JP2014159412A - 9,10-bis(long chain acyloxy)anthracene compound, production method thereof and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photo-cationic polymerization sensitizer which can sensitize an iodonium salt or a sulfonium salt, a photo-cationic polymerization initiator, in a photo-cationic polymerization and which a cured product of a photo-cationically polymerizable composition with high transmittance.SOLUTION: A photo-cationic polymerization sensitizer contains a 9,10-bis(long chain acyloxy)anthracene compound represented by formula (1) which ic obtained by acylation of a compound of formula (2). (In reaction formula 1, R represents a 5-12C alkyl group; and X and Y may be the same or different and represents a hydrogen atom or a 1-8C alkyl group).

Description

The present invention relates to a 9,10-bis (long-chain acyloxy) anthracene compound useful as a photocationic polymerization sensitizer, its use, and a production method thereof.

Photocationic polymerizable compositions that are polymerized by light such as ultraviolet rays are widely used in various applications. The photocationically polymerizable composition includes a radical polymerization type and a cationic polymerization type. As a radical polymerization type, a compound having an unsaturated double bond such as a compound having a (meth) acryloyl group or an unsaturated polyester compound is known. As a cationic polymerization type, a compound having an epoxy group, vinyl ether A compound having a group is known. These compounds are used together with a suitable photopolymerization initiator and, if necessary, a photopolymerization sensitizer. In general, the radical polymerization type has characteristics that the polymerization rate is high and the hardness of the coating film to be formed is high, but there are drawbacks in that the adhesion to the substrate is weak. In addition, it is easily affected by oxygen, and particularly in forming a thin film, a facility such as nitrogen sealing is required. On the other hand, the cationic polymerization type is characterized by high adhesion to the substrate, excellent flexibility, and is hardly affected by oxygen. Therefore, a photocationically polymerizable composition is used in the field of electronic materials.

For this photocationic polymerization, a photocationic polymerization initiator is usually used. As the photocationic polymerization initiator, onium salts are known, and aryliodonium salts and arylsulfonium salts are particularly used. This cationic photopolymerization initiator is a compound that absorbs light such as ultraviolet rays and excites it, and decomposes its excited species to generate an acid.

However, since the absorption wavelength of aryliodonium salt is as low as around 250 nm and it cannot be sufficiently excited by ultraviolet rays such as a high-pressure mercury lamp, when it is polymerized with a high-pressure mercury lamp or the like, the irradiation wavelength of the high-pressure mercury lamp or the like is 360. It is necessary to add 9,10-dialkoxyanthracene having absorption in the vicinity of ˜400 nm as a photocationic polymerization sensitizer (Patent Documents 1, 2, and 3).

On the other hand, the arylsulfonium salt has an absorption around 366 nm which is the wavelength of light of a high pressure mercury lamp or the like, so that it can generate an acid by irradiating the high pressure mercury lamp or the like and polymerize a photocationically polymerizable compound. . Therefore, the necessity of a photocationic polymerization sensitizer has not been felt.

However, in recent years, an ultraviolet LED having a wavelength longer than 366 nm has been developed, and since this LED generates little heat and has a long life, there is a tendency to gradually use this ultraviolet LED as a light source. In this case, since neither iodonium salt nor sulfonium salt can be excited alone, a photocationic polymerization sensitizer such as 9,10-dialkoxyanthracene must be used.

JP-A-10-147608 JP 2001-348497 A Special Table 2000-515182

However, when the 9,10-dialkoxyanthracene compound described above is used as a sensitizer and photocured, the transparency of the film is low and there is a problem in transparency in the thick film field. That is, an object of the present invention is an anthracene which is useful as a photocationic polymerization sensitizer and has a high transparency of a cured product obtained by polymerizing a photocationic polymerizable composition containing the photocationic polymerization sensitizer. It is to provide a compound.

  As a result of intensive studies on the structure and light absorption characteristics of the anthracene compound, the present inventors have found that the 9,10-bis (long-chain acyloxy) anthracene compound has excellent photocationic sensitization performance and the photocationic polymerization sensitizer. As a result, the present inventors have found that the cured product of the photocationically polymerizable composition containing a polymer has a high transmittance.

  That is, the gist of the present invention is the gist of the following.

(Invention 1) A 9,10-bis (long-chain acyloxy) anthracene compound represented by the general formula (1) is provided.

In General formula (1), R shows a C5-C12 alkyl group, X and Y may be the same or different, and show a hydrogen atom or a C1-C8 alkyl group.

(Invention 2) A process for producing a 9,10-bis (long-chain acyloxy) anthracene compound according to Invention 1, characterized by acylating the 9,10-dihydroxyanthracene compound represented by the general formula (2) To do.

In the general formula (2), X and Y may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

(Invention 3) A photocationic polymerization sensitizer containing the 9,10-bis (long-chain acyloxy) anthracene compound described in Invention 1 is provided.

(Invention 4) A cationic photopolymerizable composition comprising the cationic photopolymerization sensitizer, the cationic photopolymerization initiator and the cationic photopolymerizable compound according to Invention 3 is provided.

(Invention 5) The cationic photopolymerizable composition according to Invention 4, wherein the cationic photopolymerization initiator is an aryl iodonium salt or an aryl sulfonium salt.

(Invention 6) Provided is a method for curing a cationic photopolymerizable composition, which comprises irradiating the cationic photopolymerizable composition according to Invention 4 or Invention 5 with an energy ray containing light having a wavelength range of 350 nm to 420 nm. .

  The 9,10-bis (long-chain acyloxy) anthracene compound of the present invention can be easily obtained industrially by acylating the 9,10-dihydroxyanthracene compound, and is useful as a sensitizer for photocationic polymerization. In addition, a photocationically polymerizable composition containing a 9,10-bis (long chain acyloxy) anthracene compound as a photocationic polymerization sensitizer and a cured product obtained by photocuring it are colorless and transparent.

