JP6695565B2 - 2-SUBSTITUTED-9,10-BIS (2-HYDROXYALKOXY) ANTHRACENE COMPOUND, PROCESS FOR PRODUCING THE SAME AND USE THEREOF - Google Patents

Description

The present invention relates to a 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound, a method for producing the same, and use as a photopolymerization sensitizer.

A photo-curable resin that polymerizes with active energy rays such as ultraviolet rays and visible light cures quickly and can significantly reduce the amount of organic solvent used compared to thermosetting resins, thus improving the working environment and reducing the environmental burden. It is excellent in that it can be reduced. The conventional photocurable resin itself has a poor polymerization initiation function, and thus it is usually necessary to use a photopolymerization initiator for curing. As the photopolymerization initiator, an alkylphenone-based polymerization initiator such as hydroxyacetophenone or benzophenone, an acylphosphine oxide-based photopolymerization initiator, or an onium salt is used (Patent Documents 1, 2, and 3). When an onium salt-based initiator is used among these photopolymerization initiators, the light absorption of the onium salt is in the vicinity of 225 nm to 350 nm and there is no absorption at 350 nm or more, so a lamp with a long wavelength of 350 nm or more is used as a light source. In this case, there is a problem that the photo-curing reaction is difficult to proceed, and it is common to add a photopolymerization sensitizer. Anthracene and thioxanthone compounds are known as photopolymerization sensitizers, and in particular, anthracene compounds are often used due to problems such as color shade (Patent Document 4).

A 9,10-dialkoxyanthracene compound is used as the anthracene-based photopolymerization sensitizer. For example, a 9,10-dialkoxyanthracene compound such as 9,10-dibutoxyanthracene or 9,10-diethoxyanthracene is used as a photopolymerization sensitizer for an iodonium salt which is a photopolymerization initiator in photopolymerization. (Patent Documents 5, 6, 7, and 8).

However, this 9,10-dialkoxyanthracene compound is known to cause problems such as dusting and coloring of the cured product due to blooming of the photopolymerization sensitizer on the surface due to blooming during photocuring or during storage of the cured product. Has been. For example, when these photopolymerization sensitizers are used as one component of a photoadhesive for adhering films to each other, the photopolymerization sensitizers may migrate to a film overlaid on the upper film. On the other hand, it may cause dusting and coloring problems of the photopolymerization sensitizer.

The introduction of hydroxyl groups is considered to be effective for suppressing migration. Therefore, the present inventors have synthesized a 9,10-bis (2-hydroxyalkoxy) anthracene compound by introducing a hydroxyl group into the alkoxy group of 9,10-dialkoxyanthracene which is a known photopolymerization sensitizer. Although migration was suppressed, the solubility in solvents and monomers was extremely low, and the dissolution rate was also extremely slow, making it difficult to use as a photopolymerization sensitizer.

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

Therefore, during photocuring or during storage of the cured product, the photopolymerization sensitizer does not bleed to the surface due to blooming, etc., and does not cause problems such as dusting or coloring of the cured product, and practically sufficient solubility for the monomer. It is desired to develop a photopolymerization sensitizer having

As a result of further diligent study on the structure and physical properties of the anthracene compound, the present inventor has shown that the 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound having a substituent at the 2-position shown in the present invention is It exhibits an excellent effect as a photopolymerization sensitizer in a polymerization reaction and, at the same time, has a high solubility in a monomer when preparing a photopolymerizable composition, and further has a film on the photopolymerizable composition. The inventors have found that the photopolymerization sensitizer is less likely to cause migration even when it is covered with the above, and have completed the present invention.

That is, the first gist of the present invention resides in a 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound represented by the following general formula (1).

In the general formula (1), R represents a hydrogen atom, a methyl group or an ethyl group, A represents an alkyl group having 1 to 8 carbon atoms, a halogen atom, an alkoxy group having 1 to 8 carbon atoms, or 6 carbon atoms. Represents an aryloxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, or an arylthio group having 6 to 12 carbon atoms.

A second gist of the present invention is to reduce a 2-substituted-9,10-anthraquinone compound represented by the following general formula (2), and then to react it with an alkylene oxide or a haloalkanol. ). The method for producing a 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound represented by

In the general formula (2), A is an alkyl group having 1 to 8 carbon atoms, a halogen atom, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, or a carbon atom. It represents any of the arylthio groups of the formulas 6 to 12.

In the general formula (1), R represents a hydrogen atom, a methyl group or an ethyl group, A represents an alkyl group having 1 to 8 carbon atoms, a halogen atom, an alkoxy group having 1 to 8 carbon atoms, or 6 carbon atoms. Represents an aryloxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, or an arylthio group having 6 to 12 carbon atoms.

A third gist of the present invention resides in a photopolymerization sensitizer containing a 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound represented by the following general formula (1).

In the general formula (1), R represents a hydrogen atom, a methyl group or an ethyl group, A represents an alkyl group having 1 to 8 carbon atoms, a halogen atom, an alkoxy group having 1 to 8 carbon atoms, or 6 carbon atoms. It represents either an aryloxy group having 12 carbon atoms, an alkylthio group having 1 to 8 carbon atoms or an arylthio group having 6 to 12 carbon atoms.

A fourth gist of the present invention resides in a photopolymerization initiator composition containing the photopolymerization sensitizer described in the third gist and a photopolymerization initiator.

A fifth gist of the present invention resides in a photopolymerizable composition containing the photopolymerization initiator composition described in the fourth gist and a photopolymerizable compound.

A sixth gist of the present invention resides in a curing method in which the photopolymerizable composition described in the fifth gist is cured by irradiating the photopolymerizable composition with an energy ray containing light in the wavelength range of 250 nm to 500 nm.

The 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound of the present invention has a practically sufficient solubility and dissolution rate for a monomer in a photopolymerization reaction, and serves as a photopolymerization sensitizer. When the film is coated on the photopolymerizable composition containing the compound of the present invention as a photopolymerization sensitizer, the degree of migration of the compound of the present invention to the coating film is extremely low. That is a useful compound.

(Compound)
The 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound of the present invention is a compound represented by the following general formula (1).

In the general formula (1), R represents a hydrogen atom, a methyl group or an ethyl group, A represents an alkyl group having 1 to 8 carbon atoms, a halogen atom, an alkoxy group having 1 to 8 carbon atoms, or 6 carbon atoms. It represents either an aryloxy group having 12 carbon atoms, an alkylthio group having 1 to 8 carbon atoms or an arylthio group having 6 to 12 carbon atoms.

In the general formula (1), the alkyl group having 1 to 8 carbon atoms represented by A includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and a t- group. Examples thereof include a butyl group, an n-pentyl group, an i-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group and a 2-ethylhexyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group and butoxy group. Examples of the aryloxy group having 6 to 12 carbon atoms include a phenoxy group and a naphthyloxy group. Examples of the alkylthio group having 1 to 8 carbon atoms include a methylthio group, an ethylthio group, a butylthio group and a 2-hydroxyethylthio group. Examples of the arylthio group having 6 to 12 carbon atoms include phenylthio group and naphthylthio group.

