JP2019199405A - Reactive photopolymerization sensitizer - Google Patents

Abstract

To provide a photopolymerization sensitizer without causing problems of powdering or coloring of a cured article since an additive such as the photopolymerization sensitizer or the like bleeds to a surface due to blooming or the like during photopolymerization or storage of the cured article, and providing practically efficient photosetting rate.SOLUTION: There is provided a 9,10-bis(hydroxyalkoxy)anthracene compound having primary hydroxyl group represented by the following general formula (1). In the general formula (1), A represents an alkylene group having 2 to 20 carbon atoms, the alkylene group may be branched, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring, or a naphthalene ring, X and Y may be same or different, and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.SELECTED DRAWING: None

Description

The present invention relates to a 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group, a method for producing the same, and a photopolymerization sensitizer containing the 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group. .

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. Similarly, many photopolymerization initiators such as alkylphenone polymerization initiators have no absorption at 350 nm or more. Anthracene compounds and thioxanthone compounds are known as photopolymerization sensitizers for these photopolymerization initiators, and 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, this 9,10-dialkoxy anthracene compound is exposed to the photopolymerization sensitizer and the like due to blooming during storage of the photopolymerizable composition before photocuring or the cured product after photocuring. It is known to cause powdering and coloring problems.

As for the photopolymerizable composition, for example, when these photopolymerization sensitizers are used as one component of a photoadhesive for adhering the film to the film, the photopolymerization sensitizer is transferred to a film covered on top ( Migration) and may cause problems with powdering and coloring of the photopolymerization sensitizer on the upper film. Furthermore, there are cases where problems (sublimation) such as contamination of surrounding facilities are caused by powdering of the photopolymerization sensitizer.

In addition, dry film resists are used in processes such as printed wiring board manufacturing, lead frame manufacturing, and metal mask manufacturing. However, resists that are compatible with 405 nm semiconductor lasers are required, and optical resists are used to support these wavelengths. As the polymerization sensitizer, thioxanthone and 9,10-dialkoxyanthracene compounds are used. However, dry film resists are stored and traded with a cover film on the photosensitive resin composition. Polyethylene film or polypropylene film is used for this cover film, and photopolymerization sensitization is applied to the film. There is a problem that the agent migrates and the sensitization effect is lowered, or powder blowing occurs on the film (Patent Document 9).

Concerning the cured product after photocuring of the photopolymerizable composition, for example, in a flexographic ink for food packaging, there is a concern about contamination of food due to blooming of the photopolymerization sensitizer from the ink printed on the packaging paper to the film. Is done.

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 Japanese Patent No. 4605223

Therefore, during storage of the photopolymerizable composition before photocuring and the cured product after photocuring, it has migration resistance and sublimation resistance, causing problems with powdering and coloring of the cured product. Development of a new photopolymerization sensitizer that does not occur is desired.

As a result of further intensive studies on the structure and physical properties of the anthracene compound, the present inventors have shown that the 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group shown in the present invention is photosensitized in the photopolymerization reaction. The photopolymerization sensitizer migrates both before and after photocuring of the photopolymerizable composition by having a primary hydroxyl group that is both a polar group and a reactive group. It was found that blooming is difficult to occur, and the 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group was found to be a compound excellent in sublimation resistance, and the present invention was completed.

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

In the general formula (1), A represents an alkylene group having 2 to 20 carbon atoms, and the alkylene group may be branched and may contain an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring. Good. X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom.

The second gist of the present invention resides in a 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the following general formula (2).

In general formula (2), n represents an integer of 2 to 20, X and Y may be the same or different, and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom. .

The third gist of the present invention is characterized in that a 9,10-dihydroxyanthracene compound represented by the following general formula (3) is reacted with a halogenated alcohol compound represented by the following general formula (4). The present invention resides in a method for producing a 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the following general formula (1).

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

In the general formula (4), A represents an alkylene group having 2 to 20 carbon atoms, and the alkylene group may be branched and may contain an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring. Good. Z represents a halogen atom.

In the general formula (1), A represents an alkylene group having 2 to 20 carbon atoms, and the alkylene group may be branched and may contain an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring. Good. X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom.

The fourth gist of the present invention is characterized in that a 9,10-dihydroxyanthracene compound represented by the following general formula (3) is reacted with a halogenated alcohol compound represented by the following structural formula (5). The present invention resides in a method for producing a 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the following general formula (2).

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

In the general formula (5), n represents an integer of 2 to 20, and Z represents a halogen atom.

In the general formula (2), n represents an integer of 2 to 20, X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom. .

The fifth gist of the present invention resides in a photopolymerization sensitizer containing a 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the following general formula (1).

In the general formula (1), A represents an alkylene group having 2 to 20 carbon atoms, and the alkylene group may be branched and may contain an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring. Good. X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom.

The sixth gist of the present invention resides in a photopolymerization sensitizer containing a 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the following general formula (2).

In general formula (2), n represents an integer of 2 to 20, X and Y may be the same or different, and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom. .

The seventh aspect of the present invention resides in a photopolymerization initiator composition containing the photopolymerization sensitizer described in the fifth or sixth aspect and 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 is a polymerization method in which the photopolymerizable composition according to the eighth aspect or the ninth aspect is polymerized by irradiating an energy beam containing light having a wavelength range of 300 nm to 500 nm. Exist.

The eleventh aspect of the present invention is that the irradiation source of energy rays including light in the wavelength range of 300 nm to 500 nm is an ultraviolet LED having a central wavelength of 365 nm, 375 nm, 385 nm, 395 nm or 405 nm or a semiconductor laser having a wavelength of 405 nm. The polymerization method according to the tenth aspect is characterized.

The 9,10-bis (hydroxyalkoxy) anthracene compound having the primary hydroxyl group of the present invention not only has a high effect as a photopolymerization sensitizer in the photopolymerization reaction, but also photopolymerization sensitization of the compound of the present invention. About the photopolymerizable composition contained as an agent, the photopolymerization sensitizer is a useful compound that has a very low degree of migration or blooming both before and after photocuring.

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

In the general formula (1), A represents an alkylene group having 2 to 20 carbon atoms, and the alkylene group may be branched and may contain an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring. Good. X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom.

In the general formula (1), the alkylene group having 2 to 20 carbon atoms represented by A includes an ethylene group, an n-propylene group, an i-propylene group, an n-butylene group, an i-butylene group, and an n-pentylene group. I-pentylene group, n-hexylene group, n-heptylene group, n-octylene group or 2-ethylhexylene group, n-nonylene group, n-decylene group, n-undecylene group, n-dodecylene group, n- A tridecylene group, an n-tetradecylene group, an n-pentadecylene group, an n-hexadecylene group, an n-heptadecylene group, an n-octadecylene group, an n-nonadecylene group, an n-icosylene group, and the like, and an oxygen atom in the alkylene group , A nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring may be contained.

In the general formula (1), the alkyl group having 1 to 8 carbon atoms represented by X or Y includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group. N-pentyl group, i-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, 4-methyl-3-pentenyl group, etc. An atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned.

