-ethyl -9,10-di (n-butoxy) anthracene, 2-ethyl-9,10-di (i-butoxy) anthracene, 2-ethyl-9,10-di (n-pe Tiloxy) anthracene, 2-ethyl-9,10-di (n-hexyloxy) anthracene, 2-t-butyl-9,10-dimethoxyanthracene, 2-t-butyl-9,10-diethoxyanthracene, 2- t-butyl-9,10-di (n-propoxy) anthracene, 2-t-butyl-9,10-di (i-propoxy) anthracene, 2-t-butyl-9,10-di (n-butoxy) Anthracene, 2-t-butyl-9,10-di (i-butoxy) anthracene, 2-t-butyl-9,10-di (n-pentyloxy) anthracene, 2-t-butyl-9,10-di (N-hexyloxy) anthracene, 2- (4-methylpentyl) -9,10-dimethoxyanthracene, 2- (4-methylpentyl) -9,10-diethoxyan Helix, 2- (4-methylpentyl) -9,10-di (n-propoxy) anthracene, 2-t-butyl-9,10-di (i-propoxy) anthracene, 2- (4-methylpentyl)- 9,10-di (n-butoxy) anthracene, 2- (4-methylpentyl) -9,10-di (i-butoxy) anthracene, 2- (4-methylpentyl) -9,10-di (n- Pentyloxy) anthracene, 2- (4-methylpentyl) -9,10-di (n-hexyloxy) anthracene, 2-chloro-9,10-dimethoxyanthracene, 2-chloro-9,10-diethoxyanthracene, 2-chloro-9,10-di (n-propoxy) anthracene, 2-chloro-9,10-di (i-propoxy) anthracene, 2-chloro-9,10-di (n- Butoxy) anthracene, 2-chloro-9,10-di (i-butoxy) anthracene, 2-chloro-9,10-di (n-pentyloxy) anthracene, 2-chloro-9,10-di (n-hexyl) Oxy) anthracene, 2-phenoxy-9,10-dimethoxyanthracene, 2-phenoxy-9,10-diethoxyanthracene, 2-phenoxy-9,10-di (n-propoxy) anthracene, 2-phenoxy-9,10 -Di (i-propoxy) anthracene, 2-phenoxy-9,10-di (n-butoxy) anthracene, 2-phenoxy-9,10-di (i-butoxy) anthracene, 2-phenoxy-9,10-di (N-pentyloxy) anthracene, 2-phenoxy-9,10-di (n-hexyloxy) anthracene, 2, -Dimethyl-9,10-dimethoxyanthracene, 2,3-dimethyl-9,10-diethoxyanthracene, 2,3-dimethyl-9,10-di (n-propoxy) anthracene, 2,3-dimethyl-9, 10-di (i-propoxy) anthracene, 2,3-dimethyl-9,10-di (n-butoxy) anthracene, 2,3-dimethyl-9,10-di (i-butoxy) anthracene, 2,3- Examples include dimethyl-9,10-di (n-pentyloxy) anthracene and 2,3-dimethyl-9,10-di (n-hexyloxy) anthracene. Examples of the structural formula are shown below.

(In the above structural formula, Et represents an ethyl group, n-Pr represents an n-propyl group, n-Bu represents an n-butyl group, and t-Bu represents a t-butyl group.)
Of these anthracene-9,10-diether compounds, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-di (n-propoxy) anthracene, 9,10-di (n -Butoxy) anthracene or 9,10-bis (2-ethylhexyloxy) anthracene, particularly preferably 9,10-di (n-butoxy) anthracene.

  The naphthalene derivative compound in the sensitizer of the present invention is a compound represented by the formula (2).

（式（２）中、Ｒ₂，Ｒ₃はそれぞれ独立して、水素原子又はアルキル基を示す。また、ｐは０、１又は２の整数であり、ｑは０、１〜４から選ばれる整数である。なお、ｐ、ｑが０の場合は、無置換の水素原子を表す。Ｘ₂及びＹ₂はそれぞれ独立して、水素原子、アルキル基、アルコキシ基、ハロゲン原子、ニトロ基、スルホン酸基、水酸基、アミノ基又はカルボアルコキシ基を示し、ｐ、ｑが２以上の場合は、Ｘ₂同士あるいはＹ₂同士が同一でも異なっていてもよい。）

(In the formula (2), R ₂ and R ₃ each independently represent a hydrogen atom or an alkyl group . Further, p is an integer of 0, 1 or 2 , and q is selected from 0 and 1-4. In addition, when p and q are 0, it represents an unsubstituted hydrogen atom, X ₂ and Y ₂ are each independently a hydrogen atom, alkyl group, alkoxy group, halogen atom, nitro group, sulfone. An acid group, a hydroxyl group, an amino group or a carboalkoxy group, and when p and q are 2 or more, X _{2 s} or Y _{2 s} may be the same or different.

In the above formula (2), the alkyl groups represented by R ₂ and R ₃ are methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, n-pentyl group. , n- hexyl group, a 2-ethylhexyl group, n- decyl group, Ru include n- dodecyl group and the like.

In the above formula (2), examples of the alkyl group represented by X ₂ and Y ₂ include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group. As amino group, amino group, methylamino group, ethylamino group, n-propylamino group, n-butylamino group, dimethylamino group, diethylamino group, di (n-propyl) amino group, di (n-butyl) amino Groups and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the carboalkoxy group include a hydroxylcarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, and a phenoxycarbonyl group. Examples of the sulfonic acid group include a methanesulfonic acid group and an ethanesulfonic acid group in addition to the sulfonic acid group.

