JP2008169156A - New anthracene compound, method for producing the same and application thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new 9,10-bis(2-(meth)acryloyloxyalkoxy)-1,4-dihydroanthracene compound, a method for producing the compound and a photopolymerization sensitizer using the compound as an active ingredient. <P>SOLUTION: The new anthracene compound is exemplified by 9,10-bis(2-(meth)acryloyloxyethoxy)-1,4-dihydroanthracene and 9,10-bis(2-(meth)acryloyloxypropoxy)-1,4-dihydroanthracene. The method for producing the compound includes reacting an alkylene oxide, a halogenated alcohol or the like with a 9,10-dihydroxyanthracene compound, and thereafter reacting a (meth)acryloyl chloride compound with the product. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a novel anthracene compound, a method for producing the compound, and a use thereof. The anthracene compound of the present invention is particularly useful as a photopolymerization sensitizer.

  Conventionally, it is known that 9,10-dialkoxyanthracene functions as a sensitizer in photoradical polymerization or photocationic polymerization. For example, 9,10-diethoxyanthracene is used as a sensitizer for tetraethylene glycol dimethacrylate in applications of radical photopolymerization (see Patent Document 1). An example is described in which 2-ethyl-9,10-dimethoxyanthracene is used as a sensitizer for a cyclic epoxy compound (manufactured by Dow, trade name: UVR6110) (see Patent Document 2). Further, 9,10-dialkoxy-1,4-dihydroanthracene compounds in which the 1,4-positions of the anthracene skeleton are hydrogenated are also known to exhibit a sensitizing effect in photocationic polymerization (see Patent Document 3). ).

Japanese Patent Laid-Open No. 06-059380 JP 11-279212 A JP 2001-81116 A

  However, the conventional dialkoxyanthracene or dialkoxy-1,4-dihydroanthracene has high volatility (sublimation), and volatilizes (sublimates) during the formation of a coating on the substrate surface, so that an anthracene compound is formed on the substrate surface. There is a problem that oozes out. For this reason, the present inventors tried to introduce an acryloyl group into the anthracene skeleton, but the resulting anthracene compound into which the acryloyl group was introduced was poor in polymerization performance and was not satisfactory.

  The present inventors have completed the present invention as a result of intensive studies on the structure, characteristics, physical properties and the like of dialkoxy-1,4-dihydroanthracene compounds in order to provide a technique that eliminates the above-mentioned drawbacks. That is, the object of the present invention is as follows.

1. To provide a novel compound excellent in photosensitization performance.
2. To provide a photocurable composition containing the above compound as a photopolymerization sensitizer.
3. To provide a photocurable composition containing the above-mentioned compound as a photopolymerization sensitizer and having little oozing or volatilization even when time passes after heating, or after curing.

  In order to achieve the above object, the first invention provides a 9,10-bis (2- (meth) acryloyloxyalkoxy) -1,4-dihydroanthracene compound represented by the following formula (1). .

{In Formula (1), R ¹ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxymethyl group, an allyloxymethyl group, or an aryloxymethyl group, R ² represents a hydrogen atom or a methyl group, X and Y may be the same or different and each represents a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, an alkylthio group, an arylthio group, a carboxyl group, or a sulfonic acid group. }

  In the second invention, the 9,10-dihydroxy-1,4-dihydroanthracene compound is reacted with alkylene oxide, glycidyl ether or halogenated alcohol (halohydrin) to produce 9,10-bis (2-hydroxyalkoxy) -1, 9,10-bis (2- (meth) acryloyloxyalkoxy) -1,4-dihydro, characterized in that it is a 4-dihydroanthracene compound and then this compound is reacted with an acryloyl chloride compound or a methacryloyl chloride compound. A method for producing an anthracene compound is provided.

  In the third invention, a photopolymerization sensitization comprising the 9,10-bis (2- (meth) acryloyloxyalkoxy) -1,4-dihydroanthracene compound according to the first invention as an active ingredient. Provide the agent. Furthermore, the fourth invention provides a photocurable composition comprising the photopolymerization sensitizer, photopolymerization initiator, and photopolymerizable monomer according to the third invention.

  The present invention is as described in detail below, has the following particularly advantageous effects, and its industrial utility value is extremely large.

  1. The 9,10-bis (2- (meth) acryloyloxyalkoxy) -1,4-dihydroanthracene compound according to the present invention is a novel compound and has higher solubility in a photopolymerizable monomer than a dialkoxyanthracene compound. .

  2. The 9,10-bis (2- (meth) acryloyloxyalkoxy) -1,4-dihydroanthracene compound according to the present invention functions as a photosensitizer, promotes photopolymerization of a photopolymerizable monomer, and is photocured. The effective composition is cured.

  3. The photocurable composition containing the 9,10-bis (2- (meth) acryloyloxyalkoxy) -1,4-dihydroanthracene compound according to the present invention as a photopolymerization sensitizer includes a heating step when photocuring, The anthracene compound does not volatilize (sublimate) after photocuring.

  Hereinafter, the present invention will be described in detail. The compound according to the first aspect of the present invention is a 9,10-bis (2- (meth) acryloyloxyalkoxy) -1,4-dihydroanthracene compound represented by the above formula (1).

In the formula (1), examples of the alkyl group represented by R ¹ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, n-pentyl group, n- hexyl, n- heptyl group. Examples of the aryl group represented by ^{R 1,} a phenyl group, o- tolyl group, m- tolyl group, p- tolyl group, p- methoxyphenyl group, p- ethoxy Examples thereof include a phenyl group and a naphthyl group. Examples of the alkoxymethyl group represented by R ¹ include a methoxymethyl group, an n-butoxymethyl group, a 2-ethylhexyloxymethyl group, and a 2-octyloxymethyl group. the allyloxymethyl group represented by ^1, allyloxymethyl group, a methallyl oxymethyl group and the like, also, aryloxy methyl group represented by R ¹ , Like phenoxymethyl group.

  In the formula (1), examples of the alkyl group represented by X or Y include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, n-amyl group, i -Amyl group, 2-ethylhexyl group, 4-methylpentyl, 4-methyl-3-pentenyl group etc. are mentioned. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Furthermore, examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-hexyloxy group, and a phenoxy group. Examples of the alkylthio group include a methylthio group, an ethylthio group, an n-propylthio group, an n-butylthio group, and an n-hexylthio group. Examples of the arylthio group include a phenylthio group, an o-tolylthio group, an m-tolylthio group, a p-tolylthio group, and a p-hydroxyphenylthio group.

  Specific examples of the 9,10-bis (2- (meth) acryloyloxyalkoxy) -1,4-dihydroanthracene compound represented by the formula (1) include the following compounds. That is, 9,10-bis (2-acryloyloxyethoxy) -1,4-dihydroanthracene, 9,10-bis (2-methacryloyloxyethoxy) -1,4-dihydroanthracene, 9,10-bis (2- Acryloyloxypropoxy) -1,4-dihydroanthracene, 9,10-bis (2-methacryloyloxypropoxy) -1,4-dihydroanthracene, 9,10-bis (2-acryloyloxybutoxy) -1,4-dihydro Anthracene, 9,10-bis (2-methacryloyloxybutoxy) -1,4-dihydroanthracene, 9,10-bis (2-acryloyloxyheptyloxy) -1,4-dihydroanthracene, 9,10-bis (2 -Methacryloyloxyheptyloxy) -1,4-dihydroant Cene, 9,10-bis (2-acryloyloxyoctyloxy) -1,4-dihydroanthracene, 9,10-bis (2-methacryloyloxyoctyloxy) -1,4-dihydroanthracene, 9,10-bis ( 2-acryloyloxy-2-phenylethoxy) -1,4-dihydroanthracene, 9,10-bis (2-methacryloyloxy-2-phenylethoxy) -1,4-dihydroanthracene, 9,10-bis (2- Acryloyloxy-3-methoxypropoxy) -1,4-dihydroanthracene, 9,10-bis (2-methacryloyloxy-3-methoxypropoxy) -1,4-dihydroanthracene, 9,10-bis (2-acryloyloxy) -3-butoxypropoxy))-1,4-dihydroanthracene, 9 10-bis (2-methacryloyloxy-3-butoxypropoxy) -1,4-dihydroanthracene, 9,10-bis (2-acryloyloxy-3-allyloxypropoxy) -1,4-dihydroanthracene, 9,10 -Bis (2-methacryloyloxy-3-allyloxypropoxy) -1,4-dihydroanthracene, 9,10-bis (2-acryloyloxy-3- (2-ethyl) hexyloxypropoxy) -1,4-dihydro Anthracene, 9,10-bis (2-methacryloyloxy-3- (2-ethyl) hexyloxypropoxy) -1,4-dihydroanthracene, 9,10-bis (2-acryloyloxy-3-stearyloxypropoxy)- 1,4-dihydroanthracene, 9,10-bis (2-methacryloyl Ruoxy-3-stearyloxypropoxy) -1,4-dihydroanthracene, 9,10-bis (2-acryloyloxy-3-phenoxypropoxy) -1,4-dihydroanthracene, 9,10-bis (2-methacryloyloxy) -3-phenoxypropoxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-acryloyloxyethoxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2- Methacryloyloxyethoxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-acryloyloxypropoxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-methacryloyloxy) Propoxy) -1,4-dihydroanthracene, 2-methyl-9,1 -Bis (2-acryloyloxybutoxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-methacryloyloxybutoxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-acryloyloxyheptyloxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-methacryloyloxyheptyloxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-acryloyloxyoctyloxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-methacryloyloxyoctyloxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-acryloyloxy-2-phenylethoxy) -1,4-dihydroanthrace , 2-methyl-9,10-bis (2-methacryloyloxy-2-phenylethoxy) -1,4-dihydro-anthracene, and the like.

