JP5967345B2 - 9,9'-Bianthracene-10,10'-diether compound, production method thereof and use thereof. - Google Patents

Description

The present invention relates to a 9,9'-bianthracene-10,10'-diether compound, a method for producing the same, and a use as a photopolymerization sensitizer.

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

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

However, conventionally used photopolymerization sensitizers often generate sublimates when they are post-baked (heat treatment) after curing the photopolymerizable composition, and adhere to exhaust ducts, etc. In addition, the attached sublimate may cause troubles such as falling on a cured product such as a film. In addition, when there is a pre-baking (solvent evaporation operation) step, the photopolymerization sensitizer flows out of the system by sublimation in the pre-baking step, so that the concentration of the photopolymerization sensitizer during photocuring is insufficient. In some cases, photocuring may be insufficient.

Furthermore, when these sensitizers are used as a component of a photo-adhesive that bonds the film to each other, the sensitizer may migrate to the film overlaid (migration) and increase on the upper film. It may cause problems with powdering and coloring of sensitizers.

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

Therefore, there is a demand for the development of a photopolymerizable composition that hardly causes migration to the adhered film layer and that generates a small amount of sublimation in the baking process.

As a result of intensive studies on the structure and physical properties of anthracene compounds, the present inventors have found that the 9,9′-bianthracene-10,10′-diether compound of the present invention is a photopolymerization sensitizer in photocationic polymerization and photoradical polymerization. In addition to exhibiting an excellent effect as a photopolymerization sensitizer, the film is put on a photopolymerizable composition containing the 9,9′-bianthracene-10,10′-diether compound as a photopolymerization sensitizer. The present invention has been completed by finding that the degree is remarkably reduced and that the degree of sublimation of the photopolymerization sensitizer when the photocured product is heated is low.

That is, the first gist of the present invention resides in a 9,9'-bianthracene-10,10'-diether compound represented by the following general formula (1).

(In the general formula (1), R represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group, and X, X ′, Y and Y ′ may be the same or different, and may be a hydrogen atom, carbon Represents an alkyl group or a halogen atom of formula 1-8.)

The second gist of the present invention is 9,9′-bianthracene-10, which comprises etherification of the 9,9′-bianthracene-10,10′-diol compound represented by the general formula (2). It exists in the manufacturing method of 10'- diether compound.

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

The third gist of the present invention consists of enolization and then etherification of the 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione compound represented by the general formula (3). , 9,9'-Bianthracene-10,10'-diether compound.

(In the general formula (3), X, X ′, Y and Y ′ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.)

The fourth gist of the present invention is that the 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione compound represented by the general formula (3) is an anthrone compound and 2-substituted-1, It exists in the manufacturing method of the 9,9'-bianthracene-10,10'-diether compound as described in the 3rd summary characterized by obtaining by reaction with a 4-naphthoquinone compound.

(In the general formula (3), X, X ′, Y and Y ′ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.)

The fifth gist of the present invention is that the 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione compound represented by the general formula (3) is an anthrone compound and a 2,6-disubstituted compound. The present invention resides in a method for producing a 9,9′-bianthracene-10,10′-diether compound according to the third aspect, which is obtained by a reaction with a -1,4-benzoquinone compound.

(In the general formula (3), X, X ′, Y and Y ′ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.)

The sixth gist of the present invention resides in a photopolymerization sensitizer containing a 9,9'-bianthracene-10,10'-diether compound represented by the general formula (1).

(In the general formula (1), R represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group, and X, X ′, Y and Y ′ may be the same or different, and may be a hydrogen atom, carbon Represents an alkyl group or a halogen atom of formula 1-8.)

The seventh aspect of the present invention resides in a photopolymerization initiator composition containing the photopolymerization sensitizer described in the sixth aspect and an onium salt as a photopolymerization initiator.

An eighth aspect of the present invention resides in a photopolymerizable composition containing the photopolymerization initiator composition described in the seventh aspect and a photocationically polymerizable compound.

A ninth aspect of the present invention resides in a photopolymerizable composition containing the photopolymerization initiator composition described in the seventh aspect and a photoradical polymerizable compound.

A tenth aspect of the present invention resides in a photocured product obtained by curing the photopolymerizable composition described in the eighth aspect or the ninth aspect.

In addition, the position number of the carbon atom which shows the position of the substituent of a bianthracene skeleton in the compound of General formula (1), (2) and (3) shall be as showing in the following chemical structural formula.

The 9,9′-bianthracene-10,10′-diether compound represented by the general formula (1) of the present invention is a reaction between an anthrone compound and a 2-substituted naphthoquinone compound, or an anthrone compound and 2,6-disubstituted. A film on a photopolymerizable composition which is easily produced via reaction with a benzoquinone compound and is not only highly active as a photopolymerization sensitizer but also contains the compound of the present invention as a photopolymerization sensitizer. Even when covered, the migration of the compound of the present invention to the film is low, and furthermore, the photocured product obtained by the present invention is a photopolymerization sensitizer of the present invention contained in the photocured product in the heat treatment process. It is a useful compound with extremely low sublimation properties.

(Compound)
The 9,9′-bianthracene-10,10′-diether compound which is the photopolymerization sensitizer of the present invention is a compound having a structure described in the general formula (1).

(In the general formula (1), R represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group, and X, X ′, Y and Y ′ may be the same or different, and may be a hydrogen atom, carbon Represents an alkyl group or a halogen atom of formula 1-8.)

In the general formula (1) of the present invention, the alkyl group having 1 to 8 carbon atoms represented by R is methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i -Butyl group, n-pentyl group, i-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, etc. are mentioned. As the aralkyl group, a benzyl group or a phenethyl group is exemplified. Can be mentioned.

In general formula (1), examples of the alkyl group having 1 to 8 carbon atoms represented by X, X ′, Y, and Y ′ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and n-butyl. Group, i-butyl group, pentyl group, 2-ethylhexyl group and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Hereinafter, specific examples of the 9,9'-bianthracene-10,10'-diether compound represented by the general formula (1) of the present invention will be illustrated for each substituent. Specific examples of X, X ′, Y, and Y ′ in general formulas (2) and (3) described later are the same as the specific examples of general formula (1).

In the general formula (1) of the present invention, examples of the case where X, X ′, Y and Y ′ are hydrogen atoms include 9,9′-bianthracene-10,10′-dimethyl ether, 9,9′- Bianthracene-10,10′-diethyl ether, 9,9′-bianthracene-10,10′-bis (n-propyl) ether, 9,9′-bianthracene-10,10′-bis (n-butyl) ) Ether, 9,9′-bianthracene-10,10′-bis (n-pentyl) ether, 9,9′-bianthracene-10,10′-bis (n-hexyl) ether, 9,9′- Bianthracene-10,10′-bis (n-heptyl) ether, 9,9′-bianthracene-10,10′-bis (n-octyl) ether, 9,9′-bianthracene-10,10′- Screw (2 Ethylhexyl) ether, 9'-bi anthracene -10,10'- dibenzyl ether, 9,9'-bi anthracene -10,10'- di phenethyl ether, and the like.

Further, in the general formula (1) of the present invention, examples of the case where X, X ′ and / or Y, Y ′ are alkyl groups include 2,2′-dimethyl-9,9′-bianthracene. -10,10'-dimethyl ether, 2,2'-diethyl-9,9'-bianthracene-10,10'-dimethyl ether, 2,2'-dimethyl-9,9'-bianthracene-10,10'- Diethyl ether, 2,2′-diethyl-9,9′-bianthracene-10,10′-diethyl ether, 2,2′-dimethyl-9,9′-bianthracene-10,10′-dibutyl ether, 2 2,2'-diethyl-9,9'-bianthracene-10,10'-dibutyl ether, 2,3'-dimethyl-9,9'-bianthracene-10,10'-dimethyl ether, 2,3'-diethyl -9,9'-bianthracene-10,10'-dimethyl ether, 2,3'-dimethyl-9,9'-bianthracene-10,10'-diethyl ether, 2,3'-diethyl-9,9 ' -Bianthracene-10,10'-diethyl ether, 2,3'-dimethyl-9,9'-bianthracene-10,10'-dibutyl ether, 2,3'-diethyl-9,9'-bianthracene- 10,10′-dibutyl ether, 3,3′-dimethyl-9,9′-bianthracene-10,10′-dimethyl ether, 3,3′-diethyl-9,9′-bianthracene-10,10′- Dimethyl ether, 3,3′-dimethyl-9,9′-bianthracene-10,10′-diethyl ether, 3,3′-diethyl-9,9′-bianthracene-10,10 ′ Diethyl ether, 3,3′-dimethyl-9,9′-bianthracene-10,10′-dibutyl ether, 3,3′-diethyl-9,9′-bianthracene-10,10′-dibutyl ether, etc. Can be mentioned.

Furthermore, in the general formula (1) of the present invention, examples where X, X ′ and / or Y, Y ′ are halogen atoms include 2,2′-dichloro-9,9′-bianthracene -10,10'-dimethyl ether, 2,2'-dibromo-9,9'-bianthracene-10,10'-dimethyl ether, 2,2'-dichloro-9,9'-bianthracene-10,10'- Diethyl ether, 2,2′-dibromo-9,9′-bianthracene-10,10′-diethyl ether, 2,2′-dichloro-9,9′-bianthracene-10,10′-dibutyl ether, 2 2,2'-dibromo-9,9'-bianthracene-10,10'-dibutyl ether, 2,3'-dichloro-9,9'-bianthracene-10,10'-dimethyl ether, 2,3'-dibu Mo-9,9'-bianthracene-10,10'-dimethyl ether, 2,3'-dichloro-9,9'-bianthracene-10,10'-diethyl ether, 2,3'-dibromo-9,9 '-Bianthracene-10,10'-diethyl ether, 2,3'-dichloro-9,9'-bianthracene-10,10'-dibutyl ether, 2,3'-dibromo-9,9'-bianthracene -10,10'-dibutyl ether, 3,3'-dichloro-9,9'-bianthracene-10,10'-dimethyl ether, 3,3'-dibromo-9,9'-bianthracene-10,10 ' -Dimethyl ether, 3,3'-dichloro-9,9'-bianthracene-10,10'-diethyl ether, 3,3'-dibromo-9,9'-bianthracene-10,10 -Diethyl ether, 2,3'-dichloro-9,9'-bianthracene-10,10'-dibutyl ether, 3,3'-dibromo-9,9'-bianthracene-10,10'-dibutyl ether, etc. Is mentioned.