Specific examples of the 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the general formula (1) of the present invention include 9,10-bis (3-hydroxypropoxy) anthracene, 9,10 -Bis (4-hydroxybutoxy) anthracene, 9,10-bis (5-hydroxypentyloxy) anthracene, 9,10-bis (6-hydroxyhexyloxy) anthracene, 9,10-bis (7-hydroxyheptyloxy) Anthracene, 9,10-bis (8-hydroxyoctyloxy) anthracene, 9,10-bis (9-hydroxynonyloxy) anthracene, 9,10-bis (10-hydroxydecyloxy) anthracene, 9,10-bis ( 11-hydroxyundecyloxy) anthracene, 9,10- (12-hydroxydodecyloxy) anthracene, 9,10-bis (13-hydroxytridecyloxy) anthracene, 9,10-bis (14-hydroxytetradecyloxy) anthracene, 9,10-bis (15-hydroxypenta) Decyloxy) anthracene, 9,10-bis (16-hydroxyhexadecyloxy) anthracene, 9,10-bis (17-hydroxyheptadecyloxy) anthracene, 9,10-bis (18-hydroxyoctadecyloxy) anthracene, 9 , 10-bis (19-hydroxynonadecyloxy) anthracene, 9,10-bis (20-hydroxyicosyloxy) anthracene, 9,10-bis [(2-hydroxyethoxy) ethoxy] anthracene, 2-methyl-9 , 10-bis ( -Hydroxypropoxy) anthracene, 2-methyl-9,10-bis (4-hydroxybutoxy) anthracene, 2-methyl-9,10-bis (5-hydroxypentyloxy) anthracene, 2-methyl-9,10-bis (6-hydroxyhexyloxy) anthracene, 2-methyl-9,10-bis [(2-hydroxyethoxy) ethoxy] anthracene, 2-ethyl-9,10-bis (3-hydroxypropoxy) anthracene, 2-ethyl- 9,10-bis (4-hydroxybutoxy) anthracene, 2-ethyl-9,10-bis (5-hydroxypentyloxy) anthracene, 2-ethyl-9,10-bis (6-hydroxyhexyloxy) anthracene, 2 -Ethyl-9,10-bis [(2-hydroxyethoxy) ethoxy Anthracene, 2-t-pentyl-9,10-bis (3-hydroxypropoxy) anthracene, 2-t-pentyl-9,10-bis (4-hydroxybutoxy) anthracene, 2-t-pentyl-9,10 -Bis (5-hydroxypentyloxy) anthracene, 2-t-pentyl-9,10-bis (6-hydroxyhexyloxy) anthracene, 2-t-pentyl-9,10-bis [(2-hydroxyethoxy) ethoxy Anthracene, 2,6-dimethyl-9,10-bis (3-hydroxypropoxy) anthracene, 2,6-dimethyl-9,10-bis (4-hydroxybutoxy) anthracene, 2,6-dimethyl-9,10 -Bis (5-hydroxypentyloxy) anthracene, 2,6-dimethyl-9,10-bis (6- Loxyhexyloxy) anthracene, 2,6-dimethyl-9,10-bis [(2-hydroxyethoxy) ethoxy] anthracene, 2-chloro-9,10-bis (3-hydroxypropoxy) anthracene, 2-chloro-9 , 10-bis (4-hydroxybutoxy) anthracene, 2-chloro-9,10-bis (5-hydroxypentyloxy) anthracene, 2-chloro-9,10-bis (6-hydroxyhexyloxy) anthracene, 2- Chloro-9,10-bis [(2-hydroxyethoxy) ethoxy] anthracene, 2-bromo-9,10-bis (3-hydroxypropoxy) anthracene, 2-bromo-9,10-bis (4-hydroxybutoxy) Anthracene, 2-bromo-9,10-bis (5-hydroxypentyloxy) ) Anthracene, 2-bromo-9,10-bis (6-hydroxyhexyloxy) anthracene, 2-bromo-9,10-bis [(2-hydroxyethoxy) ethoxy] anthracene, 2- (4-methyl-3- Pentenyl) -9,10-bis (3-hydroxypropoxy) anthracene, 2- (4-methyl-3-pentenyl) -9,10-bis (4-hydroxybutoxy) anthracene, 2- (4-methyl-3- Pentenyl) -9,10-bis (5-hydroxypentyloxy) anthracene, 2- (4-methyl-3-pentenyl) -9,10-bis (6-hydroxyhexyloxy) anthracene, 2- (4-methyl-) 3-pentenyl) -9,10-bis [(2-hydroxyethoxy) ethoxy] anthracene and the like.

Among the compounds exemplified above, 9,10-bis (3-hydroxypropoxy) anthracene, 9,10-bis (4-hydroxybutoxy) anthracene, 9,10-bis (5-hydroxy) are highly effective. Pentyloxy) anthracene, 9,10-bis (6-hydroxyhexyloxy) anthracene, 2-methyl-9,10-bis (4-hydroxybutoxy) anthracene, 2-methyl-9,10-bis (5-hydroxypentyl) Oxy) anthracene, 2-methyl-9,10-bis (6-hydroxyhexyloxy) anthracene, 2-ethyl-9,10-bis (4-hydroxybutoxy) anthracene, 2-ethyl-9,10-bis (5 -Hydroxypentyloxy) anthracene, 2-ethyl-9,10-bis (6-hydroxy) Xyloxy) anthracene, 2-chloro-9,10-bis (4-hydroxybutoxy) anthracene, 2-chloro-9,10-bis (5-hydroxypentyloxy) anthracene, 2-chloro-9,10-bis (6 -Hydroxyhexyloxy) anthracene, 2- (4-methyl-3-pentenyl) -9,10-bis (4-hydroxybutoxy) anthracene, 2- (4-methyl-3-pentenyl) -9,10-bis ( 5-hydroxypentyloxy) anthracene, 2- (4-methyl-3-pentenyl) -9,10-bis (6-hydroxyhexyloxy) anthracene are preferred, 9,10-bis (3-hydroxypropoxy) anthracene, 9 , 10-bis (4-hydroxybutoxy) anthracene, 9,10-bis (5-hydride) Carboxymethyl pentyloxy) anthracene, 9,10-bis (6-hydroxyhexyl oxy) anthracene is particularly preferable. From the viewpoint of easy production and compatibility with the monomer, 9,10-bis (6-hydroxyhexyloxy) anthracene is more preferable. On the other hand, 9,10-bis (3-hydroxyethoxy) anthracene is not preferable from the viewpoint of compatibility with the monomer.

The 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention has a property of being easily soluble in a solvent such as alcohol while having an anthracene skeleton because the primary hydroxyl group functions as a hydrophilic group. In addition, it has a feature that it is easily soluble in monomers and oligomers having a hydrophilic group such as hydroxyethyl acrylate and oxetane alcohol. On the other hand, the 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention is more compatible with lipophilic monomers and oligomers than the anthracene compound having a secondary hydroxyl group and a large number of hydroxyl groups. It has the feature of being high.

(Production method)
Next, a method for producing a 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention will be described. The 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the general formula (1) of the present invention is the following reaction of the 9,10-dihydroxyanthracene compound represented by the general formula (3). According to Formula-1, it can obtain by making it react with the alcohol compound represented by the corresponding general formula (4) in the presence or absence of a basic compound.

In Reaction Formula-1, A represents an alkylene group having 2 to 20 carbon atoms, and the alkylene group may be branched and may contain an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring. . X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom. Z represents a halogen atom.

In Reaction Formula-1, the 9,10-dihydroxyanthracene compound represented by the general formula (3) used as a raw material is obtained by reducing the corresponding 9,10-anthraquinone compound.

Specific examples of the 9,10-dihydroxyanthracene compound used as a raw material in the reaction include 9,10-dihydroxyanthracene, 2-methyl-9,10-dihydroxyanthracene, and 2-ethyl-9,10-dihydroxyanthracene. 2-tert-pentyl-9,10-dihydroxyanthracene, 2,6-dimethyl-9,10-dihydroxyanthracene, 2-chloro-9,10-dihydroxyanthracene, 2-bromo-9,10-dihydroxyanthracene, 2 -(4-Methyl-3-pentenyl) -9,10-dihydroxyanthracene and the like.

