JP2017137413A - Photopolymerization sensitizer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel photopolymerization sensitizer that prevents migration from occurring during storage.SOLUTION: A photosensitizer comprises a 9-(2-hydroxyalkoxy) anthracene compound represented by formula (1) [A is H, a C1-8 alkyl group or a substituted oxymethyl group represented by formula (2); X and Y independently represent H, a C1-8 alkyl group or a halogen atom (B is a C1-8 alkyl group, an allyl group or a C6-12 aryl group)].SELECTED DRAWING: None

Description

The present invention relates to a photopolymerization sensitizer containing a 9- (2-hydroxyalkoxy) anthracene compound.

Photo-curing resins that are polymerized by active energy rays such as ultraviolet rays and visible rays cure quickly and can significantly reduce the amount of organic solvent used compared to thermosetting resins. It is excellent in that it can be reduced. Conventional photocurable resins themselves have a poor polymerization initiating function, and it is usually necessary to use a photopolymerization initiator for curing. As the photopolymerization initiator, alkylphenone-based polymerization initiators such as hydroxyacetophenone and benzophenone, acylphosphine oxide-based photopolymerization initiators, or onium salts are used (Patent Documents 1, 2, and 3). Among these photopolymerization initiators, when an onium salt-based initiator is used, the light absorption of the onium salt is in the vicinity of 225 nm to 350 nm and does not absorb at 350 nm or more. Therefore, a long wavelength lamp of 350 nm or more is used as a light source. In such a case, there is a problem that the photocuring reaction does not easily proceed, and a photopolymerization sensitizer is generally added. Anthracene and thioxanthone compounds are known as photopolymerization sensitizers, and anthracene compounds are particularly often used due to color problems (Patent Document 4).

As an anthracene 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 that is a photopolymerization initiator in photopolymerization. (Patent Documents 5, 6, 7, and 8).

However, the 9,10-dialkoxyanthracene compound may cause problems such as powdering of the cured product and coloring due to blooming during photocuring or storage of the cured product due to blooming. Are known. For example, when these photopolymerization sensitizers are used as a component of a photoadhesive that bonds the film to the film, the photopolymerization sensitizer may migrate to the film overlaid (migration). On top of this, it may cause problems with powdering and coloring of the photopolymerization sensitizer.

Japanese Patent Laid-Open No. 06-345614 Japanese Patent Application Laid-Open No. 07-062010 JP 05-249606 A JP-A-10-195117 JP 2002-302507 A JP 11-279212 A JP 2000-344704 A WO2007 / 126066

Therefore, it is hoped to develop a photopolymerization sensitizer that does not bleed out of the surface of the photopolymerization sensitizer due to blooming or the like during photocuring or during storage of the cured product and cause problems with powdering or coloring of the cured product. It is rare.

As a result of further intensive studies on the structure and physical properties of the anthracene compound, the present inventors show that the 9- (2-hydroxyalkoxy) anthracene compound shown in the present invention has an excellent effect as a photopolymerization sensitizer in the photopolymerization reaction. At the same time, even when a film is placed on the photopolymerizable composition containing the 9- (2-hydroxyalkoxy) anthracene compound of the present invention as a photopolymerization sensitizer, the photopolymerization sensitizer migrates to the film. As a result, the present invention has been completed.

That is, the first gist of the present invention resides in a photopolymerization sensitizer containing a 9- (2-hydroxyalkoxy) anthracene compound represented by the following general formula (1).

In the general formula (1), A represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a substituted oxymethyl group represented by the general formula (2), and X and Y are the same or different. Or a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

In General Formula (2), B represents an alkyl group having 1 to 8 carbon atoms, an allyl group, or an aryl group having 6 to 12 carbon atoms.

The second gist of the present invention resides in a photopolymerization initiator composition containing the photopolymerization sensitizer described in the first gist and a photopolymerization initiator.

The 3rd summary of this invention exists in the photopolymerizable composition containing the photoinitiator composition as described in a 2nd summary, and a photopolymerizable compound.

  The fourth gist of the present invention resides in a curing method in which the photopolymerizable composition described in the third gist is cured by irradiating an energy beam containing light having a wavelength in the range of 250 nm to 500 nm.

The 9- (2-hydroxyalkoxy) anthracene compound of the present invention not only has a high effect as a photopolymerization sensitizer in a photopolymerization reaction, but also contains a compound of the present invention as a photopolymerization sensitizer. When a film is covered on the conductive composition, the compound of the present invention is a useful compound having extremely low migration property to the coating film.

(Compound)
The 9- (2-hydroxyalkoxy) anthracene compound of the present invention is a compound represented by the following general formula (1).

In the general formula (1), A represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a substituted oxymethyl group represented by the general formula (2), and X and Y are the same or different. Or a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

In General Formula (2), B represents an alkyl group having 1 to 8 carbon atoms, an allyl group, or an aryl group having 6 to 12 carbon atoms.

In the general formula (1), examples of the alkyl group having 1 to 8 carbon atoms represented by A include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t -Butyl group, n-pentyl group, i-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and the like. Moreover, in General formula (2), as a C1-C8 alkyl group represented by B, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group , T-butyl group, n-pentyl group, i-pentyl group, n-hexyl group, n-heptyl group, n-octyl group or 2-ethylhexyl group. Examples of the allyl group represented by B include an allyl group and a methallyl group. Examples of the aryl group having 6 to 12 carbon atoms represented by B include a phenyl group, a tolyl group, and a naphthyl group.

In the general formula (1), the alkyl group having 1 to 8 carbon atoms represented by X or Y includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group. , T-butyl group, n-pentyl group, i-pentyl group, n-hexyl group, n-heptyl group, n-octyl group or 2-ethylhexyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Specific examples of the 9- (2-hydroxyalkoxy) anthracene compound represented by the general formula (1) of the present invention include, for example, 9- (2-hydroxyethoxy) when X and Y are hydrogen atoms. Anthracene, 9- (2-hydroxypropoxy) anthracene, 9- (2-hydroxybutoxy) anthracene, 9- (2-hydroxypentyloxy) anthracene, 9- (2-hydroxyhexyloxy) anthracene, 9- (2-hydroxy Heptyloxy) anthracene, 9- (2-hydroxyoctyloxy) anthracene, 9- (2-hydroxy-3-methoxypropoxy) anthracene, 9- (2-hydroxy-3-ethoxypropoxy) anthracene, 9- (2-hydroxy) -3-propoxypropoxy) anthracene, 9- ( -Hydroxy-3-butoxypropoxy) anthracene, 9- (2-hydroxy-3-pentyloxypropoxy) anthracene, 9- (2-hydroxy-3-hexyloxypropoxy) anthracene, 9- (2-hydroxy-3-heptyl) Oxypropoxy) anthracene, 9- (2-hydroxy-3-octyloxypropoxy) anthracene, 9- (2-hydroxy-3-allyloxypropoxy) anthracene, 9- (2-hydroxy-3-methallyloxypropoxy) anthracene 9- (2-hydroxy-3-phenoxypropoxy) anthracene, 9- [2-hydroxy-3- (tolyloxy) propoxy] anthracene, 9- (2-hydroxy-3-naphthyloxypropoxy) anthracene and the like.