  Furthermore, 2-methyl-9,10-bis (2-acryloyloxy-3-methoxypropoxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-methacryloyloxy-3-methoxypropoxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-acryloyloxy-3-butoxypropoxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-methacryloyloxy) -3-butoxypropoxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-acryloyloxy-3-allyloxypropoxy) -1,4-dihydroanthracene, 2-methyl-9,10 -Bis (2-methacryloyloxy-3-allyloxypropoxy) -1,4-dihydroanthrace 2-methyl-9,10-bis (2-acryloyloxy-3- (2-ethyl) hexyloxypropoxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-methacryloyloxy- 3- (2-ethyl) hexyloxypropoxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-acryloyloxy-3-stearyloxypropoxy) -1,4-dihydroanthracene, 2- Methyl-9,10-bis (2-methacryloyloxy-3-stearyloxypropoxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-acryloyloxy-3-phenoxypropoxy) -1, 4-dihydroanthracene, 2-methyl-9,10-bis (2-methacryloyloxy-3-phenyl) Nokishipuropokishi) -1,4-dihydro-anthracene, and the like.

  Furthermore, 2-chloro-9,10-bis (2-acryloyloxyethoxy) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2-methacryloyloxyethoxy) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2-acryloyloxypropoxy) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2-methacryloyloxypropoxy) -1,4-dihydroanthracene, 2- Chloro-9,10-bis (2-acryloyloxybutoxy) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2-methacryloyloxybutoxy) -1,4-dihydroanthracene, 2-chloro- 9,10-bis (2-acryloyloxyheptyloxy) -1,4-dihydroanthracene 2-chloro-9,10-bis (2-methacryloyloxyheptyloxy) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2-acryloyloxyoctyloxy) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2-methacryloyloxyoctyloxy) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2-acryloyloxy-2-phenylethoxy) -1,4- Dihydroanthracene, 2-chloro-9,10-bis (2-methacryloyloxy-2-phenylethoxy) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2-acryloyloxy-3-methoxypropoxy) ) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2-methacryloyl) Oxy-3-methoxypropoxy) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2-acryloyloxy-3-butoxypropoxy) -1,4-dihydroanthracene, 2-chloro-9,10 -Bis (2-methacryloyloxy-3-butoxypropoxy) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2-acryloyloxy-3-allyloxypropoxy) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2-methacryloyloxy-3-allyloxypropoxy) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2-acryloyloxy-3- (2-ethyl) ) Hexyloxypropoxy) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2 -Methacryloyloxy-3- (2-ethyl) hexyloxypropoxy) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2-acryloyloxy-3-stearyloxypropoxy) -1,4-dihydro Anthracene, 2-chloro-9,10-bis (2-methacryloyloxy-3-stearyloxypropoxy) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2-acryloyloxy-3-phenoxypropoxy) ) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2-methacryloyloxy-3-phenoxypropoxy) -1,4-dihydroanthracene.

  Furthermore, 2-phenoxy-9,10-bis (2-acryloyloxyethoxy) -1,4-dihydroanthracene, 2-phenoxy-9,10-bis (2-methacryloyloxyethoxy) -1,4-dihydroanthracene, 2-phenoxy-9,10-bis (2-acryloyloxypropoxy) -1,4-dihydroanthracene, 2-phenoxy-9,10-bis (2-methacryloyloxypropoxy) -1,4-dihydroanthracene, 2- Phenoxy-9,10-bis (2-acryloyloxybutoxy) -1,4-dihydroanthracene, 2-phenoxy-9,10-bis (2-methacryloyloxybutoxy) -1,4-dihydroanthracene, 2-phenoxy- 9,10-bis (2-acryloyloxyheptyloxy)- , 4-Dihydroanthracene, 2-phenoxy-9,10-bis (2-methacryloyloxyheptyloxy) -1,4-dihydroanthracene, 2-phenoxy-9,10-bis (2-acryloyloxyoctyloxy) -1 , 4-Dihydroanthracene, 2-phenoxy-9,10-bis (2-methacryloyloxyoctyloxy) -1,4-dihydroanthracene, 2-phenoxy-9,10-bis (2-acryloyloxy-2-phenylethoxy) ) -1,4-dihydroanthracene, 2-phenoxy-9,10-bis (2-methacryloyloxy-2-phenylethoxy) -1,4-dihydroanthracene, 2-phenoxy-9,10-bis (2-acryloyl) Oxy-3-methoxypropoxy) -1,4-dihydroant Sen, 2-phenoxy-9,10-bis (2-methacryloyloxy-3-methoxypropoxy) -1,4-dihydroanthracene, 2-phenoxy-9,10-bis (2-acryloyloxy-3-butoxypropoxy) -1,4-dihydroanthracene, 2-phenoxy-9,10-bis (2-methacryloyloxy-3-butoxypropoxy) -1,4-dihydroanthracene, 2-phenoxy-9,10-bis (2-acryloyloxy) -3-allyloxypropoxy) -1,4-dihydroanthracene, 2-phenoxy-9,10-bis (2-methacryloyloxy-3-allyloxypropoxy) -1,4-dihydroanthracene, 2-phenoxy-9, 10-bis (2-acryloyloxy-3- (2-ethyl) hexyloxy) Cypropoxy) -1,4-dihydroanthracene, 2-phenoxy-9,10-bis (2-methacryloyloxy-3- (2-ethyl) hexyloxypropoxy) -1,4-dihydroanthracene, 2-phenoxy-9, 10-bis (2-acryloyloxy-3-stearyloxypropoxy) -1,4-dihydroanthracene, 2-phenoxy-9,10-bis (2-methacryloyloxy-3-stearyloxypropoxy) -1,4-dihydro Anthracene, 2-phenoxy-9,10-bis (2-acryloyloxy-3-phenoxypropoxy) -1,4-dihydroanthracene, 2-phenoxy-9,10-bis (2-methacryloyloxy-3-phenoxypropoxy) -1,4-dihydroanthracene and the like.

  Furthermore, 2-phenylthio-9,10-bis (2-acryloyloxyethoxy) -1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-methacryloyloxyethoxy) -1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-acryloyloxypropoxy) -1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-methacryloyloxypropoxy) -1,4-dihydroanthracene, 2- Phenylthio-9,10-bis (2-acryloyloxybutoxy) -1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-methacryloyloxybutoxy) -1,4-dihydroanthracene, 2-phenylthio- 9,10-bis (2-acryloyloxyhept Ruoxy) -1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-methacryloyloxyheptyloxy) -1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-acryloyloxyoctyl) Oxy) -1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-methacryloyloxyoctyloxy) -1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-acryloyloxy-) 2-Phenylethoxy) -1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-methacryloyloxy-2-phenylethoxy) -1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-acryloyloxy-3-methoxypropoxy -1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-methacryloyloxy-3-methoxypropoxy) -1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-acryloyloxy) -3-butoxypropoxy) -1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-methacryloyloxy-3-butoxypropoxy) -1,4-dihydroanthracene, 2-phenylthio-9,10- Bis (2-acryloyloxy-3-allyloxypropoxy) -1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-methacryloyloxy-3-allyloxypropoxy) -1,4-dihydroanthracene, 2-Phenylthio-9,10-bis (2-acryloyl) Oxy-3- (2-ethyl) hexyloxypropoxy) -1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-methacryloyloxy-3- (2-ethyl) hexyloxypropoxy) -1, 4-dihydroanthracene, 2-phenylthio-9,10-bis (2-acryloyloxy-3-stearyloxypropoxy) -1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-methacryloyloxy-3) -Stearyloxy) propoxyanthracene, 2-phenylthio-9,10-bis (2-acryloyloxy-3-phenoxypropoxy) -1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-methacryloyloxy- 3-phenoxypropoxy) -1,4-dihydride Anthracene, and the like.