It is the graph which plotted the transmittance | permeability in 400 nm measured every predetermined time in Example 9, 10 and Comparative Example 5. FIG. 9,10-bis (2-ethylhexanoyloxy) anthracene, 9,10-bis (n-nonanoyloxy) anthracene, which is a photocationic polymerization sensitizer of the present invention, and 9, which is a known photocationic polymerization sensitizer, It is the figure which compared the transparency of the hardened | cured material of the photocationic polymerizable composition when 10-dibutoxyanthracene was used.

The 9,10-bis (long-chain acyloxy) anthracene compound of the present invention is a compound having the structure described in the general formula (1).

In General formula (1), R shows a C5-C12 alkyl group, X and Y may be same or different, and show a hydrogen atom or a C1-C8 alkyl group.

In the general formula (1), the alkyl group having 5 to 12 carbon atoms represented by R includes an n-pentyl group, i-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 1- An ethylpentyl group, n-nonyl group, n-decyl group, n-dodecyl group, etc. are mentioned.

In general formula (1), the alkyl group having 1 to 8 carbon atoms represented by X and Y includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an n-pentyl group, Examples include n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and the like.

Examples of the 9,10-bis (long chain acyloxy) anthracene compound represented by the general formula (1) include the following compounds.

That is, when both X and Y are hydrogen atoms, 9,10-bis (n-pentanoyloxy) anthracene, 9,10-bis (n-hexanoyloxy) anthracene, 9,10-bis (n- Heptanoyloxy) anthracene, 9,10-bis (n-octanoyloxy) anthracene, 9,10-bis (2-ethylhexanoyloxy) anthracene, 9,10-bis (n-nonanoyloxy) anthracene, 9,10 -Bis (n-decanoyloxy) anthracene, 9,10-bis (n-dodecanoyloxy) anthracene and the like can be mentioned.

Examples of the case where X is an alkyl group and Y is a hydrogen atom include 1-methyl-9,10-bis (n-hexanoyloxy) anthracene, 1-methyl-9,10-bis (n-hepta). Noyloxy) anthracene, 1-methyl-9,10-bis (n-octanoyloxy) anthracene, 1-methyl-9,10-bis (2-ethylhexanoyloxy) anthracene, 1-methyl-9,10- Bis (n-nonanoyloxy) anthracene, 1-methyl-9,10-bis (n-decanoyloxy) anthracene, 1-methyl-9,10-bis (n-dodecanoyloxy) anthracene, 2-methyl-9, 10-bis (n-hexanoyloxy) anthracene, 2-methyl-9,10-bis (n-heptanoyloxy) anthracene, 2-methyl- , 10-bis (n-octanoyloxy) anthracene, 2-methyl-9,10-bis (2-ethylhexanoyloxy) anthracene, 2-methyl-9,10-bis (n-nonanoyloxy) anthracene, 2- Methyl-9,10-bis (n-decanoyloxy) anthracene, 2-methyl-9,10-bis (n-dodecanoyloxy) anthracene, 1-ethyl-9,10-bis (n-hexanoyloxy) ) Anthracene, 1-ethyl-9,10-bis (n-heptanoyloxy) anthracene, 1-ethyl-9,10-bis (n-octanoyloxy) anthracene, 1-ethyl-9,10-bis (2 -Ethylhexanoyloxy) anthracene, 1-ethyl-9,10-bis (n-nonanoyloxy) anthracene, 1-ethyl 9,10-bis (n-decanoyloxy) anthracene, 1-ethyl-9,10-bis (n-dodecanoyloxy) anthracene, 2-ethyl-9,10-bis (n-hexanoyloxy) anthracene, 2-ethyl-9,10-bis (n-heptanoyloxy) anthracene, 2-ethyl-9,10-bis (n-octanoyloxy) anthracene, 2-ethyl-9,10-bis (2-ethylhexa) Noyloxy) anthracene, 2-ethyl-9,10-bis (n-nonanoyloxy) anthracene, 2-ethyl-9,10-bis (n-decanoyloxy) anthracene, 2-ethyl-9,10-bis (n -Dodecanoyloxy) anthracene and the like.

Examples where X and Y are both alkyl groups include 2,3-dimethyl-9,10-bis (n-hexanoyloxy) anthracene, 2,3-dimethyl-9,10-bis (n -Heptanoyloxy) anthracene, 2,3-dimethyl-9,10-bis (n-octanoyloxy) anthracene, 2,3-dimethyl-9,10-bis (2-ethylhexanoyloxy) anthracene, 2, 3-dimethyl-9,10-bis (n-nonanoyloxy) anthracene, 2,3-dimethyl-9,10-bis (n-decanoyloxy) anthracene, 2,3-dimethyl-9,10-bis (n- Dodecanoyloxy) anthracene, 2,6-dimethyl-9,10-bis (n-hexanoyloxy) anthracene, 2,6-dimethyl-9,10-bis ( -Heptanoyloxy) anthracene, 2,6-dimethyl-9,10-bis (n-octanoyloxy) anthracene, 2,6-dimethyl-9,10-bis (2-ethylhexanoyloxy) anthracene, 2, 6-dimethyl-9,10-bis (n-nonanoyloxy) anthracene, 2,6-dimethyl-9,10-bis (n-decanoyloxy) anthracene, 2,6-dimethyl-9,10-bis (n- Dodecanoyloxy) anthracene, 2,7-dimethyl-9,10-bis (n-hexanoyloxy) anthracene, 2,7-dimethyl-9,10-bis (n-heptanoyloxy) anthracene, 2,7- Dimethyl-9,10-bis (n-octanoyloxy) anthracene, 2,7-dimethyl-9,10-bis (2-ethylhexa) Yloxy) anthracene, 2,7-dimethyl-9,10-bis (n-nonanoyloxy) anthracene, 2,7-dimethyl-9,10-bis (n-decanoyloxy) anthracene, 2,7-dimethyl-9, And 10-bis (n-dodecanoyloxy) anthracene.

Among the specific examples of the 9,10-bis (long-chain acyloxy) anthracene compounds described above, in particular, 9,10-bis (n-hexanoyloxy) anthracene, 9,10 due to the ease of synthesis and high performance. -Bis (n-heptanoyloxy) anthracene, 9,10-bis (n-octanoyloxy) anthracene, 9,10-bis (2-ethylhexanoyloxy) anthracene, 9,10-bis (n-nonanoyloxy) Anthracene is preferred.

