JP6859683B2 - (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) Anthracene compounds having a carbonyloxy group, their production methods and their uses - Google Patents

Description

The present invention relates to an anthracene compounds having a (2-carboxy- mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group, and in particular, a method for producing the anthracene compound and its (2-carboxy- mono-substituted or 1,2-). The present invention relates to a photopolymerization sensitizer containing an anthracene compound having a di-substituted-ethyl) carbonyloxy group.

Photocurable resins that polymerize with active energy rays such as ultraviolet rays and visible light cure quickly, and the amount of organic solvent used can be significantly reduced compared to thermosetting resins, which improves the working environment and reduces the environmental burden. It is excellent in that it can be reduced. Therefore, it is widely used in paints, inks, adhesives, coating agents, and the like. Conventional photocurable resins have a poor polymerization initiator function by themselves, and it is usually necessary to use a photopolymerization initiator to cure them. An onium salt or the like is generally used as the photopolymerization initiator, but the light absorption of the photopolymerization initiator is in the vicinity of 225 nm to 350 nm, and has no absorption above 350 nm. Therefore, when a medium-pressure or high-pressure mercury lamp, an LED light source, or the like is used as a light source, there is a problem that the photocuring reaction does not proceed easily, and it is common to add a photopolymerization sensitizer as needed. Anthracene compounds, phenothiazines, and perylene compounds are known as photopolymerization sensitizers.

As the anthracene-based photopolymerization sensitizer, a 9,10-dialkoxyanthracene compound is used. For example, a 9,10-dialkoxyanthracene compound such as 9,10-dibutoxyanthracene or 9,10-diethoxyanthracene is used as a photopolymerization sensitizer for an iodonium salt which is a photopolymerization initiator in photocationic polymerization. (Patent Document 1). Further, 2-ethyl-9,10-dimethoxyanthracene is used as a photopolymerization sensitizer for photocationic polymerization of an alicyclic epoxy compound (manufactured by Dow Chemical, trade name: UVR6110) (Patent Document 2). 3).

However, in the conventionally used photopolymerization sensitizer, the photopolymerization sensitizer oozes out on the surface of the cured product due to migration during photocuring or during storage of the cured product, resulting in powder blowing or coloring of the cured product. It is known to cause problems.

Furthermore, when these photopolymerization sensitizers are used as a component of the photoadhesive that adheres the films, the photopolymerization sensitizer may migrate to the film overlaid and on the top film. It may also cause problems with powder blowing and coloring of photopolymerization sensitizers.

JP-A-2002-302507 Japanese Unexamined Patent Publication No. 11-279212 Japanese Unexamined Patent Publication No. 2000-344704

Therefore, in both cases of photoradical polymerization and photocationic polymerization, it is desired to develop a highly active photopolymerization sensitizer that is less likely to cause migration.

As a result of further diligent studies on the structure and physical properties of the 9,10-dioxyanthracene compound, the present inventor has the {(2-carboxy- mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group of the present invention. anthracene compounds not only show an excellent effect as a photopolymerization sensitizer cationic photopolymerization and / or photo-radical polymerization, found that it becomes difficult to cause a migration by having a carboxyl group (-CO 2 _H), The present invention has been completed.

The first gist of the present invention lies in the anthracene compound having a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the following general formula (1).

In the general formula (1), Q is a hydrogen atom or P, and P represents a (2-carboxy- mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the following general formula (2). .. X and Y may be the same or different, and represent an alkyl group or a halogen atom having 1 to 8 carbon atoms.

In the general formula (2), A and B each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group may have a double bond in a part thereof. However, this does not apply when both A and B are hydrogen atoms. Further, A and B may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring. * Marks indicate the joining position.

The second gist of the present invention is the first gist of the general formula (2), wherein A and B are bonded to each other to form a saturated or unsaturated ring which may have a substituent. It resides in the anthracene compounds having the described (2-carboxy- mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy groups.

The third gist of the present invention is the first gist that P is a (2-carboxy-1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (3) or the general formula (4). It exists in the anthracene compound having a (2-carboxy- mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group described in 1.

In the general formula (3), R represents an alkyl group having 1 to 5 carbon atoms. * Marks indicate the joining position.

In the general formula (4), R represents an alkyl group having 1 to 5 carbon atoms. * Marks indicate the joining position.

The fourth gist of the present invention is the (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy described in any one of the first to third gist where Q is a hydrogen atom. It exists in anthracene compounds having a group.

The fifth gist of the present invention is the (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group described in any one of the first to third gist in which Q is P. It exists in the anthracene compound having.

The sixth gist of the present invention is to describe the 9-anthrone compound represented by the following general formula (5) and the mono-substituted or 1,2-di-substituted succinic anhydride represented by the following general formula (6). It exists in the method for producing a 9- (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxyanthracene compound represented by the following general formula (7) by reacting according to the reaction formula-1.

In the reaction formula-1, X and Y may be the same or different, and represent an alkyl group or a halogen atom having 1 to 8 carbon atoms, and A and B are independently hydrogen atoms or 1 carbon atoms, respectively. It represents 10 to 10 alkyl groups, and the alkyl group may have a double bond in a part thereof. However, this does not apply when both A and B are hydrogen atoms. Further, A and B may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring.

The compound of the general formula (7) is a compound in which Q is a hydrogen atom in the compound of the general formula (1).

The seventh gist of the present invention is a 9,10-dihydroxyanthracene compound represented by the following general formula (8) and a mono-substituted or 1,2-di-substituted succinic anhydride represented by the following general formula (6). , The 9,10-bis {(2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy} anthracene compound represented by the following general formula (9) by reacting according to the following reaction formula-2. It exists in the manufacturing method of.

In the reaction formula-2, X and Y may be the same or different, and represent an alkyl group or a halogen atom having 1 to 8 carbon atoms, and A and B are independently hydrogen atoms or 1 carbon atoms, respectively. It represents 10 to 10 alkyl groups, and the alkyl group may have a double bond in a part thereof. However, this does not apply when both A and B are hydrogen atoms. Further, A and B may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring.

The compound of the general formula (9) is a compound in which Q is P in the compound of the general formula (1).

The eighth gist of the present invention is a photopolymerization sensitizer containing an anthracene compound having a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the following general formula (1). It exists in the agent.

In the general formula (1), Q is a hydrogen atom or P, and P represents a (2-carboxy- mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (2). X and Y may be the same or different, and represent an alkyl group or a halogen atom having 1 to 8 carbon atoms.

In the general formula (2), A and B each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group may have a double bond in a part thereof. Further, A and B may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring. * Marks indicate the joining position.

A ninth gist of the present invention resides in a photoradical polymerization initiator composition containing a photopolymerization sensitizer and a photoradical polymerization initiator described in the eighth gist.

A tenth gist of the present invention resides in a photocationic polymerization initiator composition containing a photopolymerization sensitizer and a photocationic polymerization initiator described in the eighth gist.

The eleventh gist of the present invention resides in the photoradical polymerization initiator composition and the photoradical polymerizable compound described in the ninth gist.

The twelfth gist of the present invention lies in the photocationic polymerizable composition containing the photocationic polymerization initiator composition and the photocationic polymerizable compound described in the tenth gist.

The anthracene compound having a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (1) of the present invention has an effect as a photopolymerization sensitizer in a photopolymerization reaction. In addition to having, the compound has excellent migration resistance in a photopolymerizable composition containing the compound as a photopolymerization sensitizer because the compound has a carboxyl group.

(Compound)
The anthracene compound having a (2-carboxy- mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group of the present invention is a compound having the structure described in the general formula (1).

In the general formula (1), Q is a hydrogen atom or P, and P represents a (2-carboxy- mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (2). X and Y may be the same or different, and represent an alkyl group or a halogen atom having 1 to 8 carbon atoms.

In the general formula (2), A and B each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group may have a double bond in a part thereof. Further, A and B may be bonded to each other to form a saturated or unsaturated ring which may have a substituent. * Marks indicate the joining position.

Here, when Q is a hydrogen atom in the anthracene compound having a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (1), the general formula (2) It is a carbonyloxyanthracene compound represented by (2-carboxy- mono-substituted or 1,2-di-substituted-ethyl).

In the general formula (7), A and B each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group may have a double bond in a part thereof. Further, A and B may be bonded to each other to form a saturated or unsaturated ring which may have a substituent. X and Y may be the same or different, and represent an alkyl group or a halogen atom having 1 to 8 carbon atoms.

In the general formula (7), the alkyl groups represented by X and Y are methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, n-pentyl group and n. -Hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and the like can be mentioned, and examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

As typical compounds of the general formula (7), first, as an example when both A and B are hydrogen atoms, 9- (2-carboxyethyl) carbonyloxyanthracene and 2-methyl-9- (2) -Carboxyethyl) carbonyloxyanthracene, 2-ethyl-9- (2-carboxyethyl) carbonyloxyanthracene, 2- (t-butyl) -9- (2-carboxy-ethyl) carbonyloxyanthracene, 1-methyl-9 -(2-carboxyethyl) carbonyloxyanthracene, 1-ethyl-9- (2-carboxyethyl) carbonyloxyanthracene, 1- (t-butyl) -9- (2-carboxyethyl) carbonyloxyanthracene, 3-methyl -9- (2-carboxyethyl) carbonyloxyanthracene, 3-ethyl-9- (2-carboxyethyl) carbonyloxyanthracene, 3- (t-butyl) -9- (2-carboxyethyl) carbonyloxyanthracene, 4 -Methyl-9- (2-carboxyethyl) carbonyloxyanthracene, 4-ethyl-9- (2-carboxyethyl) carbonyloxyanthracene, 4- (t-butyl) -9- (2-carboxy-ethyl) carbonyloxy Anthracene, 2,6-dimethyl-9- (2-carboxyethyl) carbonyloxyanthracene, 2,6-diethyl-9- (2-carboxyethyl) carbonyloxyanthracene, 2,6-bis (t-butyl) -9 -(2-carboxyethyl) carbonyloxyanthracene, 1,5-dimethyl-9- (2-carboxyethyl) carbonyloxyanthracene, 1,5-diethyl-9- (2-carboxyethyl) carbonyloxyanthracene, 1,5 -Bis (t-butyl) -9- (2-carboxyethyl) carbonyloxyanthracene, 2-chloro-9- (2-carboxyethyl) carbonyloxyanthracene, 1-chloro-9- (2-carboxyethyl) carbonyloxy Examples thereof include anthracene, 3-chloro-9- (2-carboxyethyl) carbonyloxyanthracene, 4-chloro-9- (2-carboxyethyl) carbonyloxyanthracene and the like.