Specific examples of the 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound represented by the general formula (1) of the present invention include 2-methyl-9,10-bis (2-hydroxyethoxy). Anthracene, 2-ethyl-9,10-bis (2-hydroxyethoxy) anthracene, 2- (t-butyl) -9,10-bis (2-hydroxyethoxy) anthracene, 2- (4-methyl-3-pentenyl) ) -9,10-Bis (2-hydroxyethoxy) anthracene, 2-fluoro-9,10-bis (2-hydroxyethoxy) anthracene, 2-chloro-9,10-bis (2-hydroxyethoxy) anthracene, 2 -Bromo-9,10-bis (2-hydroxyethoxy) anthracene, 2-methoxy-9,10-bis (2-hydroxyethoxy) anthracene, 2-ethoxy-9,10-bis (2-hydroxyethoxy) anthracene, 2-Butoxy-9,10-bis (2-hydroxyethoxy) anthracene, 2-phenoxy-9,10-bis (2-hydroxyethoxy) anthracene, 2-methylthio-9,10-bis (2-hydroxyethoxy) anthracene , 2-ethylthio-9,10-bis (2-hydroxyethoxy) anthracene, 2-butylthio-9,10-bis (2-hydroxyethoxy) anthracene, 2- (2-hydroxyethylthio) -9,10-bis (2-hydroxyethoxy) anthracene, 2-phenylthio-9,10-bis (2-hydroxyethoxy) anthracene, 2-methyl-9,10-bis (2-hydroxypropoxy) anthracene, 2-ethyl-9,10-. Bis (2-hydroxypropoxy) anthracene, 2- (t-butyl) -9,10-bis (2-hydroxypropoxy) anthracene, 2- (4-methyl-3-pentenyl) -9,10-bis (2- Hydroxypropoxy) anthracene, 2-fluoro-9,10-bis (2-hydroxypropoxy) anthracene, 2-chloro-9,10-bis (2-hydroxypropoxy) anthracene, 2-bromo-9,10-bis (2 -Hydroxypropoxy) anthracene, 2-methoxy-9,10-bis (2-hydroxypropoxy) anthracene, 2-propoxy 9,10-bis (2-hydroxypropoxy) anthracene, 2-butoxy-9,10-bis (2 -Hydroxypropoxy) anthracene, 2-phenoxy-9,1 0-bis (2-hydroxypropoxy) anthracene, 2-methylthio-9,10-bis (2-hydroxypropoxy) anthracene, 2-ethylthio-9,10-bis (2-hydroxypropoxy) anthracene, 2-butylthio-9 , 10-bis (2-hydroxypropoxy) anthracene, 2- (2-hydroxyethylthio) -9,10-bis (2-hydroxypropoxy) anthracene, 2-phenylthio-9,10-bis (2-hydroxypropoxy) Anthracene, 2-methyl-9,10-bis (2-hydroxybutoxy) anthracene, 2-ethyl-9,10-bis (2-hydroxybutoxy) anthracene, 2- (t-butyl) -9,10-bis ( 2-hydroxybutoxy) anthracene, 2- (4-methyl-3-pentenyl) -9,10-bis (2-hydroxybutoxy) anthracene, 2-fluoro-9,10-bis (2-hydroxybutoxy) anthracene, 2 -Chloro-9,10-bis (2-hydroxybutoxy) anthracene, 2-bromo-9,10-bis (2-hydroxybutoxy) anthracene, 2-methoxy-9,10-bis (2-hydroxybutoxy) anthracene, 2-butoxy9,10-bis (2-hydroxybutoxy) anthracene, 2-butoxy-9,10-bis (2-hydroxybutoxy) anthracene, 2-phenoxy-9,10-bis (2-hydroxybutoxy) anthracene, 2-Methylthio-9,10-bis (2-hydroxybutoxy) anthracene, 2-ethylthio-9,10-bis (2-hydroxybutoxy) anthracene, 2-butylthio-9,10-bis (2-hydroxybutoxy) anthracene , 2- (2-hydroxyethylthio) -9,10-bis (2-hydroxybutoxy) anthracene, 2-phenylthio-9,10-bis (2-hydroxybutoxy) anthracene and the like.

Among these exemplified compounds, 2-methyl-9,10-bis (2-hydroxy) shown below is easy to produce, has a large effect as a photopolymerization sensitizer, and has a high solubility in a monomer. Propoxy) anthracene (Compound A), 2-ethyl-9,10-bis (2-hydroxypropoxy) anthracene (Compound B), 2- (t-butyl) -9,10-bis (2-hydroxypropoxy) anthracene ( Compound C), 2-methyl-9,10-bis (2-hydroxybutoxy) anthracene (Compound D) and 2-ethyl-9,10-bis (2-hydroxybutoxy) anthracene (Compound E) are preferred. 2-Ethyl-9,10-bis (2-hydroxypropoxy) anthracene (Compound B) and 2-ethyl-9,10-bis (2-hydroxybutoxy) anthracene (Compound E) are particularly preferred because of their high solubility.

(Production method)
Next, a method for producing the 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound of the present invention will be described. The 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound of the present invention reduces a 2-substituted-9,10-anthraquinone compound represented by the general formula (2), and then a hydroxyetherifying agent. It can be synthesized by reacting with.

Specifically, the 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound of the present invention is synthesized as follows. That is, the corresponding 2-substituted-9,10-anthraquinone compound is reduced in a solvent (first reaction), and then the obtained 2-substituted-9,10-dihydroxyanthracene compound is added in the presence or absence of a base compound. , Hydroxyetherified (second reaction).

In the first reaction, A is an alkyl group having 1 to 8 carbon atoms, a halogen atom, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an alkylthio group having 1 to 8 carbon atoms or 6 carbon atoms. 1 to 12 of arylthio groups.

In the second reaction, R represents a hydrogen atom, a methyl group or an ethyl group, A represents an alkyl group having 1 to 8 carbon atoms, a halogen atom, an alkoxy group having 1 to 8 carbon atoms, or an alkyl group having 6 to 12 carbon atoms. It represents either an aryloxy group, an alkylthio group having 1 to 8 carbon atoms or an arylthio group having 6 to 12 carbon atoms.

In the 2-substituted-9,10-anthraquinone compound represented by the general formula (2), which is used as a raw material in the first reaction, A is an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a carbon atom having 1 to 8 carbon atoms. It represents an alkoxy group, an aryloxy group having 6 to 12 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, or an arylthio group having 6 to 12 carbon atoms.

Examples of the alkyl group having 1 to 8 carbon atoms represented by A in the general formula (2) include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, n- Examples thereof include a pentyl group, n-hexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the aryloxy group having 6 to 12 carbon atoms include a phenoxy group and a naphthyloxy group. Examples of the alkylthio group having 1 to 8 carbon atoms include methylthio group, ethylthio group, propylthio group, butylthio group and 2-hydroxyethylthio group. Examples of the arylthio group having 6 to 12 carbon atoms include phenylthio group and naphthylthio group.

Specific examples of the 2-substituted-9,10-anthraquinone compound represented by the general formula (2) include 2-methyl-9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, and 2- (n. -Propyl) -9,10-anthraquinone, 2- (i-propyl) -9,10-anthraquinone, 2- (n-butyl) -9,10-anthraquinone, 2- (i-butyl) -9,10- Anthraquinone, 2- (n-pentyl) -9,10-anthraquinone, 2- (n-hexyl) -9,10-anthraquinone, 2- (n-heptyl) -9,10-anthraquinone, 2- (n-octyl) ) -9,10-Anthraquinone, 2- (2-ethylhexyl) -9,10-anthraquinone, 2-fluoro-9,10-anthraquinone, 2-chloro-9,10-anthraquinone, 2-bromo-9,10-. Anthraquinone, 2-methoxy-9,10-anthraquinone, 2-ethoxy-9,10-anthraquinone, 2-butoxy-9,10-anthraquinone, 2-phenoxy-9,10-anthraquinone, 2-methylthio-9,10-. Examples thereof include anthraquinone, 2-ethylthio-9,10-anthraquinone, 2-butylthio-9,10-anthraquinone, 2- (2-hydroxyethylthio) -9,10-anthraquinone and 2-phenylthio-9,10-anthraquinone. Be done.