In the case of 9,10-dihydroxyanthracene, as an industrial method, 1,4,4a, 9a-tetrahydroanthraquinone which is a Diels-Alder reaction product of 1,4-naphthoquinone and 1,3-butadiene or By reducing 9,10-anthraquinone using an alkali metal salt of 1,4-dihydro-9,10-dihydroxyanthracene which is the isomer, 9,10-dihydroxyanthracene can be obtained more easily. That is, 1,4,4a, 9a-tetrahydroanthraquinone obtained by reaction of 1,4-naphthoquinone and 1,3-butadiene is prepared in an aqueous medium in the presence of an alkaline compound such as an alkali metal hydroxide. , 10-anthraquinone can be reacted to obtain an aqueous solution of an alkali metal salt of 9,10-dihydroxyanthracene.

A precipitate of 9,10-dihydroxyanthracene can be obtained by acidifying an aqueous solution of an alkali metal salt of 9,10-dihydroxyanthracene obtained in this reaction in the absence of oxygen. By purifying the precipitate, 9,10-dihydroxyanthracene can be obtained. A 9,10-dihydroxyanthracene compound having a substituent can be obtained in the same manner.

Specific examples of the halogenated alcohol compound represented by the general formula (4) as a raw material in Reaction Formula-1 include 3-chloro-1-propanol, 4-chloro-1-butanol, and 5-chloro-1- Pental, 6-chloro-1-hexanol, 7-chloro-1-heptanol, 8-chloro-1-octanol, 9-chloro-1-nonanol, 10-chloro-1-decanol, 11-chloro-1-undecanol, 12-chloro-1-dodecanol, 13-chloro-1-tridecanol, 14-chloro-1-tetradecanol, 15-chloro-1-pentadecanol, 16-chloro-1-hexadecanol, 17-chloro- 1-heptadecanol, 18-chloro-1-octadecanol, 19-chloro-1-nonadecanol, 20-chloro-1-ico Alcohol, ethylene glycol mono-2-chloroethyl ether, 3-bromo-1-propanol, 4-bromo-1-butanol, 5-bromo-1-pental, 6-bromo-1-hexanol, 7-bromo-1 -Heptanol, 8-Bromo-1-octanol, 9-Bromo-1-nonanol, 10-Bromo-1-decanol, 11-Bromo-1-undecanol, 12-Bromo-1-dodecanol, 13-Bromo-1-tridecanol , 14-bromo-1-tetradecanol, 15-bromo-1-pentadecanol, 16-bromo-1-hexadecanol, 17-bromo-1-heptadecanol, 18-bromo-1-octadecanol 19-bromo-1-nonadecanol, 20-bromo-1-icosyl alcohol, ethylene glycol Mono-2-bromoethyl ether.

As the usage-amount of the halogenated alcohol compound represented by General formula (4) in Reaction formula-1, Preferably it is 2.0 mol times or more and less than 10.0 mol times with respect to a 9,10- dihydroxyanthracene compound. More preferably, it is 2.2 mol times or more and less than 5.0 mol times. If it is less than 2.0 mol times, the reaction is not completed, and if it is 10.0 mol times or more, side reactions occur and the yield and purity are unfavorable.

The basic compound used in Reaction Scheme-1 includes sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, lithium hexamethyldisilazide, lithium diisopropylamide, triethylamine, triethylamine, Examples include butylamine, trihexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dimethylaniline, pyridine, piperidine, γ-picoline, and lutidine.

The addition amount of the basic compound is preferably 2.0 mol times or more and less than 5.0 mol times, more preferably 2.2 mol times or more, 3.0 mol times with respect to the 9,10-dihydroxyanthracene compound. It is less than mole times. If it is less than 2.0 mol times, the reaction will not be completed, and if it is 5.0 mol times or more, side reactions will occur and the yield and purity will be reduced.

The reaction is performed in a solvent or without a solvent. The solvent to be used is not particularly selected as long as it does not react with the halogenated alcohol compound to be used, for example, an aromatic solvent such as toluene, xylene and ethylbenzene, an ether solvent such as tetrahydrofuran and 1,4-dioxane, acetone, Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, amide solvents such as dimethylacetamide and dimethylformamide, halogenated carbon solvents such as methylene chloride, ethylene dichloride and chlorobenzene, and alcohol solvents such as methanol, ethanol and 1-propanol. Used.

When a 9,10-dihydroxyanthracene compound is dissolved in an aqueous solution of an inorganic base and reacted with a halogenated alcohol compound, 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. , Benzyldimethyloctadecyl ammonium 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 amount of the phase transfer catalyst added is preferably 0.01 mol times or more and less than 1.0 mol times, more preferably 0.2 mol times or more, 0.5 mol times or more with respect to the 9,10-dihydroxyanthracene compound. It is less than mole times. If it is less than 0.01 mol times, the reaction rate is slow, and if it is 1.0 mol times or more, the purity of the product decreases, which is not preferable.

The reaction temperature of the reaction is usually 20 ° C. or higher and 200 ° C. or lower, preferably 50 ° C. or higher and 150 ° C. or lower. If it is less than 20 ° C., it takes too much reaction time, and if it is heated above 200 ° C., impurities increase and the purity of the target compound decreases, both of which are not preferable.

The reaction time in the reaction varies depending on the reaction temperature, but is usually about 0.5 to 20 hours. More preferably, it is 1 hour to 10 hours.

After completion of the reaction, if necessary, the unreacted raw material, solvent and catalyst are removed by a method such as washing, distillation under reduced pressure, and filtration alone or in combination. When the product is a solid, crystals are precipitated during the concentration, and can be recrystallized from a poor solvent such as alcohol or hexane, or dried up as it is to obtain crystals. When the product is a liquid, it can be dried up as it is and purified as necessary by distillation or the like to obtain a 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group.

(Photopolymerization sensitizer)
The 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the general formula (1) of the present invention acts as a photopolymerization sensitizer. A photopolymerization initiator composition can be obtained by mixing the photopolymerization sensitizer and a photopolymerization initiator, and a photopolymerizable composition can be obtained by further mixing a photopolymerizable compound. it can. The photopolymerizable composition can be easily photocured by irradiation with light having a long wavelength such as ultraviolet LED light having a central wavelength of 395 nm.

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

Examples of the benzylmethyl ketal-based radical polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651” manufactured by BAS Corporation), and the like. -Hydroxyalkylphenone-based radical polymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name “Darocur 1173” manufactured by BASF), 1-hydroxycyclohexylphenyl Ketone (trade name “Irgacure 184” manufactured by BSF Corporation), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one ( Trade name “Irgacure 2959” manufactured by BSF Corporation), 2-hydroxy-1- {4- [4- (2-hydroxy 2-methyl-propionyl) - benzyl] phenyl} -2-methyl-1-one (trade name "Irgacure 127" BAS-F Inc.).

In particular, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651” manufactured by BAS Corporation), which is a benzylmethyl ketal radical polymerization initiator, α-hydroxyalkyl 2-Hydroxy-2-methyl-1-phenylpropan-1-one (trade name “Darocur 1173” manufactured by BASF), which is a phenone radical polymerization initiator, 1-hydroxycyclohexyl phenyl ketone (product) The name “Irgacure 184” manufactured by BSF Corporation) is preferred.

Further, acetophenone radical polymerization initiators such as acetophenone, 2-hydroxy-2-phenylacetophenone, 2-ethoxy-2-phenylacetophenone, 2-methoxy-2-phenylacetophenone, 2-isopropoxy-2-phenylacetophenone, 2 -Isobutoxy-2-phenylacetophenone, benzyl radical polymerization initiator benzyl, 4,4'-dimethoxybenzyl, anthraquinone radical polymerization initiator 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-phenoxyanthraquinone 2- (phenylthio) anthraquinone, 2- (hydroxyethylthio) anthraquinone, and the like can also be used.

Of the illustrated photopolymerization initiators, onium salts are particularly preferable. One of the features of the 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention is not only an iodonium salt but also a sulfonium salt as an onium salt is that it has a photopolymerization sensitizing effect. One.