The representative naphthalene derivative compound in the present invention is, for example, 4-alkoxy-1-naphthol, and examples thereof include 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4- (n -Propoxy) -1-naphthol, 4- (i-propoxy) -1-naphthol, 4- (n-butoxy) -1-naphthol, 4- (i-butoxy) -1-naphthol, 4- (n-pentyl) Oxy) -1-naphthol, 4- (n-hexyloxy) -1-naphthol, 4- (n-octyloxy) -1-naphthol, 4- (2-ethylhexyloxy) -1-naphthol , 2 -methyl- 4-methoxy-1-naphthol, 2-methoxy-4-methoxy-1-naphthol, 2-chloro-4-methoxy-1-naphthol, 2-amino-4-methoxy Ci-1-naphthol and the like. Examples of naphthalene-1,4-diether include 1,4-dimethoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-di (n-propoxy) naphthalene, 1,4-di (i-propoxy). ) Naphthalene, 1,4-di (n-butoxy) naphthalene, 1,4-di (i-butoxy) naphthalene, 1,4-di (n-pentyloxy) naphthalene, 1,4-di (n-hexyloxy) ) Naphthalene, 1,4-bis (2-ethylhexyloxy) naphthalene, 1,4-di (n-dodecyloxy) naphthalene , 1 -methoxy-4-ethoxynaphthalene , 1 -ethoxy-4-butoxynaphthalene , 2 -methyl -1,4-dimethoxynaphthalene, 2-methyl-1,4-diethoxynaphthalene, 2-methyl-1,4-di (n-propoxy) naphthalene, 2 Methyl-1,4-di (i-propoxy) naphthalene, 2-methyl-1,4-di (n-butoxy) naphthalene, 2-methyl-1,4-di (i-butoxy) naphthalene, 2-methyl- 1,4-di (n-pentyloxy) naphthalene, 2-methyl-1,4-di (n-hexyloxy) naphthalene, 2-methyl-1,4-bis (2-ethylhexyloxy) naphthalene, 2-methyl 1,4-di (n- dodecyloxy) naphthalene, 2 - methyl-1-methoxy-4-ethoxy-naphthalene, 2 - methyl-1-ethoxy-4-butoxy-naphthalene, 2 - chloro-1,4-dimethoxynaphthalene 2-chloro-1,4-diethoxynaphthalene, 2-methyl-1,4-di (n-propoxy) naphthalene, 2-chloro-1,4-di (i-propoxy) naphthalene 2-chloro-1,4-di (n-butoxy) naphthalene, 2-chloro-1,4-di (i-butoxy) naphthalene, 2-chloro-1,4-di (n-pentyloxy) naphthalene 2-chloro-1,4-di (n-hexyloxy) naphthalene, 2-chloro-1,4-bis (2-ethylhexyloxy) naphthalene, 2-chloro-1,4-di (n-dodecyloxy) naphthalene, 2 - chloro-1-methoxy-4-ethoxy-naphthalene, 2 - chloro-1-ethoxy-4-butoxy-naphthalene, 1, 2,4-trimethoxy-naphthalene, 1,2,4-triethoxy-naphthalene, 2, 3-dichloro-1,4-diethoxynaphthalene, 2,3-dimethoxy-1,4-diethoxynaphthalene, 2-amino-3-chloro-1,4-diethoxynaphthalene, 2, 3-dichloro-1,4-dimethoxynaphthalene, 2,3-dimethoxy-1,4-dimethoxynaphthalene, 2-amino-3-chloro-1,4-dimethoxynaphthalene, 1,4,5-triethoxynaphthalene, 1,4 , 5-trimethoxynaphthalene, 6-methyl-1,4-diethoxynaphthalene, 6-methyl-1,4-dimethoxynaphthalene and the like. Furthermore, examples of naphthalate down-1,4-diol, 1,4-naphthohydroquinone, 2-methyl-1,4-naphthohydroquinone, 2-hydroxy-1,4-naphthohydroquinone, 2-methoxy - 1,4-naphthohydroquinone, 2-ethoxy-1,4-naphthohydroquinone, 2-chloro-1,4-naphthohydroquinone, 2-carboxy-1,4-naphthohydroquinone, 1,4-dihydroxynaphthalen-2-ylsulfur -Ylsulfonic acid, 5-methoxy-1,4-naphthohydroquinone, 5-ethoxy-1,4-naphthohydroquinone, 5-hydroxy-1,4-naphthohydroquinone, 5-amino-1,4-naphthohydroquinone, 6- Methyl-1,4-naphthohydroquinone, 6-chloro-1,4-naphthohydroquinone, 2,3-dichloro-1,4 Naphthohydroquinone, 2,3-dihydroxy-1,4-naphthohydroquinone, 2,3-dimethoxy-1,4-naphthohydroquinone, 2-amino-3-chloro-1,4-naphthohydroquinone the like. Examples of structural formulas are shown below. In the following structural formulas, Et represents an ethyl group, n-Pr represents an n-propyl group, n-Bu represents an n-butyl group, and n-Hx represents an n-hexyl group.

  When the naphthalene derivative compound is a 4-alkoxy-1-naphthol compound, it is preferably 4-methoxy-1-naphthol or 4-ethoxy-1-naphthol, particularly preferably 4-methoxy-1-naphthol. . In the case of a naphthalene-1,4-diether compound, 1,4-dimethoxynaphthalene or 1,4-diethoxynaphthalene is preferable, and 1,4-diethoxynaphthalene is particularly preferable. Furthermore, in the case of a naphthalene-1,4-diol compound, 1,4-naphthohydroquinone or 2-methyl-1,4-naphthohydroquinone is preferable, and 1,4-naphthohydroquinone is particularly preferable.

  The benzene derivative compound in the present invention is a compound represented by the formula (3).

（式（３）中、Ｒ₄，Ｒ₅はそれぞれ独立して、水素原子又はアルキル基を示し、置換基ＯＲ₄，ＯＲ₅は互いにオルト（ｏ）又はパラ（ｐ）に位置する。また、ｒは０、１〜４から選ばれる整数である。なお、ｒが０の場合は、無置換の水素原子を表す。Ｘ₃は水素原子、アルキル基、アルコキシ基、ハロゲン原子、ニトロ基、スルホン酸基、水酸基、アミノ基又はカルボアルコキシ基を示し、ｒが２以上の場合は、Ｘ₃同士が同一でも異なっていてもよい。）

(In Formula (3), R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group, and the substituents OR ₄ and OR ₅ are located in ortho (o) or para (p). r is an integer selected from 0 and 1 to 4. When r is 0, it represents an unsubstituted hydrogen atom, and X ₃ represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group, a sulfone. An acid group, a hydroxyl group, an amino group, or a carboalkoxy group, and when r is 2 or more, X ₃ may be the same or different.

In the above formula (3), examples of the alkyl group represented by R ₄ and R ₅ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and n-pentyl. Group, n-hexyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group and the like .

In the above formula (3), examples of the alkyl group represented by X ₃ include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group. As amino group, amino group, methylamino group, ethylamino group, n-propylamino group, n-butylamino group, dimethylamino group, diethylamino group, di (n-propyl) amino group, di (n-butyl) amino Groups and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the carboxyl group include a hydroxylcarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, and a phenoxycarbonyl group. Examples of the sulfonic acid group include a methanesulfonic acid group and an ethanesulfonic acid group in addition to the sulfonic acid group.

In the above formula (3), the substituents OR ₄ and OR ₅ are located in ortho (o) or para (p) with each other. As a representative compound located in the ortho, there is catechol, and a representative located in para. A typical compound is hydroquinone. On the other hand, examples of the compound in which the substituents OR ₄ and OR ₅ are located at the meta (m) include resorcinol (1,3-dihydroxybenzene). It is not preferable.

Representative benzene derivative compounds in the present invention include, for example, hydroquinone (1,4-dihydroxybenzene), catechol (1,2-dihydroxybenzene), alkoxyphenol, dialkoxybenzene and derivatives thereof. Can be mentioned. Examples of hydroquinone derivatives include 2-methyl-hydroquinone, 2-ethyl-hydroquinone, 2-n-propyl-hydroquinone, 2-i-propyl-hydroquinone, 2-n-butyl-hydroquinone, 2-s-butyl- Hydroquinone, 2-t-butyl-hydroquinone, 2,5-bis (1,1-dimethyl-n-butyl) -hydroquinone, 2,5-bis (1,1,3,3-tetramethyl-n-butyl) -Hydroquinone etc. are mentioned.
Examples of the catechol derivative include 3-methyl-catechol, 4-methyl-catechol, 3-ethyl-catechol and the like.
Examples of alkoxyphenols include 4-methoxyphenol (methoquinone), 4-ethoxyphenol, 4-butoxyphenol , 2 -methoxyphenol (guaiacol), 2-ethoxyphenol (guetol), and the like. Examples of similar compounds include arbutin.
Furthermore, examples of dialkoxybenzene include 1,2-dimethoxybenzene (veratol), 1,4-dimethoxybenzene, 1,4-diethoxybenzene, and the like.
Examples of structural formulas are shown below. In the following structural formulas, Et represents an ethyl group, n-Pr represents an n-propyl group, n-Bu represents an n-butyl group, and t-Bu represents a t-butyl group.

  When the benzene derivative is an ortho-substituted benzene derivative compound, it is preferably catechol, and when it is a para-substituted benzene derivative compound, it is preferably hydroquinone or 4-methoxyphenol (methoquinone), and among these, Hydroquinone or catechol is preferred.

  The photosensitizer of the present invention is a composition containing the above anthracene derivative compound and a naphthalene derivative compound or a benzene derivative compound, and the content ratio in the composition is 1 part by weight of the anthracene derivative compound. On the other hand, the amount of naphthalene derivative compound or benzene derivative compound is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight. When the naphthalene derivative compound or the benzene derivative compound is less than 0.1 parts by weight, a synergistic effect is not observed, and even when the amount is more than 10 parts by weight, it is difficult to obtain an effect according to the amount.