Among the above compounds, 9,9′-bianthracene-10,10′-diethyl ether (A), 9, 9 shown in the following structural formula is particularly preferred because of the ease of synthesis and the performance as a photopolymerization sensitizer. 9'-Bianthracene-10,10'-bis (n-propyl) ether (B), 9,9'-Bianthracene-10,10'-bis (n-butyl) ether (C), 9,9 ' -Bianthracene-10,10'-bis (i-butyl) ether (D), 9,9'-bianthracene-10,10'-bis (n-pentyl) ether (E) 9,9'-bianthracene -10,10'-bis (n-heptyl) ether (F), 9,9'-bianthracene-10,10'-bis (2-ethylhexyl) ether (G), 9,9'-bianthracene-10 , 10'-Dibenzyle Ether (H) is preferable.

(Production method)
Next, a method for producing the 9,9′-bianthracene-10,10′-diether compound represented by the general formula (1) will be described. The 9,9′-bianthracene-10,10′-diether compound represented by the general formula (1) uses a 9-anthrone compound as a starting material. Then, the 9-anthrone compound is reacted with a 2-substituted-1,4-naphthoquinone compound or a 2,6-disubstituted-1,4-benzoquinone compound in the presence of an acid, and is represented by the general formula (3). 9,9′-Bianthracene-10,10 ′ (9H, 9′H) -dione compound is obtained (first reaction). Subsequently, the 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione compound is enolized to give 9,9′-bianthracene-10,10′-diol represented by the general formula (2) The 9,9′-bianthracene-10,10 is obtained by etherifying the 9,9′-bianthracene-10,10′-diol compound obtained as the last compound (second reaction) (third reaction). This is a method for producing a '-diether compound.

In the first reaction formulas (a) and (b), X, X ′, Y and Y ′ may be the same or different, and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom. L, M and N may be the same or different and each represents a hydroxyl group, a methyl group, an ethyl group, an acetoxy group, a chlorine atom or a bromine atom. Hereinafter, the first reaction (a) and the first reaction (b) may be collectively referred to as the first reaction.

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

In the third reaction formula, R represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group, and X, X ′, Y, and Y ′ may be the same or different from each other. -8 alkyl groups or halogen atoms are shown.

First, the first reaction will be described. In the first reaction, a 9-anthrone compound and a 2-substituted-1,4-naphthoquinone compound or a 2,6-disubstituted-1,4-benzoquinone compound are used as starting materials.

As anthrone compounds used in the first reaction, 9-anthrone, 2-methyl-9-anthrone, 3-methyl-9-anthrone, 2-ethyl-9-anthrone, 3-ethyl-9-anthrone, 2-chloro- Examples include 9-anthrone, 3-chloro-9-anthrone, 2-bromo-9-anthrone, and 3-bromo-9-anthrone. Examples of the 2-substituted-1,4-naphthoquinone compound include 2-methyl-1,4-naphthoquinone, 2-ethyl-1,4-naphthoquinone, 2-chloro-1,4-naphthoquinone, 2-bromo-1 , 4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, 2-acetoxy-1,4-naphthoquinone and the like. Examples of the 2,6-disubstituted-1,4-benzoquinone compound include 2,6-dimethyl-1,4-benzoquinone, 2,6-diethyl-1,4-benzoquinone, and 2,6-di (t- Butyl) -1,4-benzoquinone, 2,3,5-trimethyl-1,4-benzoquinone, 2,3,5,6-tetramethyl-1,4-benzoquinone, 2,6-dichloro-1,4- Examples include benzoquinone and 2,6-dibromo-1,4-benzoquinone.

In the first reaction, when one kind of anthrone compound is used as a raw material, X and X 'and Y and Y' are the same. However, it is also possible to obtain a compound of the general formula (3) in which X and X ′ and Y and Y ′ are different by using two types of anthrone compounds having different substituents. In this case, a mixture of X and X ′, and Y and Y ′ are the same, but each can be isolated by a column or the like and used for the application of the present invention. Moreover, it is also possible to use these for the use of this invention as a mixture, without isolating these as a single compound.

As the acid used in the first reaction, either an inorganic acid or an organic acid can be used. Examples of the inorganic acid include sulfuric acid, methanesulfonic acid, hydrochloric acid, nitric acid, phosphoric acid, polyphosphoric acid, titanium tetrachloride, and four. Examples include tin chloride. Examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid and the like.

The solvent used in the first reaction is not particularly limited. Examples thereof include aromatic solvents such as toluene, xylene and chloronaphthalene, ether solvents such as tetrahydrofuran and 1,4-dioxane, and ketone solvents such as acetone, methyl ethyl ketone, methyl-i-butyl ketone and cyclohexanone. Among these, a solvent having high solubility of the 2-substituted-1.4-naphthohydroquinone compound by-produced in the first reaction is preferable. Particularly preferred solvents are water-soluble ether solvents such as tetrahydrofuran and 1,4-dioxane.

The amount of acid used in the first reaction is about 1% by weight with respect to the raw material anthrone compound. The reaction temperature is 50 ° C. or higher and lower than 150 ° C., more preferably 90 ° C. or higher and lower than 120 ° C. If it is less than 50 ° C., the reaction takes too much time, and if it is 150 ° C. or more, impurities derived from the decomposition product of naphthoquinone increase and the purity of the product does not increase. The reaction time depends on the reaction temperature, but is usually 1 hour or more and less than 4 hours.

Next, the second reaction will be described. In the second reaction, the 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione compound obtained in the first reaction is heated in the presence of a base in a solvent, and then acidified. Is done.

As the base used in the second reaction, both an inorganic base and an organic base can be used. As the inorganic base, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide and the like can be used. Among these, sodium hydroxide is particularly preferable. Examples of the organic base include pyridine, quinoline, piperidine and the like.

The addition ratio of the base to the 9,9'-bianthracene-10,10 '(9H, 9'H) -dione compound varies depending on whether the base is an inorganic base or an organic base. In the case of an inorganic base, it is preferably 2 mol times or more and less than 15 mol times, more preferably 5 mol times or more and less than 10 mol times. If it is less than 2 mol times, the raw material 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione compound remains unreacted, and even if added more than 15 mol times, the reaction results are There is no improvement.

On the other hand, when the base is an organic base, the lower limit value of the preferred range of the addition ratio and the lower limit value of the more preferred range are the same as in the case of the inorganic base, but the organic base can also be used as a solvent. The value is not specified. When the organic base is used as a solvent and reaction reagent, the addition ratio to the raw material 9,9'-bianthracene-10,10 '(9H, 9'H) -dione compound may reach 100 mole times. However, if it is used excessively more than necessary, not only is it not economical, but the reaction concentration becomes thin and it is not efficient.

The solvent used in the second reaction is not particularly limited as long as the 9,9'-bianthracene-10,10 '(9H, 9'H) -dione compound is dissolved. For example, amide solvents such as N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methylpyrrolidone, ether solvents such as tetrahydrofuran and 1,4-dioxane, nitrile solvents such as acetonitrile and propionitrile Examples of the solvent include ketone solvents such as acetone and methyl ethyl ketone, and alcohol solvents such as methanol, ethanol, and i-propanol. Of these, amide solvents such as N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methylpyrrolidone and the like are preferable because of the ease of enolization reaction. When an inorganic base is used, a solvent such as an amide that is miscible with water is preferable because the inorganic base is dissolved in water and reacted.

The reaction temperature of the second reaction is usually 50 ° C to 100 ° C. The reaction time is not constant depending on the reaction temperature, but is usually about 30 minutes to 2 hours. After adding the base, the reaction proceeds by heating, and the slurry of 9,9'-bianthracene-10,10 '(9H, 9'H) -dione compound dissolves to give a red solution. Thereafter, when the red solution is poured into an acidic aqueous solution while cooling, a white precipitate of 9,9'-bianthracene-10,10'-diol compound is formed. In addition, the 9,9'-bianthracene-10,10'-diol compound obtained may form a salt with an organic base compound.

Finally, the third reaction will be described. The third reaction is produced by etherifying the 9,9'-bianthracene-10,10'-diol compound obtained in the second reaction using an etherifying agent in the presence of an inorganic base.

Examples of the inorganic base used in the third reaction include sodium hydroxide, potassium hydroxide, and lithium hydroxide. Among these, sodium hydroxide is particularly preferable.

The amount of inorganic base added in the third reaction is preferably 2 mol times or more and less than 5 mol times, more preferably 3 mol times or more, relative to the raw material 9,9′-bianthracene-10,10′-diol compound. It is less than 4 mole times.

As the etherifying agent used in the third reaction, dialkyl sulfuric acid or an alkyl halide compound can be used. Dialkyl sulfuric acid includes dimethyl sulfuric acid, diethyl sulfuric acid, di-n-propyl sulfuric acid and the like. Examples of the halogenated alkyl compound include methyl bromide, ethyl bromide, -n-propyl bromide, -n-butyl bromide, bromide-n-pentyl, bromide-i-pentyl, bromide-n-hexyl, -N-heptyl bromide, n-octyl bromide, 2-ethylhexyl bromide, n-nonyl bromide, n-decyl bromide, n-dodecyl bromide, benzyl bromide, phenethyl bromide, Methyl chloride, ethyl chloride, -n-propyl chloride, -n-butyl chloride, -n-pentyl chloride, -i-pentyl chloride, -n-hexyl chloride, -n-heptyl chloride, -n-octyl chloride, chloride- Examples include 2-ethylhexyl, benzyl chloride, phenethyl chloride and the like.