(Production method)
The 9,10-bis (long-chain acyloxy) anthracene compound of the present invention can be produced by acylating the 9,10-dihydroxyanthracene compound represented by the general formula (2).

In the general formula (2), X and Y may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

In the general formula (2), as the alkyl group having 1 to 8 carbon atoms represented by X and Y, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an n-pentyl group, Examples include n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and the like.

That is, as described in the following reaction formula 1, it can be produced by reacting a corresponding 9,10-dihydroxyanthracene compound with a long-chain acylating agent in the presence or absence of a base compound.

In Reaction Scheme 1, R represents an alkyl group having 5 to 12 carbon atoms, X and Y may be the same or different, and represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

The 9,10-dihydroxyanthracene compound used in Reaction Scheme 1 includes 9,10-dihydroxyanthracene, 1-methyl-9,10-dihydroxyanthracene, 2-methyl-9,10-dihydroxyanthracene, 2,6- Dimethyl-9,10-dihydroxyanthracene, 2,7-dimethyl-9,10-dihydroxyanthracene, 1,5-dimethyl-9,10-dihydroxyanthracene, 1-ethyl-9,10-dihydroxyanthracene, 2-ethyl- Examples include 9,10-dihydroxyanthracene, 2,6-diethyl-9,10-dihydroxyanthracene, 2,7-diethyl-9,10-dihydroxyanthracene, 1,5-diethyl-9,10-dihydroxyanthracene.

Next, an acyl halide is used as the long-chain acylating agent to be used. Examples of acyl halides include n-hexanoyl chloride, n-heptanoyl chloride, n-octanoyl chloride, 2-ethylhexanoyl chloride, n-nonanoyl chloride, n-decanoyl chloride, n-dodecanoyl chloride, n-hexanoyl bromide, and odor. N-heptanoyl bromide, n-octanoyl bromide, 2-ethylhexanoyl bromide, n-nonanoyl bromide, n-decanoyl bromide, n-dodecanoyl bromide and the like.

The addition molar ratio of the long-chain acylating agent to the 9,10-dihydroxyanthracene compound is 2.0 or more and 5.0 or less, preferably 2.2 or more and 3.0 or less. If it is less than 2.0, the 9,10-dihydroxyanthracene compound remains unreacted, and if it exceeds 5.0, the solubility of the produced 9,10-bis (long-chain acyloxy) anthracene compound in the reaction solution increases, and the reaction It is difficult to crystallize from the product and the yield is lowered.

As the base compound used in carrying out the reaction in the presence of the base compound, an inorganic alkali salt that is an inorganic base is usually used. As the inorganic alkali salt, for example, sodium hydroxide, potassium hydroxide, or lithium hydroxide is used. Use of organic bases such as pyridine, piperidine and triethylamine is also possible.

In the reaction between the 9,10-dihydroxyanthracene compound and the long-chain acylating agent, a solvent is usually used. When the base compound is an organic base, the solvent is not particularly selected as long as it does not react with a long-chain acylating agent. For example, water-immiscible solvents such as aromatic solvents such as benzene, toluene, xylene, chlorobenzene or halogen solvents such as methylene chloride, dichloroethane, dichloroethylene, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. A water miscible solvent such as a solvent, an amide solvent such as N-methylpyrrolidone and dimethylformamide, or an ether solvent such as tetrahydrofuran and 1,4-dioxane can be used.

On the other hand, when the base compound is an inorganic base, the inorganic base is dissolved in water. Therefore, as a solvent for dissolving the long-chain acylating agent, a water-immiscible solvent is used to avoid hydrolysis of the long-chain acylating agent with water. A solvent is preferred. When a water-miscible solvent is used, the long-chain acylating agent is easily hydrolyzed to an organic acid, which is not preferable because the yield of the product is greatly reduced. Examples of water-immiscible solvents include aromatic solvents such as benzene, toluene, o-xylene, p-xylene, chlorobenzene, methylnaphthalene, and tetralin, and halogen solvents such as methylene chloride, dichloroethane, and dichloroethylene. I can do it.

The amount of the solvent used may be an amount that can dissolve the 9,10-dihydroxyanthracene compound when a water-miscible solvent is used. Specifically, the charged concentration of the 9,10-dihydroxyanthracene compound with respect to the water-miscible solvent is usually 5 wt% or more and less than 30 wt%. On the other hand, when a water-immiscible solvent is used, it may be an amount that can dissolve the long-chain acylating agent. Usually, the concentration of the long-chain acylating agent with respect to the water-immiscible solvent is 5 wt% or more and less than 30 wt%. Moreover, when preparing the alkali salt aqueous solution of a 9, 10- dihydroxy anthracene compound using an inorganic base, the density | concentration is 5 to less than 20 wt% normally.

When a 9,10-dihydroxyanthracene compound is dissolved in an aqueous solution of an inorganic base and a water-immiscible solvent in which a long-chain acylating agent is dissolved is added and reacted, the use of a phase transfer catalyst is effective. Examples of the phase transfer catalyst include tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, trioctylmethylammonium bromide, trioctylethylammonium bromide, trioctylpropylammonium bromide, trioctylbutylammonium bromide. , Benzyldimethyloctadecylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, trioctylmethylammonium chloride, trioctylethylammonium chloride, trioctylpropylammonium chloride Id, trioctyl butyl ammonium chloride, benzyl dimethyl ammonium chloride or the like.

The addition amount of the phase transfer catalyst is preferably 0.01 wt% or more and less than 10 wt%, more preferably 0.1 wt% or more and less than 1.0 wt% with respect to the 9,10-dihydroxyanthracene compound. If it is less than 0.01 wt%, the reaction rate is slow, and if it is 10 wt% or more, the purity of the product decreases, which is not preferable.