In the general formula (7), examples of cases where A and / or B are alkyl groups include 9- (2-n-hexadecenyl-2-carboxyethyl) carbonyloxyanthracene and 2-methyl-9- (2-). n-Hexadecenyl-2-carboxyethyl) carbonyloxyanthracene, 2-ethyl-9- (2-n-hexadecenyl-2-carboxyethyl) carbonyloxyanthracene, 2- (t-butyl) -9- (2-n-) Hexadecenyl-2-carboxyethyl) carbonyloxyanthracene, 1-methyl-9- (2-n-hexadecenyl-2-carboxyethyl) carbonyloxyanthracene, 1-ethyl-9- (2-n-hexadecenyl-2-carboxyethyl) ) Carbonyloxyanthracene, 1- (t-butyl) -9- (2-n-hexadecenyl-2-carboxyethyl) carbonyloxyanthracene, 3-methyl-9- (2-n-hexadecenyl-2-carboxyethyl) carbonyl Oxyanthracene, 3-ethyl-9- (2-n-hexadecenyl-2-carboxyethyl) carbonyloxyanthracene, 3- (t-butyl) -9- (2-n-hexadecenyl-2-carboxyethyl) carbonyloxyanthracene , 4-Methyl-9- (2-n-hexadecenyl-2-carboxyethyl) carbonyloxyanthracene, 4-ethyl-9- (2-n-hexadecenyl-2-carboxyethyl) carbonyloxyanthracene, 4- (t- Butyl) -9- (2-n-hexadecenyl-2-carboxyethyl) carbonyloxyanthracene and the like can be mentioned.

In the general formula (7), as an example of the case where A and B are bonded to each other to form a saturated or unsaturated ring which may have a substituent, first, it is assumed that the saturated ring is 9 -(2-carboxycyclohexyl) carbonyloxyanthracene, 2-methyl-9- (2-carboxycyclohexyl) carbonyloxyanthracene, 2-ethyl-9- (2-carboxycyclohexyl) carbonyloxyanthracene, 2- (t-butyl) -9- (2-carboxycyclohexyl) carbonyloxyanthracene, 1-methyl-9- (2-carboxycyclohexyl) carbonyloxyanthracene, 1-ethyl-9- (2-carboxycyclohexyl) carbonyloxyanthracene, 1- (t-) Butyl) -9- (2-carboxycyclohexyl) carbonyloxyanthracene, 3-methyl-9- (2-carboxycyclohexyl) carbonyloxyanthracene, 3-ethyl-9- (2-carboxycyclohexyl) carbonyloxyanthracene, 3-( t-Butyl) -9- (2-carboxycyclohexyl) carbonyloxyanthracene, 4-methyl-9- (2-carboxycyclohexyl) carbonyloxyanthracene, 4-ethyl-9- (2-carboxycyclohexyl) carbonyloxyanthracene, 4 -(T-Butyl) -9- (2-carboxycyclohexyl) carbonyloxyanthracene, 2,6-dimethyl-9- (2-carboxycyclohexyl) carbonyloxyanthracene, 2,6-diethyl-9- (2-carboxycyclohexyl) ) Carbonyloxyanthracene, 2,6-bis (t-butyl) -9- (2-carboxycyclohexyl) carbonyloxyanthracene, 1,5-dimethyl-9- (2-carboxycyclohexyl) carbonyloxyanthracene, 1,5- Diethyl-9- (2-carboxycyclohexyl) carbonyloxyanthracene, 1,5-bis (t-butyl) -9- (2-carboxycyclohexyl) carbonyloxyanthracene, 2-chloro-9- (2-carboxycyclohexyl) carbonyl Oxyanthracene, 1-chloro-9- (2-carboxycyclohexyl) carbonyloxyanthracene, 3-chloro-9- (2-carboxycyclohexyl) carbonyloxyanthracene, 4-chloro-9- (2-carboxycyclohexyl) carbonyl oki Anthracene and the like can be mentioned.

In the general formula (7), 9- [2 is assumed to be an unsaturated ring in the case where A and B are bonded to each other to form a saturated or unsaturated ring which may have a substituent. -Carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 2-methyl-9- [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 2-ethyl-9- [2-carboxy (4-cyclohexenyl)] ] Carbonyloxyanthracene, 2- (t-butyl) -9- [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 1-methyl-9- [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene , 1-Ethyl-9- [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 1- (t-butyl) -9- [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 3-methyl -9- [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 3-ethyl-9- [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 3- (t-butyl) -9- [ 2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 4-methyl-9- [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 4-ethyl-9- [2-carboxy (4-cyclohexenyl)] )] carbonyloxyanthracene, 4- (t-butyl) -9- [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 2,6-dimethyl-9- [2-carboxy (4-cyclohexenyl)] Carbonyloxyanthracene, 2,6-diethyl-9- [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 2,6-bis (t-butyl) -9- [2-carboxy (4-cyclohexenyl) ] Carbonyloxyanthracene, 1,5-dimethyl-9- [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 1,5-diethyl-9- [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene , 1,5-bis (t-butyl) -9- [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 2-chloro-9- [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 1-Chloro-9- [2-Carboki Si (4-cyclohexenyl)] carbonyloxyanthracene, 3-chloro-9- [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 4-chloro-9- [2-carboxy (4-cyclohexenyl)] Examples thereof include carbonyloxyanthracene.

In addition, 9- [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 2-methyl-9- [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 2- Ethyl-9- [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 2- (t-butyl) -9- [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxy Anthracene, 1-methyl-9- [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 1-ethyl-9- [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxy Anthracene, 1- (t-butyl) -9- [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 3-methyl-9- [2-carboxy (4-methyl-4-cyclohexenyl)] )] carbonyloxyanthracene, 3-ethyl-9- [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 3- (t-butyl) -9- [2-carboxy (4-methyl-) 4-Cyclohexenyl)] carbonyloxyanthracene, 4-methyl-9- [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 4-ethyl-9- [2-carboxy (4-methyl-) 4-Cyclohexenyl)] carbonyloxyanthracene, 4- (t-butyl) -9- [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 2,6-dimethyl-9- [2- Carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 2,6-diethyl-9- [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 2,6-bis (t) -Butyl) -9- [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 1,5-dimethyl-9- [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxy Anthracene, 1,5-diethyl-9- [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 1,5-bis (t-butyl) -9- [2-carboxy (4-methyl) -4-Cyclohexenyl)] carbonyloxyanthracene, 2-chloro-9- [ 2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 1-chloro-9- [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 3-chloro-9- [ Examples thereof include 2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene and 4-chloro-9- [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene.

Then, in the general formula (7), in the case where A and B are bonded to each other to form a saturated or unsaturated ring which may have a substituent, the unsaturated ring is a bicyclo ring. As such, 9- [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 2-methyl-9- [2-carboxy (3,6-endomethylene-4-cyclohexenyl)). ] Carbonyloxyanthracene, 2-ethyl-9- [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 2- (t-butyl) -9- [2-carboxy (3,3) 6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 1-methyl-9- [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 1-ethyl-9- [ 2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 1- (t-butyl) -9- [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyl Oxyanthracene, 3-Methyl-9- [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 3-ethyl-9- [2-carboxy (3,6-endomethylene-4) -Cyclohexenyl)] carbonyloxyanthracene, 3- (t-butyl) -9- [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 4-methyl-9- [2- Carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 4-ethyl-9- [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 4-( t-butyl) -9- [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 2,6-dimethyl-9- [2-carboxy (3,6-endomethylene-4) -Cyclohexenyl)] carbonyloxyanthracene, 2,6-diethyl-9- [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 2,6-bis (t-butyl)- 9- [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 1 , 5-Dimethyl-9- [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 1,5-diethyl-9- [2-carboxy (3,6-endomethylene-4) -Cyclohexenyl)] carbonyloxyanthracene, 1,5-bis (t-butyl) -9- [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 2-chloro-9- [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 1-chloro-9- [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 3-Chloro-9- [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 4-chloro-9- [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] )] Examples thereof include carbonyloxyanthracene.

Furthermore, 9- [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 2-methyl-9- [2-carboxy (3,6-endomethylene-4) -Methyl-4-cyclohexenyl)] carbonyloxyanthracene, 2-ethyl-9- [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 2- (t-) Butyl) -9- [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 1-methyl-9- [2-carboxy (3,6-endomethylene-4) -Methyl-4-cyclohexenyl)] carbonyloxyanthracene, 1-ethyl-9- [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 1- (t-) Butyl) -9- [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 3-methyl-9- [2-carboxy (3,6-endomethylene-4) -Methyl-4-cyclohexenyl)] carbonyloxyanthracene, 3-ethyl-9- [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 3- (t-) Butyl) -9- [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 4-methyl-9- [2-carboxy (3,6-endomethylene-4) -Methyl-4-cyclohexenyl)] carbonyloxyanthracene, 4-ethyl-9- [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 4- (t- Butyl) -9- [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 2,6-dimethyl-9- [2-carboxy (3,6-endomethylene) -4-Methyl-4-cyclohexenyl)] carbonyloxyanthracene, 2,6-diethyl-9- [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 2 , 6-bis (t-butyl) -9- [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexyl) Senyl)] carbonyloxyanthracene, 1,5-dimethyl-9- [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 1,5-diethyl-9- [ 2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 1,5-bis (t-butyl) -9- [2-carboxy (3,6-endomethylene-) 4-Methyl-4-cyclohexenyl)] carbonyloxyanthracene, 2-chloro-9- [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 1-chloro- 9- [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 3-chloro-9- [2-carboxy (3,6-endomethylene-4-methyl-) 4-Cyclohexenyl)] carbonyloxyanthracene, 4-chloro-9- [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene and the like can be mentioned.

Further, in the anthracene compound having a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (1) , Q is (2-carboxy-mono-substituted or 1,2-). When it is a di-substituted-ethyl) carbonyloxy group, it has a 9,10-bis {(2-carboxy- mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (9). It becomes an anthracene compound.

In the general formula (9), A and B each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group may have a double bond in a part thereof. Further, A and B may be bonded to each other to form a saturated or unsaturated ring which may have a substituent. X and Y may be the same or different, and represent an alkyl group or a halogen atom having 1 to 8 carbon atoms.

In the general formula (9), the alkyl groups represented by X and Y are methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, n-pentyl group and n. Examples thereof include a −hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group and the like, and examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

As a typical compound of the general formula (9), first, as an example when both A and B are hydrogen atoms, 9,10-bis (2-carboxyethyl) carbonyloxyanthracene and 2-methyl-9 are used. , 10-Bis (2-carboxyethyl) carbonyloxyanthracene, 2-ethyl-9,10-bis (2-carboxyethyl) carbonyloxyanthracene, 2- (t-butyl) -9,10-bis (2-carboxy) Ethyl) carbonyloxyanthracene, 1-methyl-9,10-bis (2-carboxyethyl) carbonyloxyanthracene, 1-ethyl-9,10-bis (2-carboxyethyl) carbonyloxyanthracene, 1- (t-butyl) ) -9,10-Bis (2-carboxyethyl) carbonyloxyanthracene, 2,6-dimethyl-9,10-bis (2-carboxyethyl) carbonyloxyanthracene, 2,6-diethyl-9,10-bis ( 2-carboxyethyl) carbonyloxyanthracene, 2,6-bis (t-butyl) -9,10-bis (2-carboxyethyl) carbonyloxyanthracene, 1,5-dimethyl-9,10-bis (2-carboxy) Ethyl) carbonyloxyanthracene, 1,5-diethyl-9,10-bis (2-carboxyethyl) carbonyloxyanthracene, 1,5-bis (t-butyl) -9,10-bis (2-carboxyethyl) carbonyl Examples thereof include oxyanthracene, 2-chloro-9,10-bis (2-carboxyethyl) carbonyloxyanthracene, 1-chloro-9,10-bis (2-carboxyethyl) carbonyloxyanthracene and the like.