  Furthermore, 9,10-bis (2-acryloyloxyethoxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-methacryloyloxyethoxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-acryloyloxypropoxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-methacryloyloxypropoxy) -1,4-dihydroanthracene 2-carboxylic acid, 10-bis (2-acryloyloxybutoxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-methacryloyloxybutoxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10- Bis (2-acryloyloxyheptyloxy) -1,4-dihydroanthracene -Carboxylic acid, 9,10-bis (2-methacryloyloxyheptyloxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-acryloyloxyoctyloxy) -1,4-dihydroanthracene 2 -Carboxylic acid, 9,10-bis (2-methacryloyloxyoctyloxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-acryloyloxy-2-phenylethoxy) -1,4- Dihydroanthracene 2-carboxylic acid, 9,10-bis (2-methacryloyloxy-2-phenylethoxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-acryloyloxy-3-methoxypropoxy) ) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2 Methacryloyloxy-3-methoxypropoxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-acryloyloxy-3-butoxypropoxy) -1,4-dihydroanthracene 2-carboxylic acid, 9, 10-bis (2-methacryloyloxy-3-butoxypropoxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-acryloyloxy-3-allyloxypropoxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-methacryloyloxy-3-allyloxypropoxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-acryloyloxy-3- (2- Ethyl) hexyloxypropoxy) -1,4-dihydroanthracene 2-cal Boronic acid, 9,10-bis (2-methacryloyloxy-3- (2-ethyl) hexyloxypropoxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-acryloyloxy-3- Stearyloxypropoxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-methacryloyloxy-3-stearyloxypropoxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-acryloyloxy-3-phenoxypropoxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-methacryloyloxy-3-phenoxypropoxy) -1,4-dihydroanthracene 2-carboxylic acid 9,10-bis (2-acryloyloxyethoxy) -1,4-dihi Loanthracene 2-sulfonic acid, 9,10-bis (2-methacryloyloxyethoxy) -1,4-dihydroanthracene 2-sulfonic acid, 9,10-bis (2-acryloyloxypropoxy) -1,4-dihydroanthracene 2-sulfonic acid, 9,10-bis (2-methacryloyloxypropoxy) -1,4-dihydroanthracene 2-sulfonic acid, 9,10-bis (2-acryloyloxybutoxy) -1,4-dihydroanthracene 2- Sulfonic acid, 9,10-bis (2-methacryloyloxybutoxy) -1,4-dihydroanthracene 2-sulfonic acid, 9,10-bis (2-acryloyloxyheptyloxy) -1,4-dihydroanthracene 2-sulfone Acid, 9,10-bis (2-methacryloyloxyheptyloxy -1,4-dihydroanthracene 2-sulfonic acid, 9,10-bis (2-acryloyloxyoctyloxy) -1,4-dihydroanthracene 2-sulfonic acid, 9,10-bis (2-methacryloyloxyoctyloxy) -1,4-dihydroanthracene 2-sulfonic acid, 9,10-bis (2-acryloyloxy-2-phenylethoxy) -1,4-dihydroanthracene 2-sulfonic acid, 9,10-bis (2-methacryloyloxy) 2-phenylethoxy) anthrace-2-sulfonic acid, 9,10-bis (2-acryloyloxy-3-methoxypropoxy) -1,4-dihydroanthracene-2-sulfonic acid, 9,10-bis (2-methacryloyl) Oxy-3-methoxypropoxy) -1,4-dihydroanthracene 2-sulfone Acid, 9,10-bis (2-acryloyloxy-3-butoxypropoxy) -1,4-dihydroanthracene-2-sulfonic acid, 9,10-bis (2-methacryloyloxy-3-butoxypropoxy) -1,4 -Dihydroanthracene 2-sulfonic acid, 9,10-bis (2-acryloyloxy-3-allyloxypropoxy) -1,4-dihydroanthracene 2-sulfonic acid, 9,10-bis (2-methacryloyloxy-3- Allyloxypropoxy) -1,4-dihydroanthracene-2-sulfonic acid, 9,10-bis (2-acryloyloxy-3- (2-ethyl) hexyloxypropoxy) -1,4-dihydroanthracene-2-sulfonic acid, 9,10-bis (2-methacryloyloxy-3- (2-ethyl) hexyloxypropo C) -1,4-dihydroanthracene 2-sulfonic acid, 9,10-bis (2-acryloyloxy- (3-stearyloxy) propoxy) -1,4-dihydroanthracene 2-sulfonic acid, 9,10-bis (2-Methacryloyloxy-3-stearyloxypropoxy) -1,4-dihydroanthracene 2-sulfonic acid, 9,10-bis (2-acryloyloxy-3-phenoxypropoxy) -1,4-dihydroanthracene 2-sulfone And acid, 9,10-bis (2-methacryloyloxy-3-phenoxypropoxy) -1,4-dihydroanthracene-2-sulfonic acid, and the like.

  Representative examples of the 9,10-bis (2- (meth) acryloyloxyalkoxy) -1,4-dihydroanthracene compound represented by the above formula (1) include the following formulas (2) to (20 ). In the following formula, n-Bu means a normal butyl group, and Ph means a phenyl group.

<Second invention (manufacturing method)>
The 9,10-bis (2- (meth) acryloyloxyalkoxy) -1,4-dihydroanthracene compound according to the first invention is first converted into a 9,10-dihydroxy-1,4-dihydroanthracene compound by the first reaction. 9,10-bis (2-hydroxyalkoxy) -1,4-dihydroanthracene by reacting with alkylene oxide, glycidyl ether or halogenated alcohol (halohydrin) in the presence or absence of a base It is obtained as a compound and then reacted in the second reaction by (meth) acryloylation in the presence or absence of a base with acryloyl chloride or methacryloyl chloride.

  Examples of the 9,10-dihydroxy-1,4-dihydroanthracene compound that can be used in carrying out the first reaction include the following compounds. That is, 9,10-dihydroxy-1,4-dihydroanthracene, 2-methyl-9,10-dihydroxy-1,4-dihydroanthracene, 2-ethyl-9,10-dihydroxy-1,4-dihydroanthracene, 2 -(T-butyl) -9,10-dihydroxy-1,4-dihydroanthracene, 2- (4-methyl-3-pentenyl) -9,10-dihydroxy-1,4-dihydroanthracene, 2- (4- Methylpentyl) -9,10-dihydroxy-1,4-dihydroanthracene, 2-chloro-9,10-dihydroxy-1,4-dihydroanthracene, 2-ethoxy-9,10-dihydroxy-1,4-dihydroanthracene 2-phenoxy-9,10-dihydroxy-1,4-dihydroanthracene, 2-ethylthio-9, 0-dihydroxy-1,4-dihydroanthracene, 2-phenylthio-9,10-dihydroxy-1,4-dihydroanthracene, 9,10-dihydroxy-1,4-dihydroanthracene-2-carboxylic acid, 9,10- And dihydroxy-1,4-dihydroanthracene 2-sulfonic acid.

  Examples of the alkylene oxide that can be used in performing the first reaction include ethylene oxide, propylene oxide, butylene oxide, 1-hexene oxide, cyclohexene oxide, and the like. Examples of glycidyl ether include methyl glycidyl ether and allyl glycidyl ether. N-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, and the like.

  Examples of the halogenated alcohol (halohydrin) that can be used in carrying out the first reaction include 2-bromoethanol, 2-iodoethanol, 1-chloro-2-propanol, 1-bromo-2-propanol, and 2-chloro. Examples include cyclohexanol and 1-chloro-3-methoxy-2-propanol.

  The amount of alkylene oxide, glycidyl ether or halogenated alcohol (halohydrin) added in carrying out the first reaction is usually 2.0 to 1.0 mol with respect to 1.0 mol of the 9,10-dihydroxy-1,4-dihydroanthracene compound. It is 10.0 mol times, Preferably it is the range of 2.2-5.0 mol times. Under these conditions where the amount used is less than 2.0 moles, unreacted 9,10-dihydroxy-1,4-dihydroanthracene remains and the purity of the product is lowered, resulting in conditions exceeding 10.0 moles. In this case, it may be difficult to precipitate product crystals from the reaction solution.

  When an alkaline compound is used as the base when performing the first reaction, for example, inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate are suitable. Usually, an inorganic alkaline compound is used as an aqueous solution. An organic base such as triethylamine or pyridine can also be used. The amount of the basic compound used is usually about equimolar with 9,10-dihydroxy-1,4-dihydroanthracene.

  Examples of the solvent in the case of using a solvent when performing the first reaction include alcohol solvents, ketone solvents, ether solvents, amide solvents, amine solvents, nitrile solvents, and the like. Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, etc., examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the ether solvent include tetrahydrofuran and 1,4-dioxane. Examples of the amide solvent include dimethylformamide and dimethylacetamide, examples of the amine solvent include pyridine and piperidine, and examples of the nitrile solvent include acetonitrile and propionitrile. .