The photosensitizer of the present invention contains an anthracene derivative compound and a naphthalene derivative compound or a benzene derivative compound. However, depending on the case, each component may be two or more kinds, or an anthracene derivative compound and naphthalene. You may contain 3 components of a derivative compound and a benzene derivative compound.
When the photosensitizer of the present invention contains an anthracene derivative compound and a naphthalene derivative compound, preferred examples thereof include the following examples.
That is, the anthracene derivative compound is 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-di (n-propoxy) anthracene, 9,10-di (n-butoxy) anthracene or 9,10- When it is any of bis (2-ethylhexyloxy) anthracene and the naphthalene derivative compound is 4-alkoxy-1-naphthol, a combination with 4-methoxy-1-naphthol is preferable. A combination of -di (n-butoxy) anthracene and 4-methoxy-1-naphthol is preferred. When the naphthalene derivative compound is naphthalene-1,4-diether, a combination with either 1,4-diethoxynaphthalene or 2-methyl-1,4-diethoxynaphthalene is preferable. , 10-di (n-butoxy) anthracene and 1,4-diethoxynaphthalene are preferred. Furthermore, when the naphthalene derivative compound is a naphthalene-1,4-diol compound, a combination with either 1,4-naphthohydroquinone or 2-methyl-1,4-naphthohydroquinone is preferable, and in particular, 9,10 -A combination of di (n-butoxy) anthracene and 1,4-naphthohydroquinone is preferred. In addition, a combination of 9,10-diethoxyanthracene and 4-methoxy-1-naphthol, 1,4-diethoxynaphthalene or 1,4-naphthohydroquinone is also preferable.

When the photosensitizer of the present invention contains an anthracene derivative compound and a benzene derivative compound, preferred examples thereof include the following examples.
That is, the anthracene derivative compound is 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-di (n-propoxy) anthracene, 9,10-di (n-butoxy) anthracene or 9,10- The combination which is either bis (2-ethylhexyloxy) anthracene and whose benzene derivative compound is any one of hydroquinone, 2-methyl-hydroquinone, 2-t-butyl-hydroquinone, catechol, and methoquinone is mentioned. Of these combinations, a combination in which the anthracene derivative is 9,10-diethoxyanthracene or 9,10-di (n-butoxy) anthracene and the benzene derivative is hydroquinone, 4-methoxyphenol or catechol is particularly preferable.

  The photosensitizer of the present invention is a monomer or solvent for dilution, an antifoaming agent, a leveling agent, a thickener, a flame retardant, a light stabilizer, and a filler as long as the effects of the present invention are not impaired. In addition, various additives such as an antistatic agent, a flow regulator, and a coupling agent may be further contained. Examples of the monomer for dilution include an epoxy compound, a vinyl compound, a dicycloorthoester compound, a spiro orthocarbonate compound, and an oxetane compound.

  The photosensitive acid generator of the present invention is a composition containing the above-described photosensitizer and a cationic photopolymerization initiator. Examples of the cationic photopolymerization initiator include onium salts such as sulfonium salts and iodonium salts. Sulphonium salts include S, S, S ′, S′-tetraphenyl-S, S ′-(4,4′-thiodiphenyl) disulfonium bishexafluorophosphate, diphenyl-4-phenylthiophenylsulfonium hexafluorophosphate And triphenylsulfonium hexafluorophosphate. For example, UVI6992 manufactured by Dow Chemical can be used. On the other hand, examples of the iodonium salt include 4-isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, and 4-isopropylphenyl-4′-methylphenyliodonium tetrakispentafluorophenylborate. For example, CGI-552 manufactured by Ciba Specialty Chemicals and 2074 manufactured by Rhodia can be used.

The composition of the photosensitive acid generator of the present invention is preferably 0.2 to 5 parts by weight, particularly preferably 0.5 to 1 part by weight of the above photosensitizer with respect to 1 part by weight of the cationic photopolymerization initiator. It is selected from the range of parts by weight. If the ratio of the photosensitizer is less than 0.2 parts by weight, the sensitizing effect may be difficult to be exhibited, and if it exceeds 5 parts by weight, the physical properties of the cured product may be adversely affected.
The photosensitive acid generator of the present invention is a monomer or solvent for dilution, an antifoaming agent, a leveling agent, a thickener, a flame retardant, a light stabilizer, as long as the effects of the present invention are not impaired. You may further contain various additives, such as a filler, an antistatic agent, a flow control agent, and a coupling agent. Examples of the monomer for dilution include an epoxy compound, a vinyl compound, a dicycloorthoester compound, a spiro orthocarbonate compound, and an oxetane compound.

  The photosensitive acid generator of the present invention can be photoexcited by irradiation with visible light, ultraviolet light or the like, and then decompose to generate an acid. In particular, irradiation with light in the wavelength range of 360 to 450 nm enables rapid photoexcitation and subsequent decomposition to generate acid. As the light source in this case, any light source can be used as long as it can irradiate light in the wavelength range, preferably 360 to 450 nm. For example, in addition to sunlight, a high-pressure mercury lamp, a xenon lamp, an ultraviolet LED, a blue-violet LED, a metal halide lamp, an H lamp, a D lamp, and a V lamp manufactured by Fusion Corporation can be suitably used.

  A photocurable composition can be obtained by combining the photo-sensitive acid generator of the present invention with a cationic polymerizable monomer. Examples of the cationic polymerizable monomer to be used include epoxy compounds and vinyl ethers. Commonly used epoxy compounds are alicyclic epoxy compounds, epoxy-modified silicones, and aromatic glycidyl ethers. Examples of alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis (3,4-epoxycyclohexyl) adipate. For example, UVR6105 and UVR6110 manufactured by Dow Chemical can be used. I can do it. Examples of the epoxy-modified silicone include UV-9300 manufactured by Toshiba GE Silicone. Examples of the aromatic glycidyl compound include 2,2'-bis (4-glycidyloxyphenyl) propane. Examples of the vinyl ether include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether and the like.

  The composition of the photocurable composition is preferably from 0.05 to 20 parts by weight, particularly preferably from 1 to 5 parts by weight, based on 100 parts by weight of the cationic polymerizable monomer. Selected. If the amount of the light-sensitive acid generator used relative to the cationic polymerizable monomer is small, the curing rate is slow, and if the amount of the light-sensitive acid generator is too large, the physical properties of the cured product may be lowered.

When an anthracene derivative compound which is a composition component of the photocurable composition of the present invention, for example, anthracene-9,10-diether is used alone, when the addition concentration is 0.5% by weight or less based on the monomer, Curing may be insufficient. Even in this case, if a naphthalene derivative compound or a benzene derivative compound coexists, the sensitizing effect of anthracene-9,10-diether is sufficiently exhibited. The reason is not clear, but it is thought that some interaction between anthracene-9,10-diether and naphthalene derivative compound or benzene derivative compound promotes electron transfer to the initiator. .
In the present invention, the anthracene derivative compound and the naphthalene derivative compound or the benzene derivative compound may be added separately, but a presensitized photosensitizer composition is preferred.

  The photocurable composition of the present invention may contain an epoxy-based diluent, an oxetane-based diluent, a vinyl ether-based diluent or a pigment as necessary. Examples of the pigment include a blue pigment, a yellow pigment, a red pigment, a white pigment, and a black pigment. Examples of the black pigment include carbon black, acetylene black, lamp black, and aniline black. Examples of yellow pigments include yellow lead, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa Yellow G, Hansa Yellow 10G, Benzidine Yellow G, and Benzidine Yellow GR. Quinoline yellow lake, permanent yellow NCG, tartrazine lake and the like. Examples of red pigments include bengara, cadmium red, red lead, mercury cadmium sulfide, permanent red 4R, risor red, lake red D, brilliant carmine 6B, eosin lake, rhodamine lake B, alizarin lake, brilliant carmine 3B, and the like. . Examples of the blue pigment include bitumen, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated product, first sky blue, and induslen blue BC. Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide. Examples of other pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white.