In the general formula (9), examples of cases where A and / or B are alkyl groups include 9,10-bis (2-n-hexadecenyl-2-carboxyethyl) carbonyloxyanthracene, 2-methyl-9, 10-Bis (2-n-hexadecenyl-2-carboxyethyl) carbonyloxyanthracene, 2-ethyl-9,10-bis (2-n-hexadecenyl-2-carboxyethyl) carbonyloxyanthracene, 2- (t-butyl) ) -9,10-Bis (2-n-hexadecenyl-2-carboxyethyl) carbonyloxyanthracene, 1-methyl-9,10-bis (2-n-hexadecenyl-2-carboxyethyl) carbonyloxyanthracene, 1- Ethyl-9,10-bis (2-n-hexadecenyl-2-carboxyethyl) carbonyloxyanthracene, 1- (t-butyl) -9,10-bis (2-n-hexadecenyl-2-carboxyethyl) carbonyloxy Anthracene, 3-methyl-9,10-bis (2-n-hexadecenyl-2-carboxyethyl) carbonyloxyanthracene, 3-ethyl-9,10-bis (2-n-hexadecenyl-2-carboxyethyl) carbonyloxy Anthracene, 3- (t-butyl) -9,10-bis (2-n-hexadecenyl-2-carboxyethyl) carbonyloxyanthracene, 4-methyl-9,10-bis (2-n-hexadecenyl-2-carboxyethyl) Ethyl) carbonyloxyanthracene, 4-ethyl-9,10-bis (2-n-hexadecenyl-2-carboxyethyl) carbonyloxyanthracene, 4- (t-butyl) -9,10-bis (2-n-hexadecenyl) -2-carboxyethyl) carbonyloxyanthracene and the like.

In the general formula (9), as an example of the case where A and B are bonded to each other to form a saturated or unsaturated ring which may have a substituent, first, it is assumed that the saturated ring is 9 , 10-Bis (2-carboxycyclohexyl) carbonyloxyanthracene, 2-methyl-9,10-bis (2-carboxycyclohexyl) carbonyloxyanthracene, 2-ethyl-9,10-bis (2-carboxycyclohexyl) carbonyloxy Anthracene, 2- (t-butyl) -9,10-bis (2-carboxycyclohexyl) carbonyloxyanthracene, 1-methyl-9,10-bis (2-carboxycyclohexyl) carbonyloxyanthracene, 1-ethyl-9, 10-bis (2-carboxycyclohexyl) carbonyloxyanthracene, 1- (t-butyl) -9,10-bis (2-carboxycyclohexyl) carbonyloxyanthracene, 3-methyl-9,10-bis (2-carboxycyclohexyl) ) Carbonyloxyanthracene, 3-ethyl-9,10-bis (2-carboxycyclohexyl) carbonyloxyanthracene, 3- (t-butyl) -9,10-bis (2-carboxycyclohexyl) carbonyloxyanthracene, 4-methyl -9,10-bis (2-carboxycyclohexyl) carbonyloxyanthracene, 4-ethyl-9,10-bis (2-carboxycyclohexyl) carbonyloxyanthracene, 4- (t-butyl) -9,10-bis (2) -Carboxycyclohexyl) carbonyloxyanthracene, 2,6-dimethyl-9,10-bis (2-carboxycyclohexyl) carbonyloxyanthracene, 2,6-diethyl-9,10-bis (2-carboxycyclohexyl) carbonyloxyanthracene, 2,6-bis (t-butyl) -9,10-bis (2-carboxycyclohexyl) carbonyloxyanthracene, 1,5-dimethyl-9,10-bis (2-carboxycyclohexyl) carbonyloxyanthracene, 1,5 -Diethyl-9,10-bis (2-carboxycyclohexyl) carbonyloxyanthracene, 1,5-bis (t-butyl) -9,10-bis (2-carboxycyclohexyl) carbonyloxyanthracene, 2-chloro-9, 10-Bis (2-carboxycyclohexyl) carbonyloxyanthracene, 1-chloro-9,1 0-bis (2-carboxycyclohexyl) carbonyloxyanthracene, 3-chloro-9,10-bis (2-carboxycyclohexyl) carbonyloxyanthracene, 4-chloro-9,10-bis (2-carboxycyclohexyl) carbonyloxyanthracene And so on.

In the general formula (9), when A and B are bonded to each other to form a saturated or unsaturated ring which may have a substituent, 9, 10- is assumed to be an unsaturated ring. Bis [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 2-methyl-9,10-bis [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 2-ethyl-9,10-bis [ 2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 2- (t-butyl) -9,10-bis [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 1-methyl-9,10- Bis [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 1-ethyl-9,10-bis [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 1- (t-butyl) -9, 10-Bis [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 3-methyl-9,10-bis [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 3-ethyl-9,10- Bis [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 3- (t-butyl) -9,10-bis [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 4-methyl-9, 10-Bis [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 4-ethyl-9,10-bis [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 4- (t-butyl)- 9,10-bis [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 2,6-dimethyl-9,10-bis [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 2,6- Diethyl-9,10-bis [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 2,6-bis (t-butyl) -9,10-bis [2-carboxy (4-cyclohexenyl)] carbonyl Oxyanthracene, 1,5-dimethyl-9,10-bis [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 1,5-diethyl-9,10-bis [2-carboxy (4-cyclohexenyl)] ] Carbonyloxyanthracene, 1,5-bis (t-butyl) -9,10-bis [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 2-chloro-9,10-bis [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 1-chloro-9,10-bis [2] -Carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 3-chloro-9,10-bis [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene, 4-chloro-9,10-bis [2-carboxy (4-Cyclohexenyl)] carbonyloxyanthracene and the like can be mentioned.

In addition, 9,10-bis [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 2-methyl-9,10-bis [2-carboxy (4-methyl-4-cyclohexenyl)]. Carbonyloxyanthracene, 2-ethyl-9,10-bis [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 2- (t-butyl) -9,10-bis [2-carboxy (2-carboxy) 4-Methyl-4-cyclohexenyl)] carbonyloxyanthracene, 1-methyl-9,10-bis [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 1-ethyl-9,10- Bis [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 1- (t-butyl) -9,10-bis [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxy Anthracene, 3-methyl-9,10-bis [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 3-ethyl-9,10-bis [2-carboxy (4-methyl-4-methyl-4-) Cyclohexenyl)] carbonyloxyanthracene, 3- (t-butyl) -9,10-bis [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 4-methyl-9,10-bis [ 2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 4-ethyl-9,10-bis [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 4- (t) -Butyl) -9,10-bis [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 2,6-dimethyl-9,10-bis [2-carboxy (4-methyl-4-methyl-4-)] Cyclohexenyl)] carbonyloxyanthracene, 2,6-diethyl-9,10-bis [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 2,6-bis (t-butyl) -9 , 10-bis [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 1,5-dimethyl-9,10-bis [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyl Oxyanthracene, 1,5-diethyl-9,10-bis [2-carboxy (4-methyl-4-cycl) Rohexenyl)] carbonyloxyanthracene, 1,5-bis (t-butyl) -9,10-bis [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 2-chloro-9,10- Bis [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 1-chloro-9,10-bis [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 3- Chloro-9,10-bis [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 4-chloro-9,10-bis [2-carboxy (4-methyl-4-cyclohexenyl)] Examples thereof include carbonyloxyanthracene.

Then, in the general formula (9), in the case where A and B are bonded to each other to form a saturated or unsaturated ring which may have a substituent, the unsaturated ring is a bicyclo ring. As such, 9,10-bis [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 2-methyl-9,10-bis [2-carboxy (3,6-endomethylene)] -4-Cyclohexenyl)] carbonyloxyanthracene, 2-ethyl-9,10-bis [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 2- (t-butyl)- 9,10-bis [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 1-methyl-9,10-bis [2-carboxy (3,6-endomethylene-4-4) Cyclohexenyl)] carbonyloxyanthracene, 1-ethyl-9,10-bis [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 1- (t-butyl) -9,10 -Bis [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 3-methyl-9,10-bis [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] ] Carbonyloxyanthracene, 3-ethyl-9,10-bis [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 3- (t-butyl) -9,10-bis [ 2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 4-methyl-9,10-bis [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxy Anthracene, 4-ethyl-9,10-bis [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 4- (t-butyl) -9,10-bis [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 2,6-dimethyl-9,10-bis [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene , 2,6-diethyl-9,10-bis [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyl Oxyanthracene, 2,6-bis (t-butyl) -9,10-bis [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 1,5-dimethyl-9,10 -Bis [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 1,5-diethyl-9,10-bis [2-carboxy (3,6-endomethylene-4-cyclo) Hexenyl)] carbonyloxyanthracene, 1,5-bis (t-butyl) -9,10-bis [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 2-chloro-9 , 10-bis [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 1-chloro-9,10-bis [2-carboxy (3,6-endomethylene-4-cyclo) Hexenyl)] carbonyloxyanthracene, 3-chloro-9,10-bis [2-carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene, 4-chloro-9,10-bis [2-] Carboxy (3,6-endomethylene-4-cyclohexenyl)] carbonyloxyanthracene and the like can be mentioned.

Furthermore, 9,10-bis [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 2-methyl-9,10-bis [2-carboxy (3,3) 6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 2-ethyl-9,10-bis [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] Carbonyloxyanthracene, 2- (t-butyl) -9,10-bis [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 1-methyl-9,10 -Bis [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 1-ethyl-9,10-bis [2-carboxy (3,6-endomethylene-4) -Methyl-4-cyclohexenyl)] carbonyloxyanthracene, 1- (t-butyl) -9,10-bis [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxy Anthracene, 3-methyl-9,10-bis [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 3-ethyl-9,10-bis [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 3- (t-butyl) -9,10-bis [2-carboxy (3,6-endomethylene-4-methyl) -4-Cyclohexenyl)] carbonyloxyanthracene, 4-methyl-9,10-bis [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 4-ethyl- 9,10-bis [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 4- (t-butyl) -9,10-bis [2-carboxy (3) , 6-Endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 2,6-dimethyl-9,10-bis [2-carboxy (3,6-endomethylene-4-methyl-4-cyclo) Hexenyl)] carbonyloxyanthracene, 2,6-diethyl-9,10-bis [2-carboxy (3,6-endomethylene-4-methyl-4-) Cyclohexenyl)] carbonyloxyanthracene, 2,6-bis (t-butyl) -9,10-bis [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 1,5-dimethyl-9,10-bis [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 1,5-diethyl-9,10-bis [2] -Carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 1,5-bis (t-butyl) -9,10-bis [2-carboxy (3,6-end) Methylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 2-chloro-9,10-bis [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene , 1-Chloro-9,10-bis [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 3-chloro-9,10-bis [2-carboxy (2-carboxy) 3,6-endomethylene-4-methyl-4-cyclohexenyl)] carbonyloxyanthracene, 4-chloro-9,10-bis [2-carboxy (3,6-endomethylene-4-methyl-4-cyclohexenyl) )] Examples thereof include carbonyloxyanthracene.