The amount of the etherifying agent used in the third reaction is preferably 2 mol times or more and less than 5 mol times, more preferably 3 mol times with respect to the raw material 9,9′-bianthracene-10,10′-diol compound. As mentioned above, it is less than 4 mole times.

The third reaction is usually performed in a solvent, and a water-soluble solvent or a water-insoluble solvent is used as the solvent. Examples of the water-soluble solvent include alcohol solvents such as methanol, ethanol and i-propanol, ether solvents such as tetrahydrofuran and 1,4-dioxane, and amide solvents such as dimethylacetamide and dimethylformamide. Examples of the water-insoluble solvent include aromatic solvents such as toluene, xylene, methylnaphthalene and chloronaphthalene.

The reaction temperature for the third reaction is usually 0 ° C. or higher and lower than 100 ° C., preferably 20 ° C. or higher and lower than 60 ° C. If it is less than 0 ° C, it takes too much reaction time, and if it is 100 ° C or more, impurities are increased and the purity of the target compound is lowered, which is not preferable. The reaction time varies depending on the reaction temperature, but is usually about 1 to 4 hours. In addition, with the progress of the reaction, the diether compound often precipitates. In that case, the target compound is obtained by filtering and drying the precipitate.

As described above, the 9,9'-bianthracene-10,10'-diether compound of the present invention can be obtained simply and with a good yield through the first reaction, the second reaction and the third reaction.

In the second reaction and the third reaction, the 9,9′-bianthracene-10,10′-diol compound, which is a product of the second reaction, can be continuously performed without isolation. Further, the enolization reaction as the second reaction and the etherification reaction as the third reaction can be performed simultaneously.

(Method of continuous etherification without isolating the diol form)
As a method for continuously etherifying the diol compound without isolation, first, as described in the second reaction, 9,9′-bianthracene-10,10 ′ (9H, The 9′H) -dione compound is enolized by heating in the presence of a base in a solvent. In the second reaction described above, the 9,9′-bianthracene-10,10′-diol compound was isolated by the acid precipitation treatment, but when the reaction was performed continuously, the acid precipitation treatment was not carried out. The etherification is subsequently carried out by adding the etherifying agent directly to the liquid.

In this case, the base used for the enolization reaction is preferably an inorganic base. Examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. Among these, sodium hydroxide is particularly preferable.

The addition ratio of the inorganic base to the 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione compound is preferably 2 mol times or more, less than 15 mol times, more preferably 5 mol times or more, It is less than 10 mole times. If it is less than 2 mol times, the raw material 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione compound remains unreacted, and even if added more than 15 mol times, the reaction results are There is no improvement.

Examples of the solvent in the case of continuous etherification include amide solvents such as N, N′-dimethylformamide, N, N′-dimethylacetamide and N-methylpyrrolidone, tetrahydrofuran, 1,4-dioxane and the like. Examples include ether solvents, nitrile solvents such as acetonitrile and propionitrile, ketone solvents such as acetone and methyl ethyl ketone, and alcohol solvents such as methanol, ethanol, and i-propanol. Of these, amide solvents such as N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methylpyrrolidone and the like are preferable because of the ease of enolization reaction.

The reaction temperature for enolization is usually 50 ° C to 100 ° C. The reaction time is not constant depending on the reaction temperature, but is usually about 30 minutes to 2 hours.

Following the enolization reaction, an etherification reaction is performed.

As the etherifying agent used in the etherification reaction, dialkyl sulfuric acid or an alkyl halide compound can be used. Dialkyl sulfuric acid includes dimethyl sulfuric acid, diethyl sulfuric acid, di-n-propyl sulfuric acid and the like. Examples of the halogenated alkyl compound include methyl bromide, ethyl bromide, -n-propyl bromide, -n-butyl bromide, bromide-n-pentyl, bromide-i-pentyl, bromide-n-hexyl, -N-heptyl bromide, n-octyl bromide, 2-ethylhexyl bromide, n-nonyl bromide, n-decyl bromide, n-dodecyl bromide, benzyl bromide, phenethyl bromide, Methyl chloride, ethyl chloride, -n-propyl chloride, -n-butyl chloride, -n-pentyl chloride, -i-pentyl chloride, -n-hexyl chloride, -n-heptyl chloride, -n-octyl chloride, chloride- Examples include 2-ethylhexyl, benzyl chloride, phenethyl chloride and the like.

The reaction temperature for the etherification reaction is usually 0 ° C. or higher and lower than 100 ° C., preferably 20 ° C. or higher and lower than 60 ° C. If it is less than 0 ° C, it takes too much reaction time, and if it is 100 ° C or more, impurities are increased and the purity of the target compound is lowered, which is not preferable. The reaction time varies depending on the reaction temperature, but is usually about 1 to 4 hours. In addition, with the progress of the reaction, the diether compound often precipitates. In that case, the target compound is obtained by filtering and drying the precipitate.

(Method of performing enolization reaction and etherification reaction simultaneously)
Next, a method for simultaneously performing the enolization reaction as the second reaction and the etherification reaction as the third reaction will be described. In this method, the 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione compound obtained in the first reaction is previously mixed with an etherifying agent in a solvent. And it is the method of obtaining the target 9,9'-bianthracene-10,10'-diether compound by adding an inorganic base to the said mixture, and enolating simultaneously with etherification.

Examples of the solvent include amide solvents such as N, N′-dimethylformamide, N, N′-dimethylacetamide and N-methylpyrrolidone, ether solvents such as tetrahydrofuran and 1,4-dioxane, acetonitrile, propionitrile. Nitrile solvents such as acetone, ketone solvents such as acetone and methyl ethyl ketone, and alcohol solvents such as methanol, ethanol and i-propanol. Of these, amide solvents such as N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methylpyrrolidone and the like are preferable because of the ease of enolization reaction.

As the etherifying agent, dialkyl sulfuric acid or an alkyl halide compound can be used. Dialkyl sulfuric acid includes dimethyl sulfuric acid, diethyl sulfuric acid, di-n-propyl sulfuric acid and the like. Examples of the halogenated alkyl compound include methyl bromide, ethyl bromide, -n-propyl bromide, -n-butyl bromide, bromide-n-pentyl, bromide-i-pentyl, bromide-n-hexyl, -N-heptyl bromide, n-octyl bromide, 2-ethylhexyl bromide, n-nonyl bromide, n-decyl bromide, n-dodecyl bromide, benzyl bromide, phenethyl bromide, Methyl chloride, ethyl chloride, -n-propyl chloride, -n-butyl chloride, -n-pentyl chloride, -i-pentyl chloride, -n-hexyl chloride, -n-heptyl chloride, -n-octyl chloride, chloride- Examples include 2-ethylhexyl, benzyl chloride, phenethyl chloride and the like.

As a base used for this reaction, an inorganic base is preferable. Examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. Among these, sodium hydroxide is particularly preferable.

The addition ratio of the inorganic base to the 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione compound is preferably 2 mol times or more, less than 15 mol times, more preferably 5 mol times or more, It is less than 10 mole times. If it is less than 2 mol times, the raw material 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione compound remains unreacted, and even if added more than 15 mol times, the reaction results are There is no improvement.

The reaction temperature of the reaction is usually 0 ° C. or higher and lower than 100 ° C., preferably 20 ° C. or higher and lower than 60 ° C. If it is less than 0 ° C, it takes too much reaction time, and if it is 100 ° C or more, impurities are increased and the purity of the target compound is lowered, which is not preferable. The reaction time varies depending on the reaction temperature, but is usually about 1 to 4 hours.

(Photopolymerization sensitizer)
The 9,9′-bianthracene-10,10′-diether compound represented by the general formula (1) of the present invention can be used as a photopolymerization sensitizer in photocationic polymerization and photoradical polymerization.

(In the general formula (1), R represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group, and X, X ′, Y and Y ′ may be the same or different, and may be a hydrogen atom, carbon Represents an alkyl group or a halogen atom of formula 1-8.)

The photopolymerization sensitizer of the present invention is used for enhancing the polymerization initiation ability of the photopolymerization initiator. The photopolymerization initiator and the photopolymerization sensitizer may be added separately to the photopolymerizable compound, but as a photopolymerization initiator composition in which the photopolymerization initiator and the photopolymerization sensitizer are mixed, It may be added to the compound. Further, the 9,9′-bianthracene-10,10′-diether compound represented by the general formula (1) of the present invention can be used alone as a photopolymerization sensitizer, but is represented by the general formula (1). A plurality of these 9,9′-bianthracene-10,10′-diether compounds may be used in combination. Furthermore, a photopolymerization sensitizer other than the 9,9′-bianthracene-10,10′-diether compound represented by the general formula (1) of the present invention is used in combination as long as the effects of the present invention are not impaired. May be.

(Photopolymerization initiator composition)
Next, the photopolymerization initiator composition of the present invention will be described. The photopolymerization initiator composition of the present invention comprises a 9,9′-bianthracene-10,10′-diether compound represented by the general formula (1) of the present invention as a photopolymerization sensitizer, and a photopolymerization initiator. It is a composition to contain. As the photopolymerization initiator, an onium salt can be used. As the onium salt, a sulfonium salt or an iodonium salt is usually used. Examples of the sulfonium salt include S, S, S ′, S′-tetraphenyl-S, S ′-(4,4′-thiodiphenyl) disulfonium bishexamethoxyphosphate, diphenyl-4-phenylthiophenylsulfonium hexamethoxy. Examples thereof include phosphate and triphenylsulfonium hexamethoxyphosphate. For example, UVI6992 manufactured by Dow Chemical Company can be used. On the other hand, examples of the iodonium salt include 4-isobutylphenyl-4′-methylphenyliodonium hexamethoxyphosphate, bis (dodecylphenyl) iodonium hexamethoxyantimonate, 4-isopropylphenyl-4′-methylphenyliodonium tetrakispentamethoxyphenylborate. For example, Irgacure 250 manufactured by Ciba Specialty Chemicals (Irgacure is a registered trademark of Ciba Specialty Chemicals) and 2074 manufactured by Rhodia can be used. These photopolymerization initiators may be used alone or in combination of two or more.