When X and Y are other than a hydrogen atom, for example, 2-methyl-9- (2-hydroxyethoxy) anthracene or 2-methyl-9- (2-hydroxypropoxy) in which X and / or Y is an alkyl group Anthracene, 2-methyl-9- (2-hydroxybutoxy) anthracene, 2-methyl-9- (2-hydroxypentyloxy) anthracene, 2-methyl-9- (2-hydroxyhexyloxy) anthracene, 2-methyl- 9- (2-hydroxyheptyloxy) anthracene, 2-methyl-9- (2-hydroxyoctyloxy) anthracene, 2-methyl-9- (2-hydroxy-3-methoxypropoxy) anthracene, 2-methyl-9- (2-hydroxy-3-ethoxypropoxy) anthracene, 2-methyl-9- (2-hydroxy 3-propoxypropoxy) anthracene 2-methyl-, 9- (2-hydroxy-3-butoxypropoxy) anthracene, 2-methyl-9- (2-hydroxy-3-pentyloxypropoxy) anthracene, 2-methyl-9- (2-hydroxy-3-hexyloxypropoxy) anthracene, 2-methyl-9- (2-hydroxy-3-heptyloxypropoxy) anthracene, 2-methyl-9- (2-hydroxy-3-octyloxypropoxy) anthracene 2-methyl-9- (2-hydroxy-3-allyloxypropoxy) anthracene, 2-methyl-9- (2-hydroxy-3-methallyloxypropoxy) anthracene, 2-methyl-9- (2-hydroxy -3-phenoxypropoxy) anthracene, 2-methyl- - [2-hydroxy-3- (tolyloxy) propoxy] anthracene, 2-methyl-9- (2-hydroxy-3-naphthyloxy propoxy) anthracene, and the like.

Further, 2-ethyl-9- (2-hydroxyethoxy) anthracene, 2-ethyl-9- (2-hydroxypropoxy) anthracene, 2-ethyl-9- (2-hydroxybutoxy) anthracene, 2-ethyl-9- (2-hydroxypentyloxy) anthracene, 2-ethyl-9- (2-hydroxyhexyloxy) anthracene, 2-ethyl-9- (2-hydroxyheptyloxy) anthracene, 2-ethyl-9- (2-hydroxyoctyl) Oxy) anthracene, 2-ethyl-9- (2-hydroxy-3-methoxypropoxy) anthracene, 2-ethyl-9- (2-hydroxy-3-ethoxypropoxy) anthracene, 2-ethyl-9- (2-hydroxy) -3-propoxypropoxy) anthracene 2-ethyl-, 9- (2-hi Loxy-3-butoxypropoxy) anthracene, 2-ethyl-9- (2-hydroxy-3-pentyloxypropoxy) anthracene, 2-ethyl-9- (2-hydroxy-3-hexyloxypropoxy) anthracene, 2-ethyl -9- (2-hydroxy-3-heptyloxypropoxy) anthracene, 2-ethyl-9- (2-hydroxy-3-octyloxypropoxy) anthracene, 2-ethyl-9- (2-hydroxy-3-allyloxy) Propoxy) anthracene, 2-ethyl-9- (2-hydroxy-3-methallyloxypropoxy) anthracene, 2-ethyl-9- (2-hydroxy-3-phenoxypropoxy) anthracene, 2-ethyl-9- [2 -Hydroxy-3- (tolyloxy) propoxy] anthracene 2-Ethyl-9- (2-hydroxy-3-naphthyloxy propoxy) anthracene, and the like.

Furthermore, 2,6-dimethyl-9- (2-hydroxyethoxy) anthracene, 2,6-dimethyl-9- (2-hydroxypropoxy) anthracene, 2,6-dimethyl-9- (2-hydroxybutoxy) anthracene 2,6-dimethyl-9- (2-hydroxypentyloxy) anthracene, 2,6-dimethyl-9- (2-hydroxyhexyloxy) anthracene, 2,6-dimethyl-9- (2-hydroxyheptyloxy) Anthracene, 2,6-dimethyl-9- (2-hydroxyoctyloxy) anthracene, 2,6-dimethyl-9- (2-hydroxy-3-methoxypropoxy) anthracene, 2,6-dimethyl-9- (2- Hydroxy-3-ethoxypropoxy) anthracene, 2,6-dimethyl-9- (2-hydroxy-) -Propoxypropoxy) anthracene, 2,6-dimethyl-, 9- (2-hydroxy-3-butoxypropoxy) anthracene, 2,6-dimethyl-9- (2-hydroxy-3-pentyloxypropoxy) anthracene, 2, 6-dimethyl-9- (2-hydroxy-3-hexyloxypropoxy) anthracene, 2,6-dimethyl-9- (2-hydroxy-3-heptyloxypropoxy) anthracene, 2,6-dimethyl-9- (2 -Hydroxy-3-octyloxypropoxy) anthracene, 2,6-dimethyl-9- (2-hydroxy-3-allyloxypropoxy) anthracene, 2,6-dimethyl-9- (2-hydroxy-3-methallyloxy) Propoxy) anthracene, 2,6-dimethyl-9- (2-hydroxy-3- Enoxypropoxy) anthracene, 2,6-dimethyl-9- [2-hydroxy-3- (tolyloxy) propoxy] anthracene, 2,6-dimethyl-9- (2-hydroxy-3-naphthyloxypropoxy) anthracene, etc. Is mentioned.