Although the usage-amount with respect to the photoinitiator of the photoinitiator of the photopolymerization sensitizer containing the 9, 10-bis (hydroxy alkoxy) anthracene compound which has a primary hydroxyl group represented by General formula (1) of this invention is not specifically limited. The range is usually from 5% by weight to 100% by weight, preferably from 10% by weight to 50% by weight, based on the photopolymerization initiator. If the amount of the photopolymerization sensitizer used is less than 5% by weight, it takes too much time to photopolymerize the photopolymerizable compound. On the other hand, even if it exceeds 100% by weight, an effect commensurate with the addition is obtained. Absent.

(Photopolymerization initiator composition)
The photopolymerization sensitizer containing the 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the general formula (1) of the present invention can be directly added to the photopolymerizable compound. However, after preparing a photopolymerization initiator composition by blending with a photopolymerization initiator in advance, it can also be added to the photopolymerizable compound. That is, the photopolymerization initiator composition of the present invention includes at least a photopolymerization sensitizer containing a 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the general formula (1) and light. It is a composition containing a polymerization initiator.

(Photopolymerizable composition)
Furthermore, a photopolymerizable composition can also be prepared by blending the photopolymerization initiator composition and a photopolymerizable compound. The photopolymerizable composition of the present invention comprises a photopolymerization sensitizer containing a 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention and a photopolymerization initiator composition containing a photopolymerization initiator. And a radically polymerizable compound or a cationic photopolymerizable compound. Since the photopolymerization sensitizer containing the 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention has a photopolymerization sensitizing action in both photoradical polymerization and photocationic polymerization, It can be used as a radical photopolymerizable composition together with a radical polymerization initiator and a radical photopolymerizable compound, and can also be used together with a cationic photopolymerization initiator and a cationic photopolymerizable compound as a cationic photopolymerizable composition. . The photopolymerization sensitizer and the photopolymerization initiator containing the 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention are separately added to the photoradical polymerizable compound or the photocationic polymerizable compound. As a result, a photopolymerization initiator composition may be formed in the photo radical polymerizable compound or the photo cationic polymerizable compound. Furthermore, it is good also as a hybrid composition containing both a radical photopolymerizable compound and a photocationic polymerizable compound.

As the photoradical polymerizable compound, for example, an organic compound having a double bond such as styrene, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, acrylic acid ester, and methacrylic acid ester can be used. . Of these radical polymerizable compounds, acrylic acid esters and methacrylic acid esters (hereinafter, both are referred to as (meth) acrylic acid esters) are preferable from the viewpoint of film forming ability and the like. (Meth) acrylic acid esters include methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, methyl methacrylate, butyl methacrylate, methacrylic acid Cyclohexyl, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tricyclo [5,2,1,02,6] decandimethanol diacrylate, isobornyl methacrylate, epoxy acrylate, urethane acrylate, polyester acrylate, Polybutadiene acrylate, polyol acrylate, polyether acrylate, silicone resin acrylate, imide acrylate, etc. It is. These radical photopolymerizable compounds may be one kind or a mixture of two or more kinds.

In particular, the 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention is also highly compatible with a monomer having a hydroxyl group.

Examples of the photocationically polymerizable compound include an epoxy compound, an oxetane compound, and vinyl ether. Examples of general epoxy compounds include alicyclic epoxy compounds, epoxy-modified silicones, and aromatic glycidyl ethers. As the alicyclic epoxy compound, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, trade name: Celoxide 2021P, Celoxide is a registered trademark of Daicel Corporation), bis (3 4-epoxycyclohexyl) adipate and the like. 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. As the oxetane compound, 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol) (manufactured by Toa Gosei Co., Ltd., trade name: OXT-101), 2-ethylhexyl oxetane (manufactured by Toagosei Co., Ltd., trade name: OXT-212), Xylylenebisoxetane (manufactured by Toagosei Co., Ltd., trade name: OXT-121), 3-ethyl-3 {[((3-ethyloxetane-3-yl) methoxy] methyl} oxetane (manufactured by Toagosei Co., Ltd., trade name: OXT) -221). Examples of the vinyl ether include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether and the like. These photocationically polymerizable compounds may be one kind or a mixture of two or more kinds.

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

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

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

A photocured product is obtained by irradiating a coating film made of the photopolymerizable composition thus prepared with ultraviolet light having a wavelength range of 300 nm to 500 nm at an intensity of about 1 to 1000 mW / cm ^2. Can do. As a light source to be used, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a xenon lamp, a gallium doped lamp, a black light, a 405 nm ultraviolet LED, a 395 nm ultraviolet LED, a 385 nm ultraviolet LED, a 375 nm ultraviolet LED, a 365 nm ultraviolet LED, a blue LED, A white LED, a laser, a D bulb manufactured by Fusion, a V bulb, and the like can be given. Natural light such as sunlight can also be used. In particular, 405 nm UV LED, 395 nm UV LED, 385 nm UV LED, 375 nm UV LED, 365 nm UV LED, and 405 nm semiconductor lasers have a sensitizing effect even in light having a long wavelength range of 365 nm to 405 nm. It is characteristic and preferable.

(Optical DSC measurement)
In the present invention, the optical DSC measurement method can be used as a method for quantitatively evaluating the photopolymerization rate of the photopolymerizable composition under light irradiation. According to this method, the calorific value accompanying curing can be continuously and simply measured while directly irradiating the sample with light. When a sample set in the optical DSC measuring apparatus is irradiated with light, a light curing reaction starts and heat generation is observed. The baseline of the DSC curve, which was horizontal before photocuring, is shifted to the exothermic side, and returns to the original baseline position when the reaction is completed. The calorific value can be obtained from the peak size of the DSC curve. That is, the progress of polymerization can be evaluated by irradiating the photopolymerizable composition with light and measuring and comparing the calorific value per 1 mg.

(Determination of migration resistance of the composition)
As a method for determining whether or not the photopolymerization sensitizer contained in the photopolymerizable composition of the present invention migrates to a film or the like, the photopolymerizable composition containing the photopolymerization sensitizer is a thin film. Create a product applied to the object, cover it with a polyethylene film, store it at a constant temperature (26 ° C) for a certain period of time, then peel off the polyethylene film, and examine whether the photopolymerization sensitizer has transferred to the polyethylene film The migration resistance was determined. The peeled polyethylene film was washed after washing the surface composition with acetone, measured for UV resistance of the polyethylene film, and measured for migration resistance by examining the increase in absorption intensity caused by the photopolymerization sensitizer. did. For the measurement, an ultraviolet / visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV2600) was used. In order to quantitatively compare with 9,10-dibutoxyanthracene, which is the compound of the comparative example, the obtained absorbance was converted to the absorbance value of 9,10-dibutoxyanthracene. In conversion, the absorbance at 260 nm of the compound of the present invention and 9,10-dibutoxyanthracene was measured with an ultraviolet / visible spectrophotometer, the respective molar extinction coefficients were calculated from the absorbance value and molar concentration, and the ratio And converted.

(Determination of migration resistance of photocured product)
(Elution test of photopolymerization sensitizer)
Light from the photocured product as a method for determining whether the photopolymerization sensitizer present in the photocured product obtained by photocuring the photopolymerizable composition of the present invention migrates to a film or the like. A dissolution test of the polymerization sensitizer was conducted. The 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the general formula (1) of the present invention has not only an effect as a photopolymerization sensitizer in a photopolymerization reaction, but also the compound. By polymerizing a photopolymerizable composition contained as a photopolymerization sensitizer, it is presumed that the photopolymerization sensitizer itself causes a photopolymerization reaction and is taken into the photocured product. The self-polymerization property of the photopolymerization sensitizer was evaluated by the following method. That is, after photocuring a photopolymerizable composition containing a photopolymerization sensitizer, the photocured product is extracted with acetone in which the photopolymerization sensitizer of the present invention is dissolved, and photopolymerized in an organic solvent. This was confirmed by measuring the elution rate of the sensitizer. The amount of the photopolymerization sensitizer contained in the photocured product before and after the extraction treatment with acetone was measured by UV spectrum. For the UV spectrum measurement, an ultraviolet / visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV2600) was used.