In the photopolymerization initiator composition of the present invention, the amount of the 9,9′-bianthracene-10,10′-diether compound represented by the general formula (1) of the present invention which is a photopolymerization sensitizer is particularly Although not limited, it is usually in the range of 5 wt% or more and less than 100 wt%, preferably 10 wt% or more and less than 50 wt% with respect to the photopolymerization initiator. If the amount used is less than 5% by weight, it takes too much time to photopolymerize the photopolymerizable compound. On the other hand, even if it is used in an amount of 100% by weight or more, an effect commensurate with the addition cannot be obtained.

(Photopolymerizable composition)
Next, the photopolymerizable composition of the present invention will be described. The photopolymerizable composition of the present invention is a composition containing the photopolymerization initiator composition of the present invention and a photocationically polymerizable compound or a photoradical polymerizable compound.

Examples of the photocationic polymerizable compound that can be used in the photopolymerizable composition of the present invention include an epoxy compound and a vinyl ether compound. Common examples of the epoxy compound include alicyclic epoxy compounds, epoxy-modified silicones, aromatic glycidyl ethers, and the like. Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis (3,4-epoxycyclohexyl) adipate. For example, UVR6105 and UVR6110 manufactured by Dow Chemical Company are used. Can do. 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 the vinyl ether include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether and the like. These photocationically polymerizable compounds may be a single compound or a mixture of two or more.

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. . Of these radically polymerizable compounds, acrylic acid esters and methacrylic acid esters (hereinafter referred to as “(meth) acrylic acid esters” together) are preferred from the standpoint of film-forming ability. (Meth) acrylic acid esters include methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, tetraethylene Examples include glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, epoxy acrylate, urethane acrylate, polyester acrylate, polybutadiene acrylate, polyol acrylate, polyether acrylate, silicone resin acrylate, and imide acrylate. These radical photopolymerizable compounds may be a single compound or a mixture of two or more.

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

  The photopolymerizable composition of the present invention includes a diluent, a colorant, an organic or inorganic filler, a leveling agent, a surfactant, an antifoaming agent, a thickener, and a flame retardant, as long as the effects of the present invention are not impaired. Various resin additives such as antioxidants, stabilizers, lubricants, and plasticizers may be blended.

(Photocured product)
Next, the photocured product of the present invention will be described. When the photopolymerizable composition of the present invention is irradiated with light, a photocured product can be obtained. When photocuring the photopolymerizable composition of the present invention, the photopolymerizable composition can be molded into a film and photocured, or the photopolymerizable composition can be molded into a block and photocured. You can also When it is formed into a film and photocured, the liquid photopolymerizable composition can be applied to a substrate such as a polyester film so as to have a film thickness of 5 to 300 microns using a bar coater or the like. On the other hand, it can also be applied with a thinner or thicker film by spin coating or screen printing. A photocured product can be obtained by irradiating the thus prepared film with ultraviolet light containing a wavelength range of 250 to 500 nm with an intensity of about 1 to 1000 mW / cm ² . Examples of the light source used include a metal halide lamp, a xenon lamp, a 395 nm ultraviolet LED, a 385 nm ultraviolet LED, a 365 nm ultraviolet LED, a blue LED, a white LED, a D bulb and a V bulb manufactured by Fusion. It can also be photocured with sunlight.

(Tack free test)
As a method for determining whether or not the photopolymerizable composition of the present invention has been photocured, for example, a tack-free test (a finger test) can be used. That is, when the photopolymerizable composition is irradiated with light, it hardens and takes a tack on the surface. Therefore, measure the time from the start of light irradiation until the tack (stickiness) is removed, and measure the photocuring time. It is a method to do.

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

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

(1) Melting point: Melting point measuring device manufactured by Guerencamp, Model MFB-595 (JIS
According to 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 of Photopolymerization Sensitizer)
(Synthesis Example 1) Synthesis of 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione with 9-anthrone and 2-methyl-1,4-naphthoquinone 500 ml three-neck equipped with stirrer The flask was charged with 21.2 g (110 mmol) of 9-anthrone, 17.2 g (100 mmol) of 2-methyl-1,4-naphthoquinone, 85 g of 1,4-dioxane, and 0.2 g of methanesulfonic acid in a nitrogen atmosphere. . When the slurry was heated in an oil bath at 106 ° C. and heated, the slurry once melted into a yellow solution, and then a few crystals were precipitated in a few minutes. The reaction mixture is cooled to room temperature, filtered with suction, washed with 1,4-dioxane and dried to give 16.5 g of white crystals of 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione ( 42 mmol). The yield based on 9-anthrone as a raw material was 76 mol%.

Physical property values of 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione (1) Melting point: 260 ° C. or higher (2)
IR (KBr, cm ⁻¹ ): 1662, 1600, 1463, 1322, 1100, 940, 790, 693.
(3)
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 4.79 (s, 2H), 6.88 (d, J = 8 Hz, 4H), 7.36-7.48 (m, 8H), 7. 94 (d, J = 8 Hz, 4H).

Synthesis Example 2 Synthesis of 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione with 9-anthrone and 2,6-dimethyl-1,4-benzoquinone, equipped with a stirrer In a 200 ml three-necked flask, 9.27 g (22 mmol) of 9-anthrone, 2.72 g (20 mmol) of 2,6-dimethyl-1,4-benzoquinone, 20 g of 1,4-dioxane, 0.2 g of methanesulfonic acid in a nitrogen atmosphere. 1 g was charged. When the slurry was heated in an oil bath at 106 ° C. and heated, it once melted to become a yellow solution, and then a few crystals were precipitated in a few minutes. The reaction mixture is cooled to room temperature, filtered with suction, washed with 1,4-dioxane, dried and 3.70 g of 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione white crystals ( 9.5 mmol). The yield based on the starting 9-anthrone was 87 mol%.

When the obtained white crystals were analyzed by IR and ¹ H-NMR, the same analysis results as in Synthesis Example 1 were obtained, and 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione was obtained. It was confirmed that.

Synthesis Example 3 Synthesis of 9,9′-bianthracene-10,10′-diol by enolization of 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione (inorganic base If used)
9,9′-Bianthracene-10,10 ′ (9H, 9′H) -dione 3.86 g (10) obtained in the same manner as in Synthesis Example 1 in a 200 ml three-necked flask equipped with a thermometer and a stirrer Mmol) was dispersed in 50 ml of dimethylacetamide. Then a solution of 3.0 g (75 mmol) sodium hydroxide in 15 g water was added at room temperature. Then, the white slurry suddenly turned red and began to melt. Then, when the bath temperature was heated at 65 ° C., the slurry was completely dissolved after 30 minutes, and a red solution was obtained. After further heating for 30 minutes, the reaction solution was cooled to room temperature, and the reaction solution was added to 250 ml of an acidic aqueous solution. Then, since a large amount of precipitate was formed, it was suction filtered, washed with water and dried to obtain 4.60 g (8.2 mmol) of a light yellow powder. This was a product obtained by adding two molecules of dimethylacetamide as a solvent to 9,9′-bianthracene-10,10′-diol. The isolated yield based on the raw material 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione was 82 mol%.

Physical property value of dimethylacetamide bimolecular adduct of 9,9′-bianthracene-10,10′-diol (1) Melting point: 260 ° C. or higher (2) IR (KBr, cm ⁻¹ ): 3440, 3060, 1620, 1560, 1422, 1380, 1365, 1300, 1224, 1210, 1090, 1021, 766, 673.
(3) ¹ H-NMR (400 MHz, acetone-d ₆ ): δ = 1.96 (s, 6H), 3.02 (s, 12H), 6.97-7.04 (m, 4H), 7 12-7.20 (m, 4H), 7.43 (d, J = 8 Hz, 4H), 8.63 (d, J = 8 Hz, 4H), 9.46 (s, 2H).

Synthesis Example 4 Synthesis of 9,9′-bianthracene-10,10′-diol by enolization of 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione (an organic base If used)
In a 300 ml three-necked flask equipped with a thermometer and a stirrer, 3.86 g (10 mmol) of 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione obtained in the same manner as in Synthesis Example 1 was added. Disperse in 80 g of pyridine. Subsequently, when it heated at the bath temperature of 106 degreeC, it became a yellow solution rapidly. After further heating for 30 minutes, the reaction solution was cooled to room temperature and poured into 400 ml of hexane. As a result, a large amount of precipitate was formed, which was suction filtered and dried to obtain 3.55 g (6.5 mmol) of a yellowish green powder. This was a product in which two molecules of pyridine were added to 9,9′-bianthracene-10,10′-diol. Next, the obtained 9,9′-bianthracene-10,10′-diol / pyridine bimolecular adduct was dissolved in 50 ml of acetone, and 1.5 g (15.6 mmol) of methanesulfonic acid was added. As a result, a light brown liquid was gradually formed. After further 1 hour, the precipitate was suction filtered and dried to obtain 2.20 g (5.7 mmol) of 9,9′-bianthracene-10,10′-diol as a light brown powder. The isolated yield based on the raw material 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione was 57 mol%.

Properties of intermediate 9,9'-bianthracene-10,10'-diol / pyridine bimolecular adduct (1) Melting point: 260 ° C. or higher (2) IR (KBr, cm ⁻¹ ): 3420, 3026 2930, 1680, 1620, 1596, 1560, 1440, 1340, 1320, 1216, 1170, 1092, 900, 768, 700, 672.
(3) ¹ H-NMR (400 MHz, acetone-d ₆ ): δ = 7.02 (d, J = 8 Hz, 4H), 7.11-7.18 (m, 4H), 7.28-7. 38 (m, 4H), 7.39-7.49 (m, 4H), 7.74 (t, J = 8 Hz, 2H), 8.58 (d, J = 8 Hz, 4H), 8.65 ( d, J = 8 Hz, 4H), 9.48 (bs, 2H).