Among the exemplified compounds, the following 9- (2-carboxyethyl) carbonyloxyanthracene (7-1) and 9- (2-carboxycyclohexyl) carbonyloxy are considered because of the ease of synthesis and the magnitude of the photopolymerization sensitizing effect. Anthracene (7-2), 9- [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene (7-3), 9- [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene (7-3) 7-4), 9,10-bis (2-carboxyethyl) carbonyloxyanthracene (9-1), 9,10-bis (2-carboxycyclohexyl) carbonyloxyanthracene (9-2), 9,10-bis [2-carboxy (4-cyclohexenyl)] carbonyloxyanthracene (9-3), 9,10-bis [2-carboxy (4-methyl-4-cyclohexenyl)] carbonyloxyanthracene (9-4) are preferred. ..

The anthracene compound having a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (1) of the present invention has a carboxyl group containing a free hydroxyl group in its molecule. It is a feature that it does. The presence of this group creates a characteristic affinity with other organic compounds, for example, suppressing migration of the compound of the present invention in a cured product of a polymerizable composition containing the compound of the present invention. The effect of Further, it has been confirmed that the UV absorption of the anthracene compound shifts to the longer wavelength side as compared with the case where the hydroxyl group is made into a carboxylic acid ester by esterification or the like. This shift in UV absorption causes hydrogen bonds between the ketone group of the carboxy group directly attached to the anthracene skeleton and the hydroxyl group of the carboxyl group, weakening the electron attraction of the ketone group, resulting in an electron density of the anthracene skeleton. It is thought that this is due to the increase.

Next, a method for producing an anthracene compound having a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (1) will be described.

First, the 9- (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxyanthracene compound represented by the general formula (7) in which Q is a hydrogen atom in the general formula (1) will be described. The 9- (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxyanthracene compound represented by the general formula (7) is the same as the 9-anthracene compound represented by the general formula (5). It can be produced by reacting with the mono-substituted or 1,2-di-substituted succinic anhydride represented by (6) according to the reaction formula-1.

In the reaction formula-1, X and Y may be the same or different, and represent an alkyl group or a halogen atom having 1 to 8 carbon atoms, and A and B are independently hydrogen atoms or 1 carbon atoms, respectively. It represents 10 to 10 alkyl groups, and the alkyl group may have a double bond in a part thereof. However, this does not apply when both A and B are hydrogen atoms. Further, A and B may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring.

Examples of the anthrone compound represented by the general formula (5) as a raw material include 9-anthrone, 1-methyl-9-anthrone, 1-ethyl-9-anthrone, 1- (t-butyl) -9-anthrone. , 2-Methyl-9-anthrone, 2-ethyl-9-anthrone, 2- (t-butyl) -9-anthrone, 3-methyl-9-anthrone, 3-ethyl-9-anthrone, 3- (t-) Butyl) -9-anthrone, 4-methyl-9-anthrone, 4-ethyl-9-anthrone, 4- (t-butyl) -9-anthrone, 1-chloro-9-anthrone, 2-chloro-9-anthrone , 3-Chloro-9-anthrone, 4-chloro-9-anthrone and the like.

Examples of the mono-substituted or 1,2-di-substituted succinic anhydride represented by the general formula (6) include succinic anhydride, 3-methylsuccinic anhydride, 3,4-dimethylsuccinic anhydride, and 3-. Octenyl succinic anhydride, 3-dodecenyl succinic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 4-octenylhexahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 4 -Methyl-1,2,3,6-tetrahydrophthalic anhydride, 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-3,6-endomethylene-1,2 , 3,6-tetrahydrophthalic anhydride and the like.

The reaction is usually carried out in a solvent. The solvent does not have to react with mono-substituted or 1,2-di-substituted succinic anhydride, and is an aromatic solvent such as toluene or xylene, an ether solvent such as tetrahydrofuran or 1,4-dioxane, chloroform or chloride. Examples thereof include halogen-based solvents such as methylene, amide-based solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, and ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone.

A basic catalyst is used in the reaction. As the basic catalyst, for example, an organic amine is preferably used. Examples of organic amines include tertiary amines such as triethylamine, tributylamine and tricyclohexylamine, secondary amines such as dimethylamine, diethylamine, dibutylamine and piperidine, primary amines such as methylamine, ethylamine and butylamine, pyridine, picoline and lutidine. Such as pyridine compounds. The amount of the basic compound added is preferably 0.05 mol times or more and 2 mol times or less, more preferably 0.1 mol times or more and 1.5 mol times or more with respect to the anthracene compound as a raw material. It is as follows. If it is 0.05 mol times or less, the reaction progresses slowly, and even if it is added 2 mol times or more, the reaction rate is not accelerated.

The reaction temperature is preferably 0 ° C. or higher and 150 ° C. or lower, more preferably 50 ° C. or higher and 100 ° C. or lower. If the temperature is 0 ° C. or lower, the reaction time is too long, and if the temperature is 150 ° C. or higher, a side reaction occurs and the purity of the product becomes low, which is not preferable. The reaction time depends on the reaction temperature, but is usually 2 hours or more and 6 hours or less.

After completion of the reaction, the reaction solution is poured into acidic water, and the reaction product precipitates. Therefore, suction filtration, washing with water, and drying are performed to perform 9- (2-carboxy- mono-substituted or 1,2-di-substituted-ethyl) carbonyloxyanthracene. The compound is obtained. The formation of the obtained compound ^{was identified by IR spectrum and 1} H-NMR spectrum.

Next, in the general formula (1), 9,10-bis {(2-carboxy) represented by the general formula (9) in which Q is a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) group. -A method for producing a mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy} anthracene compound will be described. The 9,10-bis {(2-carboxy- mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy} anthracene compound represented by the general formula (9) is represented by the general formula (8) 9, It can be synthesized by reacting a 10-dihydroxyanthracene compound with a mono-substituted or 1,2-di-substituted succinic anhydride represented by the general formula (6) according to the reaction formula-2.

In the reaction formula-2, X and Y may be the same or different, and represent an alkyl group or a halogen atom having 1 to 8 carbon atoms, and A and B are independently hydrogen atoms or 1 carbon atoms, respectively. It represents 10 to 10 alkyl groups, and the alkyl group may have a double bond in a part thereof. However, this does not apply when both A and B are hydrogen atoms. Further, A and B may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring.

Examples of the 9,10-dihydroxyanthracene compound represented by the general formula (8) include 9,10-dihydroxyanthracene, 2-methyl-9,10-dihydroxyanthracene, 2-ethyl-9,10-dihydroxyanthracene, and 2, -(T-butyl) -9,10-dihydroxyanthracene, 1-methyl-9,10-dihydroxyanthracene, 1-ethyl-9,10-dihydroxyanthracene, 1- (t-butyl) -9,10-dihydroxyanthracene , 2,6-dimethyl-9,10-dihydroxyanthracene, 2,6-dihydroxy-9,10-dihydroxyanthracene, 2,6-di (t-butyl) -9,10-dihydroxyanthracene, 1,5-dimethyl -9,10-dihydroxyanthracene, 1,5-diethyl-9,10-dihydroxyanthracene, 1,5-di (t-butyl) -9,10-dihydroxyanthracene, 2-chloro-9,10-dihydroxyanthracene, Examples thereof include 1-chloro-9,10-dihydroxyanthracene.

The mono-substituted or 1,2-di-substituted succinic anhydride represented by the general formula (6) is usually succinic anhydride, 3-methylsuccinic anhydride, 3,4-dimethylsuccinic anhydride, 3-. Octenyl succinic anhydride, 3-dodecenyl succinic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 4-octenylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3 , 6-Endomethylenetetrahydrophthalic anhydride, 4-3,6-methyltetrahydrophthalic anhydride and the like.

The reaction is usually carried out in a solvent. The solvent does not have to react with mono-substituted or 1,2-di-substituted succinic anhydride, and is an aromatic solvent such as toluene or xylene, an ether solvent such as tetrahydrofuran or 1,4-dioxane, chloroform or chloride. Examples thereof include halogen-based solvents such as methylene, amide-based solvents such as N, N-dimethylacetamide and N, N-dimethylformamide, and ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone.

A basic catalyst is used in the reaction. As the basic catalyst, for example, an organic amine is preferably used. Examples of organic amines include tertiary amines such as triethylamine, tributylamine and tricyclohexylamine, secondary amines such as dimethylamine, diethylamine, dibutylamine and piperidine, primary amines such as methylamine, ethylamine and butylamine, pyridine, picoline and lutidine. Such as pyridine compounds. The amount of the basic compound added is preferably 0.1 mol times or more and 4 mol times or less with respect to the raw material anthracene compound, and more preferably 0.2 mol times or more and 3 mol times or less with respect to the anthracene compound. is there. If it is 0.1 mol times or less, the reaction progresses slowly, and even if it is added 4 mol times or more, the reaction rate is not accelerated.

The reaction temperature is preferably 0 ° C. or higher and 150 ° C. or lower, more preferably 50 ° C. or higher and 100 ° C. or lower. If the temperature is 0 ° C. or lower, the reaction time is too long, and if the temperature is 150 ° C. or higher, a side reaction occurs and the purity of the product becomes low, which is not preferable. The reaction time depends on the reaction temperature, but is usually 2 hours or more and 6 hours or less.

After completion of the reaction, the reaction solution is poured into acidic water, and the reaction product precipitates. Therefore, suction filtration, washing with water, and drying are performed to perform 9- (2-carboxy- mono-substituted or 1,2-di-substituted-ethyl) carbonyloxyanthracene. The compound is obtained. The formation of the obtained compound ^{was identified by IR spectrum and 1} H-NMR spectrum.

(Photopolymerization sensitizer)
The anthracene compound having a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (1) of the present invention thus obtained is a photopolymerizable compound. It can be used as a photopolymerization sensitizer when polymerizing in the presence of a photopolymerization initiator.

In the general formula (1), Q is a hydrogen atom or P, and P represents a (2-carboxy- mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (2). X and Y may be the same or different, and represent an alkyl group or a halogen atom having 1 to 8 carbon atoms.

In the general formula (2), A and B each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group may have a double bond in a part thereof. Further, A and B may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring. * Marks indicate the joining position.

When the photopolymerizable compound is a photoradical polymerizable compound and the photopolymerizable initiator is a photoradical polymerizable initiator, it is represented by the general formula (1) (2-carboxy- mono substitution or 1,2. The anthracene compound having a −di-substituted-ethyl) carbonyloxy group acts as a photoradical polymerization sensitizer.

In addition, the total amount of the photopolymerization sensitizer containing an anthracene compound having a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (1) of the present invention. Is an anthracene compound having a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (1), and is generally used as long as the effects of the present invention are impaired. A photopolymerization sensitizer other than the anthracene compound having a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the formula (1) may be contained.

As a photopolymerization sensitizer other than the anthracene compound having a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (1), a dialkoxyanthracene compound is used. (9,10-diethoxyanthracene, 9,10-dibutoxyanthracene), thioxanthone compounds (eg 2-isopropylthioxanthone, 2,4-diethylthioxanthone), naphthalene compounds (eg 1,4-diethoxynaphthalene, 1,4) -Dimethoxynaphthalene, 1,4-dihydroxynaphthalene, 4-methoxy-1-naphthol), amine compounds (for example, methyl diethylaminobenzoate) and the like can be mentioned.