The reaction temperature is preferably 0 ° C. or higher and lower than 80 ° C., more preferably 0 ° C. or higher and lower than 20 ° C. This reaction is exothermic and requires cooling. If it is less than 0 ° C., although depending on the amount of solvent used, the solubility of the 9,10-dihydroxyanthracene compound in the solvent will be low, so the 9,10-dihydroxyanthracene compound will be in a slurry state and the reaction rate will decrease. On the other hand, when the temperature is 80 ° C. or higher, side reaction proceeds and the purity of the target product is lowered, which is not preferable.

Although the reaction time depends on the reaction temperature, it is usually 15 minutes or more and less than 3 hours.

After completion of the reaction, if the solvent is miscible with water, an alcohol solvent such as methanol is added to neutralize the unreacted long-chain acylating agent, and then water is added to crystallize the product. If the solvent is immiscible with water, the hydrochloride salt of the precipitated basic compound is dissolved in water to form a two-layer solution, then methanol is added to the separated water-immiscible solvent, and the product is concentrated. Crystallize. The target product can be obtained by separating and washing the precipitated crystals. Moreover, you may refine | purify by recrystallization etc. as needed.

The obtained compound was identified using a ¹ H-NMR spectrum and an IR spectrum, and confirmed to be a 9,10-bis (long-chain acyloxy) anthracene compound.

The 9,10-bis (long chain acyloxy) anthracene compound of the present invention is useful as a photocationic polymerization sensitizer. The photocationically polymerizable composition comprising the 9,10-bis (long-chain acyloxy) anthracene compound of the present invention as a photocationic polymerization sensitizer and comprising a photocationic polymerization initiator and a photocationic polymerizable compound has a wavelength range of 350 nm. Polymerization can be easily performed by irradiating an energy ray containing light of ˜420 nm.

(Photocationic polymerization initiator)
As the cationic photopolymerization initiator used in the cationic photopolymerizable composition of the present invention, a sulfonium salt or an iodonium salt is usually used. The sulfonium salt is preferably an arylsulfonium salt, and S, S, S ′, S′-tetraphenyl-S, S ′-(4,4′-thiodiphenyl) disulfonium bishexafluorophosphate, diphenyl-4-phenyl. Examples thereof include thiophenylsulfonium hexafluorophosphate and triphenylsulfonium hexafluorophosphate. For example, manufactured by Dow Chemical Co., Ltd., trade name: UVI6992, manufactured by San Apro Co., Ltd., trade name: CPI-100P, manufactured by BFS Corporation : Irgacure 270 (Irgacure is a registered trademark of BSF Corporation) can be used. On the other hand, the iodonium salt is preferably an aryl iodonium salt, such as 4-isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, 4-isopropylphenyl-4′-methylphenyl. Examples include iodonium tetrakispentafluorophenylborate, for example, manufactured by BSF, trade name: Irgacure 250, produced by Rhodia, trade name: Rhodosil 2074 (Lodosil is a registered trademark of Rhodia) I can do it.

(Photo-cationic polymerizable compound)
Examples of the photocationically polymerizable compound that can be used in the present invention include epoxy compounds and vinyl ether compounds. Common epoxy compounds are alicyclic epoxy compounds, epoxy-modified silicones, and aromatic glycidyl compounds. As the alicyclic epoxy compound, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (UVR6105, UVR6110 manufactured by Dow Chemical Company, Celoxide 2021P manufactured by Daicel Corporation, Celoxide is a registered trademark of Daicel Corporation) 1,2-epoxy-4-vinylcyclohexane (Delcel's Celoxide 2000), bis (3,4-epoxycyclohexyl) adipate, etc., among which 3 ′, 4′-epoxycyclohexylmethyl-3, 4-Epoxycyclohexanecarboxylate is preferably used. Examples of the aromatic glycidyl compound include 2,2′-bis (4-glycidyloxyphenyl) propane. Examples of the vinyl ether compound include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether and the like.

(Photocationic polymerizable composition)
The composition of the photocationically polymerizable composition is 0.1 to 10.0 parts by weight, preferably 1.10 parts by weight, of the sulfonium salt or iodonium salt as the photocationic polymerization initiator, based on 100 parts by weight of the photocationically polymerizable compound. It is used in the range of 0 to 5.0 parts by weight. If the amount of the photocationic polymerization initiator used for the photocationically polymerizable compound is too small, when the photocationic polymerizable composition is subjected to photocationic polymerization, the polymerization rate becomes slow, while the amount of the photocationic polymerization initiator used is small. If the amount is too large, the physical properties of the photopolymerized product obtained when the photocationically polymerizable composition is photopolymerized may be lowered, which is not preferable.

The 9,10-bis (long-chain acyloxy) anthracene compound which is a photocationic polymerization sensitizer of the present invention is 0.05 to 2.0 parts by weight, preferably 0, per 1 part by weight of the photocationic polymerization initiator. Used in the range of 1 to 1.0 parts by weight. If the amount of the photocationic polymerization sensitizer is too small, the sensitization effect may be difficult to express. On the other hand, if the amount is too large, the physical properties of the polymer may be lowered when the photocationic polymerizable composition is subjected to photocationic polymerization. This is not preferable.

(Additive)
The photocationically polymerizable composition according to the present invention further includes a diluent, a colorant, an organic or inorganic filler, a leveling agent, a surfactant, an antifoaming agent, an increase agent within the range not impairing the effects of the present invention. Various resin additives such as a sticking agent, a flame retardant, an antioxidant, a stabilizer, a lubricant, and a plasticizer can be blended in a normal use range.

Examples of the diluent used in the present invention include an epoxy diluent, an oxetane diluent, a vinyl ether diluent, and the like. Examples of epoxy diluents include, for example, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene. Monooxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, etc. Is mentioned. Examples of oxetane-based diluents include, for example, 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, and the like. It is done. Examples of vinyl ether diluents include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, and the like.