Further, 2-chloro-9- (2-hydroxyethoxy) anthracene, 2-chloro-9- (2-hydroxypropoxy) anthracene, 2-chloro-9- (2), wherein X and / or Y is a halogen atom. -Hydroxybutoxy) anthracene, 2-chloro-9- (2-hydroxypentyloxy) anthracene, 2-chloro-9- (2-hydroxyhexyloxy) anthracene, 2-chloro-9- (2-hydroxyheptyloxy) anthracene 2-chloro-9- (2-hydroxyoctyloxy) anthracene, 2-chloro-9- (2-hydroxy-3-methoxypropoxy) anthracene, 2-chloro-9- (2-hydroxy-3-ethoxypropoxy) Anthracene, 2-chloro-9- (2-hydroxy-3-propoxypropo C) Anthracene 2-chloro-, 9- (2-hydroxy-3-butoxypropoxy) anthracene, 2-chloro-9- (2-hydroxy-3-pentyloxypropoxy) anthracene, 2-chloro-9- (2- Hydroxy-3-hexyloxypropoxy) anthracene, 2-chloro-9- (2-hydroxy-3-heptyloxypropoxy) anthracene, 2-chloro-9- (2-hydroxy-3-octyloxypropoxy) anthracene, 2- Chloro-9- (2-hydroxy-3-allyloxypropoxy) anthracene, 2-chloro-9- (2-hydroxy-3-methallyloxypropoxy) anthracene, 2-chloro-9- (2-hydroxy-3- Phenoxypropoxy) anthracene, 2-chloro-9- [2-hydroxy- - (tolyloxy) propoxy] anthracene, 2-chloro-9- (2-hydroxy-3-naphthyloxy propoxy) anthracene, and the like.

And also 2-bromo-9- (2-hydroxyethoxy) anthracene, 2-bromo-9- (2-hydroxypropoxy) anthracene, 2-bromo-9- (2-hydroxybutoxy) anthracene, 2-bromo-9 -(2-hydroxypentyloxy) anthracene, 2-bromo-9- (2-hydroxyhexyloxy) anthracene, 2-bromo-9- (2-hydroxyheptyloxy) anthracene, 2-bromo-9- (2-hydroxy) Octyloxy) anthracene, 2-bromo-9- (2-hydroxy-3-methoxypropoxy) anthracene, 2-bromo-9- (2-hydroxy-3-ethoxypropoxy) anthracene, 2-bromo-9- (2- Hydroxy-3-propoxypropoxy) anthracene 2-bromo-, 9- ( -Hydroxy-3-butoxypropoxy) anthracene, 2-bromo-9- (2-hydroxy-3-pentyloxypropoxy) anthracene, 2-bromo-9- (2-hydroxy-3-hexyloxypropoxy) anthracene, 2- Bromo-9- (2-hydroxy-3-heptyloxypropoxy) anthracene, 2-bromo-9- (2-hydroxy-3-octyloxypropoxy) anthracene, 2-bromo-9- (2-hydroxy-3-allyl) Oxypropoxy) anthracene, 2-bromo-9- (2-hydroxy-3-methallyloxypropoxy) anthracene, 2-bromo-9- (2-hydroxy-3-phenoxypropoxy) anthracene, 2-bromo-9- [ 2-hydroxy-3- (tolyloxy) propoxy] ant Sen, 2-bromo-9- (2-hydroxy-3-naphthyloxy propoxy) anthracene, and the like.

Among these exemplified compounds, the following 9- (2-hydroxyethoxy) anthracene (compound A), 9- (2- Hydroxypropoxy) anthracene (compound B), 9- (2-hydroxy-3-methoxypropoxy) anthracene (compound C), and 9- (2-hydroxy-3-butoxypropoxy) anthracene (compound D) are preferred.

(Production method)
Next, a method for producing the 9- (2-hydroxyalkoxy) anthracene compound of the present invention will be described. The 9- (2-hydroxyalkoxy) anthracene compound of the present invention can be synthesized by isomerizing the 9-anthrone compound represented by the general formula (4) and then reacting with a hydroxy etherifying agent.

In the general formula (4), X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

Examples of the alkyl group having 1 to 8 carbon atoms represented by X and Y in the general formula (4) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, Examples include t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and the like. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned as a halogen atom.

Specifically, the synthesis of the 9- (2-hydroxyalkoxy) anthracene compound of the present invention is performed as follows. That is, the corresponding 9-anthrone compound is isomerized in a solvent (first reaction), and the obtained 9-hydroxyanthracene compound represented by the following general formula (3) is hydroxylated in the presence or absence of a base compound. Etherify (second reaction).

In the description of the first reaction, X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

In the description of the second reaction, X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom. In General Formula (1), A represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a substituted oxymethyl group represented by General Formula (2).

In General Formula (2), B represents an alkyl group having 1 to 8 carbon atoms, an allyl group, or an aryl group having 6 to 12 carbon atoms.

Specific examples of the 9-anthrone compound represented by the general formula (4) used as a raw material in the first reaction include 9-anthrone, 2-methyl-9-anthrone, 2-ethyl-9-anthrone, 2- (N-propyl) -9-anthrone, 2- (i-propyl) -9-anthrone, 2- (n-butyl) -9-anthrone, 2- (i-butyl) -9-anthrone, 2- (n -Pentyl) -9-anthrone, 2- (n-hexyl) -9-anthrone, 2- (n-heptyl) -9-anthrone, 2- (n-octyl) -9-anthrone, 2- (2-ethylhexyl) ) -9-anthrone, 2-fluoro-9-anthrone, 2-chloro-9-anthrone, 2-bromo-9-anthrone and the like.

As the isomerizing agent used in the first reaction, a base or an acid is used. As the base, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an organic base such as triethylamine, pyridine or piperidine is used. As the acid, sulfuric acid, hydrochloric acid, methanesulfonic acid, and p-toluenesulfonic acid are used. These isomerizing agents are preferably added in an amount of 1 to 10 moles with respect to the 9-anthrone compound. More preferably, it is 2 mol times or more and 5 mol times or less.

The isomerization reaction is usually performed in a solvent. The solvent is not particularly limited, and amide solvents such as dimethylformamide and dimethylacetamide, alcohol solvents such as methanol and ethanol, ether solvents such as tetrahydrofuran and dioxane, and water are preferably used.