(2-carboxy- mono-substituted or 1,2-di-substituted-ethyl) represented by the general formula (1) for an anthracene compound having a carbonyloxy group represented by the general formula (1) (2-carboxy- mono-substituted) Alternatively , the addition ratio of the photopolymerization sensitizer other than the anthracene compound having a 1,2-di-substituted-ethyl) carbonyloxy group is not particularly limited, but is represented by the general formula (1) (2-carboxy- mono-substituted). Alternatively, it is 0.1 times by weight or more and less than 10 times by weight with respect to the anthracene compound having a 1,2-di-substituted-ethyl) carbonyloxy group.

(Photoradical polymerization initiator)
Examples of the photoradical polymerization initiator include an onium salt-based radical polymerization initiator, a benzylmethyl ketal-based photoradical polymerization initiator, an α-hydroxyalkylphenone-based photoradical polymerization initiator, an α-aminophenone-based photoradical polymerization initiator, and acyl. Examples thereof include a phosphine oxide-based photoradical polymerization initiator, an oxime ester-based photoradical polymerization initiator, and a biimidazole-based photoradical polymerization initiator.

As the onium salt-based radical polymerization initiator, an iodonium salt is usually used. Examples of iodonium salts include 4-isobutylphenyl-4'-methylphenyl iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexamethoxyantimonate, 4-isopropylphenyl-4'-methylphenyl iodonium tetrakispentamethoxyphenylborate, 4-. Examples thereof include isopropylphenyl-4'-methylphenyliodonium tetrakispentafluorophenylborate, etc., for example, Irgacure 250 manufactured by BASF Co., Ltd. (Irgacure is a registered trademark of BASF Co., Ltd.), Solbay Japan Co., Ltd. These photoradical polymerization initiators, which can be used with PHOTOINITIATOR 2074 or the like, may be used alone or in combination of two or more.

Examples of the benzylmethyl ketal radical polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name "Irgacure 651" manufactured by BASF) and the like. Examples of the α-hydroxyalkylphenone-based radical polymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name "Irgacure 1173" manufactured by BAS), 1-hydroxy. Cyclohexylphenyl ketone (trade name "Irgacure 184" manufactured by BASF), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1- On (trade name "Irgacure 2959" manufactured by BASF), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methyl -1-On (trade name "Irgacure 127" manufactured by BASF Co., Ltd.) can be mentioned.

In particular, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name "Irgacure 651" manufactured by BASF), which is a benzylmethyl ketal radical polymerization initiator, α-hydroxyalkyl. 2-Hydroxy-2-methyl-1-phenylpropan-1-one (trade name "Irgacure 1173" manufactured by BAS), a phenone-based radical polymerization initiator, 1-hydroxycyclohexylphenylketone (commodity) The name "Irgacure 184" manufactured by BASF Co., Ltd.) is preferable.

In addition, acetophenone, 2-hydroxy-2-phenylacetophenone, 2-ethoxy-2-phenylacetophenone, 2-methoxy-2-phenylacetophenone, 2-isopropoxy-2-phenylacetophenone, which are acetophenone-based radical polymerization initiators, 2 -Isobutoxy-2-phenylacetophenone, benzophenonone, benzyl radical polymerization initiator benzyl, 4,4'-dimethoxybenzyl, anthraquinone radical polymerization initiator 2-ethylanthraquinone, 2-t-butylanthraquinone, 2 -Phenoxyanthraquinone, 2- (phenylthio) anthraquinone, 2- (hydroxyethylthio) anthraquinone, 1,5-diacetoxyanthraquinone, 1,5-bis (methoxycarbonyloxy) anthracene, 1,5-bis (trimethylsilyloxy) anthraquinone , 5-trimethylsilyloxy-1,4-naphthoquinone, a naphthoquinone-based radical polymerization initiator, 5,11-bisacetoxy-6,12-naphthacendione, 5,11-bis, a naphthacene-based radical polymerization initiator. (Methoxycarbonyloxy) -6,12-naphthacendione, 5,11-bis (trimethylsilyloxy) -6,12-naphthacendione and the like can also be used.

Photoradical polymerization initiator of a photopolymerization sensitizer containing an anthracene compound having a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (1) of the present invention. The amount to be used is not particularly limited, but is usually in the range of 5% by weight or more and 100% by weight or less, preferably in the range of 10% by weight or more and 50% by weight or less with respect to the photoradical polymerization initiator. If the amount of the photopolymerization sensitizer used is less than 5% by weight, it takes too much time to photopolymerize the photoradical polymerizable compound, while if it is used in excess of 100% by weight, an effect commensurate with the addition can be obtained. I can't.

(Photoradical Polymerization Initiator Composition)
The photopolymerization sensitizer containing an anthracene compound having a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (1) of the present invention is a direct photoradical radical. Although it can be added to a polymerizable compound, it can also be added to a photoradical polymerizable compound after preparing a photoradical polymerization initiator composition by blending it with a photoradical polymerization initiator in advance. That is, the photoradical polymerization initiator composition of the present invention contains at least an anthracene compound having a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (1). It is a composition containing a photopolymerization sensitizer and a photoradical polymerization initiator.

(Photoradical Polymerizable Composition)
A photoradical polymerizable composition can also be prepared by blending the photoradical polymerization initiator composition and a photoradical polymerizable compound. The photoradical polymerizable composition of the present invention contains an anthracene compound having a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (1) of the present invention. It is a composition containing a photoradical polymerization initiator composition containing a photopolymerization sensitizer and a photoradical polymerization initiator, and a photoradical polymerizable compound.

A photopolymerization sensitizer containing an anthracene compound having a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (1) of the present invention and photoradical polymerization initiation. The agents may be separately added to the photoradical polymerizable compound to form a photoradical polymerization initiator composition in the photoradical polymerizable compound as a result.

As the photoradical polymerizable compound, for example, an organic compound having a double bond such as styrene, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylic nitrile, acrylamide, acrylic acid ester, and methacrylic acid ester can be used. .. Among these photoradical polymerizable compounds, acrylic acid ester and methacrylic acid ester (hereinafter, both are collectively referred to as (meth) acrylic acid ester) in terms of film forming ability and the high solubility of the compound of the present invention. ) Is preferable. Examples of the (meth) acrylate ester include methyl acrylate, butyl acrylate, cyclohexyl acrylate, -2-ethylhexyl acrylate, -2-hydroxyethyl acrylate, isobornyl acrylate, methyl methacrylate, butyl methacrylate, and methacrylic acid. Examples thereof include cyclohexyl, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, epoxy acrylate, urethane acrylate, polyester acrylate, polybutadiene acrylate, polyol acrylate, polyether acrylate, silicone resin acrylate, and imide acrylate. These photoradical polymerizable compounds may be one kind or a mixture of two or more kinds.

In the photoradical polymerizable composition of the present invention, the amount of the photoradical polymerization initiator composition used is in the range of 0.1% by weight or more and 10% by weight or less, preferably 0. It is 3% by weight or more and 2% by weight or less. If it is less than 0.1% by weight, it takes time to photopolymerize the photoradical polymerizable composition, while if it is added in excess of 5% by weight, the hardness of the photocured product obtained by photopolymerization decreases. , It is not preferable because it deteriorates the physical properties of the cured product.

The photoradical polymerizable composition of the present invention is a diluent, a colorant, an organic or inorganic filler, a leveling agent, a surfactant, a defoaming agent, and a thickener as long as the effects of the present invention are not impaired. , Flame retardants, antioxidants, stabilizers, lubricants, plasticizers and other various resin additives may be blended.

(Photo-cured product)
A photocurable product can be obtained by irradiating the photoradical polymerizable composition of the present invention with light. When the photoradical polymerizable composition is irradiated with light to be polymerized and photocured, the photoradical polymerizable composition may be molded into a film and photocured, or may be molded into a lump and photocured. it can. When the film is formed into a film and photocured, the liquid photoradical polymerizable composition is applied to a substrate such as a polyester film using a bar coater or the like so as to have a film thickness of 5 to 300 microns. On the other hand, it is also possible to apply a thinner film thickness or a thicker film thickness by a spin coating method or a screen printing method.

A photocured product is obtained by irradiating the coating film composed of the photoradical polymerizable composition thus prepared with ultraviolet rays having a wavelength range of 250 to 500 nm at ^{an intensity of about 1 to 1000 mW / cm 2.} be able to. The light sources used are high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, xenon lamps, gallium-doped lamps, black lights, 405 nm UV LEDs, 395 nm UV LEDs, 385 nm UV LEDs, 365 nm UV LEDs, blue LEDs, white LEDs, and fusion. Examples include D-valves and V-valves manufactured by the same company. In addition, natural light such as sunlight can also be used. In particular, 405 nm ultraviolet LED, 395 nm ultraviolet LED, 385 nm ultraviolet LED, and 365 nm ultraviolet LED are preferable.

When the photopolymerizable compound is a photocationic polymerizable compound and the photopolymerizable initiator is a photocationic polymerizable initiator, it is represented by the general formula (1) (2-carboxy- mono substitution or 1,2. The anthracene compound having a −di-substituted-ethyl) carbonyloxy group acts as a photocationic polymerization sensitizer.

(Photocationic polymerization initiator)
A sulfonium salt or an iodonium salt is usually used as the photocationic polymerization initiator used in the photopolymerizable composition of the present invention. As the sulfonium salt, an aryl sulfonium salt is preferable, and S, S, S', S'-tetraphenyl-S, S'-(4,4'-thiodiphenyl) disulfonium bishexafluorophosphate, diphenyl-4-phenyl. Examples thereof include thiophenylsulfonium hexafluorophosphate and triphenylsulfonium hexafluorophosphate, for example, manufactured by Dow Chemical Co., Ltd., trade name: UVI6992, manufactured by San-Apro Co., Ltd. Product name: CPI-100P, manufactured by BSF Co., Ltd. : Irgacure 270 (Irgacure is a registered trademark of BASF) can be used. On the other hand, as the iodonium salt, an aryl iodonium salt is preferable, 4-isobutylphenyl-4'-methylphenyl iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, 4-isopropylphenyl-4'-methylphenyl. Examples thereof include iodonium tetrakispentafluorophenylborate, for example, BASF, trade name: Irgacure 250, Rhodia, trade name: Rhodesyl 2074 (Rhodosyl is a registered trademark of Rhodia). Can be done.

(Photocationically polymerizable compound)
Examples of the photocationically polymerizable compound that can be used in the present invention include epoxy compounds and vinyl ether compounds. Common epoxy compounds are alicyclic epoxy compounds, epoxy-modified silicones, and aromatic glycidyl compounds. As the alicyclic epoxy compound, 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (UVR6105, UVR6110 manufactured by Dow Chemical Co., Ltd., Celoxide 2021P manufactured by Daicel Co., Ltd., Celoxide is a registered trademark of Daicel Co., Ltd.) , 1,2-epoxy-4-vinylcyclohexane (Ceroxide 2000 manufactured by Daicel), bis (3,4-epoxycyclohexyl) adipate, etc. Among them, 3', 4'-epoxycyclohexylmethyl-3, It is preferable to use 4-epoxycyclohexanecarboxylate. Examples of the aromatic glycidyl compound include 2,2'-bis (4-glycidyloxyphenyl) propane. Examples of the vinyl ether compound include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether and the like.