(Determination of sublimation resistance)
The sublimation resistance of the 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the general formula (1) of the present invention is determined by heating the compound at a constant temperature for a certain period of time in a nitrogen atmosphere. The weight loss was measured with a differential calorimeter (TG / DTA 7200 manufactured by Hitachi High-Tech Science Co., Ltd.).

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

The compound of the present invention was identified using the following equipment.
Infrared (IR) spectrophotometer: manufactured by Thermo, model is50 FT-IR
Nuclear magnetic resonance apparatus (NMR): manufactured by JEOL Ltd., model ECS-400
Melting point: Melting point measuring device manufactured by Guerencamp, model MFB-595 (conforms to JIS K0064)

(Synthesis Example 1) 9,10-bis (3-hydroxypropoxy) anthracene In a nitrogen atmosphere, 10 g of N, N-dimethylacetamide as a solvent in a 50 ml four-necked flask, disodium salt of 9,10-dihydroxyanthracene 10 ml (8.8 mmol) of 20 wt% aqueous solution, 3.5 g (25 mmol) of 3-bromopropanol and 0.1 g of 50% aqueous solution of catalyst tetrabutylammonium bromide were added and stirred at room temperature for 2 hours. Then, it poured into acid water, carrying out natural filtration. The precipitate was washed well with water, dissolved in acetone and dried. The obtained solid was reslurried with methanol, and 1.4 g of 9,10-bis (3-hydroxypropoxy) anthracene (yellow crystals) was obtained by suction filtration (yield 50 mol%).

(1) Melting point: 154-162 ° C
(2) IR (cm ⁻¹ ): 3300, 1400, 1365, 1339, 1089, 1064, 1016, 971, 935, 776, 752, 674, 605, 520, 421.
(3) ¹ H-MNR (CDCl ₃ , 400 MHz): δ = 2.115 (s, 2H), 2.294 (t, J-11.6 Hz, 4H), 4.141 (t, 4H), 4 .329 (t, J = 10.8 Hz, 4H), 7.475-7.501 (m, 4H), 8.261-8.328 (m, 4H).

(Synthesis Example 2) Into a 50 ml three-necked flask equipped with a 9,10-bis (4-hydroxybutoxy) anthracene stirrer and a thermometer, 10 g of a solvent N, N-dimethylformamide was added under a nitrogen atmosphere. -3.3 g (21.4 mmol) of bromo-1-butanol, 1.5 g (7.1 mmol) of 9,10-dihydroxyanthracene powder, and 3.0 g (21.4 mmol) of potassium carbonate as a base )added. It stirred for 6 hours, keeping the temperature of a reaction system at 20-30 degreeC. Then, the anthraquinone was removed by suction filtration, the obtained filtrate was dissolved in toluene, and washed with water twice by a liquid separation operation. The obtained organic layer was cooled in a freezer to precipitate crystals. The precipitated crystals were further filtered by suction to obtain 1.0 g of 9,10-bis (4-hydroxybutoxy) anthracene (yellow crystals) (yield 38 mol%).

(1) Melting point: 114-116 ° C
(2) IR (cm ⁻¹ ): 1345, 1067, 1035, 1015, 957, 943, 772, 739, 676, 606.
(3) ¹ H-MNR (CDCl ₃ , 400 MHz): δ = 1.954-2.023 (m, 4H), 2.111-2.180 (m, 4H), 3.851 (t, J = 12.8 Hz, 4H), 4.206 (t, J = 12.8 Hz, 4H), 7.260-7.500 (m, 4H), 8.258-8.283 (m, 4H).

(Synthesis Example 3) In a 200 ml four-necked flask equipped with a 9,10-bis (5-hydroxypentyloxy) anthracene stirrer and a thermometer, 25 g of N, N-dimethylformamide as a solvent under a nitrogen atmosphere, 13.4 g (72.2 mmol) of 5-bromo-1-pentanol and 0.8 g (1.2 mmol) of a 50% aqueous solution of catalyst tetrabutylammonium bromide were added. While maintaining the temperature of the reaction system at 20 to 30 ° C., 28.9 g (23.9 mmol) of a 20 wt% aqueous solution of 9,10-dihydroxyanthracene disodium salt was added dropwise over 1 hour and stirred for 2 hours. Thereafter, the aqueous layer was removed by a liquid separation operation. Anthraquinone was removed by suction filtration, and the obtained filtrate was concentrated by an evaporator. After dissolving in 100 ml of toluene and 10 ml of ethyl acetate and washing with water three times to remove the solvent N, N-dimethylformamide, the organic layer was concentrated, recrystallized with toluene, and subjected to 9,10-bis ( 6.3 g of 5-hydroxypentyloxy) anthracene (yellow crystals) was obtained (yield 69 mol%).

(1) Melting point: 87-89 ° C
(2) IR (cm ⁻¹ ): 3298, 2924, 2861, 1404, 1344, 1015, 965, 908, 782, 760, 676, 609.
(3) ¹ H-MNR (CDCl ₃ , 400 MHz): δ = 1.356 (s, 2H), 1.719-18.03 (m, 8H), 2.047-2.116 (m, 4H) 3.560 (t, J = 11.6 Hz, 4H), 4.173 (t, J = 13.2 Hz, 4H), 7.453-7.494 (m, 4H), 8.243-8. 288 (m, 4H).

(Synthesis Example 4) In a 500 ml four-necked flask equipped with a 9,10-bis (6-hydroxyhexyloxy) anthracene thermometer, 150 g of N, N-dimethylformamide as a solvent, 6-chloro under a nitrogen atmosphere. 59.4 g (434.8 mmol) of -1-hexanol and 18.6 g (28.9 mmol) of a 50% aqueous solution of catalyst tetrabutylammonium bromide were added. The temperature of the reaction system was raised to 120 ° C. with an oil bath, and 173.4 g (143.2 mmol) of a 20 wt% aqueous solution of disodium salt of 9,10-dihydroxyanthracene was added dropwise over 1 hour and stirred for 2 hours. . Then, 52.8 g (yellow crystals) of 9,10-bis (6-hydroxyhexyloxy) anthracene was obtained by suction filtration (yield 89.8 mol%).

(1) Melting point: 120-121 ° C
(2) IR (cm ⁻¹ ): 3323, 3063, 2920, 2853, 1619, 1472, 1460, 1434, 1405, 1380, 1369, 1348, 1266, 1214, 1170, 1106, 1059, 1039, 1015, 979, 924,895,850,809,773,750,677,647,608,601,517,469,417.
(3) ¹ H-MNR (CDCl ₃ , 400 MHz): δ = 1.279 (t, J = 10.4 Hz, 2H), 1.501-1.567 (m, 4H), 1.653-1. 748 (m, 8H), 2.029-2.100 (m, 4H), 3.711 (k, J = 18.4 Hz, 4H), 4.167 (t, J = 13.2 Hz, 4H), 7.455-7.493 (m, 4H), 8.250-8.288 (m, 4H).