  The temperature for carrying out the first reaction is usually in the range of 15 to 30 ° C., which is about room temperature. When the progress of the reaction is slow, heating can be performed in the range of 40 to 100 ° C. The reaction is preferably carried out in a nitrogen atmosphere. In air, 9,10-dihydroxy-1,4-dihydroanthracene is easily oxidized and an anthraquinone compound is produced. After completion of the reaction, the reaction solution is cooled, and the precipitated crystals are separated by filtration and dried, whereby the corresponding 9,10-bis (2-hydroxyalkoxy) -1,4-dihydroanthracene compound can be obtained.

  The 9,10-bis (2- (meth) acryloyloxyalkoxy) -1,4-dihydroanthracene compound according to the present invention is the 9,10-bis (2-hydroxyalkoxy)-obtained by the above first reaction. A 1,4-dihydroanthracene compound is obtained by a second reaction by reacting with acryloyl chloride or methacryloyl chloride in the presence or absence of a base to form (meth) acryloyl.

  Examples of the 9,10-bis (2-hydroxyalkoxy) -1,4-dihydroanthracene compound used as the raw material for the second reaction include the following. That is, 9,10-bis (2-hydroxyethoxy) -1,4-dihydroanthracene, 9,10-bis (2-hydroxypropoxy) -1,4-dihydroanthracene, 9,10-bis (2-hydroxybutoxy) ) -1,4-dihydroanthracene, 9,10-bis (2-hydroxyheptyloxy) -1,4-dihydroanthracene, 9,10-bis (2-hydroxyoctyloxy) -1,4-dihydroanthracene, 9 , 10-bis (2-hydroxy-2-phenylethoxy) -1,4-dihydroanthracene, 9,10-bis (2-hydroxy-3-methoxypropoxy) -1,4-dihydroanthracene, 9,10-bis (2-hydroxy-3-butoxypropoxy) -1,4-dihydroanthracene, 9,10-bis (2- Droxy-3-allyloxypropoxy) -1,4-dihydroanthracene, 9,10-bis (2-hydroxy-3- (2-ethyl) hexyloxypropoxy) -1,4-dihydroanthracene, 9,10-bis (2-hydroxy-3-stearyloxypropoxy) -1,4-dihydroanthracene, 9,10-bis (2-hydroxy-3-phenoxypropoxy) -1,4-dihydroanthracene, 2-methyl-9,10- Bis (2-hydroxyethoxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-hydroxypropoxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2- Hydroxybutoxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-hydroxyhept Ruoxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-hydroxyoctyloxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-hydroxy-2-) Phenylethoxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-hydroxy-3-methoxypropoxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2- Hydroxy-3butoxypropoxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-hydroxy-3-allyloxypropoxy) -1,4-dihydroanthracene, 2-methyl-9,10- Bis (2-hydroxy-3- (2-ethyl) hexyloxypropoxy) -1,4-dihydroanthracene, 2-methyl-9 , 10-bis (2-hydroxy-3-stearyloxypropoxy) -1,4-dihydroanthracene, 2-methyl-9,10-bis (2-hydroxy-3-phenoxypropoxy) -1,4-dihydroanthracene, Examples include 2-chloro-9,10-bis (2-hydroxyethoxy) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2-hydroxypropoxy) -1,4-dihydroanthracene.

  Further, 2-chloro-9,10-bis (2-hydroxybutoxy) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2-hydroxyheptyloxy) -1,4-dihydroanthracene, 2 -Chloro-9,10-bis (2-hydroxyoctyloxy) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2-hydroxy-2-phenylethoxy) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2-hydroxy-3-methoxypropoxy) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2-hydroxy-3butoxypropoxy) -1,4- Dihydroanthracene, 2-chloro-9,10-bis (2-hydroxy-3-allyloxypropoxy) -1,4-dihydroanthra 2-chloro-9,10-bis (2-hydroxy-3- (2-ethyl) hexyloxypropoxy) -1,4-dihydroanthracene 2-chloro-, 9,10-bis (2-hydroxy-3) -Stearyloxypropoxy) -1,4-dihydroanthracene, 2-chloro-9,10-bis (2-hydroxy-3-phenoxypropoxy) -1,4-dihydroanthracene and the like.

  Furthermore, 2-phenoxy-9,10-bis (2-hydroxyethoxy) -1,4-dihydroanthracene, 2-phenoxy-9,10-bis (2-hydroxypropoxy) -1,4-dihydroanthracene, 2- Phenoxy-9,10-bis (2-hydroxybutoxy) -1,4-dihydroanthracene, 9,10-bis (2-hydroxyheptyloxy) -1,4-dihydroanthracene, 2-phenoxy-9,10-bis (2-hydroxyoctyloxy) -1,4-dihydroanthracene, 2-phenoxy-9,10-bis (2-hydroxy-2-phenylethoxy) -1,4-dihydroanthracene, 2-phenoxy-9,10- Bis (2-hydroxy-3-methoxypropoxy) -1,4-dihydroanthracene, 2-phenoxy 9,10-bis (2-hydroxy-3butoxy) propoxyanthracene, 2-phenoxy-9,10-bis (2-hydroxy-3-allyloxypropoxy) -1,4-dihydroanthracene, 2-phenoxy-9, 10-bis (2-hydroxy-3- (2-ethyl) hexyloxypropoxy) -1,4-dihydroanthracene, 2-phenoxy-9,10-bis (2-hydroxy-3-stearyloxy) propoxyanthracene, 2 -Phenoxy-9,10-bis (2-hydroxy-3-phenoxypropoxy) -1,4-dihydroanthracene and the like.

  Further, 2-phenylthio-9,10-bis (2-hydroxyethoxy) -1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-hydroxypropoxy) -1,4-dihydroanthracene, 2- Phenylthio-9,10-bis (2-hydroxybutoxy) -1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-hydroxyheptyloxy) -1,4-dihydroanthracene, 2-phenylthio-9 , 10-bis (2-hydroxyoctyloxy) -1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-hydroxy-2-phenylethoxy) -1,4-dihydroanthracene, 2-phenylthio- 9,10-bis (2-hydroxy-3-methoxypropoxy) -1,4-dihydride Anthracene, 2-phenylthio-9,10-bis (2-hydroxy-3-butoxypropoxy) -1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-hydroxy-3-allyloxypropoxy)- 1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-hydroxy-3- (2-ethyl) hexyloxypropoxy) -1,4-dihydroanthracene, 2-phenylthio-9,10-bis ( 2-hydroxy-3-stearyloxypropoxy) -1,4-dihydroanthracene, 2-phenylthio-9,10-bis (2-hydroxy-3-phenoxypropoxy) -1,4-dihydroanthracene, and the like.

  Furthermore, 9,10-bis (2-hydroxyethoxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-hydroxypropoxy) -1,4-dihydroanthracene 2-carboxylic acid, 10-bis (2-hydroxybutoxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-hydroxyheptyloxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-hydroxyoctyloxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-hydroxy-2-phenylethoxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10- Bis (2-hydroxy-3-methoxypropoxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bi (2-hydroxy-3-butoxypropoxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-hydroxy-3-allyloxypropoxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-hydroxy-3- (2-ethyl) hexyloxypropoxy) -1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-hydroxy-3-stearyloxypropoxy)- 1,4-dihydroanthracene 2-carboxylic acid, 9,10-bis (2-hydroxy-3-phenoxy) propoxyanthracene-2-carboxylic acid, 9,10-bis (2-hydroxyethoxy) -1,4-dihydro Anthracene 2-sulfonic acid, 9,10-bis (2-hydroxypropoxy) -1,4-dihydroan Helene 2-sulfonic acid, 9,10-bis (2-hydroxybutoxy) -1,4-dihydroanthracene 2-sulfonic acid, 9,10-bis (2-hydroxyheptyloxy) -1,4-dihydroanthracene 2- Sulfonic acid, 9,10-bis (2-hydroxyoctyloxy) -1,4-dihydroanthracene 2-sulfonic acid, 9,10-bis (2-hydroxy-2-phenylethoxy) -1,4-dihydroanthracene 2 -Sulfonic acid, 9,10-bis (2-hydroxy-3-methoxypropoxy) -1,4-dihydroanthracene 2-sulfonic acid, 9,10-bis (2-hydroxy-3butoxypropoxy) -1,4- Dihydroanthracene 2-sulfonic acid, 9,10-bis (2-hydroxy-3-allyloxypropoxy) -1,4-di Hydroanthracene 2-sulfonic acid, 9,10-bis (2-hydroxy-3- (2-ethyl) hexyloxypropoxy) -1,4-dihydroanthracene 2-sulfonic acid, 9,10-bis (2-hydroxy-) 3-stearyloxypropoxy) -1,4-dihydroanthracene 2-sulfonic acid, 9,10-bis (2-hydroxy-3-phenoxypropoxy) -1,4-dihydroanthracene 2-sulfonic acid, and the like.

  Examples of the base that can be used in the second reaction include trimethylamine, triethylamine, tripropylamine, tributylamine, diethylamine, dibutylamine, piperidine, pyridine, α-picoline, γ-picoline, organic bases such as sodium hydroxide, water Examples thereof include inorganic bases such as potassium oxide, lithium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, and potassium hydrogen carbonate. Usually, the inorganic base is used as an aqueous solution.