Physical property values of 9,9′-bianthracene-10,10′-diol (1) Melting point: 260 ° C. or higher (2) IR (KBr, cm ⁻¹ ): 3400, 3250, 1696, 1560, 1370, 1310, 1207 , 1090, 770.
(3) ¹ H-NMR (400 MHz, acetone-d ₆ ): δ = 7.01 (d, J = 8 Hz, 4H), 7.12-7.18 (m, 4H), 7.38-7. 45 (m, 4H), 8.64 (d, J = 8 Hz, 4H), 9.42 (bs, 2H).

(Example 1) Synthesis thermometer of 9,9'-bianthracene-10,10'-diethyl ether (Compound A) A 200 ml three-necked flask equipped with a stirrer was charged with 25 g of dimethylacetamide and 20 g of water. 9.86 g (10 mmol) of 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione obtained in the same manner was added. Next, a solution of 2.0 g (50 mmol) of sodium hydroxide in 10 ml of water was added to the resulting white slurry under a nitrogen atmosphere. Heat at 50 ° C. for 30 minutes to obtain a red solution. The solution was then cooled to room temperature and then a solution of 3.85 g (25 mmol) of diethylsulfate (Mw154) in 15 g of dimethylacetamide was added. After stirring for 10 hours, the red color of the solution disappeared and a large amount of precipitate was deposited. The mixture was poured into acidic water, filtered with suction, washed with methanol, and dried to obtain 4.0 g (9.0 mmol) of an orange powder of 9,9′-bianthracene-10,10′-diethyl ether (Mw442). Obtained. The yield based on the raw material 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione was 90 mol%.

Physical properties of 9,9'-bianthracene-10,10'-diethyl ether (1) Melting point: 205-207 ° C
(2) IR (KBr, cm ⁻¹ ): 3060, 2980, 2930, 1620, 1440, 1420, 1370, 1340, 1170, 1086, 1020, 848, 770, 730, 680.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 8.44 (4H, d, J = 9 Hz), 7.44 (4H, dd, J ₁ = 9 Hz, J ₂ = 2 Hz), 7. 06-7.19 (8H, m), 4.48 (4H, q, J = 8 Hz), 1.76 (6H, t, J = 8 Hz).

Example 2 Synthesis Example of 9,9′-Bianthracene-10,10′-bis (n-propyl) ether (Compound B) 20 g of dimethylacetamide was charged into a 200 ml three-necked flask equipped with a stirrer. 1,9'-bianthracene-10,10 '(9H, 9'H) -dione 1.54 g (4 mmol), 1.97 g (16 mmol) of n-propyl bromide obtained in the same manner as in Example 1. Was added. A white slurry was obtained, and a solution of 1.20 g (30 mmol) of sodium hydroxide in 6 ml of water was added to the slurry under a nitrogen atmosphere. Immediately thereafter, the color of the liquid turned red and the slurry gradually dissolved. Then, when it stirred as it was at room temperature for 10 hours, a lot of deposits precipitated. The slurry was put into acidic water, filtered with suction, washed with methanol, and dried to obtain 1.76 g of a white yellow powder of 9,9′-bianthracene-10,10′-bis (n-propyl) ether (Mw470) ( 3.72 mmol) was obtained. The yield based on the raw material 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione was 93 mol%.

Properties of 9,9′-Bianthracene-10,10′-bis (n-propyl) ether (1) Melting point: 260 ° C. or higher (2) IR (KBr, cm ⁻¹ ): 3060, 2975, 2940, 2880 1620, 1440, 1420, 1350, 1340, 1168, 1096, 980, 945, 772, 682.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 8.46 (4H, d, J = 9 Hz), 7.44 (4H, dd, J ₁ = 9 Hz, J ₂ = 2 Hz), 7. 04-7.17 (8H, m), 4.35 (4H, t, J = 8 Hz), 2.14-2.26 (4H, m), 1.31 (6H, t, J = 8 Hz).

(Example 3) Synthesis Example of 9,9'-Bianthracene-10,10'-bis (n-butyl) ether (Compound C) Thermometer, 20 g of dimethylacetamide was charged into a 200 ml three-necked flask equipped with a stirrer. 1,9'-Bianthracene-10,10 '(9H, 9'H) -dione 1.54 g (4 mmol) obtained in the same manner as 1, and 1.64 g (12 mmol) of n-butyl bromide Was added. A white slurry was obtained, and a solution of 1.20 g (30 mmol) of sodium hydroxide in 6 ml of water was added to the slurry under a nitrogen atmosphere. Immediately thereafter, the color of the liquid turned red and the slurry gradually dissolved. Thereafter, the mixture was stirred at room temperature for 10 hours as it was, and a small amount of precipitate appeared. The solution was put into acidic water, filtered with suction, washed with methanol, and dried to give 1.93 g of a white-yellow powder of 9,9′-bianthracene-10,10′-bis (n-butyl) ether (Mw496) ( 3.90 mmol) was obtained. The yield based on the raw material 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione was 97 mol%.

Properties of 9,9'-bianthracene-10,10'-bis (n-butyl) ether (1) Melting point: 252-254 ° C
(2) IR (KBr, cm ⁻¹ ): 3060, 2970, 2940, 2875, 1620, 1440, 1420, 1352, 1170, 1090, 1022, 965, 868, 772, 682.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 8.47 (4H, d, J = 9 Hz), 7.45 (4H, dd, J ₁ = 9 Hz, J ₂ = 2 Hz), 7. 06-7.18 (8H, m), 4.39 (4H, t, J = 8 Hz), 2.11-2.21 (4H, m), 1.74-1.84 (4H, m), 1.14 (6H, t, J = 8 Hz).

Example 4 Synthesis Thermometer of 9,9′-Bianthracene-10,10′-bis (i-butyl) ether (Compound D) 30 g of dimethylacetamide was charged into a 200 ml three-necked flask equipped with a stirrer. 9,9′-Bianthracene-10,10 ′ (9H, 9′H) -dione 3.86 g (10 mmol) obtained in the same manner as 1 and 5.48 g (40 mmol) of i-butyl bromide Was added. A white slurry was obtained, and a solution of 4.0 g (100 mmol) of sodium hydroxide in 10 ml of water was added to the slurry under a nitrogen atmosphere. Immediately thereafter, the color of the liquid turned red and the slurry gradually dissolved. Then, when it stirred as it was at room temperature for 10 hours, a lot of deposits precipitated. The solution was put into acidic water, filtered with suction, washed with methanol, and dried to give 7.5 g of 9,9′-bianthracene-10,10′-bis (i-butyl) ether (Mw498) white yellow powder ( 9.00 mmol). The yield based on the raw material 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione was 75 mol%.

Physical properties of 9,9′-bianthracene-10,10′-bis (i-butyl) ether (1) Melting point: 255 ° C. or higher (2) IR (KBr, cm ⁻¹ ): 3070, 2960, 2880, 1621 , 1562, 1472, 1440, 1420, 1380, 1351, 1340, 1168, 1092, 992, 772, 682.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 8.45 (4H, d, J = 9 Hz), 7.44 (4H, dd, J ₁ = 9 Hz, J ₂ = 2 Hz), 7. 03-7.18 (8H, m), 4.18 (4H, t, J = 8 Hz), 2.46-2.60 (2H, m), 1.14 (12H, t, J = 8 Hz).

(Example 5) Synthesis example of 9,9'-bianthracene-10,10'-bis (n-pentyl) ether (Compound E) 30 g of dimethylacetamide was charged into a 200 ml three-necked flask equipped with a stirrer and synthesized. 9,9′-Bianthracene-10,10 ′ (9H, 9′H) -dione 3.86 g (10 mmol) obtained in the same manner as 1 and 4.50 g (30 mmol) of n-pentyl bromide Was added. A white slurry was obtained, and a solution of 2.0 g (50 mmol) of sodium hydroxide in 10 ml of water was added to the slurry under a nitrogen atmosphere. Immediately thereafter, the color of the liquid turned red and the slurry gradually dissolved. Then, when it stirred as it was at room temperature for 10 hours, a lot of deposits precipitated. The solution was poured into acidic water, suction filtered, washed with methanol, and dried to obtain 3.8 g of a white-yellow powder of 9,9′-bianthracene-10,10′-bis (n-pentyl) ether (Mw524) ( 7.2 mmol). The yield based on the raw material 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione was 72 mol%.

Physical properties of 9,9′-bianthracene-10,10′-bis (n-pentyl) ether (1) Melting point: 204-206 ° C.
(2) IR (KBr, cm ⁻¹ ): 3090, 2950, 2940, 2890, 1620, 1440, 1420, 1347, 1164, 1090, 973, 771, 681.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 8.46 (4H, d, J = 9 Hz), 7.43 (4H, dd, J ₁ = 9 Hz, J ₂ = 2 Hz), 7. 04-7.17 (8H, m), 4.39 (4H, t, J = 8 Hz), 2.12-2.26 (4H, m), 1.66-1.80 (4H, m), 1.50-1.66 (4H, m), 1.07 (6H, t, J = 8 Hz).

Example 6 Synthesis Thermometer of 9,9′-Bianthracene-10,10′-bis (n-heptyl) ether (Compound F), 20 g of dimethylacetamide was charged into a 200 ml three-necked flask equipped with a stirrer. 1,9'-Bianthracene-10,10 '(9H, 9'H) -dione 1.54 g (4 mmol) obtained in the same manner as 1 and 2.86 g (12 mmol) of n-heptyl bromide Was added. A white slurry was obtained, and a solution of 1.20 g (30 mmol) of sodium hydroxide in 6 ml of water was added to the slurry under a nitrogen atmosphere. Immediately thereafter, the color of the liquid turned red and the slurry gradually dissolved. Thereafter, the mixture was stirred at room temperature for 10 hours as it was, and a small amount of precipitate appeared. The solution was poured into acidic water, filtered with suction, washed with methanol, and dried to give 2.25 g of a white-yellow powder of 9,9′-bianthracene-10,10′-bis (n-heptyl) ether (Mw582) ( 3.86 mmol) was obtained. The yield based on the raw material 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione was 96 mol%.