(Photocationic polymerizable composition)
The composition of the photocationic polymerizable composition is such that 0.1 to 10.0 parts by weight, preferably 1.% by weight, of a sulfonium salt or an iodonium salt as a photocationic polymerization initiator with respect to 100 parts by weight of the photocationic polymerizable compound. Use in the range of 0 to 5.0 parts by weight. If the amount of the photocationic polymerization initiator used for the photocationic polymerizable compound is too small, the polymerization rate becomes slow when the photocationic polymerizable composition is photocationically polymerized, while the amount of the photocationic polymerization initiator used increases. If the amount is too large, the physical properties of the photopolymerized product obtained when the photocationic polymerizable composition is photopolymerized may deteriorate, which is not preferable.

The anthracene compound having a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (1), which is the photopolymerization sensitizer of the present invention, is a photocationic polymerization initiator. It is used in the range of 0.1 to 5.0 parts by weight, preferably 0.2 to 1.0 parts by weight, based on 1 part by weight. If the amount of the photopolymerization sensitizer is too small, the sensitizing effect may be difficult to be exhibited, while if the amount is too large, the physical properties of the polymer may deteriorate when the photocationic polymerizable composition is photocationically polymerized. It is not preferable because it exists.

(Additive)
Further, the photocationic polymerizable composition according to the present invention includes a diluent, a colorant, an organic or inorganic filler, a leveling agent, a surfactant, a defoaming agent, and an increase, as long as the effects of the present invention are not impaired. Various resin additives such as thickeners, flame retardants, antioxidants, stabilizers, lubricants, and plasticizers can be blended within a normal range of use.

Examples of the epoxy-based diluent used in the present invention include, for example, phenylglycidyl ether, p-tert-butylphenylglycidyl ether, butylglycidyl ether, 2-ethylhexylglycidyl ether, allylglycidyl ether, 1,2-butylene oxide, and the like. 1,3-butadiene monooxide, 1,2-epoxidodecan, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3 -Vinylcyclohexene oxide and the like can be mentioned. Examples of oxetane-based diluents include 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene and the like. Be done. Examples of vinyl ether-based diluents include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether and the like.

Examples of the colorant include blue pigments, red pigments, white pigments, black pigments and the like. 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, navels yellow, naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow G, and benzidine yellow. GR, quinoline yellow rake, permanent yellow NCG, tartrajin rake and the like can be mentioned. Examples of the red pigment include red iron oxide, cadmium red, lead tan, mercury cadmium sulfide, permanent red 4R, resole red, lake red D brilliant carmine 6B, eosin lake, rodamine lake B, alizarin lake, brilliant carmine 3B and the like. .. Examples of the blue pigment include dark blue, cobalt blue, alkaline blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, first sky blue, and induslen blue BC. Examples of the white pigment include zinc white, titanium oxide, antimony white, zinc sulfide and the like. Examples of other pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, alumina white and the like.

(Polymerization method)
The photocationic polymerizable composition can be polymerized in the form of a film or can be cured in the form of a lump. When polymerizing in the form of a film, the photocationic polymerizable composition is liquefied, the photocationic polymerizable composition is applied onto a substrate such as a polyester film using, for example, a bar coater, and then ultraviolet rays or the like are used. Is irradiated with the light of the above to polymerize.

(Base material)
The base material used for polymerizing into a film is mainly film, paper, aluminum foil, metal, etc., but is not particularly limited. As the material used for the film as the base material, polyester, triacetyl cellulose (TAC), polyvinyl alcohol (PVA) and the like are used. Specifically, for example, a polyester film (Toray Industries, Inc. Lumirror, Lumirror is a registered trademark of Toray Industries, Inc.) can be used. The thickness of the polyester film is usually less than 100 μm. The bar coater used to adjust the film thickness of the polyester film is not particularly specified, but a bar coater whose film thickness can be adjusted to 1 μ or more and less than 100 μ is used.

(light source)
The coating film thus prepared can be polymerized by irradiating it with a light beam such as ultraviolet rays. As the light source used, it is preferable to use a light source containing ultraviolet rays having a wavelength of 355 to 420 nm. Specifically, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, gallium-doped lamps, microwave-excited UV lamps (for example, Fusion H-valve, D-valve, V-valve), 395 nm ultraviolet LED lamps, and 375 nm ultraviolet LEDs. Examples include a lamp, a 365 nm ultraviolet LED lamp, and the like. It is also possible to use sunlight and the like. In particular, a 395 nm ultraviolet LED is preferable. Examples of the 395 nm ultraviolet LED include a 395 ultraviolet LED manufactured by Phossonn.

(atmosphere)
The photocationic polymerizable composition of the present invention can be polymerized in a system in which the surface of the photocationic polymerizable composition is open or in a system in which the surface is shielded from air. For example, when polymerizing in the form of a film, the photocationic polymerizable composition of the present invention can be applied to a base material, and the polymer can be polymerized by irradiating a light beam such as ultraviolet rays with the coated surface open. It is also possible to apply the photocationic polymerizable composition to an oxygen-impermeable substrate and irradiate the surface of the photocation-impermeable substrate with a light beam such as ultraviolet rays for polymerization.

Examples of the surface-opening system of the photocationically polymerizable composition include applications used as coating films, that is, paints, coatings, inks, and the like. Specifically, automobile paints, woodwork coatings, PVC floor coatings, ceramic wall coatings, building material coatings, resin hard coatings, metallized base coatings, film coatings, liquid crystal display (LCD) coatings, plasma display (PDP) coatings, optical disks. Examples include coatings for metal coatings, optical fiber coatings, printing inks, flat plate inks, metal can inks, screen printing inks, inkjet inks, and gravure varnishes. Further, such a usage mode is also used in the fields of resists, displays, encapsulants, dental materials, stereolithography materials and the like.

Examples of the surface blocking system for the photocationically polymerizable composition include adhesives, pressure-sensitive adhesives, adhesives, and sealing agents. Furthermore, "Latest Trends in Photosensitive Materials for Electronic Parts III-Development Status in the Field of Semiconductors, Electronic Substrates, and Display-" (Sumibe Research Co., Ltd., July 2006), "Latest Trends in UV / EB Curing Technology" (Radtec Research (March 2006), "Optical Application Technology / Materials Encyclopedia" (edited by Ao Yamaoka, April 2006), "Photocuring Technology" (Technical Information Association, March 2000), "Photocurable Materials-Manufacturing" Technology and application development- "(Toray Research Center, September 2007) can be used as appropriate for the purposes exemplified.

(Tack free test)
As a method for determining whether or not the photopolymerizable composition of the present invention is photocured, there is a tack-free test (touch test). That is, when the photopolymerizable composition is irradiated with light, it cures and the surface tack (stickiness) disappears. Therefore, the photocuring time is measured by measuring the time from the irradiation with light until the tack (stickiness) disappears. Can be measured.

(Judgment of migration resistance)
As a method for determining whether or not the photopolymerization sensitizer contained in the photoradical polymerizable composition or the photocationic polymerizable composition of the present invention migrates to a film or the like, light containing a photopolymerization sensitizer is used. A radical-polymerizable composition or a photocationic-polymerizable composition is applied to a thin film, covered with a polyethylene film, stored at a constant temperature (26 ° C.) for a certain period of time, and then the polyethylene film is peeled off. , It was investigated whether the photopolymerization sensitizer had migrated to the polyethylene film, and the migration resistance was determined. The peeled polyethylene film is dried after washing the surface composition with acetone, the UV spectrum of the polyethylene film is measured, and the migration resistance is measured by examining the increase in absorption intensity due to the photopolymerization sensitizer. did. An ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV2200) was used for the measurement. For quantitative comparison with the compound of the comparative example, 9,10-dibutoxyanthracene, the obtained absorbance was converted into the absorbance value of 9,10-dibutoxyanthracene. For conversion, the absorbance of the compound of the present invention and 9,10-dibutoxyanthracene at 260 nm was measured with an ultraviolet / visible spectrophotometer, and each molar extinction coefficient was calculated from the absorbance value and molar concentration, and the ratio was calculated. Was converted using.

(Synthesis Example 1) Synthesis of 9- (2-carboxyethyl) carbonyloxyanthracene (7-1) In a three-necked flask equipped with a thermometer and a stirrer, 1.94 g (10 mmol) of 9-anthracene and 1.2 g of succinic anhydride (succinic anhydride). 12 mmol), N, N-dimethylacetamide 10 g was added under a nitrogen atmosphere, and 1.01 g (10 mmol) of triethylamine 1.01 g (10 mmol) of a 1.5 g solution of N, N-dimethylacetamide was added dropwise to the obtained pale yellow slurry. did. Immediately it turned into a light brown solution. Then, it was heated at 60 ° C. for 2 hours, cooled to room temperature, and then put into a 3% aqueous sulfuric acid solution. A large amount of light brown precipitate was formed. The produced precipitate was suction-filtered, washed with water, and dried to obtain 1.67 g (5.5 mmol) of a light brown powder of 9- (2-carboxyethyl) carbonyloxyanthracene. The isolated yield of the raw material with respect to 9-anthrone was 56 mol%.

(1) Melting point: 145-147 ° C
(2) IR (KBr, cm ^-1 ): 3060, 2940, 1751, 1708, 139
7,1342,1259,1220,1133,930,883,779,732,611,543.
(3) ^{1 1} H-NMR (400 MHz, deuterated acetone): δ = 2.89 (t, J = 8 Hz, 2H), 3.30 (t, J = 8 Hz, 2H), 7.46-7.55 ( m, 4H), 8.06-8.16 (m, 4H). 8.48 (s, 1H).
(4) UV absorption peak: 366 nm, 384 nm, 404 nm

(Synthesis Example 2) Synthesis of 9,10-bis (2-carboxyethyl) carbonyloxyanthracene (9-1) In a three-necked flask equipped with a thermometer and a stirrer, 2.1 g (10 mmol) of 9,10-dihydroxyanthracene, anhydrous. 2.5 g (25 mmol) of succinic anhydride and 15 g of N, N-dimethylacetamide were added under a ground atmosphere, and 2.02 g (20 mmol) of triethylamine of N, N-dimethylacetamide was added to the obtained yellow-green slurry. A 4 g solution was added dropwise. It became a slightly brownish slurry. Then, it was heated at 60 ° C. for 2 hours to obtain a brown solution. After cooling to room temperature, it was put into a 3% aqueous sulfuric acid solution, and a large amount of ocher precipitate was formed. The produced precipitate was suction-filtered, washed with water, and dried to obtain 2.7 g (6.5 mmol) of an ocher powder of 9,10-bis (2-carboxyethyl) carbonyloxyanthracene. The isolated yield for 9,10-dihydroxyanthracene was 65 mol%.