Examples of the colorant include a blue pigment, a red pigment, a white pigment, and a black pigment. Examples of the black pigment include carbon black, acetylene black, lamp black, and aniline black. Examples of yellow pigments include yellow lead, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa Yellow G, Hansa Yellow 10G, Benzidine Yellow G, and Benzidine Yellow. GR, quinoline yellow lake, permanent yellow NCG, tartrazine lake and the like. Examples of red pigments include bengara, cadmium red, red lead, mercury cadmium sulfide, permanent red 4R, risor red, lake red D brilliant carmine 6B, eosin lake, rhodamine lake B, alizarin lake, and brilliant carmine 3B. . Examples of blue pigments include bitumen, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, first sky blue, and indanthrene blue BC. Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide. Examples of other pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white.

(Polymerization method)
The polymerization of the photocationically polymerizable composition can be performed in a film form or can be cured in a lump form. When polymerizing in the form of a film, the photo-cationic polymerizable composition is liquefied, and after applying the photo-cationic polymerizable composition on a substrate such as a polyester film using a bar coater or the like, for example, ultraviolet rays or the like The polymer is irradiated with the light.

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

(light source)
The coating film thus prepared can be polymerized by irradiating it with light such as ultraviolet rays. As a light source to be used, it is preferable to use a light source containing ultraviolet rays having a wavelength of 350 to 420 nm. Specifically, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a gallium doped lamp, a microwave excitation UV lamp (for example, H bulb, D bulb, V bulb manufactured by Fusion Co., Ltd.), 395 nm ultraviolet LED lamp, 375 nm An ultraviolet LED lamp, a 365 nm ultraviolet LED lamp, etc. are mentioned. Use of sunlight or the like is also possible. In particular, a 395 nm ultraviolet LED is preferable. Examples of the 395 nm ultraviolet LED include a 395 ultraviolet LED manufactured by Phoshon.

(atmosphere)
The cationic photopolymerizable composition of the present invention can be polymerized in a system in which the surface of the cationic photopolymerizable composition is open or a system in which the surface is blocked from air. For example, when polymerizing in the form of a film, the photo-cationic polymerizable composition of the present invention can be applied to a substrate, and the polymer can be polymerized by irradiating light such as ultraviolet rays while leaving the coated surface open. The photocationically polymerizable composition can be applied to an oxygen-impermeable substrate, and the surface can be polymerized by irradiating light such as ultraviolet rays with the oxygen-impermeable substrate bonded to the surface.

Examples of the surface opening system of the cationic photopolymerizable composition include uses for use as a coating film, that is, paints, coatings, inks and the like. Specifically, automotive paint, wood coating, PVC floor coating, ceramic wall coating, building material coating, resin hard coat, metallized base coat, film coating, liquid crystal display (LCD) coating, plasma display (PDP) coating, optical disc Coating, metal coating, optical fiber coating, printing ink, lithographic ink, metal can ink, screen printing ink, inkjet ink, gravure varnish and the like. Moreover, such a use aspect is used also in field | areas, such as a resist, a display, a sealing agent, a dental material, and an optical molding material.

Examples of the surface-blocking system for the cationic photopolymerizable composition include an adhesive, a pressure-sensitive adhesive, an adhesive, and a sealing agent. Furthermore, “Latest Trends in Photosensitive Materials for Electronic Components III—Development Status in the Semiconductor, Electronic Substrate, and Display Fields” (Sumibe Research, July 2006), “Latest Trends in UV / EB Curing Technology” (Radtech Research) , March 2006), “Encyclopedia of Applied Technology and Materials” (Akio Yamaoka, April 2006), “Photocuring Technology” (Technical Information Association, March 2000), “Photocurable Materials—Manufacturing It can be suitably used for applications exemplified in “Technology and Application Development” (Toray Research Center, September 2007).

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to the following description examples, unless the meaning is exceeded. Unless otherwise noted, all parts and percentages are on a weight basis.

The product obtained by the present invention was confirmed by measurement using 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 GSX FT NMR Spectrometer

Synthesis Example 1 Synthesis of 9,10-bis (n-hexanoyloxy) anthracene
In a 200 ml three-necked flask equipped with a thermometer and stirrer, 2.10 g (10.0 mmol) of 9,10-dihydroxyanthracene was reslurried in 20 g of degassed water under a nitrogen atmosphere, and 0.92 g of sodium hydroxide (23.0 g) A solution of 9,10-dihydroxyanthracene disodium salt in an orange color solution was added. A solution of 2.96 g (22.0 mmol) of n-hexanoyl chloride in 20 g of toluene in the obtained disodium aqueous solution of 9,10-dihydroxyanthracene while adding 20 mg of tetrabutylammonium bromide to this aqueous solution and cooling with ice water. Was added. After the addition, the mixture was stirred for 2 hours and the aqueous layer was separated. Next, the toluene layer was washed twice with 10 ml of water, and then 40 ml of methanol was added and concentrated. The precipitated crystals were suction filtered and dried to obtain 3.45 g (8.5 mmol) of white crystals of 9,10-bis (n-hexanoyloxy) anthracene. The yield based on the raw material 9,10-dihydroxyanthracene was 85 mol%.

(1) Melting point: 115-117 ° C
(2) IR (KBr, cm ⁻¹ ): 2960, 2946, 2860, 1760, 1594, 1462, 1358, 1140, 1096, 758.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.98 (t, J = 8 Hz, 6H), 1.42-1.62 (m, 8H), 1.92-2.02 ( m, 4H), 2.92 (t, J = 8 Hz, 4H), 7.45-7.56 (m, 4H), 7.89-7.96 (m, 4H).

Synthesis Example 2 Synthesis of 9,10-bis (n-heptanoyloxy) anthracene
In a 200 ml three-necked flask equipped with a thermometer and stirrer, 2.10 g (10.0 mmol) of 9,10-dihydroxyanthracene was reslurried in 20 g of degassed water under a nitrogen atmosphere, and 0.92 g of sodium hydroxide (23.0 g) A solution of 9,10-dihydroxyanthracene disodium salt in an orange color solution was added. To this aqueous solution, 20 mg of tetrabutylammonium bromide was added and cooled with ice water, and a solution prepared by dissolving 3.27 g (22.0 mmol) of n-heptanoyl chloride in 20 g of toluene was added. After the addition, the mixture was stirred for 2 hours, and the aqueous layer was separated. Next, the toluene layer was washed twice with 10 ml of water, and then 40 ml of methanol was added and concentrated. The precipitated crystals were suction filtered and dried to obtain 3.39 g (7.8 mmol) of white crystals of 9,10-bis (n-hexanoyloxy) anthracene. The yield based on the raw material 9,10-dihydroxyanthracene was 78 mol%.