In the first reaction, the reaction temperature of the isomerization reaction of the 9-anthrone compound is usually 0 ° C. or higher and 120 ° C. or lower. More preferably, it is 40 degreeC or more and 80 degrees C or less. If it is less than 0 degreeC, reaction will be slow, and if it exceeds 120 degreeC, a side reaction will occur easily and the purity of a product will fall. The reduction is completed when the reaction time is 0.5 to 3 hours, usually 1 hour. The obtained 9-hydroxyanthracene compound can be used for the next hydroxyetherification reaction without being usually isolated.

Next, the second reaction will be described. The hydroxy etherifying agent used in the second reaction is ethylene oxide, propylene oxide, butylene oxide, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, octyl glycidyl ether Allyl glycidyl ether, methallyl glycidyl ether, phenyl glycidyl ether, tolyl glycidyl ether or naphthyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, and the like.

In the second reaction, the addition ratio of the hydroxy etherifying agent to the 9-hydroxyanthracene compound is 1.0 mol times or more and 20 mol times or less, preferably 1.5 mol times or more and 15 mol times or less. If it is less than 1.0 mol, the 9-hydroxyanthracene compound remains unreacted, and if it is added more than 20 mol, the solubility of the produced 9- (2-hydroxyalkoxy) anthracene compound in the reaction solution increases. It becomes difficult to crystallize from the reaction product and the yield decreases.

As the base compound used when the second reaction is carried out in the presence of the base compound, inorganic alkali salts, alkali metal carbonates and the like are usually used. As the inorganic alkali salt, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide and the like are used. Examples of the alkali metal carbonate include sodium carbonate, potassium carbonate, and lithium carbonate. In addition, pyridine, piperidine, trimethylamine, triethylamine, and the like, which are organic bases, can be used.

The hydroxy etherification reaction is usually performed in a solvent. The solvent is not particularly limited, and amide solvents such as dimethylformamide and dimethylacetamide, alcohol solvents such as methanol and ethanol, ether solvents such as tetrahydrofuran and dioxane, and water are preferably used. The solvent used in the isomerization reaction may be used as it is.

The temperature of hydroxy etherification is 0 degreeC or more and 100 degrees C or less, Preferably it is room temperature or more and 80 degrees C or less. If it is less than 0 ° C., the reaction rate is too slow and the reaction takes too much time, and if the temperature exceeds 100 ° C., side reactions occur and the purity of the product decreases. The reaction time is usually about 0.5 to 24 hours.

The product precipitates as the reaction proceeds or the base is neutralized after the reaction, and the precipitate is filtered and dried to obtain a 9- (2-hydroxyalkoxy) anthracene compound.

As described above, the first reaction and the second reaction are described separately. However, when the same basic compound is used as the isomerizing agent and the hydroxy etherifying agent in the first reaction and the first reaction, the first reaction and the second reaction are performed. It is possible to carry out at once without dividing.

(Photopolymerization sensitizer)
The 9- (2-hydroxyalkoxy) anthracene compound represented by the general formula (1) of the present invention thus obtained is a photopolymerizable compound such as a photocationically polymerizable compound or a photoradical polymerizable compound. When polymerizing in the presence of a photopolymerization initiator, it can be used as a photocationic polymerization sensitizer or a radical photopolymerization sensitizer.

The photopolymerization sensitizer containing the 9- (2-hydroxyalkoxy) anthracene compound represented by the general formula (1) of the present invention contains a 9- (2-hydroxyalkoxy) anthracene compound as an active ingredient. In addition to the 9- (2-hydroxyalkoxy) anthracene compound as a whole, a photopolymerization sensitizer other than the 9- (2-hydroxyalkoxy) anthracene compound is used as long as the effects of the present invention are not impaired. May be included.

Examples of photopolymerization sensitizers other than such 9- (2-hydroxyalkoxy) anthracene compounds include thioxanthone compounds (for example, 2-isopropylthioxanthone, 2,4-diethylthioxanthone), naphthalene compounds (for example, 1,4-diethoxy). Naphthalene, 1,4-dimethoxynaphthalene, 1,4-dihydroxynaphthalene, 4-methoxy-1-naphthol), amine compounds (for example, methyl diethylaminobenzoate) and the like.

The addition ratio of the photopolymerization sensitizer other than the 9- (2-hydroxyalkoxy) anthracene compound to the 9- (2-hydroxyalkoxy) anthracene compound is not particularly limited, but relative to the 9- (2-hydroxyalkoxy) anthracene compound And 0.1 weight times or more and less than 10 weight times.

(Photopolymerization initiator)
Photopolymerization initiators include onium salts, benzylmethyl ketal photopolymerization initiators, α-hydroxyalkylphenone photopolymerization initiators, α-aminophenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, and oximes. Examples thereof include ester photopolymerization initiators and biimidazole photopolymerization initiators.

As the onium salt, an iodonium salt or a sulfonium salt is usually used. Examples of the iodonium salt include 4-isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexamethoxyantimonate, 4-isopropylphenyl-4′-methylphenyliodonium tetrakispentamethoxyphenylborate, 4- Examples thereof include isopropylphenyl-4′-methylphenyliodonium tetrakispentafluorophenylborate and the like. For example, IRGACURE 250 manufactured by BASF (Irgacure is a registered trademark of BASF), manufactured by Rhodia A load sill 2074 (a load sill is a registered trademark of Rhodia Co., Ltd.), IK-1 manufactured by Sun Apro, etc. can be used. On the other hand, examples of the sulfonium salt include S, S, S ′, S′-tetraphenyl-S, S ′-(4,4′-thiodiphenyl) disulfonium bishexamethoxyphosphate, diphenyl-4-phenylthiophenylsulfonium hexanium. Examples thereof include methoxyphosphate, triphenylsulfonium hexamethoxyphosphate, etc., for example, CPI-100P, CPI-101P, CPI-200K manufactured by Daicel, Irgacure 270 manufactured by BAS, UVI6992 manufactured by Dow Chemical Can be used. These photopolymerization initiators 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 BSF Corporation). α-Hydroxyalkylphenone radical polymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name “Darocur 1173” manufactured by BASF Corporation), 1-hydroxycyclohexyl phenyl ketone (product) Name “Irgacure 184” manufactured by BSF Corporation), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name “Irgacure 2959” BSF Corporation) 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methyl-1-one (trade name “Irgacure 127” manufactured by BASF Corporation) ).

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, and α-hydroxyalkylphenone radical polymerization initiation 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name “Darocur 1173” manufactured by BASF), 1-hydroxycyclohexyl phenylketone (trade name “Irgacure 184” manufactured by BASF) Is preferred.