The reducing agent used in the first reaction is not particularly limited as long as it can reduce a ketone group, and sodium borohydride, lithium aluminum hydride, sodium dithionite, thiourea peroxide, etc. are used. These reducing agents are added in an amount of 2 mol times or more with respect to the 2-substituted-9,10-anthraquinone compound. Usually, it is 2 to 4 times by mole.

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

The reaction temperature for the reduction reaction of the 2-substituted-9,10-anthraquinone compound in the first reaction is usually 0 ° C or higher and 120 ° C or lower. More preferably, it is 40 ° C. or higher and 80 ° C. or lower. If it is 0 ° C. or lower, the reaction is slow, and if it is 120 ° C. or higher, side reactions are likely to occur and the purity of the product is lowered. The reaction is completed in 0.5 to 3 hours, usually 1 hour. The obtained 2-substituted-9,10-dihydroxyanthracene compound can be used for the next hydroxyetherification reaction without usually isolating.

In the first reaction, catalytic hydrogen reduction using a noble metal as a catalyst is also possible. Examples of the noble metal catalyst that can be used include palladium-supported activated carbon, palladium-supported alumina, and platinum-supported activated carbon. Particularly, 5% palladium / carbon is preferably used. The amount of the noble metal catalyst added to the 2-substituted-9,10-anthraquinone compound is usually 0.01% or more and 5% or less, more preferably 0.2% or more and 2% or less. If the addition amount of the catalyst is less than 0.01%, the hydrogenation rate is slow, and if it is added over 5%, hydrogenation of the aromatic ring occurs concurrently by a side reaction, which is not preferable. Ruthenium catalysts, which have been developed in recent years, are also useful.

The reduction reaction is usually performed in a solvent. Examples of the solvent used include alcohol solvents such as methanol and ethanol, ketone solvents such as acetone and methyl ethyl ketone, and ether solvents such as tetrahydrofuran and 1,4-dioxane. The concentration of 2-substituted-9,10-anthraquinone in the solvent depends on the solubility in the solvent, but is usually about 5% to 20%. The pressure of hydrogen is usually about 1 Pa to 10 Pa. The reaction time is about 1 to 3 hours. After completion of hydrogen reduction, the catalyst is removed by filtration, and the filtrate is subjected to the next hydroxyetherification reaction.

As the hydroxyetherifying agent used in the second reaction, alkylene oxide, haloalkanol or the like is used. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide and the like. Examples of the haloalkanol include chloroalkanol and bromoalkanol, examples of the chloroalkanol include 1-chlorobutanol and 1-chloropropanol, and examples of the bromoalkanol include 2-bromoethanol and 3-bromopropanol. -Bromobutanol and the like.

In the second reaction, the addition ratio of the hydroxyetherifying agent to the 2-substituted-9,10-dihydroxyanthracene compound is 2.0 mol times or more and 30 mol times or less, preferably 3 mol times or more and 25 mol times or less. If it is less than 2.0 mol times, the 2-substituted-9,10-dihydroxyanthracene compound remains unreacted, and if added in excess of 30 mol times, the 2-substituted-9,10-bis (2-hydroxy) formed. The solubility of the alkoxy) anthracene compound in the reaction solution becomes high, and 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, an inorganic alkali salt is usually used. As the inorganic alkali salt, for example, sodium hydroxide, potassium hydroxide or lithium hydroxide is used. It is also possible to use organic bases such as pyridine, piperidine, trimethylamine and triethylamine.

The hydroxyetherification temperature is 0 ° C. or higher and 150 ° C. or lower, preferably room temperature or higher and 80 ° C. or lower. If the temperature is lower than 0 ° C, the reaction rate is too slow and the reaction takes too long, and if the temperature is higher than 150 ° C, a side reaction occurs to lower the purity of the product. The reaction time is usually about 0.5 to 24 hours. As the reaction proceeds, crystals of the product precipitate, and the precipitate is filtered and dried to give the 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound as yellow crystals.

(Photopolymerization sensitizer)
The 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound represented by the general formula (1) of the present invention thus obtained is a cationic photopolymerizable compound or a photoradical polymerizable compound. When the photopolymerizable compound (1) is polymerized in the presence of a photopolymerization initiator, it can be used as a photocationic polymerization sensitizer or a photoradical polymerization sensitizer.

Further, the photopolymerization sensitizer containing the 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound represented by the general formula (1) of the present invention is a 2-substituted-9,10-bis. (2-Hydroxyalkoxy) anthracene compound is used as an active ingredient, and the total amount thereof is 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound, and the effect of the present invention is not impaired. As long as it contains a photopolymerization sensitizer other than the 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound.

As a photopolymerization sensitizer other than such a 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound, a thioxanthone compound (for example, 2-isopropylthioxanthone, 2,4-diethylthioxanthone), a naphthalene compound ( For example, 1,4-diethoxynaphthalene, 1,4-dimethoxynaphthalene, 1,4-dihydroxynaphthalene, 4-methoxy-1-naphthol), an amine compound (for example, methyl diethylaminobenzoate) and the like can be mentioned.

The addition ratio of the photopolymerization sensitizer other than the 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound to the 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound is not particularly limited. Is 0.1 to 10 times by weight of the 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound.

(Photopolymerization initiator)
As the photopolymerization initiator, onium salts, benzylmethyl ketal-based, α-hydroxyalkylphenone-based polymerization initiators and the like are preferable. As the onium salt, an iodonium salt or a sulfonium salt is usually used. As the iodonium salt, 4-isobutylphenyl-4'-methylphenyliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexamethoxyantimonate, 4-isopropylphenyl-4'-methylphenyliodonium tetrakispentamethoxyphenylborate, 4- Examples include isopropylphenyl-4′-methylphenyliodonium tetrakispentafluorophenylborate, and the like. For example, IRGACURE 250 manufactured by BASF Corporation (IRGACURE is a registered trademark of BASF Corporation), manufactured by Rhodia Corporation. Rhodesill 2074 (Rhodesill is a registered trademark of Rhodia), IK-1 manufactured by San-Apro, etc. can be used. On the other hand, as the sulfonium salt, S, S, S ', S'-tetraphenyl-S, S'-(4,4'-thiodiphenyl) disulfonium bishexamethoxyphosphate, diphenyl-4-phenylthiophenylsulfonium hexanium Methoxyphosphate, triphenylsulfonium hexamethoxyphosphate and the like can be mentioned. For example, use of Daicel CPI-100P, CPI101P, CPI-200K, BAS Irgacure 270, Dow Chemical UVI6992, etc. You can These photopolymerization initiators may be used alone or in combination of two or more kinds.

Further, radical polymerization initiators such as benzyl methyl ketal-based and α-hydroxyalkylphenone-based polymerization initiators can be mentioned.

Specific examples of the compound include 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name “Irgacure 651” manufactured by BSF Corporation) as a benzylmethyl ketal-based radical polymerization initiator. , 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name "Darocur 1173" manufactured by BSF Corporation) as an α-hydroxyalkylphenone radical polymerization initiator, 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 (Brand name "Irgacure 2959" BSF) Company), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methyl-1-one (trade name "Irgacure 127" manufactured by BSF Corporation). ) Is mentioned.

In particular, 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name "Irgacure 651" manufactured by BSF Corporation), 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 BSF Corporation), 1-hydroxycyclohexyl phenyl ketone (trade name "Irgacure 184" manufactured by BSF Corporation), which is an agent. 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.