(1) Melting point: 124-125 ° C
(2) IR (KBr, cm ⁻¹ ): 2930, 2860, 1758, 1472, 1418, 1367, 1135, 1042, 762, 720.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.96 (t, J = 8 Hz, 6H), 1.35-1.49 (m, 8H), 1.49-1.61 ( m, 4H), 1.91-2.01 (m, 4H), 2.91 (t, J = 8 Hz, 4H), 7.48-7.57 (m, 4H), 7.87-7. 94 (m, 4H).

(Synthesis Example 3) 9,10-bis (n-octanoyloxy) anthracene synthesis thermometer, 2.10 g (10.0 mmol) of 9,10-dihydroxyanthracene in a 200 ml three-necked flask equipped with a stirrer under a nitrogen atmosphere Was reslurried in 20 g of degassed water, and a solution of 0.92 g (23.0 mmol) of sodium hydroxide in 3 g of degassed water was added to obtain an orange-colored aqueous solution of 9,10-dihydroxyanthracene disodium salt. . To this aqueous solution, 20 mg of tetrabutylammonium bromide was added and cooled with ice water, and a solution of 3.58 g (22.0 mmol) of n-octanoyl chloride in 22 g of toluene was added. After the addition, the mixture was stirred for 2 hours, and the aqueous layer was separated. Subsequently, the toluene layer was washed twice with 10 ml of water, and then 40 ml of methanol was added and concentrated. The precipitated crystals were filtered by suction and dried to obtain 3.42 g (7.4 mmol) of white crystals of 9,10-bis (n-octanoyloxy) anthracene. The yield based on the raw material 9,10-dihydroxyanthracene was 74 mol%.

(1) Melting point: 98-99 ° C
(2) IR (KBr, cm ⁻¹ ): 2970, 2925, 2860, 1756, 1420, 1370, 1358, 1138, 1026, 762.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.92 (t, J = 8 Hz, 6H), 1.32-1.39 (m, 8H), 1.39-1.48 ( m, 4H), 1.48-1.58 (m, 4H), 1.91-2.00 (m, 4H), 2.91 (t, J = 8 Hz, 4H), 7.47-7. 53 (m, 4H), 7.88-7.96 (m, 4H).

Synthesis Example 4 Synthesis of 9,10-bis (2-ethylhexanoyloxy) anthracene Thermometer, 2.10 g (10.0 mmol) of 9,10-dihydroxyanthracene in a 200 ml three-necked flask equipped with a stirrer under a nitrogen atmosphere ) Is reslurried in 20 g of degassed water, a solution of 0.92 g (23.0 mmol) of sodium hydroxide in 3 g of degassed water is added, and an orange colored aqueous solution of disodium salt of 9,10-dihydroxyanthracene is added. did. To this aqueous solution, 20 mg of tetrabutylammonium bromide was added and cooled with ice water, and a solution of 3.58 g (22.0 mmol) of 2-ethylhexanoyl chloride in 22 g of toluene was added. After the addition, the mixture was stirred for 2 hours, and the aqueous layer was separated. Next, the toluene layer was washed twice with 10 ml of water, and then 40 ml of methanol was added and concentrated. The precipitated crystals were suction filtered and dried to obtain 3.60 g (7.8 mmol) of white crystals of 9,10-bis (2-ethylhexanoyloxy) anthracene. The yield based on the raw material 9,10-dihydroxyanthracene was 78 mol%.

(1) Melting point: 134-135 ° C
(2) IR (KBr, cm ⁻¹ ): 3065, 2960, 2940, 2870, 1760, 1628, 1462, 1290, 1280, 1270, 1152, 1093, 955, 752, 684.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 1.01 (t, J = 8 Hz, 6H), 1.21 (t, J = 8 Hz, 6H), 1.43-1.63 ( m, 8H), 1.79-1.96 (m, 4H), 1.96-2.11 (m, 4H), 2.88-2.97 (m, 4H), 7.47-7. 53 (m, 4H), 7.91-7.98 (m, 4H).

Synthesis Example 5 Synthesis of 9,10-bis (n-nonanoyloxy) anthracene In a 200 ml three-necked flask equipped with a stirrer, 2.10 g (10.0 mmol) of 9,10-dihydroxyanthracene was removed in a nitrogen atmosphere. The slurry was reslurried in 20 g of atmospheric water, and a solution of 0.92 g (23.0 mmol) of sodium hydroxide in 3 g of degassed water was added to obtain an orange-colored aqueous solution of disodium salt of 9,10-dihydroxyanthracene. To this aqueous solution, 20 mg of tetrabutylammonium bromide was added and cooled with ice water, and a solution prepared by dissolving 3.88 g (22.0 mmol) of n-nonanoyl chloride in 22 g of toluene was added. After the addition, the mixture was stirred for 2 hours, and the aqueous layer was separated. Next, the toluene layer was washed twice with 10 ml of water, and then 40 ml of methanol was added and concentrated. The precipitated crystals were suction filtered and dried to obtain 3.53 g (7.2 mmol) of 9,10-bis (n-nonanoyloxy) anthracene white crystals. The yield based on the raw material 9,10-dihydroxyanthracene was 72 mol%.

(1) Melting point: 96-97 ° C
(2) IR (KBr, cm ⁻¹ ): 3070, 2930, 2855, 1755, 1626, 1468, 1424, 1362, 1340, 1304, 1260, 1216, 1152, 1108, 760, 725.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.91 (t, J = 8 Hz, 6H), 1.27-1.48 (m, 12H), 1.51-1.60 ( m, 4H), 1.91-2.00 (m, 4H), 2.92 (t, J = 8 Hz, 4H), 7.47-7.53 (m, 4H), 7.88-7. 96 (m, 4H).