The photocurable composition of the present invention can be cured rapidly by irradiation with light included in the wave Naganori circumference 3 60~450nm. As the light source in this case, any light source capable of irradiating light included in the wavelength range of 360 to 450 nm can be used. Metal halide lamps, H lamps, D lamps, and V lamps manufactured by Fusion Corporation can be suitably used. It is also possible to cure not only the film-like material applied on the substrate but also the lump-like material.

  For example, the photocurable composition of the present invention is molded into a film as follows. That is, the photopolymerizable composition is applied on a substrate using a bar coater. The substrate is not particularly limited, such as a film, paper, aluminum foil, or metal. As the film, a polyester film, for example, Toray Lumirror can be used. The film thickness of the Lumirror film is usually about 100 μm. Although the rod number of the bar coater to be used is not particularly specified, a bar coater having a rod number such that the film thickness is several μm to several tens μm can be used. A photocurable composition such as an epoxy compound can be quickly cured by irradiating the thus obtained coated product with light using a light source as described above. As the light source, in addition to sunlight, a xenon lamp, an ultraviolet LED, a blue-violet LED, a metal halide lamp, a D lamp and a V lamp manufactured by Fusion Corporation can be suitably used. It is also possible to cure not only the film-like material applied on the substrate but also the lump-like material.

Examples of the present invention will be described below, but the present invention is not limited to these examples. All “parts” in the examples represent parts by weight.
In addition, the following abbreviations in the table mean the same as described.
UVR6105: Dow alicyclic epoxy compound UV16992: Dow sulfonium salt DBA: 9,10-di (n-butoxy) anthracene MNT: 4-methoxy-1-naphthol CGI552: iodonium salt manufactured by Ciba DEN: 1, 4-Diethoxynaphthalene EMN: 1-ethoxy-4-methoxynaphthalene NHQ: 1,4-naphthohydroquinone 2Me-DBA: 2-methyl-9,10-di (n-butoxy) anthracene 2PhO-DEA: 2-phenoxy- 9,10-diethoxyanthracene 2CI-DEA: 2-chloro-9,10-diethoxyanthracene 2Me-NHQ: 2-methyl-1,4-naphthohydroquinone HQ: hydroquinone resorcinol: 1,3-dihydroxybenzene catechol: 1 , 2-Dihydro Shibenzen

(Example 1-1)
As a monomer, 100 parts of an alicyclic epoxy compound (UVR6105 manufactured by Dow Chemical Company), 4.8 parts of a sulfonium salt (UVI6992 manufactured by Dow Chemical Company), 9,10-di (n-butoxy) anthracene (hereinafter, DBA) A photoacid generator composed of 0.25 parts of 4-methyl-1-naphthol (hereinafter also referred to as MNT) was mixed to prepare a photocuring composition. The composition was applied onto a polyester film (Toray Lumirror, Inc.) using a bar coater so that the film thickness was 12 μm. Next, light was irradiated from the surface using a UV LED manufactured by Thunder. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 3 mW / cm ² . The light irradiation time “tack free time” until tackiness disappears was 4.5 minutes.

(Example 1-2)
A photocuring composition was prepared in the same manner as in Example 1-1 except that 4-methoxy-1-naphthol was changed to 0.5 part, and the "tack free time" was measured to be 4.3 minutes. .

(Example 1-3)
A photocuring composition was prepared in the same manner as in Example 1-1 except that 4-methoxy-1-naphthol was used as 1 part, and the "tack free time" was measured and found to be 4.1 minutes.

(Comparative Example 1-1)
A photocuring composition was prepared in the same manner as in Example 1-1 except that 4-methoxy-1-naphthol was changed to 0 part, and the “tack free time” was measured and found to be 30 minutes.
(Comparative Example 1-2)
A photocuring composition was prepared in the same manner as in Example 1-3, except that 9,10-di (n-butoxy) anthracene was changed to 0 part, and the “tack free time” was measured. I didn't.

The results of Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-2 are summarized in Table 1-1.

(Example 1-4)
As a monomer, 100 parts of an alicyclic epoxy compound (UVR6105 manufactured by Dow Chemical Company), 2 parts of iodonium salt (CGI-552 manufactured by Ciba Specialty Chemicals Co., Ltd.), 9,10-di (n-butoxy) anthracene. A photo-sensitive composition was prepared by mixing 5 parts of a photosensitive acid generator consisting of 0.25 part of 4-methoxy-1-naphthol. The composition was applied onto a polyester film (Toray Lumirror, Inc.) using a bar coater so that the film thickness was 12 μm. Next, light was irradiated from the surface using a UV LED manufactured by Thunder. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 3 mW / cm ² . The light irradiation time “tack free time” until tackiness disappears was 2.9 minutes.

(Example 1-5)
A photocuring composition was prepared in the same manner as in Example 1-4, except that 0.5 part of 4-methoxy-1-naphthol was used, and the “tack free time” was measured to be 2.3 minutes. It was.

(Example 1-6)
A photocuring composition was prepared and “tack free time” was measured in the same manner as in Example 1-4 except that 4-methoxy-1-naphthol was used as 1 part, and the result was 2.2 minutes.

(Comparative Example 1-3)
A photocuring composition was prepared in the same manner as in Example 1-4 except that 4-methoxy-1-naphthol was changed to 0 part, and the "tack free time" was measured to be 23 minutes.
(Comparative Example 1-4)
A photocuring composition was prepared in the same manner as in Example 1-6, except that 9,10-di (n-butoxy) anthracene was changed to 0 part, and the “tack free time” was measured. It did not cure.
The results of Examples 1-4 to 1-6 and Comparative Examples 1-3 to 1-4 are summarized in Table 1-2.

(Example 2-1)
As a monomer, 100 parts of an alicyclic epoxy compound (UVR6105 manufactured by Dow Chemical Company), 4.8 parts of a sulfonium salt (UVI6992 manufactured by Dow Chemical Company), and 0.25 of 9,10-di (n-butoxy) anthracene A photoacid generator comprising 0.25 parts of 1,4-diethoxynaphthalene (hereinafter also referred to as DEN) was mixed to prepare a photocurable composition. The composition was applied onto a polyester film (Toray Lumirror, Inc.) using a bar coater so that the film thickness was 12 μm. Next, light was irradiated from the surface using a UV LED manufactured by Thunder. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 3 mW / cm ² . The light irradiation time “tack free time” until tackiness disappears was 5.8 minutes.

(Example 2-2)
A photocuring composition was prepared in the same manner as in Example 2-1 except that 0.5 part of 1,4-diethoxynaphthalene was used, and the “tack free time” was measured to be 5.2 minutes. .

(Example 2-3)
A photocuring composition was prepared in the same manner as in Example 2-1, except that 1 part of 1,4-diethoxynaphthalene was used, and the "tack free time" was measured to be 3.7 minutes.

(Comparative Example 2-1)
A photocuring composition was prepared in the same manner as in Example 2-1, except that 1,4-diethoxynaphthalene was changed to 0 part, and the "tack free time" was measured and found to be 30 minutes.

(Comparative Example 2-2)
A photocuring composition was prepared in the same manner as in Example 2-3 except that 9,10-di (n-butoxy) anthracene was changed to 0 part, and the “tack free time” was measured. I didn't.
The results of Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-2 are summarized in Table 2-1.

(Example 2-4)
As a monomer, 100 parts of an alicyclic epoxy compound (UVR6105 manufactured by Dow Chemical Company), 2 parts of iodonium salt (CGI-552 manufactured by Ciba Specialty Chemicals Co., Ltd.), 9,10-di (n-butoxy) anthracene. A photo-sensitive composition was prepared by mixing 5 parts of a photosensitive acid generator composed of 0.25 part of 1,4-diethoxynaphthalene. The composition was applied onto a polyester film (Toray Lumirror, Inc.) using a bar coater so that the film thickness was 12 μm. Next, light was irradiated from the surface using a UV LED manufactured by Thunder. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 3 mW / cm ² . The light irradiation time “tack free time” until tackiness disappears was 5.3 minutes.