(1) Melting point: 166-168 ° C
(2) IR (KBr, cm ^-1 ): 3060, 2940, 1746, 1708, 1589, 1356, 1331, 1282, 1201, 1136, 93,807, 758, 692, 620, 608.
(3) ^{1 1} H-NMR (400 MHz, deuterated acetone): δ = 2.87 (t, J = 8 Hz, 4H), 3.29 (t, J = 8 Hz, 4H), 7.50-7.56 ( m, 4H), 8.12-8.18 (m, 4H).
(4) UV absorption peak: 386 nm, 398 nm, 409 nm

(Synthesis Example 1) Synthesis of 9- (2-carboxycyclohexyl) carbonyloxyanthracene (7-2) In a three-necked flask equipped with a thermometer and a stirrer, 1.94 g (10 mmol) of 9-anthracene, hexahydrophthalic anhydride 2 .0 g (13 mmol), 8 g of N, N-dimethylacetamide was added under a nitrogen atmosphere, and 1.01 g (10 mmol) of triethylamine, 1.5 g of N, N-dimethylacetamide, was added to the obtained pale yellow slurry. The solution was added dropwise. Immediately it turned into an orange solution. Then, it was heated at 60 ° C. for 6 hours, cooled to room temperature, and then put into a 3% sulfuric acid aqueous solution cooled to 0 ° C. A large amount of yellow precipitate was formed. The produced precipitate was suction-filtered, washed with water, and dried to obtain 3.06 g (8.9 mmol) of a yellow powder of 9- (2-carboxycyclohexyl) carbonyloxyanthracene. The isolated yield of the raw material with respect to 9-anthrone was 89 mol%.

(1) Melting point: 118-120 ° C
(2) IR (KBr, cm ^-1 ): 3070, 2946, 2860, 1749, 1700, 1676, 1657, 1598, 1445, 1345, 1309, 1284, 1263, 1242, 1171, 1135, 1069, 1053, 931, 879, 837, 809, 786, 758, 730, 712, 695, 630, 610, 589, 503.
(3) ^{1 1} H-NMR (400 MHz, deuterated acetone): δ = 1.08-1.16 (t, J = 8 Hz, 4H), 2.89-2.97 (M, 4H), 4.35 ( s, 2H), 7.40-7.49 (m, 4H), 7.54-7.61 (m, 2H), 8.29 (s.1H), 8.30-8.36 (m, 2H).

(Synthesis Example 2) Synthesis of 9,10-bis (2-carboxycyclohexyl) carbonyloxyanthracene (9-2) In a three-necked flask equipped with a thermometer and a stirrer, 1.05 g (5 mmol) of 9,10-dihydroxyanthracene, 1.68 g (11 mmol) of hexahydrophthalic anhydride and 7 g of N, N-dimethylacetamide were added under a nitrogen atmosphere, and 1.01 g (10 mmol) of triethylamine N, N- A 1 g solution of dimethylacetamide was added dropwise. It became a reddish brownish slurry. It was heated at 60 ° C. for 2 hours to give a brown solution. After cooling to room temperature, it was put into a 3% aqueous sulfuric acid solution, and a large amount of white-yellow precipitate was formed.
By suction filtration, washing with water, and drying, 1.50 g (2.9 mmol) of a white-yellow powder of 9,10-bis (2-carboxy-cyclohexylethyloxy) anthracene was obtained. The isolated yield for 9,10-dihydroxyanthracene was 58 mol%.

(1) Melting point: 246-247 ° C
(2) IR (KBr, cm-1): 3070, 2950, 2860, 1756, 1673, 1320, 1302, 1280, 1262, 1244, 1221, 1127, 1102, 1040, 935,767, 734,620.
(3) 1H-NMR (400MHz, deuterated acetone): δ1.20-1.40 (m, 4H), 1.40-1.60 (m, 4H), 1.70-1.90 (m, 4H) ), 2.64-2.94 (m, 8H), 7.40-7.56 (m, 6H), 7.95-8.08 (m, 2H).

(Example of evaluation of radical polymerization sensitization effect)
(Evaluation Example 1) 9,10-Bis (2-carboxyethyl) carbonyloxyanthracene (9-1)
100 parts of pentaerythritol tetraacrylate (Viscoat 400 manufactured by Osaka Organic Co., Ltd.) as a photoradical polymerizable compound, 5.0 parts of Irgacure 1173 which is a benzyl methyl ketal radical polymerization initiator as a photoradical polymerization initiator, and a photopolymerization sensitizer. To prepare a photoradical polymerizable composition, 1.0 part of 9,10-bis (2-carboxyethyl) carbonyloxyanthracene synthesized by the same method as in Synthesis Example 2 was mixed. The composition prepared in this manner was applied onto a polyester film (Toray's Lumirror, Lumirror is a registered trademark of Toray Industries, Inc.) using a bar coater (No. 20) so as to have a film thickness of 30 microns. .. Then, in a nitrogen atmosphere, light was irradiated from the surface of the film to which the composition was applied using an ultraviolet LED manufactured by Phoseon. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 50 mW / cm ² . The light irradiation time "tack free time" from the start of light irradiation to the elimination of stickiness (tack) on the coated surface of the composition was 3.5 seconds.

(Evaluation Example 2) 9- (2-carboxycyclohexyl) carbonyloxyanthracene (7-2)
Synthesis of 9,10-bis (2-carboxyethyl) carbonyloxyanthracene 1.0 part as a photopolymerization sensitizer 9- (2-carboxycyclohexyl) carbonyloxyanthracene 1.0 synthesized in the same manner as in Example 1. A photopolymerization composition was prepared, coated and photocured by the same method as in Evaluation Example 1 except that the portion was formed. The light irradiation time "tack free time" from the start of light irradiation to the elimination of stickiness (tack) on the coated surface of the composition was 7 seconds.

(Evaluation Example 3) 9,10-Bis (2-carboxycyclohexyl) carbonyloxyanthracene (9-2)
As a photopolymerization sensitizer, 1.0 part of 9,10-bis (2-carboxyethyl) carbonyloxyanthracene was synthesized by the same method as in Synthesis Example 2. 9,10-bis (2-carboxycyclohexyl) carbonyloxyanthracene A photopolymerization composition was prepared in exactly the same manner as in Evaluation Example 1 except that the portion was 1.0 part, and the photopolymerization composition was applied and photocured. The light irradiation time "tack free time" from the start of light irradiation to the elimination of stickiness (tack) on the coated surface of the composition was 5 seconds.

(Evaluation comparison example 1)
A photopolymerization composition was prepared, coated and irradiated with light in exactly the same manner as in Evaluation Example 1 except that 9,10-bis (2-carboxyethyl) carbonyloxyanthracene was not added as a photopolymerization sensitizer. The light irradiation time "tack free time" from the start of light irradiation to the elimination of stickiness (tack) on the coated surface of the composition was 22 seconds.

(Evaluation Example 4) 9- (2-carboxyethyl) carbonyloxyanthracene (7-1)
100 parts of pentaerythritol tetraacrylate (Viscoat 400 manufactured by Osaka Organic Co., Ltd.) as a photoradical polymerizable compound, 5.0 parts of Irgacure 184, which is a benzyl methyl ketal radical polymerization initiator, as a photoradical polymerization initiator, and a photopolymerization sensitizer. To prepare a photoradical polymerizable composition, 1.0 part of 9- (2-carboxyethyl) carbonyloxyanthracene synthesized by the same method as in Synthesis Example 1 was mixed. The composition prepared in this manner was applied onto a polyester film (Toray's Lumirror, Lumirror is a registered trademark of Toray Industries, Inc.) using a bar coater (No. 20) so as to have a film thickness of 30 microns. .. Then, in a nitrogen atmosphere, light was irradiated from the surface of the film to which the composition was applied using an ultraviolet LED manufactured by Phoseon. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 50 mW / cm ² . The light irradiation time "tack free time" from the start of light irradiation to the elimination of stickiness (tack) on the coated surface of the composition was 9 seconds.

(Evaluation Example 5) 9,10-Bis (2-carboxyethyl) carbonyloxyanthracene (9-1)
1.0 part of 9,10-bis (2-carboxyethyl) carbonyloxyanthracene synthesized by the same method as in Synthesis Example 2 with 1.0 part of 9- (2-carboxyethyl) carbonyloxyanthracene as a photopolymerization sensitizer. The photopolymerization composition was prepared in exactly the same manner as in Evaluation Example 4, and was coated and photocured. The light irradiation time "tack free time" from the start of light irradiation to the elimination of stickiness (tack) on the coated surface of the composition was 3.5 seconds.

(Evaluation comparison example 2)
A photopolymerization composition was prepared, coated and irradiated with light in exactly the same manner as in Evaluation Example 4 except that 9- (2-carboxyethyl) carbonyloxyanthracene was not added as a photopolymerization sensitizer. The light irradiation time "tack free time" from the start of light irradiation to the elimination of stickiness (tack) on the coated surface of the composition was 19 seconds.

(Evaluation Example 6) 9,10-Bis (2-carboxyethyl) carbonyloxyanthracene (9-1)
Synthesized 100 parts of pentaerythritol tetraacrylate (Viscoat 400 manufactured by Osaka Organic Co., Ltd.) as a photoradical polymerizable compound and 2.5 parts of Irgacure 250, which is an onium salt-based radical polymerization initiator as a photopolymerization initiator, as a photopolymerization sensitizer. 1.0 part of 9,10-bis (2-carboxyethyl) carbonyloxyanthracene synthesized by the same method as in Example 2 was mixed to prepare a photoradical polymerizable composition. The composition prepared in this manner was applied onto a polyester film (Toray's Lumirror, Lumirror is a registered trademark of Toray Industries, Inc.) using a bar coater (No. 20) so as to have a film thickness of 30 microns. .. Then, in a nitrogen atmosphere, light was irradiated from the surface of the film to which the composition was applied using an ultraviolet LED manufactured by Phoseon. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 50 mW / cm ² . The light irradiation time "tack free time" from the start of light irradiation to the elimination of stickiness (tack) on the coated surface of the composition was 4.5 seconds.

(Evaluation comparison example 3)
A photopolymerization composition was prepared, coated and irradiated with light in exactly the same manner as in Evaluation Example 6 except that 9,10-bis (2-carboxyethyl) carbonyloxyanthracene was not added as a photopolymerization sensitizer. It did not cure at all even after being irradiated with light for 5 minutes.

(Example of cation sensitization evaluation)
(Evaluation Example 7) 9- (2-carboxyethyl) carbonyloxyanthracene (7-1)
Synthesized 100 parts of alicyclic epoxy compound (Ceroxide 2021P manufactured by Daicel Co., Ltd.) as a photocationic polymerizable compound and 3.0 parts of Irgacure 250, which is an onium salt-based cationic polymerization initiator as a photopolymerization initiator, as a photopolymerization sensitizer. 1.0 part of 9- (2-carboxyethyl) carbonyloxyanthracene synthesized by the same method as in Example 1 was mixed to prepare a photocationic polymerizable composition. The composition prepared in this manner was applied onto a polyester film (Toray's Lumirror, Lumirror is a registered trademark of Toray Industries, Inc.) using a bar coater (No. 20) so as to have a film thickness of 30 microns. .. Then, in a nitrogen atmosphere, light was irradiated from the surface of the film to which the composition was applied using an ultraviolet LED manufactured by Phoseon. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 50 mW / cm ² . The light irradiation time "tack free time" from the start of light irradiation to the elimination of stickiness (tack) on the coated surface of the composition was 26 seconds.

(Evaluation Example 8) 9- (2-carboxycyclohexyl) carbonyloxyanthracene (7-2)
As a photopolymerization sensitizer, 1.0 part of 9- (2-carboxyethyl) carbonyloxyanthracene is prepared as 1.0 part of 9- (2-carboxycyclohexyl) carbonyloxyanthracene synthesized by the same method as in Synthesis Example 1. A photopolymerization composition was prepared, coated and photocured in exactly the same manner as in Evaluation Example 8 except for the above. The light irradiation time "tack free time" from the start of light irradiation to the elimination of stickiness (tack) on the coated surface of the composition was 80 seconds.