Among the photopolymerization initiators exemplified, onium salts are particularly preferable. The 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound of the present invention is characterized by having a photopolymerization sensitizing effect not only for iodonium salts but also for sulfonium salts as onium salts. Is one.

The amount of the photopolymerization sensitizer containing the 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound represented by the general formula (1) of the present invention to the photopolymerization initiator is not particularly limited. However, it is usually 5% by weight or more and 100% by weight or less, preferably 10% by weight or more and 50% by weight or less with respect to the photopolymerization initiator. 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 it is used in excess of 100% by weight, an effect commensurate with the addition is obtained. Absent.

(Photopolymerization initiator composition)
The photopolymerization sensitizer containing the 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound represented by the general formula (1) of the present invention may be directly added to the photopolymerizable compound. However, it is also possible to prepare the photopolymerization initiator composition by previously mixing it with the photopolymerization initiator and then add it to the photopolymerizable compound. That is, the photopolymerization initiator composition of the present invention is a photopolymerization sensitizer containing at least a 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound represented by the general formula (1). A composition containing a photopolymerization initiator.

(Photopolymerizable composition)
Further, the photopolymerizable composition can be prepared by blending the photopolymerization initiator composition and the photopolymerizable compound. The photopolymerizable composition of the present invention comprises a photopolymerization sensitizer containing the 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound represented by the general formula (1) of the present invention, A composition containing a photopolymerization initiator composition containing a polymerization initiator and a photoradical polymerizable compound or a photocationic polymerizable compound. The photopolymerization sensitizer containing the 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound represented by the general formula (1) of the present invention and the photopolymerization initiator are separately photoradically polymerized. A photopolymerization initiator composition may be formed in the photoradical-polymerizable compound or the photocationic-polymerizable compound as a result of being added to the photopolymerizable compound or the photocationic-polymerizable compound.

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-radical-polymerizable compounds, acrylic acid ester and methacrylic acid ester (hereinafter, both are collectively referred to as (meth) acrylic acid ester) in terms of film forming ability and high solubility of the compound of the present invention. ) Is preferred. Examples of the (meth) acrylic acid ester include methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, methyl methacrylate, butyl methacrylate and methacrylic acid. Examples thereof include cyclohexyl acid, 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.

Examples of the cationic photopolymerizable compound include epoxy compounds and vinyl ether. Typical epoxy compounds include alicyclic epoxy compounds, epoxy-modified silicones, aromatic glycidyl ethers, and the like. Among these cationic photopolymerizable compounds, alicyclic epoxy compounds and epoxy-modified silicones are preferable from the viewpoint of film forming ability and the high solubility of the compound of the present invention. An alicyclic epoxy compound is particularly preferable. 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., UVR6110 or the like can be used. Examples of the epoxy-modified silicone include UV-9300 manufactured by Toshiba GE Silicone. Examples of the aromatic glycidyl compound include 2,2'-bis (4-glycidyloxyphenyl) propane. Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and 2-ethylhexyl vinyl ether. These cationic 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% by weight or more and 10% by weight or less, preferably 0.025% by weight, based on the photopolymerizable composition. It is above 5% by weight. If it is less than 0.005% by weight, it takes time to photopolymerize the photopolymerizable composition, while if it exceeds 10% by weight, the hardness of the photocured product obtained by photopolymerization is lowered, It is not preferable because it deteriorates the physical properties of the cured product.

The photopolymerizable composition of the present invention is a diluent, a colorant, an organic or inorganic filler, a leveling agent, a surfactant, a defoaming agent, a thickener, in a range that does not impair the effects of the present invention. You may mix | blend various resin additives, such as a flame retardant, antioxidant, a stabilizer, a lubricant, and a plasticizer.

(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 to be photocured, the photopolymerizable composition can be formed into a film and photocured, or can be formed into a lump and photocured. In the case of film-forming and photocuring, the liquid photopolymerizable composition is applied to a base material such as a polyester film by using a bar coater or the like so as to have a film thickness of 5 to 300 μm. On the other hand, it is also possible to apply a thinner or thicker film by spin coating or screen printing.

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

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

(Migration resistance judgment)
As a method for determining whether or not the photopolymerization sensitizer contained in the photopolymerization composition of the present invention migrates to a film or the like, a photopolymerization composition containing the photopolymerization sensitizer is used as a thin film. Make a product applied to the object, cover it with a polyethylene film and store it at a constant temperature (26 ° C) for a certain period of time, then peel off the polyethylene film and check whether the photopolymerization sensitizer is transferred to the polyethylene film The migration resistance was judged. The peeled polyethylene film was washed with acetone to wash the surface composition and then dried, and then the UV spectrum of the polyethylene film was measured to measure migration resistance by examining the increase in absorption intensity due to the photopolymerization sensitizer. did. An ultraviolet / visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV2200) was used for the measurement. In order to make a quantitative comparison with the compound of the comparative example, 9,10-dibutoxyanthracene, the obtained absorbance was converted into the absorbance value of 9,10-dibutoxyanthracene. In the conversion, the absorbance of the compound of the present invention and 9,10-dibutoxyanthracene at 260 nm was measured by an ultraviolet / visible spectrophotometer, and the molar absorption coefficient was calculated from the absorbance value and the molar concentration, and the ratio thereof was calculated. It was converted using.

The invention is illustrated by the following examples, which do not limit the scope of the invention. Also, all parts are parts by weight unless otherwise noted. The product was confirmed based on the measurement by the following equipment.

(1) Melting point: Melting point measuring device manufactured by Gelencamp, model MFB-595 (based on JIS K0064)
(2) Infrared (IR) spectrophotometer: manufactured by JASCO Corporation, model IR-810
(3) Nuclear magnetic resonance apparatus (NMR): Model GSX FT NMR Spectrometer manufactured by JEOL Ltd.

Synthesis Example 1 2-Methyl-9,10-bis (2-hydroxypropoxy) anthracene (Compound A)
In a 100 ml three-necked flask equipped with a thermometer and a condenser, 2.2 g (10 mmol) of 2-methylanthraquinone and 6.7 g (40 mmol) of thiourea dioxide were dispersed by adding 25 g of N, N-dimethylacetamide, and the mixture was white. A solution of 4.0 g (100 mmol) of sodium hydroxide in 20 g of water was added dropwise to the yellow dispersion slurry. The white-yellow slurry turned brown and became a red-black solution. After heating at 60 ° C. for 10 minutes, a solution of 5.8 g (100 mmol) of propylene oxide in 10 g of N, N-dimethylacetamide was added dropwise to the obtained dark reddish-brown solution. After stirring for one day, a light orange slurry resulted. Next, when the reaction solution was added dropwise to 100 ml of a 10% sulfuric acid aqueous solution, a yellow precipitate was generated. After suction filtration, washing with water, washing with toluene and drying, 1.85 g (5.47 mmol) of yellow powder of 2-methyl-9,10-bis (2-hydroxypropoxy) anthracene was obtained. The isolated yield based on the starting material 2-methyl-9,10-anthraquinone was 55 mol%.

(1) Melting point: 158-159 ° C
(2) IR (KBr, cm ^-1 ): 3340, 2965, 2920, 2870, 1630, 1361, 1337, 1059, 1000, 923, 818, 769, 683.
(3) ¹ H-MNR (400 MHz, CDCl ₃ ): δ1.35 (d, J = 8 Hz, 6H), 2.53 (s, 3H), 2.91 (bs, 2H), 3.96-4. 0.08 (m, 4H), 4.44-4.55 (m, 2H), 7.28 (d, J = 9Hz, 1H), 7.39-7.47 (m, 2H), 8.00 (S, 1H), 8.16 (d, J = 9Hz, 1H), 8.21-8.28 (m, 2H).