(Example 2-5)
A photocuring composition was prepared in the same manner as in Example 2-4 except that 0.5 part of 1,4-diethoxynaphthalene was used, and the “tack free time” was measured to be 3.5 minutes. It was.

(Example 2-6)
A photocuring composition was prepared in the same manner as in Example 2-4 except that 1 part of 1,4-diethoxynaphthalene was used, and the “tack free time” was measured and found to be 3.0 minutes.

(Comparative Example 2-3)
A photocuring composition was prepared in the same manner as in Example 2-4 except that 0 part of 1,4-diethoxynaphthalene was used, and the “tack free time” was measured and found to be 23 minutes.

(Comparative Example 2-4)
A photocuring composition was prepared in the same manner as in Example 2-6 except that the amount of 9,10-di (n-butoxy) anthracene was changed to 0 part, and the “tack free time” was measured. It did not cure.
The results of Examples 2-4 to 2-6 and Comparative Examples 2-3 to 2-4 are summarized in Table 2-2.

(Example 2-7)
As a monomer, 100 parts of an alicyclic epoxy compound (UVR6105 manufactured by Dow Chemical Company), 4.8 parts of a sulfonium salt (UVI6992 manufactured by Dow Chemical Company), and 0.38 of 9,10-di (n-butoxy) anthracene A photoacid generator comprising 0.25 parts of 1-ethoxy-4-methoxynaphthalene (hereinafter also referred to as EMN) was mixed to prepare a photocuring composition. The composition was applied onto a polyester film (Toray Lumirror, Inc.) using a bar coater so that the film thickness was 12 μm. Next, light was irradiated from the surface using a UV LED manufactured by Thunder. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 3 mW / cm ² . The light irradiation time “tack free time” until tackiness disappears was 8.5 minutes.

(Example 2-8)
A photocuring composition was prepared in the same manner as in Example 2-7, except that 0.5 part of 1-ethoxy-4-methoxynaphthalene was used, and the “tack free time” was measured to be 6.3 minutes. It was.

(Example 2-9)
A photocuring composition was prepared in the same manner as in Example 2-7 except that 1-ethoxy-4-methoxynaphthalene was used as 1 part, and the “tack free time” was measured to be 4.8 minutes.

(Comparative Example 2-5)
A photocuring composition was prepared in the same manner as in Example 2-7 except that 0 part of 1-ethoxy-4-methoxynaphthalene was used, and the “tack free time” was measured and found to be 30 minutes.

(Comparative Example 2-6)
A photocuring composition was prepared in the same manner as in Example 2-9, except that 9,10-di (n-butoxy) anthracene was changed to 0 part, and the “tack free time” was measured. I didn't.
The results of Examples 2-7 to 2-9 and Comparative Examples 2-5 to 2-6 are summarized in Table 2-3.

(Example 2-10)
As a monomer, 100 parts of an alicyclic epoxy compound (UVR6105 manufactured by Dow Chemical Company), 2 parts of iodonium salt (CGI-552 manufactured by Ciba Specialty Chemicals Co., Ltd.), 9,10-di (n-butoxy) anthracene. A photo-sensitive composition was prepared by mixing 5 parts of a photosensitive acid generator composed of 0.25 part of 1-ethoxy-4-methoxynaphthalene. The composition was applied onto a polyester film (Toray Lumirror, Inc.) using a bar coater so that the film thickness was 12 μm. Next, light was irradiated from the surface using a UV LED manufactured by Thunder. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 3 mW / cm ² . The light irradiation time “tack free time” until tackiness disappears was 5.2 minutes.

(Example 2-11)
A photocuring composition was prepared in the same manner as in Example 2-10 except that 0.5 part of 1-ethoxy-4-methoxynaphthalene was used, and “tack free time” was measured. there were.

(Example 2-12)
A photocuring composition was prepared in the same manner as in Example 2-10 except that 1 part of 1-ethoxy-4-methoxynaphthalene was used, and the “tack free time” was measured to be 3.5 minutes. .

(Comparative Example 2-7)
A photocuring composition was prepared in the same manner as in Example 2-10 except that 1 part of 1-ethoxy-4-methoxynaphthalene was changed to 0 part, and the “tack free time” was measured to be 23 minutes.

(Comparative Example 2-8)
A photocuring composition was prepared in the same manner as in Example 2-12 except that the amount of 9,10-di (n-butoxy) anthracene was changed to 0 part, and the “tack free time” was measured. It did not cure.
The results of Examples 2-10 to 2-12 and Comparative Examples 2-7 to 2-8 are summarized in Table 2-4.

(Example 3-1)
As a monomer, 100 parts of an alicyclic epoxy compound (UVR6105 manufactured by Dow Chemical Company), 4.8 parts of a sulfonium salt (UVI6992 manufactured by Dow Chemical Company), and 0.25 of 9,10-di (n-butoxy) anthracene A photoacid generator composed of 0.25 part of 1,4-naphthohydroquinone (hereinafter also referred to as NHQ) was mixed to prepare a photocurable composition. The composition was applied onto a polyester film (Toray Lumirror, Inc.) using a bar coater so that the film thickness was 12 μm. Next, light was irradiated from the surface using a UV LED manufactured by Thunder. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 3 mW / cm ² . The light irradiation time “tack free time” until tackiness disappears was 4.0 minutes.

(Example 3-2)
A photocuring composition was prepared in the same manner as in Example 3-1, except that 0.5 part of 1,4-naphthohydroquinone was used, and the "tack free time" was measured and found to be 3.2 minutes.

(Example 3-3)
A photocuring composition was prepared in the same manner as in Example 3-1, except that 1 part of 1,4-naphthohydroquinone was used, and the "tack free time" was measured to be 3.0 minutes.

(Comparative Example 3-1)
A photocuring composition was prepared in the same manner as in Example 3-1, except that 0 part of 1,4-naphthohydroquinone was used, and the "tack free time" was measured and found to be 30 minutes.

(Comparative Example 3-2)
A photocuring composition was prepared in the same manner as in Example 3-3 except that 9,10-di (n-butoxy) anthracene was changed to 0 part, and the “tack free time” was measured. I didn't.
The results of Examples 3-1 to 3-3 and Comparative Examples 3-1 to 3-2 are summarized in Table 3-1.

Example 3-4
As a monomer, 100 parts of an alicyclic epoxy compound (UVR6105 manufactured by Dow Chemical Company), 2 parts of iodonium salt (CGI-552 manufactured by Ciba Specialty Chemicals Co., Ltd.), 9,10-di (n-butoxy) anthracene. A photo-sensitive composition was prepared by mixing 5 parts of a photosensitive acid generator consisting of 0.25 part of 1,4-naphthohydroquinone. The composition was applied onto a polyester film (Toray Lumirror, Inc.) using a bar coater so that the film thickness was 12 μm. Next, light was irradiated from the surface using a UV LED manufactured by Thunder. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 3 mW / cm ² . The light irradiation time “tack free time” until tackiness disappears was 2.7 minutes.

(Example 3-5)
A photocuring composition was prepared in the same manner as in Example 3-4 except that 0.5 part of 1,4-naphthohydroquinone was used, and the “tack free time” was measured to be 2.4 minutes. .

(Example 3-6)
A photocuring composition was prepared and “tack free time” was measured in the same manner as in Example 3-4 except that 1 part of 1,4-naphthohydroquinone was used. The result was 2.3 minutes.

(Comparative Example 3-3)
A photocuring composition was prepared in the same manner as in Example 3-4 except that 0 part of 1,4-naphthohydroquinone was used, and the “tack free time” was measured to be 23 minutes.