Further, acetophenone radical polymerization initiators such as acetophenone, 2-hydroxy-2-phenylacetophenone, 2-ethoxy-2-phenylacetophenone, 2-methoxy-2-phenylacetophenone, 2-isopropoxy-2-phenylacetophenone, 2 -Isobutoxy-2-phenylacetophenone, 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, and the like can also be used.

Of the illustrated photopolymerization initiators, onium salts are particularly preferable. One feature of the 9- (2-hydroxyalkoxy) anthracene compound of the present invention is that it has a photopolymerization sensitizing effect not only on iodonium salts but also sulfonium salts as onium salts.

Although the usage-amount with respect to the photoinitiator of the photoinitiator of the photopolymerization sensitizer containing the 9- (2-hydroxyalkoxy) anthracene compound represented by General formula (1) of this invention is not specifically limited, On the other hand, it is usually in the range of 5 to 100% by weight, preferably in the range of 10 to 50% by weight. If the amount of the photopolymerization sensitizer used is less than 5% by weight, it takes too much time to photopolymerize the photopolymerizable compound. On the other hand, if the amount exceeds 100% by weight, an effect commensurate with the addition is obtained. Absent.

(Photopolymerization initiator composition)
Although the photopolymerization sensitizer containing the 9- (2-hydroxyalkoxy) anthracene compound represented by the general formula (1) of the present invention can be directly added to the photopolymerizable compound, photopolymerization is started in advance. After preparing a photopolymerization initiator composition by blending with an agent, it can be added to the photopolymerizable compound. That is, the photopolymerization initiator composition of the present invention contains at least a photopolymerization sensitizer containing a 9- (2-hydroxyalkoxy) anthracene compound represented by the general formula (1) and a photopolymerization initiator. It is a composition.

(Photopolymerizable composition)
A photopolymerizable composition can also be prepared by blending the photopolymerization initiator composition and a photopolymerizable compound. The photopolymerizable composition of the present invention is a photopolymerization sensitizer containing a 9- (2-hydroxyalkoxy) anthracene compound represented by the general formula (1) of the present invention, and light containing a photopolymerization initiator. It is a composition containing a polymerization initiator composition and a photocationic polymerizable compound or a photoradical polymerizable compound.

The photopolymerization sensitizer containing the 9- (2-hydroxyalkoxy) anthracene compound represented by the general formula (1) of the present invention and the photopolymerization initiator are separately a photocationically polymerizable compound or a photoradical polymerizable compound. It may be added to the compound to form a photopolymerization initiator composition as a result in the photocationically polymerizable compound or the radical photopolymerizable compound.

Examples of the cationic photopolymerizable compound include epoxy compounds and vinyl ethers. Examples of general epoxy compounds include alicyclic epoxy compounds, epoxy-modified silicones, and aromatic glycidyl ethers. Of these photocationically polymerizable compounds, alicyclic epoxy compounds and epoxy-modified silicones are preferred in terms of film-forming ability and the like and the high solubility of the compounds of the present invention. Examples of the alicyclic epoxy compound include 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexyl) adipate, and the like, for example, UVR6105 manufactured by Dow Chemical Co., Ltd. UVR6110 etc. can be used. Examples of the epoxy-modified silicone include UV-9300 manufactured by Momentive Performance Materials. Examples of the aromatic glycidyl compound include 2,2'-bis (4-glycidyloxyphenyl) propane. Examples of the vinyl ether include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether and the like. These photocationically polymerizable compounds may be one kind or a mixture of two or more kinds.

As the photoradical polymerizable compound, for example, an organic compound having a double bond such as styrene, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, acrylic acid ester, and methacrylic acid ester can be used. . Among these photo-radically polymerizable compounds, in terms of film-forming ability and the like and the solubility of the compound of the present invention is high, acrylic acid esters and methacrylic acid esters (hereinafter referred to as (meth) acrylic acid esters together). ) Is preferred. (Meth) acrylic acid esters include methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, methyl methacrylate, butyl methacrylate, methacrylic acid Examples include cyclohexyl, tetraethylene 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 photopolymerizable compounds may be one kind or a mixture of two or more kinds.

In the photopolymerizable composition of the present invention, the amount of the photopolymerization initiator composition used is in the range of 0.005 wt% or more and 10 wt% or less, preferably 0.025 wt% with respect to the photopolymerizable composition. The content is 5% by weight or less. If it is less than 0.005% by weight, it takes time to photopolymerize the photopolymerizable composition. On the other hand, if it exceeds 10% by weight, the hardness of the photocured product obtained by photopolymerization decreases. This is not preferable because the physical properties of the cured product are deteriorated.

In addition, the photopolymerizable composition of the present invention has a diluent, a colorant, an organic or inorganic filler, a leveling agent, a surfactant, an antifoaming agent, a thickener, within a range not impairing the effects of the present invention. Various resin additives such as flame retardants, antioxidants, stabilizers, lubricants, and plasticizers may be blended.

(Photocured product)
A photocured product can be obtained by irradiating the photopolymerizable composition of the present invention with light. When the photopolymerizable composition is irradiated with light to be polymerized and photocured, the photopolymerizable composition can be formed into a film and photocured, or can be formed into a lump and photocured. In the case where it is molded into a film and photocured, the liquid photopolymerizable composition is applied to a substrate such as a polyester film so as to have a film thickness of 5 to 300 microns using a bar coater or the like. On the other hand, it can also be applied with a thinner or thicker film by spin coating or screen printing.

A photocured product is obtained by irradiating the coating film made of the photopolymerizable composition thus prepared with ultraviolet light having a wavelength range of 250 to 500 nm at an intensity of about 1 to 1000 mW / cm ^2. Can do. As a light source to be used, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, xenon lamp, gallium doped lamp, black light, 395 nm ultraviolet LED, 385 nm ultraviolet LED, 365 nm ultraviolet LED, blue LED, white LED, D manufactured by Fusion Examples thereof include a valve and a V valve. Natural light such as sunlight can also be used. In particular, a 395 nm ultraviolet LED, a 385 nm ultraviolet LED, and a 365 nm ultraviolet LED are preferable.