Properties of 9,9'-bianthracene-10,10'-bis (n-heptyl) ether (1) Melting point: 151-152 ° C
(2) IR (KBr, cm ⁻¹ ): 2940, 2860, 1348, 1092, 770, 680.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 1.34-1.48 (m, 8H), 1.48-1.60 (m, 4H), 1.68-1.81 ( m, 4H), 2.10-2.23 (m, 4H), 4.37 (d, J = 8 Hz, 4H), 7.02-7.17 (m, 8H), 7.44 (dd, J ₁ = 9 Hz, J ₂ = 2 Hz, 4H), 8.44 (d, J = 9 Hz, 4H).

Example 7 Synthesis of 9,9′-Bianthracene-10,10′-bis (2-ethylhexyl) ether (Compound G) 50 g of dimethylacetamide was charged into a 200 ml three-necked flask equipped with a thermometer and a stirrer. 9,9′-bianthracene-10,10 ′ (9H, 9′H) -dione 3.86 g (10 mmol) obtained in the same manner as in Example 1, 7.72 g (40 mmol) of 2-ethylhexyl bromide Was added. A white slurry was obtained, and a solution of 4.0 g (100 mmol) of sodium hydroxide in 15 ml of water was added to the slurry under a nitrogen atmosphere. Immediately thereafter, the color of the liquid turned red and the slurry gradually dissolved. Thereafter, the mixture was stirred at room temperature for 10 hours as it was, and as a result, the entire slurry was solated. Upon stirring, the sol became a thick liquid. When the sol was poured into acidic water, a large amount of yellow precipitate appeared. Filtration with suction, washing with methanol, and drying gave 5.4 g (9.0 mmol) of a white-yellow powder of 9,9′-bianthracene-10,10′-bis (2-ethylhexyl) ether (Mw610). The yield based on the raw material 9,9′-bianthracene-10,10 ′-(9H, 9H ′)-dione was 90 mol%.

Physical properties of 9,9'-bianthracene-10,10'-bis (2-ethylhexyl) ether (1) Melting point: 174-175 ° C
(2) IR (KBr, cm ⁻¹ ): 3065, 2960, 2930, 2875, 1620, 1600, 1560, 1460, 1440, 1418, 1380, 1344, 1163, 1090, 1020, 768, 680.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 8.45 (4H, d, J = 9 Hz), 7.46 (4H, dd, J ₁ = 9 Hz, J ₂ = 2 Hz), 7. 06-7.19 (8H, m), 4.27 (4H, t, J = 8 Hz), 2.10-2.21 (2H, m), 1.87-1.97 (2H, m), 1.75-1.86 (4H, m), 1.62-1.75 (2H, m), 1.42-1.57 (8H, m), 1.14 (6H, t, J = 8 Hz) ), 1.01 (6H, t, J = 8 Hz).

(Example 8) Synthesis of 9,9'-bianthracene-10,10'-dibenzyl ether (Compound H) 30 g of dimethylacetamide was charged into a 200 ml three-necked flask equipped with a thermometer and a stirrer in the same manner as in Synthesis Example 4. Then, 9.86 g (10 mmol) of 9,9′-bianthracene-10,10′-diol and 5.10 g (30 mmol) of benzyl bromide were added. A white slurry was obtained, and a solution of 2.0 g (50 mmol) of sodium hydroxide in 14 ml of water was added to the slurry under a nitrogen atmosphere. Immediately thereafter, the color of the liquid turned red and the slurry gradually dissolved. Then, when it stirred as it was at room temperature for 10 hours, a lot of deposits precipitated. The solution was poured into acidic water, suction filtered, washed with methanol, and dried to give 4.8 g (8.5) of a white-yellow powder of 9,9′-bianthracene-10,10′-dibenzyldiether (Mw566)). Mmol). The yield based on the raw material 9,9′-bianthracene-10,10′-diol was 85 mol%.

Properties of 9,9'-bianthracene-10,10'-dibenzyl ether (1) Melting point: 199-201 ° C
(2) IR (KBr, cm ⁻¹ ): 3060, 3036, 2940, 2880, 1620, 1416, 1414, 1342, 1165, 1090, 986, 772, 732, 682, 608.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 8.50 (4H, d, J = 9 Hz), 7.77 (4H, d, J = 8 Hz), 7.54 (4H, d, J = 8 Hz), 7.46 (4H, dd, J ₁ = 9 Hz, J ₂ = 2 Hz), 7.22-7.29 (2H, m), 7.10-7.1 (8H, m), 5.55 (4H, s).

<Example of curing test>
<Example of cationic curing> Iodonium salt (Example 9)
As a photocationically polymerizable compound, 100 parts of an alicyclic epoxy compound (UVR6105 manufactured by Dow Chemical Company), as a photopolymerization initiator, 2 parts of iodonium salt (Irgacure 250 manufactured by Ciba Specialty Chemical Company), and as a photopolymerization sensitizer A photopolymerization initiator composition obtained by mixing 1.0 part of 9,9′-bianthracene-10,10′-diethyl ether (Compound A) synthesized in Example 1 was added, and the photopolymerizable composition was added. Was prepared. The composition prepared as described above was formed on a polyester film having a thickness of 100 microns (Toray Lumirror, Lumirror is a registered trademark of Toray Industries, Inc.) using a bar coater (No. 8) to a thickness of 12 microns. It applied so that it might become. Further, the composition was covered with a low-density polyethylene film having a thickness of 30 microns, and a light-cured product was obtained by irradiating with light using a UV LED manufactured by Thunder. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 4 mW / cm ² . The polyethylene film was peeled off at regular intervals, and stickiness was confirmed by touch. The light irradiation time “tack free time” from the start of light irradiation until the tackiness of the coated surface of the composition disappeared was 10 seconds.

(Example 10)
In place of 9,9′-bianthracene-10,10′-diethyl ether as a photopolymerization sensitizer, 9,9′-bianthracene-10,10′-bis (synthesized in the same manner as in Example 2) A photocured composition was prepared in the same manner as in Example 9 except that n-propyl) ether (Compound B) was used, and a photocured product was obtained by light irradiation. The time “tack free time” from the start of light irradiation until tack disappears was 9 seconds.

(Example 11)
In place of 9,9′-bianthracene-10,10′-diethyl ether as a photopolymerization sensitizer, 9,9′-bianthracene-10,10′-bis (synthesized in the same manner as in Example 3) A photocured composition was prepared in the same manner as in Example 9 except that n-butyl) ether (Compound C) was used, and a photocured product was obtained by light irradiation. The time “tack free time” from the start of light irradiation until tack disappears was 10 seconds.

(Example 12)
In place of 9,9′-bianthracene-10,10′-diethyl ether as a photopolymerization sensitizer, 9,9′-bianthracene-10,10′-bis (synthesized in the same manner as in Example 4) A photocured composition was prepared in the same manner as in Example 9 except that i-butyl) ether (Compound D) was used, and a photocured product was obtained by light irradiation. The time “tack free time” from the start of light irradiation until tack disappears was 10 seconds.

(Example 13)
In place of 9,9′-bianthracene-10,10′-diethyl ether as a photopolymerization sensitizer, 9,9′-bianthracene-10,10′-bis (synthesized in the same manner as in Example 5) A photocured composition was prepared in the same manner as in Example 9 except that n-pentyl) ether (Compound E) was used, and a photocured product was obtained by light irradiation. The time “tack free time” from the start of light irradiation until tack disappears was 11 seconds.

(Example 14)
In place of 9,9′-bianthracene-10,10′-diethyl ether as a photopolymerization sensitizer, 9,9′-bianthracene-10,10′-bis (synthesized in the same manner as in Example 6) A photocured composition was prepared in the same manner as in Example 9 except that n-heptyl) ether (Compound F) was used, and a photocured product was obtained by light irradiation. The time “tack free time” from the start of light irradiation until tack disappears was 11 seconds.

(Example 15)
In place of 9,9′-bianthracene-10,10′-diethyl ether as a photopolymerization sensitizer, 9,9′-bianthracene-10,10′-bis (synthesized in the same manner as in Example 7) A photocured composition was prepared in the same manner as in Example 9 except that 2-ethylhexyl) ether (Compound G) was used, and a photocured product was obtained by light irradiation. The time “tack free time” from the start of light irradiation until tack disappears was 11 seconds.

(Example 16)
9,9′-Bianthracene-10,10′-dibenzyl synthesized in the same manner as in Example 8 instead of 9,9′-bianthracene-10,10′-diethyl ether as a photopolymerization sensitizer A photocured composition was prepared in the same manner as in Example 9 except that ether (Compound H) was used, and a photocured product was obtained by light irradiation. The time “tack free time” from the start of light irradiation until tack disappears was 12 seconds.

(Comparative Example 1)
A photopolymerizable composition was prepared in the same manner as in Example 9 except that 9,9′-bianthracene-10,10′-diethyl ether was not added as a photopolymerization sensitizer. The composition thus prepared was applied on a polyester film having a thickness of 100 microns using a bar coater (No. 8) so as to have a thickness of 12 microns. Further, the composition was covered with a low-density polyethylene film having a thickness of 30 microns, and irradiated with light using a UV LED manufactured by Thunder. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 4 mW / cm ² . The polyethylene film was peeled off at regular intervals, and stickiness was confirmed by touch. However, the composition did not cure upon irradiation for 5 minutes.