  In carrying out the second reaction, the molar ratio of acryloyl chloride or methacryloyl chloride to 1 mol of 9,10-bis (2-hydroxyalkoxy) -1,4-dihydroanthracene compound is usually 2.0 to 10. 0, preferably 2.2 to 6.0, more preferably 2.2 to 3.0. When the molar ratio of the latter to the former is less than 2.0, an unreacted anthracene compound remains, and when the molar ratio of addition exceeds 10.0, acryloyl chloride or methacryloyl chloride itself used in the second reaction is polymerized. Therefore, the purity of the target product is lowered, and it is difficult to separate the 9,10-bis (2- (meth) acryloyloxyalkoxy) -1,4-dihydroanthracene compound that is the target product.

  The solvent used in the second reaction is not particularly limited as long as it does not react with acryloyl chloride or methacryloyl chloride. Specific examples include aromatic solvents, halogenated hydrocarbon solvents, amide solvents, ether solvents, ketone solvents, and nitrile solvents. Examples of the aromatic solvent include benzene, toluene, o-xylene, m-xylene, ethylbenzene, i-propylbenzene, chlorobenzene, o-dichlorobenzene, methylnaphthalene, chloronaphthalene and the like. Examples of the halogenated hydrocarbon solvent include methylene chloride, chloroform, 1,2-dichloroethane, 1,2-dichloroethylene, and the amide solvent includes methyl pyrrolidone, dimethylformamide, dimethylacetamide, and the like. Examples of the solvent include tetrahydrofuran and 1,4-dioxane, examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone, and examples of the nitrile solvent include acetonitrile and propionitrile. . The concentration of the reactant with respect to the solvent is not particularly limited, and when not dissolved in the solvent, the reaction can be performed in a slurry state.

  The temperature for carrying out the second reaction is usually in the range of 0 ° C to 80 ° C, preferably 20 ° C to 50 ° C. If the reaction temperature is less than 0 ° C., the reaction rate is slow and takes too much time. If the reaction temperature exceeds 80 ° C., acryloyl chloride or methacryloyl chloride itself is polymerized, so that the purity of the target product decreases, and Separation of the bis (2- (meth) acryloyloxyalkoxy) -1,4-dihydroanthracene compound becomes difficult.

The obtained reaction product was converted into 9,10-bis (2- (meth) acryloyloxyalkoxy) -1 by an infrared spectrum analysis method, a mass spectrum analysis method, a ¹ H-NMR spectrum analysis method or the like. , 4-dihydroanthracene. Both compounds show strong CO stretching vibration attributed to the ester group in the vicinity of 1720 cm ⁻¹ in the infrared spectrum analysis method, and the ¹ H-NMR spectrum analysis shows a spectrum peculiar to the AMX type acryloyl group. Can be easily confirmed.

  In addition, when performing a 1st reaction, the addition amount of alkylene oxide, glycidyl ether, or halogenated alcohol (halohydrin) is 2.0 mol times with respect to 1.0 mol of 9,10-dihydroxy-1, 4- dihydroanthracene compounds. In the case of exceeding 3, a compound added by 3 mol or more as shown by the following formula (20) is by-produced depending on the reaction conditions.

(In Formula (20), R ¹ and R ³ represent any one of a hydrogen atom, an alkyl group, an aryl group, an alkoxymethyl group, an allyloxymethyl group, and an aryloxymethyl group, provided that R ¹ and R ³ At least one is a hydrogen atom, and X and Y may be the same or different, and are a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, an alkylthio group, an arylthio group, a carboxyl group, a sulfone group. Represents any one of acid groups, and m and n represent an integer of 1 or more, provided that m and n are not 1 at the same time.)

  In this case, when the second reaction is continued without any particular purification, a 1,4-dihydroanthracene derivative represented by the following formula (21) is by-produced. However, when used as a photosensitizer described below, These by-products may be mixed as long as they do not affect the properties of the target polymer.

(In the formula (21), R ¹ and R ^{3 each} represent a hydrogen atom, an alkyl group, an aryl group, an alkoxymethyl group, an allyloxymethyl group, or an aryloxymethyl group, provided that R ¹ and R ³ At least one is a hydrogen atom, R ² represents a hydrogen atom or a methyl group, and X and Y may be the same or different, and are a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group. Represents an alkylthio group, an arylthio group, a carboxyl group, or a sulfonic acid group, where m and n represent an integer of 1 or more, provided that m and n are not 1 at the same time.

<Uses of compounds>
The compound according to the first invention obtained by the above reaction, that is, the 9,10-bis (2- (meth) acryloyloxyalkoxy) -1,4-dihydroanthracene compound is a novel compound. The compound according to the first invention can be used as a photosensitizer when the photopolymerizable monomer is subjected to cationic polymerization and radical polymerization, and a photocurable composition can be prepared by blending this compound.

  When using the compound which concerns on 1st invention as a photosensitizer, the compound which concerns on 1st invention is mix | blended with a photoinitiator with a photopolymerizable monomer, and a photocurable composition is prepared. This photocurable composition can be easily cured by irradiation with light in the ultraviolet region.

  The photopolymerizable monomer may be either a cationic polymerizable monomer or a radical polymerizable monomer, or a mixture thereof. Examples of the photopolymerizable cationic polymerizable monomer include epoxy compounds and vinyl ethers. Common epoxy compounds include alicyclic epoxy compounds, epoxy-modified silicones, aromatic glycidyl ethers, and the like. Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis (3,4-epoxycyclohexyl) adipate. As a product marketed, the Dow Chemical company make, brand name: UV6105, brand name: UVR6110 etc. are mentioned, for example. As an epoxy modified silicone, Toshiba GE silicone company make, brand name: UV-9300 etc. are mentioned, for example. Examples of the aromatic glycidyl compound include 2,2′-bis (4-glycidyloxyphenyl) propane, and examples of the vinyl ether include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and 2-ethylhexyl vinyl ether.

  Specific examples of the photopolymerizable radical polymerizable monomer include styrene, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, acrylic acid ester, (meth) acrylic acid ester, and the like. (Meth) acrylic acid esters include methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, tetraethylene Examples include glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, epoxy acrylate, urethane acrylate, polyester acrylate, polybutadiene acrylate, polyol acrylate, polyether acrylate, silicone resin acrylate, and imide acrylate. These radical polymerizable monomers may be a mixture of two or more.

  An onium salt is mentioned as a photoinitiator mix | blended with a photocurable composition. Examples of onium salts include sulfonium salts and iodonium salts. Examples of the former sulfonium salts include S, S, S ′, S′-tetraphenyl-S, S ′-(4,4′-thiodiphenyl) disulfonium bishexafluorophosphate, diphenyl-4-phenylthiophenylsulfonium. Examples of commercially available products include hexafluorophosphate and triphenylsulfonium hexafluorophosphate. For example, trade name: UVI6992 manufactured by Dow Chemical Co., Ltd. is available. Examples of the latter iodonium salt include 4-isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, 4-isopropylphenyl-4′-methylphenyliodonium tetrakispentafluorophenylborate. Examples of commercially available products include Ciba Specialty Chemicals, trade name: Irgacure 250, Rhodia, brand name: 2074, and the like.

  The amount added when the 9,10-bis (2- (meth) acryloyloxyalkoxy) -1,4-dihydroanthracene compound according to the first invention is used as a sensitizer of the photocurable composition is photopolymerization. It is usually 0.01 to 5.0% by weight, preferably 0.05 to 2.0% by weight, more preferably 0.1 to 1.5% by weight, based on the amount of the monomer. If the addition amount with respect to the photopolymerizable monomer is less than 0.01% by weight, the curing rate of the photocurable composition becomes slow, and if it exceeds 5.0% by weight, the physical properties of the cured product deteriorate.

  The photocurable composition is composed of the compound according to the first invention (photosensitizer), the photopolymerizable monomer, and the photopolymerization initiator, but is further diluted within a range not impairing the effect of the invention. Various resin additives such as additives, colorants, organic and / or inorganic fillers, leveling agents, surfactants, antifoaming agents, thickeners, flame retardants, antioxidants, stabilizers, lubricants, plasticizers, It can mix | blend in a normal use range.

  Diluents include epoxy diluents such as epoxy acrylate, oxetane diluents such as oxacyclobutane, vinyl ether diluents, (meth) acryloyl monomer diluents, and the like. Examples of the colorant include a blue pigment, a red pigment, a white pigment, and a black pigment. Examples of the black pigment include carbon black, acetylene black, lamp black, and aniline black. Examples of yellow pigments include yellow lead, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa Yellow G, Hansa Yellow 10G, Benzidine Yellow G, and Benzidine Yellow. GR, quinoline yellow lake, permanent yellow NCG, tartrazine lake and the like.