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

(Determination of migration resistance)
As a method for determining whether or not the photopolymerization sensitizer contained in the photopolymerizable composition of the present invention migrates to a film or the like, the photopolymerizable composition containing the photopolymerization sensitizer is a thin film. Create a product applied to the object, cover it with a polyethylene film, store it at a constant temperature (26 ° C) for a certain period of time, then peel off the polyethylene film, and examine whether the photopolymerization sensitizer has transferred to the polyethylene film The migration resistance was determined. The peeled polyethylene film was washed after washing the surface composition with acetone, measured for UV resistance of the polyethylene film, and measured for migration resistance by examining the increase in absorption intensity caused by the photopolymerization sensitizer. did. For the measurement, an ultraviolet / visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV2200) was used. In order to quantitatively compare with 9,10-dibutoxyanthracene, which is the compound of the comparative example, the obtained absorbance was converted to the absorbance value of 9,10-dibutoxyanthracene. In conversion, the absorbance at 260 nm of the compound of the present invention and 9,10-dibutoxyanthracene was measured with an ultraviolet / visible spectrophotometer, the respective molar extinction coefficients were calculated from the absorbance value and molar concentration, and the ratio It converted using.

The present invention is illustrated by the following examples which are not intended to limit the scope of the invention. Unless otherwise specified, all parts are parts by weight. The product was confirmed based on the measurement by the following equipment.

(1) Melting point: Melting point measuring device manufactured by Gelen Camp, model MFB-595 (conforms to JIS K0064)
(2) Infrared (IR) spectrophotometer: Model IR-810 manufactured by JASCO Corporation
(3) Nuclear magnetic resonance apparatus (NMR): manufactured by JEOL Ltd., model ECS-400 FT NMR Spectrometer

(Synthesis Example 1) Synthesis of 9- (2-hydroxyethoxy) anthracene (Compound A) In a nitrogen box, 4.9 g (25 mmol) of 9-anthrone was dissolved in methanol in an autoclave equipped with a stirrer. An aqueous solution (4 g of sodium hydroxide, 100 mmol, 13 g of water) was added and sealed. After heating at 60 ° C. for 20 minutes to convert 9-anthrone to 9-hydroxyanthracene, the temperature of the reaction solution was lowered to 45 ° C. Thereto, 11 g (250 mmol) of ethylene oxide was introduced over 60 minutes while maintaining the temperature at 50 ° C. or lower and the pressure at 0.3 MPa or lower. Furthermore, the reaction was continued for 3 hours while maintaining the reaction temperature at 40 ° C. After completion of the reaction, it is cooled to room temperature and neutralized with 5% sulfuric acid. Crystals precipitated as a result of neutralization, and the obtained crystals were filtered and washed with water. By drying at 80 ° C., 3.7 g (15.5 mmol) of 9- (2-hydroxyethoxy) anthracene was obtained. The isolation yield based on the raw material anthrone was 62 mol%.

(1) Melting point: 108-109 ° C
(2) IR (KBr, cm ⁻¹ ): 3250, 3060, 2930, 2860, 1414, 1334, 1277, 1101, 1064, 1032, 883, 836, 787, 727, 654, 639, 621, 611, 580.
(3) ¹ H-NMR (CDCl ₃ , 400 MHz): δ 4.17 (t, J = 8 Hz, 2H), 4.32 (t, J = 8 Hz, 2H), 7.43-7.49 (m, 4H), 7.98 (d, J = 9 Hz, 2H), 8.22 (s, 1H), 8.32 (d, J = 9 Hz, 2H).

(Synthesis Example 2) Synthesis of 9- (2-hydroxypropoxy) anthracene (Compound B) 4.9 g (25 mmol) of anthrone was dissolved in methanol, and an aqueous solution of sodium hydroxide (4 g of sodium hydroxide, 100 mmol, 13 g of water). After heating at 60 ° C. for 20 minutes, the temperature of the reaction solution was lowered to 45 ° C. Next, 14 g (260 mmol) of propylene oxide was added little by little, the temperature of the liquid was kept at about 50 ° C., and the mixture was heated as it was for 1 hour. Then, it cooled to room temperature and neutralized with 5% sulfuric acid. Crystals were precipitated as a result of neutralization, and the crystals were suction filtered and dried to obtain 2.7 g (10.7 mmol) of 9- (2-hydroxypropoxy) anthracene of khaki powder. The isolation yield based on the raw material anthrone was 43 mol%.

(1) Melting point: 128-129 ° C
(2) IR (KBr, cm ⁻¹ ): 3330, 3060, 2970, 2920, 2860, 1334, 1320, 1279, 1074, 1002, 931, 847, 787, 701, 657, 630, 610, 586
(3) ¹ H-NMR (CDCl ₃ , 400 MHz): δ 1.37 (d, J = 8 Hz, 3H), 4.11 (d, J = 8 Hz, 2H), 4.47-4.54 (m, 1H), 7.43-7.50 (m, 4H), 7.98 (d, J = 9 Hz, 2H), 8.22 (s, 1H), 8.31 (d, J = 9 Hz, 2H) .

Synthesis Example 3 Synthesis of 9- (2-hydroxy-3-methoxypropoxy) anthracene (Compound C) 1.94 g (10 mmol) of anthrone was dissolved in 10 g of N, N-dimethylacetamide, and an aqueous solution of sodium hydroxide (water Sodium oxide (1.2 g, 30 mmol, water 4 g) was added and the mixture was heated at 60 ° C. for 20 minutes, and then the temperature of the reaction solution was lowered to 45 ° C. Next, 1.76 g (20 mmol) of methyl glycidyl ether was added little by little, the temperature of the liquid was kept at about 50 ° C., and the mixture was heated as it was for 5 hours. Thereafter, it is cooled to room temperature and neutralized with 5% sulfuric acid. Following neutralization, a red candy was precipitated. The supernatant was discarded, the candy was washed well, extracted with 15 ml of acetone, concentrated to dryness, and 1.17 g (4.2 mmol) of khaki candy of 9- (2-hydroxy-3-methoxypropoxy) anthracene. Got. The isolation yield based on the raw material anthrone was 42 mol%.

(1) Melting point: room temperature liquid (2) IR (Nujol, cm ⁻¹ ): 3400, 3040, 2920, 2870, 2830, 1411, 1338, 1079, 995, 960, 879, 789, 735, 653, 632, 610 559.
(3) ¹ H-NMR (CDCl ₃ , 400 MHz): δ 3.45 (s, 3H), 3.73 (d, J = 8 Hz, 2H), 4.24 (d, J = 8 Hz, 2H), 4 .41-4.48 (m, 1H), 7.40-7.51 (m, 2H), 7.96 (d, J = 9 Hz, 1H), 8.19 (s, 1H), 8.32 (D, J = 9 Hz, 1H).