(Comparative Example 2)
As a photopolymerization sensitizer, instead of 9,9'-bianthracene-10,10'-diethyl ether, 1.0 part of 9,10-dibutoxyanthracene (Compound I) which is a known photopolymerization sensitizer is added. Except that, a photopolymerizable composition was prepared in the same manner as in Example 9, and a photocured product was obtained by light irradiation. The time “tack free time” from the start of light irradiation until tack disappears was 11 seconds.

  The results of Examples 9 to 16 and Comparative Examples 1 and 2 are tabulated as follows.

In addition, compound AH of this invention and the well-known compound I are compounds of the following chemical structural formula.

<Example of cationic curing> Sulfonium salt (Example 17)
100 parts of alicyclic epoxy compound (UVR6105 manufactured by Dow Chemical Co., Ltd.) as a photocationically polymerizable compound, 4 parts of sulfonium salt (UVI-6922 manufactured by Dow Chemical Co., Ltd.) as a photopolymerization initiator, implemented as a photopolymerization sensitizer A photopolymerization initiator composition obtained by mixing 1.0 part of 9,9′-bianthracene-10,10′-bis (n-propyl) ether (Compound B) synthesized in the same manner as in Example 2 was added. Then, a photopolymerizable composition was prepared. The composition prepared in this way was coated on a polyester film film having a thickness of 100 microns (Toray Lumirror, Lumirror is a registered trademark of Toray Industries, Inc.) using a bar coater (No. 8) and having a thickness of 12 microns. It applied so that it might become. Further, the composition was covered with a low-density polyethylene film having a thickness of 30 microns, and a light-cured product was obtained by irradiating with light using a UV LED manufactured by Thunder. The polyethylene film was peeled off at regular intervals, and stickiness was confirmed by touch. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 4 mW / cm ² . The light irradiation time “tack free time” from the start of light irradiation until the tackiness of the coated surface of the composition disappeared was 23 seconds.

(Example 18)
9,9′-Bianthracene-10,10 synthesized in the same manner as in Example 3 instead of 9,9′-Bianthracene-10,10′-bis (n-propyl) ether as a photopolymerization sensitizer A photocured composition was prepared in the same manner as in Example 17 except that '-bis (n-butyl) ether (Compound C) was used, and a photocured product was obtained by light irradiation. The time “tack free time” from the start of light irradiation until tack disappears was 25 seconds.

(Example 19)
9,9′-Bianthracene-10,10 synthesized in the same manner as in Example 7 instead of 9,9′-Bianthracene-10,10′-bis (n-propyl) ether as a photopolymerization sensitizer A photocured composition was prepared in the same manner as in Example 17 except that '-bis (2-ethylhexyl) ether (Compound G) was used, and a photocured product was obtained by light irradiation. The time “tack free time” from the start of light irradiation until tack disappears was 27 seconds.

(Comparative Example 3)
A photopolymerizable composition was prepared in the same manner as in Example 17 except that 9,9′-bianthracene-10,10′-bis (n-propyl) ether was not added as a photopolymerization sensitizer. The composition thus prepared was applied on a polyester film having a thickness of 100 microns using a bar coater (No. 8) so as to have a thickness of 12 microns. Further, the composition was covered with a low-density polyethylene film having a thickness of 30 microns, and irradiated with light using a UV LED manufactured by Thunder. The polyethylene film was peeled off at regular intervals, and stickiness was confirmed by touch. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 4 mW / cm ² . However, the composition did not cure upon irradiation for 5 minutes.

(Comparative Example 4)
9,10-dibutoxyanthracene (Compound I) 1 which is a known photopolymerization sensitizer instead of 9,9′-bianthracene-10,10′-bis (n-propyl) ether as a photopolymerization sensitizer A photopolymerizable composition was prepared in the same manner as in Example 17 except that 0.0 part was added, and a photocured product was obtained by light irradiation. The time “tack free time” from the start of light irradiation until tack disappears was 25 seconds.

  The results of Examples 17 to 19 and Comparative Examples 3 and 4 are tabulated as follows.

<Radical curing example>
(Example 20)
Synthesized in the same manner as in Example 2 as photoradical polymerizable compound, 100 parts of trimethylolpropane triacrylate, 2 parts of iodonium salt (Irgacure 250, manufactured by Ciba Specialty Chemical Co.) as photopolymerization initiator A photopolymerization composition obtained by mixing 1.0 part of the 9,9′-bianthracene-10,10′-bis (n-propyl) ether (Compound B) was added to form a photopolymerizable composition. Was prepared. The composition prepared as described above was formed on a polyester film having a thickness of 100 microns (Toray Lumirror, Lumirror is a registered trademark of Toray Industries, Inc.) using a bar coater (No. 8) to a thickness of 12 microns. It applied so that it might become. Further, the composition was covered with a low-density polyethylene film having a thickness of 30 microns, and a light-cured product was obtained by irradiating with light using a UV LED manufactured by Thunder. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 4 mW / cm ² . The polyethylene film was peeled off at regular intervals, and stickiness was confirmed by touch. The light irradiation time “tack free time” from the start of light irradiation until the tackiness of the coated surface of the composition disappeared was 2 seconds.

(Example 21)
9,9′-Bianthracene-10,10 synthesized in the same manner as in Example 3 instead of 9,9′-Bianthracene-10,10′-bis (n-propyl) ether as a photopolymerization sensitizer A photocured composition was prepared in the same manner as in Example 20 except that '-bis (n-butyl) ether (Compound C) was used, and a photocured product was obtained by light irradiation. The time “tack free time” from the start of light irradiation until tack disappears was 2.5 seconds.

(Example 22)
9,9′-Bianthracene-10,10 synthesized in the same manner as in Example 5 instead of 9,9′-Bianthracene-10,10′-bis (n-propyl) ether as a photopolymerization sensitizer A photocured composition was prepared in the same manner as in Example 20 except that '-bis (n-pentyl) ether (Compound E) was used, and a photocured product was obtained by light irradiation. The time “tack free time” from the start of light irradiation until tack disappears was 2.5 seconds.

(Example 23)
9,9′-Bianthracene-10,10 synthesized in the same manner as in Example 7 instead of 9,9′-Bianthracene-10,10′-bis (n-propyl) ether as a photopolymerization sensitizer A photocured composition was prepared in the same manner as in Example 20 except that '-bis (2-ethylhexyl) ether (Compound G) was used, and a photocured product was obtained by light irradiation. The time “tack free time” from the start of light irradiation until tack disappears was 3 seconds.

(Example 24)
9,9′-Bianthracene-10,10 synthesized in the same manner as in Example 8 instead of 9,9′-Bianthracene-10,10′-bis (n-propyl) ether as a photopolymerization sensitizer A photocured composition was prepared in the same manner as in Example 20 except that '-dibenzyl ether (Compound H) was used, and a photocured product was obtained by light irradiation. The time “tack free time” from the start of light irradiation until tack disappears was 3 seconds.

(Comparative Example 5)
A photopolymerizable composition was prepared in the same manner as in Example 20 except that 9,9′-bianthracene-10,10′-bis (n-propyl) ether was not added as a photopolymerization sensitizer, and a photocuring test was conducted. Carried out. The light irradiation time “tack free time” from the start of light irradiation until the tackiness of the coated surface of the composition disappeared was measured, but the composition did not cure even after irradiation for 5 minutes.

(Comparative Example 6)
9,10-dibutoxyanthracene (Compound I) 1 which is a known photopolymerization sensitizer instead of 9,9′-bianthracene-10,10′-bis (n-propyl) ether as a photopolymerization sensitizer A photopolymerizable composition was prepared in the same manner as in Example 20 except that 0.0 part was added, and a photocured product was obtained by light irradiation. The time “tack free time” from the start of light irradiation until tack disappears was 2.5 seconds.

The results of Examples 20 to 24 and Comparative Examples 5 and 6 are tabulated as follows.

From the results of Examples 9 to 24 and Comparative Examples 1 to 6, the following is clear. That is, the 9,9′-bianthracene-10,10′-dialkyl ether compound of the present invention has a photopolymerization sensitizing effect in both photocationic polymerization and photoradical polymerization, and is a known photopolymerization sensitizer. It can be seen that even if compared with a certain 9,10-dibutoxyanthracene, it has an equivalent sensitizing effect.

<Example of migration test>
(Example 25)
9,9′-Bianthracene-10,10 synthesized in the same manner as in Example 2 as a photopolymerization sensitizer in 100 parts of an alicyclic epoxy compound (UVR6105 manufactured by Dow Chemical Company) as a photocationically polymerizable compound. 1.0 parts of '-bis (n-propyl) ether (Compound B) was added, and the prepared composition was formed on a polyester film (Toray Lumirror, Lumirror is a registered trademark of Toray Industries, Inc.) to a film thickness of 12 microns. This was applied using a bar coater (No. 8). Next, a low-density polyethylene film (film thickness of 30 microns) was put on the obtained coated material, and the one stored in the dark for one day and the one stored for two days were each stored, then the polyethylene film was peeled off, and then the polyethylene film After washing with acetone and drying, the UV spectrum of the film was measured and the absorbance at 260 nm was measured. When the absorbance of the obtained 9-propoxy-10- (1,4-dipropoxy-2-naphthyl) anthracene was converted to 9,10-dibutoxyanthracene, the absorbance was 0.01 days after storage for one day and two days for storage. After 0.02.

(Example 26)
9,9′-Bianthracene-10,10′-bis (n—synthesized in the same manner as in Example 5 instead of 9,9′-bianthracene-10,10′-bis (n-propyl) ether The test was conducted in the same manner as in Example 25 except that (pentyl) ether (Compound E) 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 9-pentyloxy-10- (1,4-dipentyloxy-2-naphthyl) anthracene into 9,10-dibutoxyanthracene is one. It was 0.05 after storage for 2 days and 0.06 after storage for 2 days.