(Synthesis Example 5) 2.9 g of N, N-dimethylacetamide as a solvent in a 200 ml four-necked flask equipped with a 9,10-bis [(2-hydroxyethoxy) ethoxy] anthracene thermometer under a nitrogen atmosphere Then, 9.0 g (72.0 mmol) of ethylene glycol mono-2-chloroethyl ether and 0.8 g (1.2 mmol) of a 50% aqueous solution of catalyst tetrabutylammonium bromide were added. The temperature of the reaction system was raised to 75 ° C. with a water bath, 28.9 g (23.9 mmol) of a 20 wt% disodium salt solution of 9,10-dihydroxyanthracene was added dropwise over 1 hour and stirred for 5 hours. did. Since the progress of the reaction was slow, the temperature was raised to 100 ° C. with an oil bath and stirred for 9 hours. Thereafter, the anthraquinone was removed by suction filtration, and the obtained filtrate was concentrated by an evaporator, toluene was added, and washing was performed twice with water by a liquid separation operation. Furthermore, toluene and methanol were added, extraction was performed, and the resulting methanol layer was dried up to obtain 4.0 g of 9,10-bis [(2-hydroxyethoxy) ethoxy] anthracene (brown solid). Obtained (yield 43 mol%).

(1) Melting point: 86-95 ° C
(2) IR (cm ⁻¹ ): 3452, 2913, 2865, 1662, 1620, 1451, 1437, 1401, 1365, 1338, 1291, 1270, 1236, 1170, 1110, 1053, 1023, 916, 892, 817, 793, 761, 694, 676, 607, 548, 480, 421.
(3) ¹ H-MNR (CDCl ₃ , 400 MHz): δ = 3.751-3.774 (m, 4H), 3.853 (t, J = 8.4 Hz, 4H), 3.989-4. 010 (m, 4H), 4.349-4.371 (m, 4H), 7.459-7.501 (m, 4H), 8.323-8.364 (m, 4H).

(Optical DSC measurement in a system using an iodonium salt as a photopolymerizable composition and a photopolymerization initiator)
In this example, optical DSC measurement was performed as follows. That is, the DSC measurement apparatus used was XDSC-7200 manufactured by Hitachi High-Tech Co., Ltd., and a DSC measurement unit was mounted on the DSC measurement apparatus so that DSC measurement could be performed while irradiating light. As a light source for light irradiation, LA-410UV manufactured by Hayashi Watch Industry Co., Ltd. was used, and the sample was irradiated with 405 nm light by a band pass filter. The illuminance of light was 50 mW / cm ² . The light from the light source can be guided to the top of the sample using a glass fiber, and the shutter of the light source can be trigger controlled so that DSC measurement can be performed simultaneously with the start of light irradiation. For optical DSC measurement, a sample was precisely weighed in an aluminum pan for measurement of about 1 mg, placed in a DSC measurement unit, and then an optical DSC unit was mounted. Thereafter, the inside of the measurement part was kept in a nitrogen atmosphere and allowed to stand for 10 minutes, and measurement was started. The measurement was continued for 6 minutes with normal light irradiation. After the first measurement, the sample was again measured under the same conditions, and the value obtained by subtracting the second measurement result from the first measurement result was taken as the measurement result of the sample. The results were compared by the total calorific value per 1 mg of sample in 1 minute after light irradiation unless otherwise specified. Depending on the measurement conditions, the photoreaction may not be completed in 1 minute, but in order to compare the reaction behavior at the initial stage of light irradiation, the total calorific value for 1 minute was compared. When polymerization of a sample (photopolymerizable composition) occurs with light irradiation, reaction heat is generated along with the polymerization, but the reaction heat can be measured by optical DSC. Therefore, the progress of polymerization by light irradiation can be measured by optical DSC. In this example, the total calorific value for 1 minute after light irradiation is measured, but as long as the same polymerizable compound is used, when the value is compared, the larger the value, the more efficiently the polymerization proceeds. Can be considered.

Thus, the photopolymerization performance evaluation test of the photopolymerizable composition using the 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention as a photopolymerization sensitizer will be described below.

(Evaluation Example 1 for Photocuring Rate)
As a photocationically polymerizable compound, 100 parts by weight of 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel, trade name: Celoxide 2021P, Celoxide is a registered trademark of Daicel Corporation) , 2 parts by weight of 4-isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate (manufactured by BASF, trade name Irgacure 250) as a photopolymerization initiator, synthesized as a photopolymerization sensitizer A photopolymerizable composition was prepared by mixing 0.5 parts by weight of 9,10-bis (3-hydroxypropoxy) anthracene obtained by the same method as in Example 1 at room temperature. When this photopolymerizable composition was subjected to optical DSC measurement by the above-described method, the total calorific value per minute from the start of light irradiation was 103 mJ / mg. The results are shown in Table 1. The results are shown in Table 1.

(Example 2 of photocuring rate evaluation)
Photocuring rate evaluation In place of 9,10-bis (3-hydroxypropoxy) anthracene of Example 1, 9,10-bis (4-hydroxybutoxy) anthracene obtained in the same manner as in Synthesis Example 2 was used. Except for the above, optical DSC measurement was carried out in the same manner as in Photocuring Rate Evaluation Example 1, and the total calorific value for 1 minute from the start of light irradiation was 129 mJ / mg. The results are shown in Table 1.

(Evaluation Example 3 for Photocuring Rate)
Photocuring rate evaluation In place of 9,10-bis (3-hydroxypropoxy) anthracene in Example 1, 9,10-bis (5-hydroxypentyloxy) anthracene obtained in the same manner as in Synthesis Example 3 was used. Except for the above, optical DSC measurement was performed in the same manner as in Photocuring Rate Evaluation Example 1, and the total calorific value for 1 minute from the start of light irradiation was 119 mJ / mg. The results are shown in Table 1.

(Photocuring rate evaluation example 4)
Photocuring rate evaluation In place of 9,10-bis (3-hydroxypropoxy) anthracene of Example 1, 9,10-bis (6-hydroxyhexyloxy) anthracene obtained in the same manner as in Synthesis Example 4 was used. Except that, optical DSC measurement was performed in the same manner as in Photocuring Rate Evaluation Example 1, and the total calorific value per minute from the start of light irradiation was 115 mJ / mg. The results are shown in Table 1.

(Example 5 of photocuring rate evaluation)
Photocuring rate evaluation 9,10-bis [(2-hydroxyethoxy) ethoxy] anthracene obtained in the same manner as in Synthesis Example 5 instead of 9,10-bis (3-hydroxypropoxy) anthracene in Example 1 The optical DSC measurement was carried out in the same manner as in Example 1 except for using the photocuring rate evaluation. As a result, the total calorific value per minute from the start of light irradiation was 120 mJ / mg. The results are shown in Table 1.

(Photocuring rate evaluation comparative example 1)
Photo-curing rate evaluation Except for not using 9,10-bis (3-hydroxypropoxy) anthracene of Example 1, the optical DSC measurement was performed in the same manner as in photo-curing rate evaluation Example 1, and 1 minute from the start of light irradiation. The total calorific value of was 0.3 mJ / mg. The results are shown in Table 1.

(Photocuring rate evaluation comparative example 2)
Photocuring rate evaluation Photocuring rate evaluation was carried out except that 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer, was used in place of 9,10-bis (3-hydroxypropoxy) anthracene in Example 1. When optical DSC measurement was performed in the same manner as in Example 1, the total calorific value per minute from the start of light irradiation was 147 mJ / mg. The results are shown in Table 1.

(Example 6 of photocuring rate evaluation)
As a photoradical polymerizable compound, (4-methylphenyl) [4- (2-methylpropyl) phenyl as a photopolymerization initiator for 100 parts by weight of 2-hydroxyethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) ] 9 and 10 obtained in the same manner as in Synthesis Example 1 using 2 parts by weight of iodonium-hexafluorophosphine candy (trade name Irgacure 250, manufactured by BASF Corporation) and a photopolymerization sensitizer. 1 part by weight of bis (3-hydroxypropoxy) anthracene was mixed at room temperature to prepare a photopolymerizable composition. When this photopolymerizable composition was subjected to optical DSC measurement, the total calorific value per minute from the start of light irradiation was 392 mJ / mg. The results are shown in Table 2.