(Synthesis Example 4) Synthesis of 9- (2-hydroxy-3-butoxypropoxy) anthracene (Compound D) 1.94 g (10 mmol) of anthrone was dissolved in 10 g of N, N-dimethylacetamide, and an aqueous solution of sodium hydroxide (water Sodium oxide (1.2 g, 30 mmol, water 4 g) was added and the mixture was heated at 60 ° C. for 20 minutes, and then the temperature of the reaction solution was lowered to 45 ° C. Next, 2.60 g (20 mmol) of butyl glycidyl ether was added little by little, the temperature of the liquid was kept at about 50 ° C., and the mixture was heated as it was for 5 hours. Thereafter, it is cooled to room temperature and neutralized with 5% sulfuric acid. Following neutralization, a red candy was precipitated. Discard the supernatant, wash the candy well with water, extract with 15 ml of acetone, concentrate to dryness, and 1.00 g (3.1 mmol) of khaki candy of 9- (2-hydroxy-3-butoxypropoxy) anthracene. Got. The isolation yield based on the raw material anthrone was 31 mol%.

(1) Melting point: room temperature liquid (2) IR (Nujol, cm ⁻¹ ): 3370, 3040, 2970, 2940, 1412, 1338, 1082, 995, 878, 840, 789, 735, 610, 559.
(3) ¹ H-NMR (CDCl ₃ , 400 MHz): δ 0.92 (t, J = 8 Hz, 3H), 1.34-1.43 (m, 2H), 1.56-1.64 (m, 2H), 3.58 (t, J = 8 Hz, 2H), 3.78 (d, J = 8 Hz, 1H), 4.26 (d, J = 8 Hz, 2H), 4.38-4.46 ( m, 1H), 7.40-7.50 (m, 2H), 7.97 (d, J = 9 Hz, 1H), 8.21 (s, 1H), 8.30 (d, J = 9 Hz, 1H).

(Evaluation Example 1) Cationic polymerization using 9- (2-hydroxyethoxy) anthracene (Compound A) As a cation polymerizable compound, an alicyclic epoxy compound 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxy 100 parts of cyclohexanecarboxylate (Delcel's Celoxide 2021P, Celoxide is a registered trademark of Daicel), isobutylphenyl (4-methylphenyl) iodonium hexafluorophosphate (manufactured by BASF) as a photopolymerization initiator A photopolymerizable composition was prepared by mixing 5 parts of Irgacure 250) and 2 parts of 9- (2-hydroxyethoxy) anthracene (Compound A) synthesized in the same manner as in Synthesis Example 1 as a photopolymerization sensitizer. . The composition was applied on a polyester film having a film thickness of 100 microns (Toray Lumirror, Lumirror is a registered trademark of Toray Industries, Inc.) using a bar coater (No. 8) so as to have a film thickness of 12 microns. Then, the photocured material was obtained by irradiating light from the top using UV LED made from Phoseon. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 50 mW / cm ² . The stickiness (tack) of the coating film was confirmed by finger touch at regular intervals. The light irradiation time “tack free time” from the start of light irradiation to the elimination of tackiness on the coated surface of the composition was 3.5 seconds.

(Evaluation Example 2) As a cationic polymerization photopolymerization sensitizer using 9- (2-hydroxypropoxy) anthracene (Compound B), instead of 9- (2-hydroxyethoxy) anthracene (Compound A), Synthesis Example A photopolymerizable composition was prepared in the same manner as in Evaluation Example 1 except that 9- (2-hydroxypropoxy) anthracene (Compound B) synthesized in the same manner as in Example 2 was added, and coating and light irradiation were performed. The light irradiation time “tack free time” from the start of light irradiation to the elimination of tackiness on the coated surface of the composition was 3.5 seconds.

(Evaluation Example 3) Instead of 9- (2-hydroxyethoxy) anthracene (Compound A) as a cationic polymerization photopolymerization sensitizer using 9- (2-hydroxy-3-methoxypropoxy) anthracene (Compound C) A photopolymerizable composition was prepared in the same manner as in Evaluation Example 1 except that 9- (2-hydroxy-3-methoxypropoxy) anthracene (Compound C) synthesized in the same manner as in Synthesis Example 3 was added. Application and light irradiation. The light irradiation time “tack free time” from the start of light irradiation until the sticking (tack) of the coated surface of the composition disappeared was 4.0 seconds.

(Evaluation Example 4) Cationic polymerization photopolymerization sensitizer using 9- (2-hydroxy-3-butoxypropoxy) anthracene (Compound D) instead of 9- (2-hydroxyethoxy) anthracene (Compound A) A photopolymerizable composition was prepared in the same manner as in Evaluation Example 1 except that 9- (2-hydroxy-3-butoxypropoxy) anthracene (Compound D) synthesized in the same manner as in Synthesis Example 4 was added. Application and light irradiation. The light irradiation time “tack free time” from the start of light irradiation until the tackiness of the coated surface of the composition disappeared was 5.0 seconds.

(Evaluation Comparative Example 1) As a cationic polymerization photopolymerization sensitizer using 9,10-dibutoxyanthracene (DBA), instead of 9- (2-hydroxyethoxy) anthracene (compound A), a commercially available photopolymerization increase A photopolymerizable composition was prepared in the same manner as in Evaluation Example 1 except that the sensitizing agent 9,10-dibutoxyanthracene (DBA) was added, and was coated and irradiated with light. The light irradiation time “tack free time” from the start of light irradiation to the elimination of tackiness on the coated surface of the composition was 3.5 seconds.

(Evaluation Comparative Example 2) A photopolymerizable composition was prepared in the same manner as in Evaluation Example 1 except that no cationic polymerization photopolymerization sensitizer was used without using a photopolymerization sensitizer. Irradiated. However, even after 300 seconds of irradiation from the start of light irradiation, the tackiness of the coated surface of the composition did not disappear.

The results of (Evaluation Example 1) to (Evaluation Example 4) and (Evaluation Comparative Example 1) and (Evaluation Comparative Example 2) are summarized in Table 1.