  Examples of red pigments include bengara, cadmium red, red lead, mercury cadmium sulfide, permanent red 4R, resol red, lake red D brilliant carmine 6B, eosin lake, rhodamine lake B, alizarin lake, and brilliant carmine 3B. . Examples of the blue pigment include bitumen, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, first sky blue, and induslen blue BC. Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide. Examples of other pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white.

  The photocurable composition can be cured by irradiating the coating film with light in the ultraviolet region after coating on the substrate. The application method is not particularly limited as long as it can apply the photocurable composition to the substrate surface, and examples thereof include a bar coating method and a spray coating method. The substrate may be any one of a steel plate, a printing plate, a film, paper, an aluminum foil, and the like that have a flat appearance, a curved surface, and a solid shape. The photocurable composition applied to the surface of the substrate can be quickly cured, particularly by irradiating light in the wavelength region of 300 to 400 nm. The light source in this case is not particularly limited as long as it is a light source capable of emitting light in the wavelength region of 300 to 400 nm. For example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a halogen lamp, sunlight, a metal halide lamp, a xenon lamp. , Ultraviolet (UV) LED lamps, H lamps manufactured by Fusion, D lamps, and the like.

  When photo radical curing is performed, it is preferable to perform light irradiation in the absence of oxygen. When light is irradiated in the presence of oxygen, the progress of the photopolymerization reaction is inhibited by oxygen, tackiness (stickiness) on the surface of the cured film is not eliminated, and a large amount of initiator needs to be added. Examples of the photocuring method in the absence of oxygen include a method performed in an inert gas atmosphere such as nitrogen gas or helium gas. It is also possible to employ a method of covering with an oxygen-impermeable film and irradiating light from above the film. On the other hand, when carrying out photocationic curing, the light irradiation may be in the presence or absence of oxygen.

  In addition, confirmation of completion of photocuring can be performed by a tack (stickiness) free test (a finger touch test). In this tack-free test, the cured film on the surface of a substrate such as a film is touched with a fingertip, the tack is confirmed, and the time until tack of the cured film disappears is the curing time (tack-free time). The slowness of the curing reaction can be determined by the length of A shorter curing time means a faster curing rate.

  The photocurable composition is applied to the surface of a substrate such as a film, for example, and the coated surface is cured, and the procedure is as follows. That is, first, a photocurable composition is applied to the substrate surface by a bar coating method or the like. When the base material is a film, a thickness of about 30-100 μm is usually used, and a rod number bar coater with a coating film thickness of several μm to several tens of μm is used. Apply. Next, the photopolymerizable composition containing the photopolymerizable monomer can be quickly cured by irradiating the coating film thus obtained with light from the above-described light source.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to the following description examples, unless the summary is exceeded. Various characteristics of the obtained product were confirmed as follows.

(1) When the product was a solid, the melting point was measured with a melting point measuring device (melting point measuring device manufactured by Gelen Camp, model: MFB-595 based on JIS K0064).

(2) IR spectrum measurement was performed using an infrared (IR) spectrophotometer (manufactured by JASCO Corporation, model: IR-810).

(3) ¹ H-NMR analysis was performed using a nuclear magnetic resonance apparatus (NMR) (manufactured by JEOL Ltd., model: GSX FT NMR Spectrometer).

(4) Mass spectrum measurement was performed (manufactured by Shimadzu Corporation, mass spectrometer, model: using GCMS-QP5000).

[Example 1]
<Synthesis of 9,10-bis (2-acryloyloxyethoxy) -1,4-dihydroanthracene>

(First reaction)
A three-necked flask equipped with a stirrer and a thermometer and having a capacity of 100 ml was charged with 20 ml (20 mmol) of a sodium salt aqueous solution of 9,10-dihydroxy-1,4-dihydroanthracene (20% by weight) and 50 ml of methanol at room temperature. After stirring and mixing the contents of the flask, 6 g (50 mmol) of bromoethanol was added, the temperature was raised to 65 ° C., and stirring was continued at this temperature for 2 hours. The reaction solution was poured into 30 ml of pure water to precipitate crystals. The precipitated crystals were separated by filtration, and the obtained crystals were washed with 20 ml of pure water and 15 ml of methanol, then dried under reduced pressure, and 9,10-bis (2-hydroxyethoxy) -1,4-dihydro of white crystals. Anthracene 4.5 g (15.1 mmol) was obtained. The yield of the product based on 9,10-dihydroxy-1,4-dihydroanthracene was 76 mol%.

  The results of the above measurements on the product are as follows, and it was confirmed that the product was 9,10-bis (2-hydroxyethoxy) -1,4-dihydroanthracene.

(1) Melting point: 203-204 ° C.
(2) IR spectrum (KBr, cm ⁻¹ ): Absorption was observed at wavelengths such as 755, 885, 1025, 1055, 1080, 1330, 1348, and 3400.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 3.52 (s, 4H), 3.84 (t, J = 5 Hz, 4H), 3.94 (t, J = 5 Hz, 4H) , 5.06 (s, 2H), 6.04 (s, 2H), 7.44-7.50 (m, 2H), 8.12-8.17 (m, 2H).
(4) Mass spectrum: (EI-MS) m / z = 300 (M ^<+> ).

(Second reaction)
To a 100 ml three-necked flask having the same capacity as that used in the first reaction, 2.0 g (6.7) of 9,10-bis (2-hydroxyethoxy) -1,4-dihydroanthracene obtained by the first reaction was added. Mmol), 30 ml of acetonitrile, 2.6 g (25.5 mmol) of triethylamine, and the contents of the flask were stirred and mixed in an ice bath. Then, 2.3 g (25.5 mmol) of acryloyl chloride was dissolved in 10 ml of acetonitrile. The solution was added and stirring was continued for 1 hour at room temperature. After adding 20 ml of pure water to this flask and continuing stirring for 10 minutes, 40 ml of saturated saline and 80 ml of ethyl acetate were further added. The obtained reaction product was washed by adding 20 ml of pure water, and this washing operation was repeated three times. The organic layer was separated from the liquid after washing with pure water. The oily substance obtained by concentrating the separated organic layer was purified by silica gel column chromatography using hexane and ethyl acetate as developing solvents, and 9,10-bis (2-acryloyloxyethoxy) -1 as white crystals. , 4-dihydroanthracene (1.4 g, 3.4 mmol) was obtained. The yield of the product with respect to 9,10-bis (2-hydroxyethoxy) -1,4-dihydroanthracene was 51 mol%.

  The results of the above measurements on the product are as follows, and it was confirmed that the product was 9,10-bis (2-acryloyloxyethoxy) -1,4-dihydroanthracene.

(1) Melting point: 71-72 ° C.
(2) IR spectrum (KBr, cm ⁻¹ ): Absorption was observed at wavelengths of 650, 750, 805, 925, 975, 1035, 1065, 1200, 1298, 1325, 1415, 1635, 1722 and the like.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 3.55 (s, 4H), 4.21 (t, J = 5 Hz, 4H), 4.61 (t, J = 5 Hz, 4H) 5.93 (dd, J ₁ = 2 Hz, J ₂ = 11 Hz, 2H), 6.06 (s, 2H), 6.26 (dd, J ₁ = 11 Hz, J ₂ = 17 Hz, 2H), _{52 (dd, J 1 = 1Hz} , J 2 = 17Hz, 2H), 7.41-7.51 (m, 2H), 8.05-8.11 (m, 2H).
(4) Mass spectrum: (EI-MS) m / z = 408 (M ^<+> ).

[Example 2]
<Synthesis of 9,10-bis (2-methacryloyloxyethoxy) -1,4-dihydroanthracene>

  In a four-necked flask having a volume of 50 ml, 0.5 g (1.7 mmol) of 9,10-bis (2-hydroxyethoxy) -1,4-dihydroanthracene obtained by the first reaction of Example 1 above. Then, 10 ml of acetonitrile and 0.7 g (6.5 mmol) of triethylamine were charged, and the contents of the flask were mixed in an ice bath. Then, 0.6 g (6.7 mmol) of acryloyl chloride was added and stirred at room temperature for 4 hours. Continued. After adding 5 ml of pure water to the flask and continuing stirring for 10 minutes, 10 ml of saturated saline and 20 ml of ethyl acetate were further added. The obtained reaction product was washed with 5 ml of pure water, and this washing operation was repeated three times. The organic layer was separated from the liquid after washing with pure water. The oily substance obtained by concentrating the separated organic layer was recrystallized from a methanol solution to give 0.4 g (0 of yellow crystalline 9,10-bis (2-methacryloyloxyethoxy) -1,4-dihydroanthracene. 8 mmol). The yield of the product with respect to 9,10-bis (2-hydroxyethoxy) -1,4-dihydroanthracene was 55 mol%.

  About the obtained product, the result of having performed said characteristic measurement is as follows, and it was confirmed that it is 9,10-bis (2-methacryloyloxyethoxy) -1,4-dihydroanthracene.