(Comparative Example 3-4)
A photocuring composition was prepared in the same manner as in Example 3-6, except that the amount of 9,10-di (n-butoxy) anthracene was changed to 0 part, and the “tack free time” was measured. It did not cure.
The results of Examples 3-4 to 3-6 and Comparative Examples 3-3 to 3-4 are summarized in Table 3-2.

(Example 4-1)
As a monomer, 100 parts of an alicyclic epoxy compound (UVR6105 manufactured by Dow Chemical Company), 5 parts of a sulfonium salt (UVI6992 manufactured by Dow Chemical Company), 2-methyl-9,10-diethoxyanthracene (hereinafter referred to as 2Me-DEA) A photoacid generator comprising 0.2 part and 0.2 part of 4-methoxy-1-naphthol was mixed to prepare a photocuring composition. The composition was applied onto a polyester film (Toray Lumirror, Inc.) using a bar coater so that the film thickness was 12 microns. Next, light was irradiated from the surface using a UV LED manufactured by Thunder. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 3 mW / cm ² . The light irradiation time “tack free time” until stickiness disappears was 2 minutes.

(Comparative Example 4-1)
A photocuring composition was prepared in the same manner as in Example 4-1, except that 4-methoxy-1-naphthol was changed to 0 part, and the "tack free time" was measured and found to be 10 minutes.

(Example 4-2)
A photocurable composition was prepared in the same manner as in Example 4-1, except that 2-methyl-9,10-diethoxyanthracene was changed to 2-phenoxy-9,10-diethoxyanthracene (hereinafter also referred to as 2PhO-DEA). It was 2 minutes when preparing and measuring "tack free time".

(Comparative Example 4-2)
A photocuring composition was prepared in the same manner as in Example 4-2 except that 4-methoxy-1-naphthol was changed to 0 part, and the “tack free time” was measured and found to be 15 minutes.

(Example 4-3)
A photocurable composition was prepared in the same manner as in Example 4-1, except that 2-methyl-9,10-diethoxyanthracene was changed to 2-chloro-9,10-diethoxyanthracene (hereinafter also referred to as 2Cl-DEA). It was 2 minutes when preparing and measuring "tack free time".

(Comparative Example 4-3)
The photocuring composition was prepared and the “tack free time” was measured in the same manner as in Example 4-3 except that 4-methoxy-1-naphthol was changed to 0 part.

(Comparative Example 4-4)
A photocuring composition was prepared in the same manner as in Example 4-1, except that 2-methyl-9,10-diethoxyanthracene was changed to 0 part, and the “tack free time” was measured. I didn't.
The results of Examples 4-1 to 4-3 and Comparative Examples 4-1 to 4-4 are summarized in Table 4-1.

(Example 4-4)
As a monomer, 100 parts of an alicyclic epoxy compound (UVR6105 manufactured by Dow Chemical Company), 2 parts of iodonium salt (CGI552 manufactured by Ciba), 0.2 part of 2-methyl-9,10-diethoxyanthracene, 4-methoxy A photoacid generator composed of 0.2 part of -1-naphthol was mixed to prepare a photocurable composition. The composition was applied onto a polyester film (Toray Lumirror, Inc.) using a bar coater so that the film thickness was 12 microns. Next, light was irradiated from the surface using a UV LED manufactured by Thunder. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 3 mW / cm ² . The light irradiation time “tack free time” until tackiness disappears was 3 minutes.

(Comparative Example 4-5)
A photocuring composition was prepared in the same manner as in Example 4-4 except that 4-methoxy-1-naphthol was changed to 0 part, and the “tack free time” was measured and found to be 9 minutes.

(Example 4-5)
A photocuring composition was prepared in the same manner as in Example 4-4 except that 2-methyl-9,10-diethoxyanthracene was changed to 2-phenoxy-9,10-diethoxyanthracene, and “tack free time” was prepared. Was 4.5 minutes.

(Comparative Example 4-6)
A photocuring composition was prepared in the same manner as in Example 4-5 except that 4-methoxy-1-naphthol was changed to 0 part, and the “tack free time” was measured.

(Example 4-6)
A photocuring composition was prepared in the same manner as in Example 4-4 except that 2-methyl-9,10-diethoxyanthracene was changed to 2-chloro-9,10-diethoxyanthracene, and “tack free time” was prepared. Was 4 minutes.

(Comparative Example 4-7)
A photocuring composition was prepared in the same manner as in Example 4-6 except that 4-methoxy-1-naphthol was changed to 0 part, and the “tack free time” was measured and found to be 20 minutes.

(Comparative Example 4-8)
A photocuring composition was prepared in the same manner as in Example 4-1, except that 2-methyl-9,10-diethoxyanthracene was changed to 0 part, and the “tack free time” was measured. I didn't.
The results of “Examples 4-4 to 4-6” and “Comparative Examples 4-5 to 4-8” are summarized in Table 4-2.

(Example 5-1)
As a monomer, 1.3 parts of a sulfonium salt (UVI6992 manufactured by Dow Chemical Co.) and 0.25 parts of 9,10-di (n-butoxy) anthracene per 100 parts of an alicyclic epoxy compound (UVR6105 manufactured by Dow Chemical Co., Ltd.) A photoacid generator composed of 0.25 part of 2-methyl-1,4-naphthohydroquinone (hereinafter also referred to as 2Me-NHQ) was mixed to prepare a photocuring composition. The composition was applied onto a polyester film (Toray Lumirror, Inc.) using a bar coater so that the film thickness was 12 μm. Next, light was irradiated from the surface using a UV LED manufactured by Thunder. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 3 mW / cm ² . The light irradiation time “tack free time” until stickiness disappeared was 12 minutes.

(Example 5-2)
A photocuring composition was prepared in the same manner as in Example 5-1, except that 0.5 part of 2-methyl-1,4-naphthohydroquinone was used, and the “tack free time” was measured. It was.

(Comparative Example 5-1)
A photocuring composition was prepared in the same manner as in Example 5-1, except that 2-methyl-1,4-naphthohydroquinone was changed to 0 part, and the “tack free time” was measured.

(Comparative Example 5-2)
A photocuring composition was prepared in the same manner as in Example 5-2 except that 9,10-di (n-butoxy) anthracene was changed to 0 part, and the “tack free time” was measured. I didn't.
The results of Examples 5-1 and 5-2 and Comparative Examples 5-1 and 5-2 are summarized in Table 5-1.

(Example 5-3)
As a monomer, 100 parts of an alicyclic epoxy compound (UVR6105 manufactured by Dow Chemical Company), 2.0 parts of iodonium salt (CGI552 manufactured by Ciba), 0.25 part of 9,10-di (n-butoxy) anthracene, 2 -A photoacid generator composed of 0.25 part of methyl-1,4-naphthohydroquinone was mixed to prepare a photocuring composition. The composition was applied onto a polyester film (Toray Lumirror, Inc.) using a bar coater so that the film thickness was 12 μm. Next, light was irradiated from the surface using a UV LED manufactured by Thunder. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 3 mW / cm 2. The light irradiation time “tack free time” until stickiness disappeared was 3.5 minutes.

(Example 5-4)
A photocuring composition was prepared in the same manner as in Example 5-3 except that 0.5 part of 2-methyl-1,4-naphthohydroquinone was used, and the “tack free time” was measured. It was.

(Comparative Example 5-3)
A photocuring composition was prepared in the same manner as in Example 5-3 except that 2-methyl-1,4-naphthohydroquinone was changed to 0 part, and the “tack free time” was measured and found to be 30 minutes.

(Comparative Example 5-4)
A photocuring composition was prepared in the same manner as in Example 5-2 except that 9,10-di (n-butoxy) anthracene was changed to 0 part, and the “tack free time” was measured. I didn't.
The results of Examples 5-3 and 5-5 and Comparative Examples 5-3 and 5-4 are summarized in Table 5-2.