From Table 1 that summarizes the above Evaluation Examples 1 to 4, Evaluation Comparative Examples 1 and 2, and the results, the following is clear. That is, when 9- (2-hydroxyalkoxy) anthracene compound of the present invention is used as a photopolymerization sensitizer and photocationic polymerization is carried out, it shows an excellent photopolymerization sensitization effect, and also from the results of the tack-free test. It can be seen that the photopolymerization sensitizer has almost the same photopolymerization sensitizing ability as 9,10-dibutoxyanthracene (DBA), which is a known photopolymerization sensitizer.

This effect is caused when the 9- (2-hydroxyalkoxy) anthracene compound of the present invention is excited by light irradiation, the energy is transferred to the photopolymerization initiator, and the photopolymerization initiator is activated. The same effect is also exhibited in photo radical polymerization.

(Evaluation example of migration resistance)
(Evaluation Example 5) Migration test using 9- (2-hydroxyethoxy) anthracene (Compound A) As a cationic polymerizable compound, an alicyclic epoxy compound 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxy 1 part of 9- (2-hydroxyethoxy) anthracene (Compound A) synthesized in the same manner as in Synthesis Example 1 was mixed as a photopolymerization sensitizer with 100 parts of cyclohexanecarboxylate (Celoxide 2021P manufactured by Daicel). The prepared photopolymerizable composition was applied on a polyester film using a bar coater so as to have a film thickness of 12 microns. Next, a low-density polyethylene film (film thickness of 30 microns) was put on the obtained coating and stored in the dark for one day, stored for two days, or stored for four days. The film was peeled off, the polyethylene film was washed with acetone and dried, then the UV spectrum of the film was measured, and the absorbance at 260 nm was measured. The absorbance of the obtained 9- (2-hydroxyethoxy) anthracene (Compound A) was converted to 9,10-dibutoxyanthracene. The absorbance was 0.024 after 1 day storage, 0.025 after 2 days storage, and 0.025 after 4 days storage.

(Evaluation Example 6) Migration test using 9- (2-hydroxypropoxy) anthracene (Compound B) As a photopolymerization sensitizer, the same method as in Synthesis Example 2 instead of 9- (2-hydroxyethoxy) anthracene A photopolymerizable composition was prepared and tested in the same manner as in Evaluation Example 5 except that 9- (2-hydroxypropoxy) anthracene (Compound B) synthesized in Step 1 was used. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance of 9- (2-hydroxypropoxy) anthracene (compound D) was converted to 9,10-dibutoxyanthracene. The absorbance was 0.031 after 1 day storage, 0.035 after 2 days storage, and 0.032 after 4 days storage.

(Evaluation Example 7) Migration test using 9- (2-hydroxy-3-methoxypropoxy) anthracene (Compound C) As a photopolymerization sensitizer, Synthesis Example 3 instead of 9- (2-hydroxyethoxy) anthracene A photopolymerizable composition was prepared and tested in the same manner as in Evaluation Example 5 except that 9- (2-hydroxy-3-methoxypropoxy) anthracene (Compound C) synthesized in the same manner as described above was used. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance of 9- (2-hydroxy-3-methoxypropoxy) anthracene (Compound C) was converted to 9,10-dibutoxyanthracene. The absorbance was 0.024 after 1 day storage, 0.025 after 2 days storage, and 0.025 after 4 days storage.

(Evaluation Example 8) Migration test using 9- (2-hydroxy-3-butoxypropoxy) anthracene (Compound D) As a photopolymerization sensitizer, Synthesis Example 4 instead of 9- (2-hydroxyethoxy) anthracene A photopolymerizable composition was prepared and tested in the same manner as in Evaluation Example 5 except that 9- (2-hydroxy-3-butoxypropoxy) anthracene (Compound D) synthesized in the same manner as described above was used. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance of 9- (2-hydroxy-3-butoxypropoxy) anthracene (compound D) was converted to 9,10-dibutoxyanthracene. The absorbance was 0.027 after 1 day storage, 0.029 after 2 days storage, and 0.028 after 4 days storage.

(Evaluation Comparative Example 3) Migration test using 9,10-dibutoxyanthracene (compound D) As a photopolymerization sensitizer, 9,10-dibutoxyanthracene (compound) instead of 9- (2-hydroxyethoxy) anthracene A photopolymerizable composition was prepared and tested as in Evaluation Example 4 except that D) was used. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance of 9,10-dibutoxyanthracene was 0.76 after 1 day storage, 0.73 after 2 days storage, and 0.75 after 4 days storage. It was.

The results of (Evaluation Example 5) to (Evaluation Example 8) and (Evaluation Comparative Example 3) are summarized in Table 2.

From Table 2 that summarizes the above Evaluation Examples 5 to 8, Evaluation Comparative Example 3, and the results, the following is clear. That is, when the 9- (2-hydroxyalkoxy) anthracene compound of the present invention is used as a photopolymerization sensitizer, the amount of the photopolymerization sensitizer transferred to the film overlaid on the prepared photopolymerizable composition is extremely small. It can be seen that it has excellent migration resistance. On the other hand, it can be seen that 9,10-dibutoxyanthracene (DBA), which is a known photopolymerization sensitizer, is transferred to the film over 20 times the 9- (2-hydroxyalkoxy) anthracene compound of the present invention. .

From the above results, the 9- (2-hydroxyalkoxy) anthracene compound of the present invention only has a photopolymerization sensitizing ability equivalent to 9,10-dibutoxyanthracene (DBA) which is a known photopolymerization sensitizer. In addition, it can be seen that the photopolymerizable composition containing the photopolymerization sensitizer is an excellent compound with high migration resistance and is a very useful compound as a photopolymerization sensitizer.

Claims (4)

A photopolymerization sensitizer containing a 9- (2-hydroxyalkoxy) anthracene compound represented by the general formula (1).

(In General Formula (1), A represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a substituted oxymethyl group represented by General Formula (2), and X and Y are the same or different. It may be a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.)

(In General Formula (2), B represents an alkyl group having 1 to 8 carbon atoms, an allyl group, or an aryl group having 6 to 12 carbon atoms.) A photopolymerization initiator composition comprising the photopolymerization sensitizer according to claim 1 and a photopolymerization initiator. A photopolymerizable composition comprising the photopolymerization initiator composition according to claim 2 and a photopolymerizable compound. The hardening method which hardens | cures by irradiating the photopolymerizable composition of Claim 3 with the energy beam containing the light of the wavelength of the range of 250 nm to 500 nm.