(Synthesis Example 2) 2-Ethyl-9,10-bis (2-hydroxypropoxy) anthracene (Compound B)
In a 100 ml three-necked flask equipped with a thermometer and a condenser, 4.72 g (20 mmol) of 2-ethylanthraquinone and 13.4 g (80 mmol) of thiourea dioxide were dispersed by adding 50 g of N, N-dimethylacetamide, and the mixture was white. A solution of 8.0 g (200 mmol) of sodium hydroxide in 40 g of water was added dropwise to the yellow dispersion slurry. The white-yellow slurry turned brown and became a red-black solution. After heating at 60 ° C. for 10 minutes, a solution of 11.6 g (200 mmol) of propylene oxide in 20 g of N, N-dimethylacetamide was added dropwise to the obtained dark reddish-brown solution. After stirring for one day, a light orange slurry resulted. Next, when the reaction solution was added dropwise to 200 ml of a 10% aqueous solution of sulfuric acid, a yellow starch syrup was precipitated. The supernatant was discarded and the bottom starch syrup was thoroughly washed with water to obtain 6.33 g (18 mmol) of an orange starch syrup of 2-ethyl-9,10-bis (2-hydroxypropoxy) anthracene. The isolated yield based on the starting material 2-ethyl-9,10-anthraquinone was 90 mol%.

(1) Melting point: room temperature syrup (2) IR (nujol, cm ⁻¹ ): 3375, 2965, 2935, 2880, 1630, 1397, 1348, 1320, 1059, 994, 924, 820, 766, 678, 623.
(3) ¹ H-MNR (400 MHz, CDCl ₃ ): δ1.27-1.41 (m, 9H), 2.96 (q, J = 8 Hz, 4H), 2.99 (bs, 2H), 4 0.000-4.10 (m, 4H), 4.44-4.55 (m, 2H), 7.32 (d, J = 9Hz, 1H), 7.39-7.48 (m, 2H) , 8.01 (s, 1H), 8.22 (d, J = 9 Hz, 1H), 8.21-8.30 (m, 2H).

(Synthesis Example 3) 2- (t-butyl) -9,10-bis (2-hydroxypropoxy) anthracene (Compound C)
In a 100 ml three-necked flask equipped with a thermometer and a condenser, 5.3 g (20 mmol) of 2- (t-butyl) anthraquinone and 13.4 g (80 mmol) of thiourea dioxide were dispersed by adding 50 g of N, N-dimethylacetamide. Then, a solution of 8.0 g (100 mmol) of sodium hydroxide in 40 g of water was added dropwise to the white-yellow dispersion slurry. The white-yellow slurry turned brown and became a red-black solution. After heating at 60 ° C. for 10 minutes, a solution of 29 g (500 mmol) of propylene oxide in 20 g of N, N-dimethylacetamide was added dropwise to the obtained dark reddish-colored solution. After stirring for one day, a light orange slurry resulted. Then, when the reaction solution was added dropwise to 200 ml of a 10% sulfuric acid aqueous solution, a yellow precipitate was generated. After suction filtration, washing with water, washing with toluene, and drying, 5.7 g (15 mmol) of yellow powder of 2- (t-butyl) -9,10-bis (2-hydroxypropoxy) anthracene was obtained. The isolation yield based on the raw material 2- (t-butyl) -9,10-anthraquinone was 75 mol%.

(1) Melting point: room temperature syrup (2) IR (nujol, cm ⁻¹ ): 3410, 2955, 2920, 2865, 1620, 1359, 1341, 1094, 1057, 994, 764, 729, 694, 640, 464.
(3) ¹ H-MNR (400 MHz, CDCl ₃ ): δ1.36 (d, J = 8 Hz, 3 H), 1.40 (d, J = 8 Hz, 3 H), 1.46 (s, 9 H), 3 .0 (bs, 2H), 4.12-4.21 (m, 4H), 4.45-4.53 (m, 2H), 7.16 (d, J = 9Hz, 1H), 7.25. (D, J = 9 Hz, 1H), 7.40-7.46 (m, 2H), 8.19-8.39 (m, 3H).

Synthesis Example 4 2-chloro-9,10-bis (2-hydroxypropoxy) anthracene thermometer, 4.8 g (20 mmol) of 2-chloroanthraquinone, 13 thiourea dioxide in a 100 ml three-necked flask equipped with a condenser. N, N-dimethylacetamide (50 g) was added and dispersed in an amount of 0.4 g (80 mmol), and a solution of sodium hydroxide (8.0 g, 100 mmol) in water (40 g) was added dropwise to the white-yellow dispersion slurry. The white-yellow slurry turned brown and became a red-black solution. After heating at 60 ° C. for 10 minutes, a solution of 29 g (500 mmol) of propylene oxide in 20 g of N, N-dimethylacetamide was added dropwise to the obtained dark reddish-colored solution. After stirring for one day, a light orange slurry resulted. Next, when the reaction solution was added dropwise to 300 ml of a 10% sulfuric acid aqueous solution, a yellow precipitate was generated. After suction filtration, washing with water, washing with toluene, and drying, 5.1 g (14.2 mmol) of yellow powder of 2-methyl-9,10-bis (2-hydroxypropoxy) anthracene was obtained. The isolated yield based on the starting material 2-chloroanthraquinone was 71 mol%.

(1) Melting point: 148-149 ° C
(2) IR (KBr, cm ^-1 ): 3260, 2950, 2920, 2860, 1615, 1361, 1336, 1288, 1145, 1075, 1054, 998, 953, 859, 818, 767, 702, 673, 631, 515,467.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ1.29-1.39 (m, 6H), 2.98 (bs, 2H), 3.94-4.04 (m, 4H), 4 .44-4.53 (m, 2H), 7.32 (d, J = 9Hz, 1H), 7.42-7.51 (m, 2H), 8.13-8.32 (m, 4H) ．

(Synthesis Example 5) 2-Methyl-9,10-bis (2-hydroxybutoxy) anthracene (Compound D)
In a 100 ml three-necked flask equipped with a thermometer and a condenser, 2.2 g (10 mmol) of 2-methylanthraquinone and 6.7 g (40 mmol) of thiourea dioxide were dispersed by adding 25 g of N, N-dimethylacetamide, and the mixture was white. A solution of 4.0 g (100 mmol) of sodium hydroxide in 20 g of water was added dropwise to the yellow dispersion slurry. The white-yellow slurry turned brown and became a red-black solution. After heating at 60 ° C. for 10 minutes, a solution of 7.2 g (100 mmol) of butylene oxide in 10 g of N, N-dimethylacetamide was added dropwise to the obtained dark reddish-brown solution. After stirring for one day, a light orange slurry resulted. Next, when the reaction solution was added dropwise to 100 ml of a 10% sulfuric acid aqueous solution, a yellow precipitate was generated. After suction filtration, washing with water, washing with toluene and drying, 1.65 g (4.5 mmol) of a yellow powder of 2-methyl-9,10-bis (2-hydroxybutoxy) anthracene was obtained. The isolation yield based on the starting material 2-methyl-9,10-anthraquinone was 45 mol%.