(Example 6-1)
As a monomer, 100 parts of an alicyclic epoxy compound (UVR6105 manufactured by Dow Chemical Company), 2.4 parts of a sulfonium salt (UVI6992 manufactured by Dow Chemical Company), and 0.25 of 9,10-di (n-butoxy) anthracene The photo-acid generator which consists of 0.13 part of hydroquinone (henceforth HQ) was mixed, and the photocuring composition was prepared. The composition was applied onto a polyester film (Toray Lumirror, Inc.) using a bar coater so that the film thickness was 12 microns. Next, light was irradiated from the surface using an ultraviolet LED (manufactured by Thunder). The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 3 mW / cm ² . The light irradiation time “tack free time” until tackiness disappears was 10 minutes.

(Example 6-2)
A photocuring composition was prepared in the same manner as in Example 6-1 except that the hydroquinone was changed to 0.25 part, and the “tack free time” was measured and found to be 6 minutes.

(Example 6-3)
A photocurable composition was prepared in the same manner as in Example 6-1 except that 0.5 part of hydroquinone was used, and the “tack free time” was measured and found to be 6 minutes.

(Comparative Example 6-1)
A photocuring composition was prepared in the same manner as in Example 6-1 except that hydroquinone was changed to 0 part, and the "tack free time" was measured and found to be 40 minutes.

(Comparative Example 6-2)
A photocuring composition was prepared in the same manner as in Example 6-3 except that 9,10-di (n-butoxy) anthracene was changed to 0 part, and the “tack free time” was measured. I didn't.

(Comparative Example 6-3)
Except that hydroquinone was resorcinol (1,3-dihydroxybenzene), the photocuring composition was prepared and the “tack free time” was measured in the same manner as in Example 6-3. I couldn't see it.
The results of Examples 6-1 to 6-3 and Comparative Examples 6-1 to 6-3 are summarized in Table 6-1.

(Example 6-4)
As a monomer, 100 parts of an alicyclic epoxy compound (UVR6105 manufactured by Dow Chemical Company), 2.0 parts of iodonium salt (CGI552 manufactured by Ciba), 0.25 part of 9,10-di (n-butoxy) anthracene, A photoacid generator composed of 0.25 part of hydroquinone was mixed to prepare a photocuring composition. The composition was applied onto a polyester film (Toray Lumirror, Inc.) using a bar coater so that the film thickness was 12 microns. Then, light was irradiated from the surface using an ultraviolet LED (manufactured by Thunder). The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 3 mW / cm ² . The light irradiation time “tack free time” until tackiness disappears was 2.4 minutes.

(Example 6-5)
A photocuring composition was prepared in the same manner as in Example 6-4 except that 0.5 part of hydroquinone was used, and the "tack free time" was measured and found to be 2.2 minutes.

(Comparative Example 6-4)
A photocuring composition was prepared in the same manner as in Example 6-4 except that hydroquinone was changed to 0 part, and the “tack free time” was measured to be 30 minutes.

(Comparative Example 6-5)
A photocuring composition was prepared in the same manner as in Example 6-5, except that 9,10-di (n-butoxy) anthracene was changed to 0 part, and the “tack free time” was measured. I didn't.
The results of Examples 6-5 and 6-5 and Comparative Examples 6-4 and 6-5 are summarized in Table 6-2.

(Example 7-1)
As a monomer, 100 parts of an alicyclic epoxy compound (UVR6105 manufactured by Dow Chemical Company), 2.4 parts of a sulfonium salt (UVI6992 manufactured by Dow Chemical Company), and 0.25 of 9,10-di (n-butoxy) anthracene A photoacid generator comprising 0.25 parts of catechol (1,2-dihydroxybenzene) was mixed to prepare a photocuring composition. The composition was applied onto a polyester film (Toray Lumirror, Inc.) using a bar coater so that the film thickness was 12 microns. Subsequently, light was irradiated from the surface using ultraviolet LED (made by Thunder). The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 3 mW / cm ² . The light irradiation time “tack free time” until tackiness disappears was 10 minutes.

(Example 7-2)
A photocuring composition was prepared in the same manner as in Example 7-1 except that the catechol was changed to 0.5 part, and the “tack free time” was measured to be 9.5 minutes.

(Comparative Example 7-1)
A photocuring composition was prepared in the same manner as in Example 7-1 except that the catechol was changed to 0 part, and the “tack free time” was measured and found to be 40 minutes.

(Comparative Example 7-2)
A photocuring composition was prepared in the same manner as in Example 7-2 except that 9,10-di (n-butoxy) anthracene was changed to 0 part, and the “tack free time” was measured. I didn't.
The results of Examples 7-1 and 7-2 and Comparative Examples 7-1 and 7-2 are summarized in Table 7-1.

(Example 7-3)
As a monomer, 100 parts of an alicyclic epoxy compound (UVR6105 manufactured by Dow Chemical Company), 2.0 parts of iodonium salt (CGI552 manufactured by Ciba), 0.25 part of 9,10-di (n-butoxy) anthracene, A photoacid generator comprising 0.5 part of catechol was mixed to prepare a photocuring composition. The composition was applied onto a polyester film (Toray Lumirror, Inc.) using a bar coater so that the film thickness was 12 microns. Next, light was irradiated from the surface using an ultraviolet LED (manufactured by Thunder). The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 3 mW / cm ² . The light irradiation time “tack free time” until tackiness disappears was 3 minutes.

(Comparative Example 7-3)
A photocuring composition was prepared in the same manner as in Example 7-3 except that the catechol was changed to 0 part, and the “tack free time” was measured and found to be 30 minutes.

(Comparative Example 7-4)
A photocuring composition was prepared in the same manner as in Example 7-3 except that 9,10-di (n-butoxy) anthracene was changed to 0 part, and the “tack free time” was measured. I didn't.
The results of Example 7-3 and Comparative Examples 7-3 and 7-4 are summarized in Table 7-2.

(Example 8-1)
As a monomer, 100 parts of an alicyclic epoxy compound (UVR6105 manufactured by Dow Chemical Company), 2.0 parts of iodonium salt (CGI552 manufactured by Ciba), 0.25 part of 9,10-di (n-butoxy) anthracene, A photoacid generator composed of 0.25 part of methoquinone (4-methoxyphenol) was mixed to prepare a photocuring composition. The composition was applied onto a polyester film (Toray Lumirror, Inc.) using a bar coater so that the film thickness was 12 microns. Next, light was irradiated from the surface using an ultraviolet LED (manufactured by Thunder). The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 3 mW / cm ² . The light irradiation time “tack free time” until tackiness disappears was 3.5 minutes.

(Example 8-2)
The photocuring composition was prepared in the same manner as in Example 8-1 except that 0.5 part of methoquinone was used, and the “tack free time” was measured and found to be 3 minutes.

(Comparative Example 8-1)
A photocuring composition was prepared in the same manner as in Example 8-1 except that the amount of methoquinone was 0 part, and the “tack free time” was measured and found to be 30 minutes.

(Comparative Example 8-2)
A photocuring composition was prepared in the same manner as in Example 8-2, except that 9,10-di (n-butoxy) anthracene was changed to 0 part, and the “tack free time” was measured. I didn't.
Table 8 summarizes the results of Examples 8-1 and 8-2 and Comparative Examples 8-1 and 8-2.

(Example 9-1)
For a mixture of 100 parts of an alicyclic epoxy compound (UVR6105 manufactured by Dow Chemical Co., Ltd.) as a monomer and 50 parts of rutile titanium oxide as a pigment, 10 parts of a sulfonium salt (UVI6992 manufactured by Dow Chemical Co., Ltd.), 9,10-di ( A photoacid generator comprising 0.25 part of n-butoxy) anthracene and 0.25 part of 4-methoxy-1-naphthol was mixed to prepare a photocurable composition. The composition was applied onto a polyester film (Toray Lumirror, Inc.) using a bar coater so that the film thickness was 12 μm. Next, light was irradiated from the surface using a UV LED manufactured by Thunder. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 3 mW / cm 2. The light irradiation time “tack free time” until stickiness disappeared was 2 minutes.