(Example 27)
9,9′-Bianthracene-10,10′-dibenzyl ether synthesized in the same manner as in Example 8 instead of 9,9′-bianthracene-10,10′-bis (n-propyl) ether ( Tested as in Example 25 except that Compound H) 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 9-benzyloxy-10- (1,4-dibenzyloxy-2-naphthyl) anthracene into 9,10-dibutoxyanthracene is It was 0.00 after 1 day storage and 0.00 after 2 days storage.

(Comparative Example 7)
Prepared in the same manner as in Example 25 except that 9,10-dibutoxyanthracene (Compound I) was used instead of 9,9′-bianthracene-10,10′-bis (n-propyl) ether. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance of 9,10-dibutoxyanthracene was 0.61 after storage for one day and 0.60 after storage for two days.

(Example 28)
9,9′-Bianthracene-10,10′-bis (n-propyl) synthesized in the same manner as in Example 2 as a photopolymerization sensitizer in 100 parts of trimethylolpropane triacrylate as a photoradical polymerizable compound 1.0 part of ether (Compound B) was added, and the prepared composition was coated on a polyester film using a bar coater so that the film thickness was 12 microns. Next, a low-density polyethylene film (film thickness of 30 microns) was put on the obtained coated material, and the one stored in the dark for one day and the one stored for two days were each stored, then the polyethylene film was peeled off, and then the polyethylene film After washing with acetone and drying, the UV spectrum of the film was measured to determine the absorbance at 260 nm. The absorbance of the obtained 9-propoxy-10- (1,4-dipropoxy-2-naphthyl) anthracene converted to 9,10-dibutoxyanthracene was 0.03 after storage for one day, and 0.03 after storage for two days. 07.

(Example 29)
9,9′-Bianthracene-10,10′-bis (n—synthesized in the same manner as in Example 5 instead of 9,9′-bianthracene-10,10′-bis (n-propyl) ether Prepared and tested as in Example 28 except that pentyl) ether (Compound E) was used. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance of 9-ethoxy-10- (1,4-diethoxy-2-naphthyl) anthracene was converted to 9,10-dibutoxyanthracene. The absorbance was 0.07 after 1 day storage and 0.08 after 2 days storage.

(Example 30)
9,9′-Bianthracene-10,10′-dibenzyl ether synthesized in the same manner as in Example 8 instead of 9,9′-bianthracene-10,10′-bis (n-propyl) ether ( Prepared and tested as in Example 28 except that compound H) was used. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance of 9-benzyloxy-10- (1,4-dibenzyloxy-2-naphthyl) anthracene was converted to 9,10-dibutoxyanthracene. The absorbance was 0.02 after 1 day storage and 0.02 after 2 days storage.

(Comparative Example 8)
The test was conducted in the same manner as in Example 28 except that 9,10-dibutoxyanthracene (Compound I) was used in place of 9,9′-bianthracene-10,10′-bis (n-propyl) ether. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance of the obtained 9,10-dibutoxyanthracene was 1.10 after one day storage and 1.08 after two days storage.

The results of Examples 25 to 30 and Comparative Examples 7 and 8 are tabulated as follows.

From the results of Examples 25 to 30 and Comparative Examples 7 and 8, the 9,9′-bianthracene-10,10′-diether compound of the present invention is a photocationically polymerizable composition as compared with 9,10-dibutoxyanthracene. It can be seen that both the product and the photo-radical polymerizable composition exhibit extremely low migration with respect to the polyethylene film.

<Example of sublimation resistance test>
<Cationic curing>
(Example 31)
The photocured material prepared in Example 10 was heated to 180 ° C. in an oven. The cured product was taken out of the oven at regular intervals, the UV spectrum was measured, and the absorption intensity at 405 nm due to 9,9′-bianthracene-10,10′-bis (n-propyl) ether was measured. As a result, even after heating for 30 minutes, no change was observed in the absorption intensity, and it was found that the added 9,9′-bianthracene-10,10′-bis (n-propyl) ether was not sublimated. did. Therefore, the sublimation rate was 0%.

(Example 32)
The photocured material prepared in Example 11 was heated to 180 ° C. in an oven. The cured product was removed from the oven at regular intervals, the UV spectrum was measured, and the absorption intensity at 405 nm due to 9,9′-bianthracene-10,10′-bis (n-butyl) ether was measured. As a result, even after heating for 30 minutes, no change was observed in the absorption intensity, and it was found that the added 9,9′-bianthracene-10,10′-bis (n-butyl) ether was not sublimated. did. Therefore, the sublimation rate was 0%.

(Comparative Example 9)
The photocured material prepared in Comparative Example 2 was heated to 180 ° C. in an oven. The cured product was removed from the oven at regular intervals, the UV spectrum was measured, and the change in absorption intensity at 405 nm caused by 9,10-dibutoxyanthracene was measured as an index of sublimation. As a result, after heating for 30 minutes, the absorption intensity decreased by 34%. Therefore, the sublimation rate was 34%.

The following is clear from the results of Examples 31 and 32 and Comparative Example 9. That is, in the photocationic polymerization, no sublimation was observed in the 9,9'-bianthracene-10,10'-diether compound of the present invention. On the other hand, since 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer, is sublimated, the 9,9′-bianthracene-10,10′-diether compound of the present invention has extremely high sublimation resistance. It can be seen that

<Radical curing><Sublimation resistance test>
(Example 33)
The photocured material prepared in Example 17 was heated to 180 ° C. in an oven. The cured product was taken out of the oven at regular intervals, the UV spectrum was measured, and the absorption intensity at 405 nm due to 9,9′-bianthracene-10,10′-bis (n-propyl) ether was measured. As a result, even after heating for 30 minutes, no change was observed in the absorption intensity, and it was found that the added 9,9′-bianthracene-10,10′-bis (n-propyl) ether was not sublimated. did. Therefore, the sublimation rate was 0%.

(Example 34)
The photocured material prepared in Example 18 was heated to 180 ° C. in an oven. The cured product was removed from the oven at regular intervals, the UV spectrum was measured, and the absorption intensity at 405 nm due to 9,9′-bianthracene-10,10′-bis (n-butyl) ether was measured. As a result, even after heating for 30 minutes, no change was observed in the absorption intensity, and it was found that the added 9,9′-bianthracene-10,10′-bis (n-propyl) ether was not sublimated. did. Therefore, the sublimation rate was 0%.

(Comparative Example 10)
The photocured material prepared in Comparative Example 3 was heated to 180 ° C. in an oven. The cured product was removed from the oven at regular intervals, the UV spectrum was measured, and the change in absorption intensity at 405 nm caused by 9,10-dibutoxyanthracene was measured as an index of sublimation. As a result, after heating for 30 minutes, the absorption intensity decreased by 41%. Therefore, the sublimation rate was 41%.

The following is clear from the results of Examples 33 and 34 and Comparative Example 10. That is, in the photoradical polymerization, no sublimation was observed in the 9,9'-bianthracene-10,10'-diether compound of the present invention. On the other hand, since 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer, is sublimated, the 9,9′-bianthracene-10,10′-diether compound of the present invention has extremely high sublimation resistance. It can be seen that

The 9,9′-bianthracene-10,10′-diether compound of the present invention is compared with the 9,10-dialkoxyanthracene compound which is a known photopolymerization sensitizer in photocationic polymerization and photoradical polymerization. In addition to having the same photopolymerization sensitizing ability, the compound is an excellent compound having high migration resistance and sublimation resistance, and is extremely useful as a photopolymerization sensitizer.

Claims (7)

In the method for manufacturing 9,9'-bi anthracene -10,10'- diether compound represented by the following following general formula (1), represented by anthrone compound represented by the following general formula represented by the following general formula (6) (4) The compound represented by the following general formula (3) is synthesized by reacting the 2-substituted-1,4-naphthoquinone compound, and then the resulting compound represented by the general formula (3) is enolized and then etherified. A process for producing a 9,9′-bianthracene-10,10′-diether compound represented by the general formula (1) .

(In the general formula (3), X, X ′, Y and Y ′ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.)

(In the general formula (1), R represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group, and X, X ′, Y and Y ′ may be the same or different, and may be a hydrogen atom, carbon Represents an alkyl group or a halogen atom of formula 1-8.)

(In General formula (4), L may be the same or different and shows a hydroxyl group, a methyl group, an ethyl group, an acetoxy group, a chlorine atom, or a bromine atom.

(In General Formula (6), X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.)
In the method for manufacturing 9,9'-bi anthracene -10,10'- diether compound represented by the following following general formula (1), represented by anthrone compound represented by the following general formula represented by the following general formula (6) (5) The compound represented by the following general formula (3) is synthesized by reacting the 2,6-disubstituted benzoquinone compound, and then the resulting compound represented by the general formula (3) is enolized and then etherified. A process for producing a 9,9′-bianthracene-10,10′-diether compound represented by the general formula (1) :

(In the general formula (3), X, X ′, Y and Y ′ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.)

(In the general formula (1), R represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group, and X, X ′, Y and Y ′ may be the same or different, and may be a hydrogen atom, carbon Represents an alkyl group or a halogen atom of formula 1-8.)

(In the general formula (5), M and N may be the same or different and each represents a hydroxyl group, a methyl group, an ethyl group, an acetoxy group, a chlorine atom or a bromine atom.

(In General Formula (6), X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.)
A photopolymerization sensitizer containing a 9,9′-bianthracene-10,10′-diether compound represented by the following general formula (1).

(In the general formula (1), R represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group, and X, X ′, Y and Y ′ may be the same or different, and may be a hydrogen atom, carbon Represents an alkyl group or a halogen atom of formula 1-8.)
A photopolymerization initiator composition comprising the photopolymerization sensitizer according to claim 3 and an onium salt as a photopolymerization initiator. A photopolymerizable composition comprising the photopolymerization initiator composition according to claim 4 and a photocationically polymerizable compound. A photopolymerizable composition comprising the photopolymerization initiator composition according to claim 4 and a photoradical polymerizable compound. A photocured product obtained by curing the photopolymerizable composition according to claim 5 or 6 .