(1) Melting point: 141-142 ° C
(2) IR (KBr, cm ⁻¹ ): 3305, 2960, 2930, 2870, 1610, 1358, 1342, 1323, 1064, 1031, 1008, 963, 819, 766, 682, 622.
(3) ¹ H-MNR (400 MHz, CDCl ₃ ): δ1.09 (t, J = 8 Hz, 6H), 1.65-1.75 (m, 4H), 2.55 (s, 3H), 2 .83 (bs, 2H), 4.01-4.14 (m, 4H), 4.19-4.28 (m, 2H), 7.30 (d, J = 9Hz, 1H), 7.40. −7.47 (m, 2H), 8.00 (s, 1H), 8.20 (d, J = 9 Hz, 1H), 8.23-8.28 (m, 2H).

Synthesis Example 6 2-Ethyl-9,10-bis (2-hydroxybutoxy) anthracene (Compound E)
In a 100 ml three-necked flask equipped with a thermometer and a condenser, 4.72 g (20 mmol) of 2-ethylanthraquinone and 13.4 g (80 mmol) of thiourea dioxide were dispersed by adding 50 g of N, N-dimethylacetamide, and the mixture was white. A solution of 8.0 g (200 mmol) of sodium hydroxide in 50 g of water was added dropwise to the yellow dispersion slurry. The white-yellow slurry turned brown and became a red-black solution. After heating at 60 ° C for 10 minutes, a solution of 11.5 g (160 mmol) of butylene oxide in 20 g of N, N-dimethylacetamide was added dropwise to the obtained dark reddish-brown solution. After stirring for one day, a light orange slurry resulted. Next, when the reaction solution was added dropwise to 100 ml of a 10% aqueous solution of sulfuric acid, a pale yellow candy sank. The supernatant was discarded, the bottom starch syrup was thoroughly washed with water, and dried to obtain 5.8 g of a crude product of 2-ethyl-9,10-bis (2-hydroxybutoxy) anthracene. This product was recrystallized from toluene / hexane to obtain 3.8 g (10 mmol) of white-yellow powder of 2-ethyl-9,10-bis (2-hydroxybutoxy) anthracene. The isolated yield based on the starting material 2-ethyl-9,10-anthraquinone was 50 mol%.

(1) Melting point: 104-105 ° C
(2) IR (KBr, cm ^-1 ): 3380, 2960, 2930, 2870, 1627, 1455, 1396, 1343, 1317, 1063, 1032, 995, 974, 882821, 765, 729, 494.
(3) ¹ H-MNR (400 MHz, CDCl ₃ ): δ1.09 (t, J = 8 Hz, 6 H), 1.36 (t, J = 8 Hz, 3 H), 1.70 (q, J = 8 Hz, 4H), 2.85 (q, J = 8Hz, 2H), 4.10 (q, J = 8Hz, 4H), 4.18-4.28 (m, 2H), 3.7 (d, J =). 9 Hz, 1 H), 7.38-7.48 (m, 2 H), 8.06 (s, 1 H), 8.22 (d, J = 9 Hz, 1 H), 8.24-8.32 (m, 2H).

(Evaluation Example in Photo Cationic Polymerization)
(Evaluation Example Example 1)
As a photo-cationic polymerizable compound, 100 parts of alicyclic epoxy compound 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021P manufactured by Daicel Corp.) is added to isobutylphenyl (4-methylphenyl) iodonium. 2-Methyl-9,10 synthesized by the same method as in Example 1 was added to a uniform composition obtained by adding 2.7 parts of hexafluorophosphate (IRGACURE 250 manufactured by BSF). When 1 part of -bis (2-hydroxypropoxy) anthracene (Compound A) was added and the mixture was stirred, it was quickly dissolved and a liquid product of a very pale yellow photopolymerizable composition was obtained. The composition was applied onto a polyester film (Lumirror manufactured by Toray) using a bar coater so that the film thickness would be 18 μm. Then, the surface was irradiated with light using a UV LED manufactured by Thunder. The central wavelength of the irradiation light was 395 nm, and the irradiation intensity was 3 mW / cm ² . The light irradiation time "tack free time" until the tackiness disappeared was 22 seconds.

(Evaluation Example 2)
As a photo-cationic polymerizable compound, 100 parts of alicyclic epoxy compound 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021P manufactured by Daicel Corp.) is added to isobutylphenyl (4-methylphenyl) iodonium. 2-Ethyl-9,10-synthesized in the same manner as in Example 2 was added to the uniform composition obtained by adding 2.7 parts of hexafluorophosphate (IRGACURE 250 manufactured by BSF). When 1 part of bis (2-hydroxypropoxy) anthracene (Compound B) was added and stirred, it was rapidly dissolved within 1 minute, and a liquid material of a very light yellow photopolymerizable composition was obtained. The composition was applied onto a polyester film (Lumirror manufactured by Toray) using a bar coater so that the film thickness would be 18 μm. Then, the surface was irradiated with light using a UV LED manufactured by Thunder. The central wavelength of the irradiation light was 395 nm, and the irradiation intensity was 3 mW / cm ² . The light irradiation time “tack free time” until the tackiness disappeared was 23 seconds.

(Evaluation Example 3)
As a photo-cationic polymerizable compound, 100 parts of alicyclic epoxy compound 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021P manufactured by Daicel Corp.) is added to isobutylphenyl (4-methylphenyl) iodonium. 2- (t-butyl) -synthesized in the same manner as in Example 3 to a uniform composition obtained by adding 2.7 parts of hexafluorophosphate (IRGACURE 250 manufactured by BSF). When 1 part of 9,10-bis (2-hydroxypropoxy) anthracene (Compound C) was added and stirred, it was quickly dissolved in a few minutes to obtain a liquid product of a very light yellow photopolymerizable composition. The composition was applied onto a polyester film (Lumirror manufactured by Toray) using a bar coater so that the film thickness would be 18 μm. Then, the surface was irradiated with light using a UV LED manufactured by Thunder. The central wavelength of the irradiation light was 395 nm, and the irradiation intensity was 3 mW / cm ² . The light irradiation time “tack free time” until tackiness disappeared was 34 seconds.

(Evaluation Example 4)
As a photo-cationic polymerizable compound, 100 parts of alicyclic epoxy compound 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021P manufactured by Daicel Corp.) is added to isobutylphenyl (4-methylphenyl) iodonium. 2-Methyl-9,10-synthesized in the same manner as in Example 5 was added to a uniform composition obtained by adding 2.7 parts of hexafluorophosphate (IRGACURE 250 manufactured by BSF). When 1 part of bis (2-hydroxybutoxy) anthracene (Compound D) was added and stirred, it was quickly dissolved in a few minutes, and a liquid material of a very pale yellow photopolymerizable composition was obtained. The composition was applied onto a polyester film (Lumirror manufactured by Toray) using a bar coater so that the film thickness would be 18 μm. Then, the surface was irradiated with light using a UV LED manufactured by Thunder. The central wavelength of the irradiation light was 395 nm, and the irradiation intensity was 3 mW / cm ² . The light irradiation time “tack free time” until the tackiness disappeared was 26 seconds.

(Evaluation Example 5)
As a photo-cationic polymerizable compound, 100 parts of alicyclic epoxy compound 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021P manufactured by Daicel Corp.) is added to isobutylphenyl (4-methylphenyl) iodonium. 2-Ethyl-9,10-synthesized in the same manner as in Example 6 was added to a uniform composition obtained by adding 2.7 parts of hexafluorophosphate (IRGACURE 250 manufactured by BSF). When 1 part of bis (2-hydroxybutoxy) anthracene (Compound E) was added and stirred, it was quickly dissolved within 1 minute, and a liquid product of a very light yellow photopolymerizable composition was obtained. The composition was applied onto a polyester film (Lumirror manufactured by Toray) using a bar coater so that the film thickness would be 18 μm. Then, the surface was irradiated with light using a UV LED manufactured by Thunder. The central wavelength of the irradiation light was 395 nm, and the irradiation intensity was 3 mW / cm ² . The light irradiation time "tack free time" until the tackiness disappeared was 25 seconds.