(Example 9-2)
A photocuring composition was prepared in the same manner as in Example 9-1 except that 4-methoxy-1-naphthol was changed to 0.5 part, and the "tack free time" was measured to be 0.75 minutes. .

(Comparative Example 9-1)
A photocuring composition was prepared in the same manner as in Example 9-1 except that 4-methoxy-1-naphthol was changed to 0 part, and the “tack free time” was measured and found to be 25 minutes.

(Comparative Example 9-2)
A photocuring composition was prepared in the same manner as in Example 9-2 except that 9,10-di (n-butoxy) anthracene was changed to 0 part, and the “tack free time” was measured. I didn't.
The results of Examples 9-1 and 9-2 and Comparative Examples 9-1 and 9-2 are summarized in Table 9.

The mixture containing an anthracene derivative compound of the present invention and a naphthalene derivative compound or a benzene derivative compound is started compared to the case of a single product for the cationic photopolymerization performed by irradiating light in the wavelength range of 360 to 450 nm. is industrially useful as photosensitizers having high sensitizing effect on the acid generator of the agent, Ru der available as photosensitive acid generator or a photo-curable composition.

Claims (15)

Photosensitizer containing an anthracene derivative compound represented by formula (1) and a naphthalene derivative compound represented by formula (2) or a benzene derivative compound represented by formula (3) , photocation polymerization initiation A curing method for a photocurable composition, which comprises curing a photocurable composition containing an agent and a cationic polymerizable monomer by irradiating with light contained in a wavelength range of 360 to 450 nm.

(In Formula (1), R ₁ represents an alkyl group . N and m are integers selected from ₀ and ₁ to 4. X ₁ and Y ₁ are each independently a hydrogen atom, an alkyl group, An alkoxy group, a halogen atom, a nitro group, a sulfonic acid group, a hydroxyl group, an amino group or a carboalkoxy group is shown. When n and m are 2 or more, X _{1 s} or Y _{1 s} may be the same or different. )

(In Formula (2), R ₂ and R ₃ each independently represent a hydrogen atom or an alkyl group . Further, p is an integer of 0, 1 or 2, and q is selected from 0 and 1-4. X ₂ and Y ₂ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group, a sulfonic acid group, a hydroxyl group, an amino group, or a carboalkoxy group, and p and q are 2 or the case of, X ₂ or between Y ₂ together may be the same or different.)

(In Formula (3), R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group, and the substituents OR ₄ and OR ₅ are located in the ortho or para position with respect to each other. X ₃ is an integer selected from 4. X ₃ represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group, a sulfonic acid group, a hydroxyl group, an amino group, or a carboalkoxy group, and when r is 2 or more, X ₃ may be the same or different.) The method for curing a photocurable composition according to claim 1, wherein in the formula (1), R ₁ is a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or a 2-ethylhexyl group. In the formula (2), R ₂ , R ₃ , X ₂ and Y ₂ are all hydrogen atoms ; R ₂ , R ₃ and Y ₂ are hydrogen atoms and X ₂ is a methyl group ; R ₂ , X ₂ and Y ₂ Is a hydrogen atom and R ₃ is a methyl group ; R ₂ and R ₃ are ethyl groups and X ₂ and Y ₂ are hydrogen atoms ; R ₂ and R ₃ are ethyl groups and X ₂ is a methyl group and Y ₂ is a hydrogen atom ; Or the curing method of the photocurable composition according to claim 1 , wherein R ₂ is an ethyl group, R ₃ is a methyl group, and X ₂ and Y ₂ are hydrogen atoms . In formula (3), all of R ₄ , R ₅ and X ₃ are hydrogen atoms; R ₄ and X ₃ are hydrogen atoms and R ₅ is a methyl group; R ₄ and R ₅ are hydrogen atoms and X ₃ is a methyl group; Or R ₄ and R ₅ are hydrogen atoms and X ₃ is a t-butyl group. The method for curing a photocurable composition according to claim 1 .

In the formula (1), R ₁ is a methyl group, an ethyl group, an n-propyl group, an n-butyl group or a 2-ethylhexyl group. In the formula (2), R ₂ and R ₃ are an ethyl group and X ₂ Y ₂ is a hydrogen atom ; R ₂ , R ₃ is an ethyl group , X ₂ is a methyl group , and Y ₂ is a hydrogen atom ; or R ₂ is an ethyl group, R ₃ is a methyl group, and X ₂ , Y ₂ are hydrogen The method for curing a photocurable composition according to claim 1 , which is an atom . In the formula (1), R ₁ is a methyl group, an ethyl group, an n-propyl group, an n-butyl group or a 2-ethylhexyl group, and in the formula (2), R ₂ , X ₂ and Y ₂ are hydrogen atoms. The method for curing a photocurable composition according to claim 1, wherein R ₃ is a methyl group. In the formula (1), R ₁ is a methyl group, an ethyl group, an n-propyl group, an n-butyl group or a 2-ethylhexyl group, and R ₂ , R ₃ , X ₂ , Y ₂ in the formula (2). The method for curing a photocurable composition according to claim 1, wherein all of are hydrogen atoms ; or R ₂ , R ₃ , Y ₂ are hydrogen atoms and X ₂ is a methyl group . In formula (1), R ₁ is an n-butyl group, and in formula (2), all of R ₂ , R ₃ , X ₂ and Y ₂ are hydrogen atoms ; R ₂ , X ₂ and Y ₂ are hydrogen atoms The method for curing a photocurable composition according to claim 1, wherein R ₃ is a methyl group ; or R ₂ and R ₃ are ethyl groups and X ₂ and Y ₂ are hydrogen atoms. In the formula (1), R ₁ is a methyl group, an ethyl group, an n-propyl group, an n-butyl group or a 2-ethylhexyl group, and all of R ₄ , R ₅ and X ₃ in the formula (3) are hydrogen atom; R _{4, X 3} is _{R 5} is a methyl group a hydrogen _atom; R 4, _{R 5} is a methyl group _{X 3} is hydrogen atom; or R _{4, R 5} is is _{X 3} is hydrogen atom t- butyl group The method for curing a photocurable composition according to claim 1. In Formula (1), R ₁ is an n-butyl group, and in Formula (3), all of R ₄ , R ₅ , and X ₃ are hydrogen atoms ; or R ₄ , X ₃ are hydrogen atoms, and R ₅ is The method for curing a photocurable composition according to claim 1, which is a methyl group. The anthracene derivative compound represented by the formula (1) is 9,10-diethoxyanthracene or 9,10-di (n-butoxy) anthracene, and the naphthalene derivative compound represented by the formula (2) is 1, The light according to claim 1, which is 4 -naphthohydroquinone , 2-methyl-1,4-naphthohydroquinone, 4-methoxy-1-naphthol , 1,4- diethoxynaphthalene, or 1-ethoxy-4-methoxynaphthalene. A method for curing a curable composition . The anthracene derivative compound represented by the formula (1) is 9,10-diethoxyanthracene or 9,10-di (n-butoxy) anthracene, and the benzene derivative compound represented by the formula (3) is hydroquinone, method for curing the photocurable composition according to claim 1 which is 4-methoxyphenol or Kateko Le. 0.1 to 10 parts by weight of the naphthalene derivative compound represented by the formula (2) or the benzene derivative compound represented by the formula (3) per 1 part by weight of the anthracene derivative compound represented by the formula (1) The photocurable composition curing method according to any one of claims 1 to 12. Furthermore , the hardening method of the photocurable composition as described in any one of Claims 1 thru | or 13 containing a pigment . The method for curing a photocurable composition according to any one of claims 1 to 14 , wherein the cationically polymerizable monomer is an epoxy compound or vinyl ether.