(Evaluation Example 9) 9,10-Bis (2-carboxycyclohexyl) carbonyloxyanthracene (9-2)
As a photopolymerization sensitizer, 1.0 part of 9- (2-carboxyethyl) carbonyloxyanthracene was synthesized by the same method as in Synthesis Example 2, 9,10-bis (2-carboxycyclohexyl) carbonyloxyanthracene 1.0. A photopolymerization composition was prepared in exactly the same manner as in Evaluation Example 8 except that the portion was formed, and the photopolymerization composition was applied and photocured. The light irradiation time "tack free time" from the start of light irradiation to the elimination of stickiness (tack) on the coated surface of the composition was 110 seconds.

(Evaluation comparison example 4)
A photopolymerization composition was prepared, coated and irradiated with light in exactly the same manner as in Evaluation Example 1 except that 9- (2-carboxyethyl) carbonyloxyanthracene was not added as a photopolymerization sensitizer. The picture was not cured at all after being irradiated with light for 5 minutes.

Table 1 shows the results of Evaluation Examples 1 to 9 and Evaluation Comparative Examples 1 to 4.

As is clear from comparing Evaluation Examples 1 to 3 with Evaluation Comparative Example 1, Evaluation Examples 4 and 5 with Evaluation Comparative Example 2, and Evaluation Example 6 with Evaluation Comparative Example 3, the light of the photoradical polymerizable composition In radical polymerization, when the photopolymerization sensitizer of the present invention is added, the tack free time becomes extremely short, so that the photopolymerization sensitizer of the present invention has an excellent photoradical polymerization sensitizing effect. I understand. Similarly, as is clear from comparing Evaluation Examples 7 to 9 and Evaluation Comparative Example 4, even in the photocationic polymerization of the photocationic polymerizable composition, when the photopolymerization sensitizer of the present invention is added, when the photopolymerization sensitizer of the present invention is added, Since the tack free time is extremely short, it can be seen that the photopolymerization sensitizer of the present invention also has an excellent photocationic polymerization sensitizing effect.

(Example of evaluation of migration resistance in photoradical polymerization)
(Evaluation Example 10) 9,10-Bis (2-carboxyethyl) carbonyloxyanthracene (9-1)
As a radically polymerizable compound, 100 parts of trimethylolpropane triacrylate and as a photopolymerization sensitizer, 1 part of 9,10-bis (2-carboxyethyl) carbonyloxyanthracene synthesized by the same method as in Synthesis Example 2 were mixed. , A photopolymerizable composition was prepared. Next, on a polyester film (trade name: Lumirror, film thickness 100 microns, "Lumilar" is a registered trademark of Toray Industries, Inc.), apply a bar coater to the prepared photopolymerizable composition so that the film thickness is 30 microns. Used and applied. Next, the obtained coating material was covered with a low-density polyethylene film (thickness: 30 microns), and the ones stored in a dark place for one day and the ones stored for three days were stored, respectively, and then the polyethylene film was peeled off to remove the polyethylene film. Was washed with acetone and dried, and then the UV spectrum of the polyethylene film was measured, and the absorbance at 253 nm was measured. The absorbance of the obtained AT + succinic anhydride was converted to 9,10-dibutoxyanthracene. The absorbance was 0.025 after storage for one day and 0.019 after storage for three days.

(Evaluation Example 11) 9- (2-carboxycyclohexyl) carbonyloxyanthracene (7-2)
Synthesis of 9,10-bis (2-carboxyethyl) carbonyloxyanthracene 1 part as a photopolymerization sensitizer 9- (2-carboxy-cyclohexyl carbonyloxy) anthracene 1 part synthesized by the same method as in Example 1. The photopolymerization composition was prepared and applied in the same manner as in Evaluation Example 10, and then the absorbance of the polyethylene film covered on the coated material was measured. The absorbance was 0.033 after storage for one day and 0.030 after storage for three days.

(Evaluation Example 12) 9,10-Bis (2-carboxycyclohexyl) carbonyloxyanthracene (9-2)
Synthesis of 9,10-bis (2-carboxyethyl) carbonyloxyanthracene 1 part as a photopolymerization sensitizer 1 part of 9,10-bis (2-carboxycyclohexyl) carbonyloxyanthracene synthesized by the same method as in Example 2. The photopolymerization composition was prepared and applied in the same manner as in Evaluation Example 10, and then the absorbance of the polyethylene film covered on the coated material was measured. The absorbance was 0.018 after storage for one day and 0.020 after storage for three days.

(Evaluation comparison example 5)
Evaluation except that 1 part of 9,10-bis (2-carboxyethyl) carbonyloxyanthracene as a photopolymerization sensitizer was used as 1 part of 9,10-dibutoxyanthracene (DBA) which is an existing photopolymerization sensitizer. A photopolymerization composition was prepared and applied in the same manner as in Example 12, and then the absorbance of the polyethylene film covered on the coated material was measured. The absorbance was 1.220 after storage for one day and 1.250 after storage for three days.

(Example of evaluation of migration resistance in photocationic polymerization)
(Evaluation Example 13) 9- (2-carboxyethyl) carbonyloxyanthracene (7-1)
As a cationically polymerizable compound, 100 parts of an alicyclic epoxy compound (celloxide 2021P manufactured by Daicel Co., Ltd.), and as a photopolymerization sensitizer, 9- (2-carboxyethyl) carbonyloxyanthracene 1 synthesized by the same method as in Synthesis Example 1. The parts were mixed to prepare a photopolymerizable composition. Next, on a polyester film (trade name: Lumirror, film thickness 100 microns, "Lumilar" is a registered trademark of Toray Industries, Inc.), apply a bar coater to the prepared photopolymerizable composition so that the film thickness is 30 microns. Used and applied. Next, the obtained coating material was covered with a low-density polyethylene film (thickness: 30 microns), and the ones stored in a dark place for one day and the ones stored for three days were stored, respectively, and then the polyethylene film was peeled off to remove the polyethylene film. Was washed with acetone and dried, and then the UV spectrum of the polyethylene film was measured, and the absorbance at 253 nm was measured. The absorbance of the obtained AT + succinic anhydride was converted to 9,10-dibutoxyanthracene. The absorbance was 0.021 after storage for one day and 0.022 after storage for three days.

(Evaluation Comparison Example 6)
Evaluation Example 13 except that 1 part of 9- (2-carboxyethyl) carbonyloxyanthracene as a photopolymerization sensitizer was used as 1 part of 9,10-dibutoxyanthracene (DBA) which is an existing photopolymerization sensitizer. The photopolymerization composition was prepared and applied in the same manner as in the above method, and then the absorbance of the polyethylene film covered on the coated material was measured. The absorbance was 0.740 after storage for one day and 0.770 after storage for three days.

Evaluation Example 10 to Evaluation Example 13, Evaluation Comparative Example 5, and Evaluation Comparative Example 6 are summarized in Table 2.

As is clear from comparing Evaluation Examples 10 to 12 with Evaluation Comparative Example 5 and Evaluation Example 13 with Evaluation Comparative Example 6, the present invention is used in both the photoradical polymerizable composition and the photocationic polymerizable composition. The amount of the photopolymerization sensitizer transferred to the polyethylene film is much smaller than that of the known photopolymerization sensitizer DBA, and the photopolymerization sensitizer of the present invention has excellent migration resistance. Understand.

Claims (12)

An anthracene compound having a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the following general formula (1).

(In the general formula (1), Q is a hydrogen atom or P, and P represents a (2-carboxy- mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (2). X and Y may be the same or different and represent an alkyl group or a halogen atom having 1 to 8 carbon atoms.)

(In the general formula (2), A and B each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group may have a double bond in a part thereof. , A and B are both hydrogen atoms. Further, A and B may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring. * Mark indicates the bonding position. Represent.) The (2-carboxy-mono-substituted or 1, 1) according to claim 1, wherein A and B are bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring in the general formula (2). 2-Disubstituted-ethyl) Anthracene compound having a carbonyloxy group. The (2-carboxy-mono-substituted ) according to claim 1, wherein P is a (2-carboxy-1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (3) or the general formula (4). Alternatively , an anthracene compound having a 1,2-di-substituted-ethyl) carbonyloxy group.

(In the general formula (3), R represents an alkyl group having 1 to 5 carbon atoms. * Mark represents a bond position.)

(In the general formula (4), R represents an alkyl group having 1 to 5 carbon atoms. * Mark represents a bond position.) The anthracene compound having a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group according to any one of claims 1 to 3, wherein Q is a hydrogen atom. The anthracene compound having a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group according to any one of claims 1 to 3, wherein Q is P. The general formula (2) by reacting the 9-anthrone compound represented by the general formula (5) with the mono-substituted or 1,2-di-substituted succinic anhydride represented by the general formula (6) according to the reaction formula-1. A method for producing a 9- (2-carboxy- mono-substituted or 1,2-di-substituted-ethyl) carbonyloxyanthracene compound represented by 7).

(In the reaction formula-1, X and Y may be the same or different, and represent an alkyl group or a halogen atom having 1 to 8 carbon atoms, and A and B are independently hydrogen atoms or carbon atoms, respectively. Represents 1 to 10 alkyl groups, the alkyl group may have a double bond in part thereof, except when both A and B are hydrogen atoms, and A and B are mutually exclusive. They may be combined to form a substituted or unsubstituted saturated or unsaturated ring.) By reacting the 9,10-dihydroxyanthracene compound represented by the general formula (8) with the mono-substituted or 1,2-di-substituted succinic anhydride represented by the general formula (6) according to the reaction formula-2. A method for producing a 9,10-bis {(2-carboxy- mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy} anthracene compound represented by the general formula (9).

(In the reaction formula-2, X and Y may be the same or different, and represent an alkyl group or a halogen atom having 1 to 8 carbon atoms, and A and B are independently hydrogen atoms or carbon atoms, respectively. Represents 1 to 10 alkyl groups, the alkyl group may have a double bond in part thereof, except when both A and B are hydrogen atoms, and A and B are mutually exclusive. They may be combined to form a substituted or unsubstituted saturated or unsaturated ring.) A photopolymerization sensitizer containing an anthracene compound having a (2-carboxy-mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the following general formula (1).

(In the general formula (1), Q is a hydrogen atom or P, and P represents a (2-carboxy- mono-substituted or 1,2-di-substituted-ethyl) carbonyloxy group represented by the general formula (2). X and Y may be the same or different and represent an alkyl group or a halogen atom having 1 to 8 carbon atoms.)

(In the general formula (2), A and B each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group may have a double bond in a part thereof. , A and B may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring. * Mark indicates a bonding position.) A photoradical polymerization initiator composition containing the photopolymerization sensitizer and the photoradical polymerization initiator according to claim 8. A photocationic polymerization initiator composition containing the photopolymerization sensitizer and the photocationic polymerization initiator according to claim 8. A photoradical polymerizable composition containing the photoradical polymerization initiator composition according to claim 9 and a photoradical polymerizable compound. A photocationic polymerizable composition containing the photocationic polymerization initiator composition according to claim 10 and a photocationic polymerizable compound.