(Evaluation Comparative Example 1)
As a cationic photopolymerizable compound, 100 parts of alicyclic epoxy compound 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021P manufactured by Daicel) is added to isobutylphenyl (4-methylphenyl) iodonium. A known composition of the photopolymerization sensitizer, 9,10-dibutoxyanthracene 1, was added to a uniform composition obtained by adding 2.7 parts of hexafluorophosphate (IRGACURE 250 manufactured by BSF). When 20 parts were added and stirred, 20 minutes were required for dissolution. The obtained liquid material of the extremely light yellow photopolymerizable composition was applied onto a polyester film (Lumirror manufactured by Toray Industries, Inc.) using a bar coater so that the film thickness would be 18 μm. Then, the surface was irradiated with light using a UV LED manufactured by Thunder. The central wavelength of the irradiation light was 395 nm, and the irradiation intensity was 3 mW / cm ² . The light irradiation time "tack free time" until the tackiness disappeared was 22 seconds.

(Evaluation Comparative Example 2)
A photopolymerizable composition was prepared in exactly the same manner as in Evaluation Example 1 except that 2-methyl-9,10-bis (2-hydroxypropoxy) anthracene was not added, and an ultraviolet LED (395 nm, irradiation intensity 3 mW / cm ^2). ) Was irradiated under the same conditions as in Evaluation Example 1 to determine the curing time, but it did not cure even after 300 seconds.

The results of (Evaluation Example 1) to (Evaluation Example 5) and (Evaluation Comparative Example 1) and (Evaluation Comparative Example 2) are summarized in Table 1.

(Evaluation Example in Photo-Radical Polymerization)
(Evaluation Example 6)
100 parts of pentaerythritol tetraacrylate (biscoat 400 manufactured by Osaka Organic Co., Ltd.) as a photo-radical polymerizable compound, and isobutylphenyl (4-methylphenyl) iodonium hexafluorophosphate (IRGACURE 250 manufactured by BSF Corporation) 2 1 part of 2-methyl-9,10-bis (2-hydroxypropoxy) anthracene (Compound A) synthesized in the same manner as in Synthesis Example 1 was added to the obtained homogeneous composition. When it was stirred, it was quickly dissolved, and a very pale yellow liquid of the photopolymerizable composition was obtained. The composition was applied onto a polyester film (Lumirror manufactured by Toray) using a bar coater so that the film thickness would be 30 μm. Thereafter, the composition was covered with a 50-micron-thick polyester film (Lumirror made by Toray) to block air, and then the surface was irradiated with light using an ultraviolet LED made by Thunder. The central wavelength of the irradiation light was 395 nm, and the irradiation intensity was 3 mW / cm ² . The light irradiation time "tack free time" until the tackiness disappeared was 6 seconds.

(Evaluation Example 7)
Photopolymerization in the same manner as in Evaluation Example 6 except that 2-methyl-9,10-bis (2-hydroxybutoxy) anthracene (Compound D) synthesized in the same manner as in Synthesis Example 5 was used as the photopolymerization sensitizer. A sex composition was prepared. The compound D of this example was also rapidly dissolved in pentaerythritol tetraacrylate, which is a photoradically polymerizable compound. This composition was applied to a polyester film (Lumirror manufactured by Toray) (film thickness 100 μm, Lumirror is a registered trademark of Toray Industries, Inc.) using a bar coater so that the film thickness would be 30 μm. After that, the composition was covered with a 30-micron-thick polyester film (Lumirror made by Toray) to block air, and then the surface was irradiated with light using an ultraviolet LED made by Thunder. The central wavelength of the irradiation light was 395 nm, and the irradiation intensity was 3 mW / cm ² . The light irradiation time "tack free time" until the tackiness disappeared was 6 seconds.

(Evaluation Comparative Example 3)
100 parts of pentaerythritol tetraacrylate (biscoat 400 manufactured by Osaka Organic Co., Ltd.) as a photo-radical polymerizable compound, and isobutylphenyl (4-methylphenyl) iodonium hexafluorophosphate (IRGACURE 250 manufactured by BSF Corporation) 2 1 part of 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer, was added to the uniform composition obtained by adding 0.7 part of the composition, and the mixture was stirred, and ultrasonic treatment for 30 minutes was required. The photopolymerizable composition thus obtained was irradiated with an ultraviolet LED (395 nm, irradiation intensity 3 mW / cm ² ) to determine the curing time, and the light irradiation time until tackiness disappeared "tack free time" Was 5 seconds.

(Evaluation Comparative Example 4)
A photopolymerizable composition was prepared in the same manner as in Evaluation Example 6 except that 2-methyl-9,10-bis (2-hydroxypropoxy) anthracene (Compound A) was not added as a photopolymerization sensitizer, and ultraviolet rays were used. An LED (395 nm, irradiation intensity 3 mW / cm ² ) was irradiated to determine the curing time, but it did not cure even after 100 seconds.

The results of (Evaluation Example 6) and (Evaluation Example 7) and (Evaluation Comparative Example 3) and (Evaluation Comparative Example 4) are summarized in Table 2.

From the results of the above-described evaluation examples and evaluation comparative examples, the following is clear. That is, from the evaluation examples 1 to 5 and the evaluation comparative examples 1 and 2, and Table 1 which summarizes the results, the 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound of the present invention was photosensitized. When it is photocationically polymerized as an agent, it exhibits an excellent photopolymerization sensitizing effect, and the results of the tack-free test show that it is almost equivalent to the known photopolymerization sensitizer 9,10-dibutoxyanthracene. It can be seen that it has a photopolymerization sensitizing ability. The 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound of the present invention rapidly dissolves in the alicyclic epoxy compound celoxide 2021P, which is a cationically polymerizable compound, while the known light It can be seen that the polymerization sensitizer 9,10-dibutoxyanthracene has a slow dissolution rate and requires a long time to dissolve.

Furthermore, from Table 2 which summarizes Evaluation Examples 6 and 7 and Evaluation Comparative Examples 3 and 4 and the results thereof, the 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound of the present invention was photosensitized. When it is photoradically polymerized as an agent, it exhibits an excellent photopolymerization sensitizing effect, and the results of the tack-free test show that it is almost the same as known photopolymerization sensitizer 9,10-dibutoxyanthracene. It can be seen that it has the same photopolymerization sensitizing ability. The 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound of the present invention rapidly dissolves in pentaerythritol tetraacrylate, which is a radical-polymerizable compound, whereas known photopolymerization sensitization It can be seen that 9,10-dibutoxyanthracene, which is an agent, has a slow dissolution rate and requires a long time for dissolution.

(Solubility measurement result for the polymerizable composition)
Solubility of a 2-substituted-9,10-bis (2-hydroxypropoxy) anthracene compound and a polymerizable compound of 9,10-bis (2-hydroxypropoxy) anthracene (unsubstituted compound) at room temperature (23 ° C) was measured. And shown in Table 3.

As is apparent from the solubility measurement results for the polymerizable compositions of Evaluation Examples 1 to 7 and Evaluation Comparative Examples 1 and 3, and Table 3, the 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracenes of the present invention are shown. The compound has a solubility of 2 g / 100 g or more in an alicyclic epoxy compound which is a photocationically polymerizable compound and an acrylic acid ester compound which is a photoradical polymerizable compound, and its dissolution rate is within several minutes. It can be seen that it has a practically no problem during the operation. The solubility and dissolution rate of this additive with respect to the polymerizable compound are important factors when preparing the polymerizable composition, and the 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound of the present invention is It can be seen that it is practically excellent as a polymerization sensitizer.