(1) Melting point: 85-86 ° C.
(2) IR spectrum (KBr, cm ⁻¹ ): Absorption was observed at wavelengths such as 755, 1072, 1160, 1295, 1708, and 2925.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 2.04 (s, 6H), 3.56 (s, 4H), 4.22 (t, J = 2 Hz, 4H), 4.59 (T, J = 2 Hz, 4H), 5.67 (t, J = 1 Hz, 2H), 5.99 (s, 2H), 6.25 (s, 2H), 7.40-7.51 (m , 2H), 8.09-8.13 (m, 2H).
(4) Mass spectrum: (EI-MS) m / z = 436 (M ^<+> ).

[Example 3]
<Synthesis of 9,10-bis (2-acryloyloxypropoxy) -1,4-dihydroanthracene>

(First reaction)
In a three-necked flask having the same volume as that used in the first reaction of the Example, 100 g of 9,10-dihydroxy-1,4-dihydroanthracene sodium salt aqueous solution (20% by weight) 30 g (26 mmol) and 20 ml of acetonitrile were added. After stirring and mixing the contents of the flask at room temperature, 12 g (207 mmol) of propylene oxide was added, the temperature was raised to 40 ° C., and stirring was continued at this temperature for 12 hours. Crystals precipitated from the cooled reaction solution were filtered off, and the obtained crystals were washed with 30 ml of pure water and 10 ml of methanol, and then dried under reduced pressure to give 9,10-bis (2-hydroxyethoxypropoxy)- 6.2 g (18.9 mmol) of 1,4-dihydroanthracene were obtained. The yield of the product based on 9,10-dihydroxy-1,4-dihydroanthracene was 73 mol%.

  The results of the above measurements on the product are as follows, and it was confirmed that the product was 9,10-bis (2-hydroxypropoxy) -1,4-dihydroanthracene.

(1) Melting point: 166-168 ° C.
(2) IR spectrum (KBr, cm ⁻¹ ): Absorption was observed at wavelengths such as 642, 758, 1060, 1320, and 3320.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 1.23 (d, J = 6 Hz, 6H), 3.50 (s, 4H), 3.75 (t, J = 5 Hz, 4H) 3.96-4.16 (m, 2H), 5.02 (d, J = 5 Hz, 2H), 5.99 (s, 2H), 7.39-7.50 (m, 2H), 8 .02-8.18 (m, 4H)
(4) Mass spectrum: (EI-MS) m / z = 328 (M ⁺ ).

(Second reaction)
To the same 100 ml three-necked flask used in Example 1, 2.0 g (6.1 mmol) of 9,10-bis (2-hydroxypropoxy) -1,4-dihydroanthracene obtained in the first reaction was used. And 30 ml of acetonitrile and 2.4 g (23.2 mmol) of triethylamine were added, and the contents of the flask were mixed in an ice bath, and then a solution of 2.1 g (23.2 mmol) of acryloyl chloride dissolved in 10 ml of acetonitrile was added. And stirring was continued for 3 hours at room temperature. After adding 20 ml of pure water to this flask and continuing stirring for 10 minutes, 40 ml of saturated saline and 80 ml of ethyl acetate were further added. The obtained reaction product was washed by adding 20 ml of pure water, and this washing operation was repeated three times. The organic layer was separated from the liquid after washing with pure water. The oily substance obtained by concentrating the separated organic layer was purified by silica gel column chromatography using hexane and ethyl acetate as eluents to give 9,10-bis (2-acryloyloxypropoxy) -1 as a yellow oil. , 4-Dihydroanthracene (1.4 g, 3.2 mmol) was obtained. The yield of the product with respect to 9,10-bis (2-hydroxypropoxy) -1,4-dihydroanthracene was 53 mol%.

  About the obtained product, the result of having carried out said measurement was as follows, and it was confirmed that it was 9,10-bis (2-acryloyloxypropoxy) -1,4-dihydroanthracene.

(1) Melting point: not measured because it is not solid.
(2) IR spectrum (neat, cm ⁻¹ ): Absorption was observed at wavelengths of 645, 762, 805, 980, 1060, 1190, 1292, 1350, 1400, 1615, 1720, 1790, and the like.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 1.50 (d, J = 6 Hz, 6H), 3.52 (s, 4H), 3.97-4.13 (m, 4H) 5.90 (dd, J ₁ = 2 Hz, J ₂ = 11 Hz, 2H), 5.98 (s, 2H), 6.23 (dd, J ₁ = 11 Hz, J ₂ = 17 Hz, 2H), _{50 (dd, J 1 = 2Hz} , J 2 = 17Hz, 1H, vinyl group), 7.27-7.49 (m, 2H) , 8.02-8.08 (m, 2H).
(4) Mass spectrum: (EI-MS) m / z = 436 (M ^<+> ).

[Example 4]
<Synthesis of 9,10-bis (2-methacryloyloxypropoxy) -1,4-dihydroanthracene>

  To the same 100 ml three-necked flask used in Example 1, 2.0 g of 9,10-bis (2-hydroxypropoxy) -1,4-dihydroanthracene obtained in the first reaction of Example 3 above ( 6.1 mmol), 30 ml of acetonitrile, 2.4 g (23.2 mmol) of triethylamine, and the contents of the flask were mixed in an ice bath. Then, 2.4 g (23.2 mmol) of methacryloyl chloride was dissolved in 10 ml of acetonitrile. The solution was added and stirring was continued at room temperature for 4 hours. After adding 20 ml of pure water to the flask and continuing stirring for 10 minutes, 40 ml of saturated saline and 80 ml of ethyl acetate were further added. The obtained reaction product was washed by adding 20 ml of pure water, and this washing operation was repeated three times. The organic layer was separated from the liquid after washing with pure water. The oily substance obtained by concentrating the separated organic layer was purified by silica gel column chromatography using hexane and ethyl acetate as developing solvents, and 9,10-bis (2-methacryloyloxypropoxy) -1 as an orange oil. , 4-Dihydroanthracene (1.4 g, 2.9 mmol) was obtained. The yield of the product with respect to 9,10-bis (2-hydroxypropoxy) -1,4-dihydroanthracene was 48 mol%.

  About the obtained product, the result of having carried out said measurement is as follows, and it was confirmed that it was 9,10-bis (2-methacryloyloxypropoxy) -1,4-dihydroanthracene.

(1) Melting point: not measured because it is not solid.
(2) IR spectrum (neat, cm ⁻¹ ): Absorption was observed at wavelengths of 645, 760, 805, 935, 1060, 1160, 1290, 1445, 1630, 1710, 1780, 2950, and the like.
(3) ¹ H-NMR (CDCl ₃ , ppm): δ = 1.47 (d, J = 9 Hz, 6H), 2.00 (s, 6H), 3.53 (s, 4H), 4.02 (T, J = 4 Hz, 4H), 5.39-5.50 (m, 2H), 5.64 (t, J = 2 Hz, 2H), 5.98 (s, 2H), 6.25 (s , 2H), 7.26-7.48 (m, 2H), 8.03-8.08 (m, 2H).
(4) Mass spectrum: (EI-MS) m / z = 464 (M ⁺ ).

<Use as a curable composition-Use as a photopolymerization sensitizer>

[Evaluation Example 1]
Example 1 describes 100 parts by weight of trimethylolpropane triacrylate as a monomer and 2 parts by weight of tolyl-i-butylphenyliodonium hexafluorophosphate (manufactured by Ciba Specialty, trade name: Irgacure 250, the same shall apply hereinafter). 1 part by weight of 9,10-bis (2-acryloyloxyethoxy) -1,4-dihydroanthracene synthesized by the above method was added to obtain a uniform photocurable composition. This photocurable composition was applied to the surface of a polyester film (trade name: Lumirror, thickness 100 μm, the same applies hereinafter) by a bar coater so as to have a film thickness of 12 μm. Next, light irradiation was performed using a high-pressure mercury lamp (the irradiation intensity at 366 nm was 0.1 mw / cm ² ) in a nitrogen atmosphere. The time until tack (stickiness) disappears in the coating film {curing time (tack free time)} was 2 minutes.

[Evaluation Example 2]
9,10-bis (2-methacryloyloxyethoxy)-synthesized by the method described in Example 2 with 100 parts by weight of trimethylolpropane triacrylate as a monomer and 2 parts by weight of tolyl-i-butylphenyliodonium hexafluorophosphate 1 part by weight of 1,4-dihydroanthracene was added to obtain a uniform curable composition. This curable composition was applied to the surface of a polyester film (the same as above) by a bar coater so that the film thickness was 12 μm. Next, irradiation was performed using a high-pressure mercury lamp (irradiation intensity at 366 nm was 0.1 mw / cm ² ) in a nitrogen atmosphere. The curing time until the coating film was free of tack (stickiness) was 2.6 minutes.