(Example 7 of photocuring rate evaluation)
Photocuring rate evaluation In place of 9,10-bis (3-hydroxypropoxy) anthracene in Example 6, 9,10-bis (4-hydroxybutoxy) anthracene obtained in the same manner as in Synthesis Example 2 was used. Except for this, optical DSC measurement was carried out in the same manner as in Example 6 for evaluating the photocuring rate. The results are shown in Table 2.

(Example 8 of photocuring rate evaluation)
Photocuring rate evaluation In place of 9,10-bis (3-hydroxypropoxy) anthracene in Example 6, 9,10-bis (5-hydroxypentyloxy) anthracene obtained in the same manner as in Synthesis Example 3 was used. Except that, optical DSC measurement was performed in the same manner as in Photocuring Rate Evaluation Example 6, and the total calorific value for 1 minute from the start of light irradiation was 551 mJ / mg. The results are shown in Table 2.

(Evaluation example 9 for photocuring rate)
Photocuring rate evaluation In place of 9,10-bis (3-hydroxypropoxy) anthracene in Example 6, 9,10-bis (6-hydroxyhexyloxy) anthracene obtained in the same manner as in Synthesis Example 4 was used. Except that, optical DSC measurement was performed in the same manner as in Photocuring Rate Evaluation Example 6, and the total calorific value per minute from the start of light irradiation was 597 mJ / mg. The results are shown in Table 2.

(Photocuring rate evaluation example 10)
Photocuring rate evaluation 9,10-bis [(2-hydroxyethoxy) ethoxy] anthracene obtained in the same manner as in Synthesis Example 5 instead of 9,10-bis (3-hydroxypropoxy) anthracene in Example 6 The optical DSC measurement was carried out in the same manner as in Example 6 except for using the photocuring rate evaluation. As a result, the total calorific value per minute from the start of light irradiation was 559 mJ / mg. The results are shown in Table 2.

(Photocuring rate evaluation comparative example 3)
Photo-curing rate evaluation Except for not using 9,10-bis (3-hydroxypropoxy) anthracene of Example 6, optical DSC measurement was performed in the same manner as in photo-curing rate evaluation Example 6, and 1 minute from the start of light irradiation. The total calorific value of was 16 mJ / mg. The results are shown in Table 2.

(Photocuring rate evaluation comparative example 4)
Photocuring rate evaluation Photocuring rate evaluation was carried out except that 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer, was used instead of 9,10-bis (3-hydroxypropoxy) anthracene in Example 6. When optical DSC measurement was performed in the same manner as in Example 6, the total calorific value per minute from the start of light irradiation was 430 mJ / mg. The results are shown in Table 2.

As is clear by comparing the results of Photocuring Rate Evaluation Examples 1 to 5 and Photocuring Rate Evaluation Comparative Example 1, 9,10-bis (hydroxyalkoxy) having the primary hydroxyl group of the present invention in photocationic polymerization. It can be seen that by adding the anthracene compound as a photopolymerization sensitizer, the total calorific value is increased and the polymerization reaction is remarkably accelerated. Further, as is clear by comparing the results of Photocuring Rate Evaluation Examples 6 to 10 and Photocuring Rate Evaluation Comparative Example 3, 9,10-bis having the primary hydroxyl group of the present invention in photoradical polymerization ( It can be seen that by adding the hydroxyalkoxy) anthracene compound, the total calorific value similarly increases, and the polymerization reaction is remarkably accelerated. That is, it can be seen that the 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention has a photopolymerization sensitizing effect in both photocationic polymerization and photoradical polymerization.

Furthermore, as is clear by comparing the results of Photocuring Rate Evaluation Examples 1 to 5 and Photocuring Rate Evaluation Comparative Example 2, 9,10-bis (hydroxy) having the primary hydroxyl group of the present invention in photocationic polymerization. It can be seen that the alkoxy) anthracene compound has a photopolymerization sensitizing effect equivalent to 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer. Further, as is apparent by comparing the results of Photocuring Rate Evaluation Examples 6 to 10 and Photocuring Rate Evaluation Comparative Example 4, 9,10-bis having the primary hydroxyl group of the present invention in photoradical polymerization ( It can be seen that the hydroxyalkoxy) anthracene compound has a photopolymerization sensitizing effect equivalent to or higher than that of 9,10-dibutoxyanthracene, which is also a known photopolymerization sensitizer. That is, the 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention is a 9,10-dibutoxyanthracene which is a known photopolymerization sensitizer in both photocationic polymerization and photoradical polymerization. It can be seen that it has a photopolymerization sensitizing effect equivalent to or higher than.

(Example 1 for evaluating migration resistance of composition)
As a photocationically polymerizable compound, 85 parts by weight of 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Delcel Celoxide 2021P) and 3-ethyl-3-hydroxymethyloxetane (Toagosei Co., Ltd.) , Trade name: OXT-101) 1 part by weight of 9,10-bis (3-hydroxypropoxy) anthracene synthesized by the same method as in Synthesis Example 1 as a photopolymerization sensitizer at 15 parts by weight at room temperature Mix to prepare the composition. The composition was applied on a polyester film using a bar coater so that the film thickness was 12 microns. Next, a low-density polyethylene film (film thickness: 30 microns) was put on the obtained coating and stored for one day in a dark place and those stored for seven days. After storage, the polyethylene film was peeled off, and the polyethylene film was removed. After washing with acetone and drying, the UV spectrum of the polyethylene film was measured, and the absorbance at 260 nm was measured. The absorbance due to the resulting 9,10-bis (3-hydroxypropoxy) anthracene was converted to 9,10-dibutoxyanthracene. The absorbance was 0.008 after storage for one day and 0.008 after storage for seven days. The results are shown in Table 3.

(Evaluation Example 2 for Migration Resistance of Composition)
Other than using 9,10-bis (4-hydroxybutoxy) anthracene synthesized in the same manner as in Synthesis Example 2 instead of 9,10-bis (3-hydroxypropoxy) anthracene as the photopolymerization sensitizer. Prepared a composition in the same manner as in Example 1 for evaluating migration resistance. The composition was applied 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 coating and stored for one day in a dark place and those stored for seven days. After storage, the polyethylene film was peeled off, and acetone was removed. After washing and drying, the UV spectrum of the polyethylene film was measured, and the absorbance of the polyethylene film at 260 nm was measured. The absorbance due to the resulting 9,10-bis (4-hydroxybutoxy) anthracene was converted to 9,10-dibutoxyanthracene. Absorbance was 0.005 after 1 day storage and 0.009 after 7 days storage. The results are shown in Table 3.

(Evaluation Example 3 for Migration Resistance of Composition)
Use 9,10-bis (5-hydroxypentyloxy) anthracene synthesized in the same manner as in Synthesis Example 3 instead of 9,10-bis (3-hydroxypropoxy) anthracene as a photopolymerization sensitizer. Except for the above, a composition was prepared in the same manner as in Migration Resistance Evaluation Example 1. The composition was applied 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 coating and stored for one day in a dark place and those stored for seven days. After storage, the polyethylene film was peeled off, and acetone was removed. After washing and drying, the UV spectrum of the polyethylene film was measured, and the absorbance of the polyethylene film at 260 nm was measured. The absorbance due to the resulting 9,10-bis (5-hydroxypentyloxy) anthracene was converted to 9,10-dibutoxyanthracene. Absorbance was 0.005 after 1-day storage and 0.010 after 7-day storage. The results are shown in Table 3.