<Migration test in cationically polymerizable composition>
(Migration evaluation example 1)
Alicyclic epoxy compound 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Daicel Corp. Celoxide 2021P) 100 parts was synthesized as a photopolymerization sensitizer in the same manner as in Example 1. The composition prepared by mixing 2 parts of 2-methyl-9,10-bis (2-hydroxypropoxy) anthracene (Compound A) was coated on a polyester film with a bar coater to a film thickness of 18 microns. did. Then, a low-density polyethylene film (thickness 30 μm) was placed on the obtained coated product, and stored in a dark place for 1 day, 2 days, or 4 days. The film was peeled off, the polyethylene film was washed with acetone and dried, and then the UV spectrum of the film was measured to measure the absorbance at 260 nm. The absorbance of the obtained 2-methyl-9,10-bis (2-hydroxyethoxy) anthracene was converted to 9,10-dibutoxyanthracene. The absorbance was 0.011 after one day storage, 0.010 after two days storage, and 0.011 after four days storage.

(Migration evaluation example 2)
2-Ethyl-9,10-bis (2-hydroxypropoxy) anthracene synthesized in the same manner as in Example 2 instead of 2-methyl-9,10-bis (2-hydroxypropoxy) anthracene as the photopolymerization sensitizer. A test was performed in the same manner as in Migration Evaluation Example 1 except that (Compound B) was used. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, a value obtained by converting the absorbance of 2-ethyl-9,10-bis (2-hydroxypropoxy) anthracene into 9,10-dibutoxyanthracene was 0 after storage for one day. It was 0.018 after storage for 2 days and 0.014 after storage for 4 days.

(Migration evaluation example 3)
As a photopolymerization sensitizer, 2-methyl-9,10-bis (2-hydroxypropoxy) anthracene was replaced with 2-methyl-9,10-bis (2-hydroxybutoxy) anthracene synthesized in the same manner as in Example 5. A test was performed in the same manner as in Migration Evaluation Example 1 except that (Compound D) was used. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the value obtained by converting the absorbance of 2-methyl-9,10-bis (2-hydroxybutoxy) anthracene into 9,10-dibutoxyanthracene was 0 after storage for one day. It was 0.010, 0.008 after two days of storage, and 0.011 after four days of storage.

(Migration comparison example 1)
Tested as in Migration Example 1 except that 9,10-dibutoxyanthracene (DBA) was used instead of 92-methyl-9,10-bis (2-hydroxyethoxy) anthracene as the photopolymerization sensitizer. did. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance of 9,10-dibutoxyanthracene was 1.51 after one day storage, 1.41 after two days storage, and 1.50 after four days storage. It was

Table 4 shows the results of migration evaluation examples 1 to 4 and migration comparative example 1.

From the results of migration evaluation examples 1 to 3 and migration comparison example 1 described above, the following is clear. That is, as can be seen from Table 4, the photopolymerization sensitizer of the present invention contained in the photocationic polymerizable composition has a very low degree of migration to the polyethylene film and a high migration resistance. On the other hand, a well-known photopolymerization sensitizer, 9,10-dibutoxyanthracene, was observed to have high transferability to a polyethylene film in the same test.

<Migration test for radically polymerizable composition>
(Migration evaluation example 4)
Radical Polymerizable Compound 2-Methyl-9,10-bis (2-hydroxypropoxy) anthracene (Compound A) synthesized as a photopolymerization sensitizer in the same manner as in Example 1 with respect to 100 parts of trimethylolpropane triacrylate. One part was mixed, and the prepared composition was applied on a polyester film using a bar coater so that the film thickness would be 30 microns. Then, a low-density polyethylene film (thickness 30 μm) was placed on the obtained coated product, and stored in a dark place for 1 day, 2 days, or 4 days. The film was peeled off, the polyethylene film was washed with acetone and dried, and then the UV spectrum of the film was measured to measure the absorbance at 260 nm. The absorbance of the obtained 2-methyl-9,10-bis (2-hydroxypropoxy) anthracene was converted to 9,10-dibutoxyanthracene. The absorbance was 0.010 after one day storage, 0.011 after two days storage, and 0.011 after four days storage.

(Migration evaluation example 5)
2-Methyl-9,10-bis (2-hydroxypropoxy) anthracene as a photopolymerization sensitizer was synthesized in the same manner as in Example 4 in place of 2-methyl-9,10-bis (2-hydroxybutoxy) anthracene. A test was conducted in the same manner as in Migration Evaluation Example 4 except that (Compound D) was used. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the value obtained by converting the absorbance of 2-methyl-9,10-bis (2-hydroxybutoxy) anthracene into 9,10-dibutoxyanthracene was 0 after storage for one day. It was 0.018 after storage for 2 days and 0.014 after storage for 4 days.

(Migration comparison example 2)
Instead of 2-methyl-9,10-bis (2-hydroxypropoxy) anthracene as a photopolymerization sensitizer, 9,10-dibutoxyanthracene (Compound H) was added to trimethylolpropanone and sonicated for 30 minutes. To obtain a uniform liquid material, and then the prepared composition was applied onto a polyester film using a bar coater so that the film thickness was 30 μm. Then, a low-density polyethylene film (thickness 30 μm) was placed on the obtained coated product, and stored in a dark place for 1 day, 2 days, or 4 days. The film was peeled off, the polyethylene film was washed with acetone and dried, and then the UV spectrum of the film was measured to measure the absorbance at 260 nm. The absorbance of 9,10-dibutoxyanthracene was 0.68 after one day storage, 0.74 after two days storage, and 0.74 after four days storage.

Table 5 shows the results of migration evaluation examples 4 and 5 and migration comparative example 2.

From the results of migration evaluation examples 4 and 5 and migration comparison example 2 described above, the following is clear. That is, as can be seen from Table 5, the photopolymerization sensitizer of the present invention contained in the photoradical polymerizable composition has a very low degree of migration to the polyethylene film and a high migration resistance. On the other hand, a well-known photopolymerization sensitizer, 9,10-dibutoxyanthracene, was observed to have high transferability to a polyethylene film in the same test.

From the above results, the 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound of the present invention is a known photopolymerization sensitizer in photocationic polymerization and photoradical polymerization. Curing of a photopolymerizable composition containing not only the same photopolymerization sensitizing ability as the butoxyanthracene compound but also excellent solubility in a polymerizable compound and containing the photopolymerization sensitizer It is found that the compound is an excellent compound having high migration resistance and is extremely useful as a photopolymerization sensitizer.

Claims (5)

A photoradical polymerization sensitizer containing a 2-substituted-9,10-bis (2-hydroxyalkoxy) anthracene compound represented by the following general formula (1).
(In the general formula (1), R represents a hydrogen atom, a methyl group or an ethyl group, A represents an alkyl group having 1 to 8 carbon atoms, a halogen atom, an alkoxy group having 1 to 8 carbon atoms, or 6 carbon atoms. Represents an aryloxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, or an arylthio group having 6 to 12 carbon atoms.) The photoradical polymerization sensitizer according to claim 1, wherein R in the general formula (1) is a methyl group or an ethyl group. A photoradical polymerization initiator composition containing the photoradical polymerization sensitizer according to claim 1 or 2 , and a photoradical polymerization initiator. Radical photopolymerizable composition containing a photo-radical polymerization initiator composition, and a photo-radical polymerizable compound according to claim 3. A method for curing, comprising irradiating the photoradical polymerizable composition according to claim 4 with an energy ray containing light having a wavelength of 250 nm to 500 nm.