"Example 1"
As a photocationically polymerizable compound, a photocation is used with respect to 100 parts by weight of an alicyclic epoxy (manufactured by Dow Chemical Co., Ltd., trade name: UVR6105 (3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate)). Photocation polymerization of 4.0 parts by weight of polymerization initiator UVI6992 (S, S, S ′, S′-tetraphenyl-S, S ′-(4,4′-thiodiphenyl) disulfonium bishexafluorophosphate) As a sensitizer, 0.8 part by weight of 9,10-bis (n-hexanoyloxy) anthracene synthesized in the same manner as in Synthesis Example 1 was mixed to prepare a photocationically polymerizable composition. The composition was applied onto a tack film using a bar coater so that the film thickness was 30 microns. Next, light was irradiated from the surface using a 395 ultraviolet LED manufactured by Phoseon (the intensity of the central wavelength of 395 nm is 1.0 W / cm ² ). The light irradiation time “tack free time” until tackiness disappears was 6.0 seconds.

"Example 2"
Except for using 9,10-bis (n-heptanoyloxy) anthracene synthesized in the same manner as in Synthesis Example 2 instead of 9,10-bis (n-hexanoyloxy) anthracene, it was exactly the same as Example 1. Thus, a photocationically polymerizable composition was prepared. The composition was applied onto a tack film using a bar coater so that the film thickness was 30 microns. Next, light was irradiated from the surface using a 395 ultraviolet LED manufactured by Phoseon (the intensity of the central wavelength of 395 nm is 1.0 W / cm ² ). The light irradiation time “tack free time” until tackiness disappears was 6.0 seconds.

"Example 3"
Except for using 9,10-bis (n-octanoyloxy) anthracene synthesized in the same manner as in Synthesis Example 3 instead of 9,10-bis (n-hexanoyloxy) anthracene, it was exactly the same as Example 1. Thus, a photocationically polymerizable composition was prepared. The composition was applied onto a tack film using a bar coater so that the film thickness was 30 microns. Next, light was irradiated from the surface using a 395 ultraviolet LED manufactured by Phoseon (the intensity of the central wavelength of 395 nm is 1.0 W / cm ² ). The light irradiation time “tack free time” until tackiness disappears was 6.0 seconds.

Example 4
Except for using 9,10-bis (2-ethylhexanoyloxy) anthracene synthesized in the same manner as in Synthesis Example 4 instead of 9,10-bis (n-hexanoyloxy) anthracene, the same as Example 1 was used. Similarly, a photocationically polymerizable composition was prepared. The composition was applied onto a tack film using a bar coater so that the film thickness was 30 microns. Next, light was irradiated from the surface using a 395 ultraviolet LED manufactured by Phoseon (the intensity of the central wavelength of 395 nm is 1.0 W / cm ² ). The light irradiation time “tack free time” until tackiness disappears was 3.0 seconds.

"Example 5"
Except for using 9,10-bis (n-nonanoyloxy) anthracene synthesized in the same manner as in Synthesis Example 5 instead of 9,10-bis (n-hexanoyloxy) anthracene, the same as Example 1 was used. A photocationically polymerizable composition was prepared. The composition was applied onto a tack film using a bar coater so that the film thickness was 30 microns. Next, light was irradiated from the surface using a 395 ultraviolet LED manufactured by Phoseon (the intensity of the central wavelength of 395 nm is 1.0 W / cm ² ). The light irradiation time “tack free time” until stickiness disappears was 2.0 seconds.

"Comparative Example 1"
A photocationically polymerizable composition was prepared in the same manner as in Example 1 except that 9,10-dibutoxyanthracene was used instead of 9,10-bis (n-hexanoyloxy) anthracene. The composition was applied onto a tack film using a bar coater so that the film thickness was 30 microns. Next, light was irradiated from the surface using a 395 ultraviolet LED manufactured by Phoseon (the intensity of the central wavelength of 395 nm is 1.0 W / cm ² ). The light irradiation time “tack free time” until tackiness disappears was 6.5 seconds.

"Comparative Example 2"
A photocationically polymerizable composition was prepared in exactly the same manner as in Example 1, except that 9,10-bis (n-hexanoyloxy) anthracene was not used. The composition was applied onto a tack film using a bar coater so that the film thickness was 30 microns. Next, light was irradiated from the surface using a 395 ultraviolet LED manufactured by Phoseon (the intensity of the central wavelength of 395 nm is 1.0 W / cm ² ). The light irradiation time “tack free time” until tackiness disappears was 310 seconds.

"Example 6"
Except that 4 parts by weight of UVI6992 is used as a photocationic polymerization initiator, 2.0 parts by weight of Irgacure 250 (4-isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate) is used, exactly as in Example 1. Thus, a photocationically polymerizable composition was prepared. The composition was applied onto a tack film using a bar coater so that the film thickness was 30 microns. Next, light was irradiated from the surface using a 395 ultraviolet LED manufactured by Phoseon (the intensity of the central wavelength of 395 nm is 1.0 W / cm ² ). The light irradiation time “tack free time” until stickiness disappears was 2.0 seconds.

"Example 7"
Except that 4 parts by weight of UVI6992 was used as a photocationic polymerization initiator, 2 parts by weight of Irgacure 250 (4-isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate) was used. A photocationically polymerizable composition was prepared. The composition was applied onto a tack film using a bar coater so that the film thickness was 30 microns. Next, light was irradiated from the surface using a 395 ultraviolet LED manufactured by Phoseon (the intensity of the central wavelength of 395 nm is 1.0 W / cm ² ). The light irradiation time “tack free time” until stickiness disappears was 2.0 seconds.