[Evaluation Example 3]
9,10-bis (2-acryloyloxypropoxy)-synthesized by the method described in Example 3 with 100 parts by weight of trimethylolpropane triacrylate as a monomer and 2 parts by weight of tolyl-i-butylphenyliodonium hexafluorophosphate 1 part by weight of 1,4-dihydroanthracene was added to obtain a uniform curable composition. This curable composition was applied to the surface of a polyester film (the same as above) by a bar coater so that the film thickness was 12 μm. Next, irradiation was performed using a high-pressure mercury lamp (irradiation intensity at 366 nm was 0.1 mw / cm ² ) in a nitrogen atmosphere. The curing time until the coating film was free of tack (stickiness) was 1.6 minutes.

[Evaluation Example 4]
9,10-bis (2-methacryloyloxypropoxy)-synthesized by the method described in Example 4 with 100 parts by weight of trimethylolpropane triacrylate as a monomer and 2 parts by weight of tolyl-i-butylphenyliodonium hexafluorophosphate 1 part by weight of 1,4-dihydroanthracene was added to obtain a uniform curable composition. This curable composition was applied to the surface of a polyester film (the same as above) by a bar coater so that the film thickness was 12 μm. Next, light irradiation was performed using a high-pressure mercury lamp (the irradiation intensity at 366 nm was 0.1 mw / cm ² ) in a nitrogen atmosphere. The curing time until the coating film was free of tack (stickiness) was 3 minutes.

[Evaluation Comparative Example 1]
In the example described in Evaluation Example 1, except that 9,10-bis (2-acryloyloxyethoxy) -1,4-dihydroanthracene was not added, the photocurable composition was prepared in the same procedure as in Evaluation Example 1. It was prepared, applied to the surface of a polyester film (same as above) so that the film thickness was 12 μm, and irradiated with the same irradiation intensity with a high-pressure mercury lamp (same as above). Even when the coating film was irradiated for 30 minutes, the tack (stickiness) was not improved and was not cured.

[Evaluation Example 5]
Implementation of 1 part by weight of tolyl-i-butylphenyliodonium hexafluorophosphate (Ciba, brand name: irgacure 205) with respect to 100 parts by weight of an alicyclic epoxy compound (manufactured by DOW, product name: UVR-6105) as a monomer 1 part by weight of 9,10-bis (2-acryloyloxyethoxy) -1,4-dihydroanthracene synthesized by the method described in Example 1 was mixed to prepare a photocurable composition. This photocurable composition was applied to the surface of a polyester film (the same as above) by a bar coater so that the film thickness was 12 μm. Next, a high pressure mercury lamp (the same as above) was used from the surface, and irradiation was performed with an irradiation intensity of 0.1 mW / cm ² . The curing time until the coating film was free of tack (stickiness) was 4 minutes.

[Evaluation Example 6]
1 part by weight of tolyl-i-butylphenyliodonium hexafluorophosphate (same as above) for 100 parts by weight of an alicyclic epoxy compound (same as that used in Evaluation Example 4) as a monomer, the method described in Example 2 1 part by weight of 9,10-bis (2-methacryloyloxyethoxy) -1,4-dihydroanthracene synthesized in Step 1 was mixed to prepare a photocuring composition. This photocurable composition was applied to the surface of a polyester film (the same as above) by a bar coater so that the film thickness was 12 μm. Next, a high pressure mercury lamp (the same as above) was used from the surface, and irradiation was performed with an irradiation intensity of 0.1 mW / cm ² . The curing time until the coating film was free from tackiness (stickiness) was 5.5 minutes.

[Evaluation Example 7]
1 part by weight of tolyl-i-butylphenyliodonium hexafluorophosphate (same as above) for 100 parts by weight of an alicyclic epoxy compound (same as that used in Evaluation Example 4) as a monomer, the method described in Example 3 1 part by weight of 9,10-bis (2-acryloyloxypropoxy) -1,4-dihydroanthracene synthesized in Step 1 was mixed to prepare a photocuring composition. This photocurable composition was applied to the surface of a polyester film (the same as above) by a bar coater so that the film thickness was 12 μm. A high pressure mercury lamp (same as above) was used from the surface, and irradiation was performed with an irradiation intensity of 0.1 mW / cm ² . The curing time until the coating film was free from tackiness (stickiness) was 5.5 minutes.

[Evaluation Example 8]
1 part by weight of tolyl-i-butylphenyliodonium hexafluorophosphate (same as above) for 100 parts by weight of an alicyclic epoxy compound (same as that used in Evaluation Example 4) as a monomer, the method described in Example 4 1 part by weight of 9,10-bis (2-methacryloyloxypropoxy) -1,4-dihydroanthracene synthesized in Step 1 was mixed to prepare a photocuring composition. This photocurable composition was applied to the surface of a polyester film (the same as above) by a bar coater so that the film thickness was 12 μm. A high pressure mercury lamp (same as above) was used from the surface, and irradiation was performed with an irradiation intensity of 0.1 mW / cm ² . The curing time until the coating film was free of tack (stickiness) was 5.2 minutes.

[Evaluation Comparative Example 2]
In Evaluation Example 4, a photocuring composition was prepared by the same procedure as in Evaluation Example 4 except that 9,10-bis (2-acryloyloxyethoxy) -1,4-dihydroanthracene was not added. The film was coated on the surface (same as above) so as to have a film thickness of 12 μm, and irradiated with the same irradiation intensity with a high-pressure mercury lamp (same as above). Even when the coating film was irradiated with 30 spectra, tack (stickiness) was not improved and did not cure.

[Sublimation test example]
The polyester film prepared in Evaluation Example 2 and having a coating film of the photocurable composition was heated in an oven adjusted to 180 ° C. The polyester film is taken out of the oven at regular intervals, and the absorption peak height at a wavelength near 318 nm is selected from the UV spectrum caused by 9,10-bis (2-methacryloyloxyethoxy) -1,4-dihydroanthracene. It was measured by an ultraviolet / visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV2200). The absorption peak height before heating and the absorption peak with a wavelength of around 318 nm were examined for the absorption peak height before heating and the rate of decrease in peak height after heating to determine 9,10-bis (2-methacryloyloxyethoxy) -1,4-dihydro The degree of sublimation of anthracene was determined. As a result, after 10 minutes, it was found to be 15% sublimation because it was 15% lower than before heating.

[Sublimation test comparative example]
In Evaluation Example 1, except that 9,10-diethoxy-1,4-dihydroanthracene was used instead of 9,10-bis (2-methacryloyloxyethoxy) -1,4-dihydroanthracene A polyester film having a coating film of a photocurable composition prepared by the same procedure was prepared. The polyester film was heated in an oven adjusted to 180 ° C. in the same manner as in the above sublimation test example, and the wavelength was around 318 nm in the UV spectrum caused by 9,10-diethoxy-1,4-dihydroanthracene. The absorption peak height of was measured. The absorption peak height before heating and the rate of decrease in peak height after heating were examined to determine the degree of sublimation of 9,10-diethoxy-1,4-dihydroanthracene. As a result, it was found that it had sublimed 55% since it was 55% lower than before heating after 10 minutes.

UV spectrum of a sample containing 9,10-bis (2-methacryloyloxyethoxy) -1,4-dihydroanthracene before heating in a sublimation test UV spectrum of a sample containing 9,10-bis (2-methacryloyloxyethoxy) -1,4-dihydroanthracene after heating in a sublimation test UV spectrum of a sample containing 9,10-diethoxy-1,4-dihydroanthracene before heating in a sublimation test comparative example UV spectrum of a sample containing 9,10-diethoxy-1,4-dihydroanthracene after heating in a sublimation test comparative example

Claims (5)

A 9,10-bis (2- (meth) acryloyloxyalkoxy) -1,4-dihydroanthracene compound represented by the following formula (1).

{In Formula (1), R ¹ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxymethyl group, an allyloxymethyl group, or an aryloxymethyl group, R ² represents a hydrogen atom or a methyl group, X and Y may be the same or different and each represents a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, an alkylthio group, an arylthio group, a carboxyl group, or a sulfonic acid group. }   9,10-bis (2-hydroxyalkoxy) -1,4-dihydroanthracene compound obtained by reacting 9,10-dihydroxy-1,4-dihydroanthracene compound with alkylene oxide, glycidyl ether or halogenated alcohol (halohydrin) And then reacting this compound with an acryloyl chloride compound or a methacryloyl chloride compound, and a method for producing a 9,10-bis (2- (meth) acryloyloxyalkoxy) -1,4-dihydroanthracene compound, .   A photopolymerization sensitizer comprising the 9,10-bis (2- (meth) acryloyloxyalkoxy) -1,4-dihydroanthracene compound according to claim 1 as an active ingredient.   A photocurable composition comprising the photopolymerization sensitizer according to claim 3, a photopolymerization initiator, and a photopolymerizable monomer. The photocurable composition according to claim 4, wherein the photopolymerization initiator is an onium salt.

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