"Example 8"
Except that 4 parts by weight of UVI6992 is used as a photocationic polymerization initiator, 2 parts by weight of Irgacure 250 (4-isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate) is used, and exactly the same as in Example 5. A photocationically polymerizable composition was prepared. The composition was applied onto a tack film using a bar coater so that the film thickness was 30 microns. Next, light was irradiated from the surface using a 395 ultraviolet LED manufactured by Phoseon (the intensity of the central wavelength of 395 nm is 1.0 W / cm ² ). The light irradiation time “tack free time” until stickiness disappears was 1.5 seconds.

“Comparative Example 3”
Except that 4 parts by weight of UVI6992 is used as a photocationic polymerization initiator, 2 parts by weight of Irgacure 250 (4-isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate) is used. A photocationically polymerizable composition was prepared. The composition was applied onto a tack film using a bar coater so that the film thickness was 30 microns. Next, light was irradiated from the surface using a 395 ultraviolet LED manufactured by Phoseon (the intensity of the central wavelength of 395 nm is 1.0 W / cm ² ). The light irradiation time “tack free time” until tackiness disappears was 3.0 seconds.

“Comparative Example 4”
A photocationically polymerizable composition was prepared in exactly the same manner as in Comparative Example 3 except that Irgacure 250 was not used as the photocationic polymerization initiator. The composition was applied onto a tack film using a bar coater so that the film thickness was 30 microns. Subsequently, light was irradiated from the surface using a 395 ultraviolet LED manufactured by Phoseon (the intensity of the central wavelength of 395 nm was 1.0 W / cm ² ), but it was not cured at all even when irradiated for 300 seconds or more.

The results of Examples 1 to 5 and Comparative Examples 1 and 2 are summarized in Table 1, and the results of Examples 6 to 8 and Comparative Examples 3 and 4 are summarized in Table 2.

As is clear by comparing Examples 1 to 5 with Comparative Example 2, Examples 6 to 8 and Comparative Example 4, the 9,10-bis (long-chain acyloxy) anthracene compound of the present invention has increased photocationic polymerization. It turns out that it has an effect as a sensitizer. Further, as is apparent from comparing Examples 1 to 5 with Comparative Example 1 and Examples 6 to 8 with Comparative Example 3, a known 9,10-- conventionally used as a photocationic polymerization sensitizer. It can be seen that the sensitization performance is equal to or better than that of dibutoxyanthracene.

(Example 9) Measurement of transmittance of cured product when 9,10-bis (2-ethylhexanoyloxy) anthracene was used as a photocationic polymerization sensitizer Photocationic polymerization prepared in the same manner as in Example 4. The adhesive composition was applied onto the tack film using a bar coater so as to have a film thickness of 30 microns, and the tack film was covered thereon. Next, light was irradiated from the surface using a 395 ultraviolet LED manufactured by Phoseon (the intensity of the central wavelength of 395 nm is 1.0 W / cm ² ). After the start of light irradiation, the UV spectrum of the photocationically polymerizable composition sandwiched between tack films was measured every predetermined time, and the transmittance of the film at 400 nm was determined. The results are plotted in FIG.

(Example 10) Measurement of transmittance of cured product when 9,10-bis (n-nonanoyloxy) anthracene was used as a photocationic polymerization sensitizer Photocationic polymerizable composition prepared in the same manner as Example 5 Was coated on the tack film using a bar coater so that the film thickness was 30 microns, and the tack film was covered thereon. Next, light was irradiated from the surface using a 395 ultraviolet LED manufactured by Phoseon (the intensity of the central wavelength of 395 nm is 1.0 W / cm ² ). After the start of light irradiation, the UV spectrum of the photocationically polymerizable composition sandwiched between tack films was measured every predetermined time, and the transmittance of the film at 400 nm was determined. The results are plotted in FIG.

(Comparative Example 5) Measurement of transmittance of cured product when 9,10-dibutoxyanthracene was used as a photocationic polymerization sensitizer A photocationically polymerizable composition prepared in the same manner as in Comparative Example 1 was used as a tack film. A bar coater was used to coat so that the film thickness was 30 microns, and a tack film was placed thereon. Next, light was irradiated from the surface using a 395 ultraviolet LED manufactured by Phoseon (the intensity of the central wavelength of 395 nm is 1.0 W / cm ² ). After the start of light irradiation, the UV spectrum of the photocationically polymerizable composition sandwiched between tack films was measured every predetermined time, and the transmittance of the film at 400 nm was determined. The results are plotted in FIG.

As is clear from the results of Examples 9 and 10 and Comparative Example 5 and FIG. 1, the cured product of the photocationically polymerizable composition prepared using 9,10-dibutoxyanthracene as a photocationic polymerization sensitizer has a transmittance. However, the 9,10-bis (2-ethylhexanoyloxy) anthracene and 9,10-bis (n-nonanoyloxy) anthracene of the present invention are used as photocationic polymerization sensitizers. It can be seen that the cured product of the prepared photocationically polymerizable composition has a transmittance of more than 90% at 400 nm. This shows that the photocured product of the photocationically polymerizable composition containing the 9,10-bis (long chain acyloxy) anthracene compound of the present invention as a photocationic polymerization sensitizer has extremely high permeability.

Claims (6)

A 9,10-bis (long-chain acyloxy) anthracene compound represented by the general formula (1).


(In the general formula (1), R represents an alkyl group having 5 to 12 carbon atoms, X and Y may be the same or different, and represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. .) The method for producing a 9,10-bis (long-chain acyloxy) anthracene compound according to claim 1, wherein the 9,10-dihydroxyanthracene compound represented by the general formula (2) is acylated.

(In general formula (2), X and Y may be the same or different, and represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) A photocationic polymerization sensitizer containing the 9,10-bis (long-chain acyloxy) anthracene compound according to claim 1. A photocationically polymerizable composition comprising the photocationic polymerization sensitizer according to claim 3, a photocationic polymerization initiator, and a photocationically polymerizable compound. The photocationic polymerizable composition according to claim 4, wherein the photocationic polymerization initiator is an aryl iodonium salt or an aryl sulfonium salt. A method for curing a photocationically polymerizable composition, comprising irradiating the photocationically polymerizable composition according to claim 4 or 5 with a light beam contained in a wavelength range of 350 nm to 420 nm.