(Evaluation Example 4 for Migration Resistance of Composition)
Use 9,10-bis (6-hydroxyhexyloxy) anthracene synthesized in the same manner as in Synthesis Example 4 instead of 9,10-bis (3-hydroxypropoxy) anthracene as a photopolymerization sensitizer. Except for the above, a composition was prepared in the same manner as in Migration Resistance Evaluation Example 1. The composition was applied 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 coating and stored for one day in a dark place and those stored for seven days. After storage, the polyethylene film was peeled off, and acetone was removed. After washing and drying, the UV spectrum of the polyethylene film was measured, and the absorbance of the polyethylene film at 260 nm was measured. The absorbance due to the resulting 9,10-bis (6-hydroxyhexyloxy) anthracene was converted to 9,10-dibutoxyanthracene. Absorbance was 0.004 after 1 day storage and 0.007 after 7 days storage. The results are shown in Table 3.

(Example 5 for evaluating migration resistance of composition)
As a photopolymerization sensitizer, 9,10-bis [(2-hydroxyethoxy) ethoxy] anthracene synthesized in the same manner as in Synthesis Example 5 was used instead of 9,10-bis (3-hydroxypropoxy) anthracene. A composition was prepared in the same manner as in Migration Resistance Evaluation Example 1 except that. The composition was applied 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 coating and stored for one day in a dark place and those stored for seven days. After storage, the polyethylene film was peeled off, and acetone was removed. After washing and drying, the UV spectrum of the polyethylene film was measured, and the absorbance of the polyethylene film at 260 nm was measured. The absorbance due to the resulting 9,10-bis [(2-hydroxyethoxy) ethoxy] anthracene was converted to 9,10-dibutoxyanthracene. Absorbance was 0.004 after 1-day storage and 0.043 after 7-day storage. The results are shown in Table 3.

(Comparative Example 1 for evaluating migration resistance of composition)
Example of evaluating migration resistance, except that 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer, is used in place of 9,10-bis (3-hydroxypropoxy) anthracene as the photopolymerization sensitizer. A composition was prepared in the same manner as in 1. The composition was applied 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 coating and stored for one day in a dark place and those stored for seven days. After storage, the polyethylene film was peeled off, and acetone was removed. After washing and drying, the UV spectrum of the polyethylene film was measured, and the absorbance of the polyethylene film at 260 nm was measured. The absorbance of 9,10-dibutoxyanthracene was 0.908 after 1 day storage and 0.898 after 7 days storage. The results are shown in Table 3.

(Example 6 for evaluating migration resistance of composition)
9,10-bis (3-hydroxypropoxy) anthracene synthesized by the same method as in Synthesis Example 1 as a photopolymerization sensitizer as a photoradical polymerizable compound with respect to 100 parts by weight of 2-hydroxyethyl acrylate One part by weight was mixed at room temperature to prepare a composition. The composition was applied 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) is placed on the obtained coated material to prepare one that has been stored for one day in a dark place and one that has been stored for seven days. After peeling off, washing the polyethylene film with acetone and drying, the UV spectrum of the polyethylene film was measured and the absorbance at 260 nm was measured. However, the absorption due to the 9,10-bis (3-hydroxypropoxy) anthracene obtained was 0.002 after storage for 1 day and 0.003 after storage for 7 days. The results are shown in Table 4.

(Example 7 for evaluating migration resistance of composition)
Other than using 9,10-bis (4-hydroxybutoxy) anthracene synthesized in the same manner as in Synthesis Example 2 instead of 9,10-bis (3-hydroxypropoxy) anthracene as the photopolymerization sensitizer. Prepared a composition by the same method as in Example 6 for evaluating migration resistance. The composition was applied 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 coating and stored for one day in a dark place and those stored for seven days. After storage, the polyethylene film was peeled off, and acetone was removed. After washing and drying, the UV spectrum of the polyethylene film was measured, and the absorbance of the polyethylene film at 260 nm was measured. The absorbance due to the resulting 9,10-bis (4-hydroxybutoxy) anthracene was converted to 9,10-dibutoxyanthracene. Absorbance was 0.004 after 1 day storage and 0.007 after 7 days storage. The results are shown in Table 4.

(Example 8 for evaluating migration resistance of composition)
Use 9,10-bis (5-hydroxypentyloxy) anthracene synthesized in the same manner as in Synthesis Example 3 instead of 9,10-bis (3-hydroxypropoxy) anthracene as a photopolymerization sensitizer. Except for the above, a composition was prepared in the same manner as in Migration Resistance Evaluation Example 6. The composition was applied 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 coating and stored for one day in a dark place and those stored for seven days. After storage, the polyethylene film was peeled off, and acetone was removed. After washing and drying, the UV spectrum of the polyethylene film was measured, and the absorbance of the polyethylene film at 260 nm was measured. The absorbance due to the resulting 9,10-bis (5-hydroxypentyloxy) anthracene was converted to 9,10-dibutoxyanthracene. Absorbance was 0.005 after 1 day storage and 0.007 after 7 days storage. The results are shown in Table 4.

(Example 9 for evaluating migration resistance of composition)
Use 9,10-bis (6-hydroxyhexyloxy) anthracene synthesized in the same manner as in Synthesis Example 4 instead of 9,10-bis (3-hydroxypropoxy) anthracene as a photopolymerization sensitizer. Except for the above, a composition was prepared in the same manner as in Migration Resistance Evaluation Example 6. The composition was applied 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 coating and stored for one day in a dark place and those stored for seven days. After storage, the polyethylene film was peeled off, and acetone was removed. After washing and drying, the UV spectrum of the polyethylene film was measured, and the absorbance of the polyethylene film at 260 nm was measured. The absorbance due to the resulting 9,10-bis (6-hydroxyhexyloxy) anthracene was converted to 9,10-dibutoxyanthracene. Absorbance was 0.006 after 1 day storage and 0.007 after 7 days storage. The results are shown in Table 4.

(Example 10 for evaluating migration resistance of composition)
As a photopolymerization sensitizer, 9,10-bis [(2-hydroxyethoxy) ethoxy] anthracene synthesized in the same manner as in Synthesis Example 2 was used instead of 9,10-bis (3-hydroxypropoxy) anthracene. A composition was prepared in the same manner as in Migration Resistance Evaluation Example 6 except that. The composition was applied 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 coating and stored for one day in a dark place and those stored for seven days. After storage, the polyethylene film was peeled off, and acetone was removed. After washing and drying, the UV spectrum of the polyethylene film was measured, and the absorbance of the polyethylene film at 260 nm was measured. The absorbance due to the resulting 9,10-bis [(2-hydroxyethoxy) ethoxy] was converted to 9,10-dibutoxyanthracene. Absorbance was 0.002 after 1 day storage and 0.004 after 7 days storage. The results are shown in Table 4.

(Comparative Example 2 for evaluating migration resistance of composition)
Example of evaluating migration resistance, except that 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer, is used in place of 9,10-bis (3-hydroxypropoxy) anthracene as the photopolymerization sensitizer. A composition was prepared in the same manner as in 6. The composition was applied 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 coating and stored for one day in a dark place and those stored for seven days. After storage, the polyethylene film was peeled off, and acetone was removed. After washing and drying, the UV spectrum of the polyethylene film was measured, and the absorbance of the polyethylene film at 260 nm was measured. The absorbance of 9,10-dibutoxyanthracene was 2.748 after 1 day storage and 2.772 after 7 days storage. The results are shown in Table 4.

Evaluation of Migration Resistance of Compositions As is clear by comparing Examples 1 to 5 and Comparative Example 1 of migration resistance of the composition, the 9,10-bis (hydroxyalkoxy) anthracene compound in the photocationic polymerization composition is Compared to 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer, it can be said that the migration resistance is extremely excellent.

In addition, as is clear by comparing the anti-migration evaluation examples 6 to 10 of the composition and the anti-migration comparative example 2 of the composition, the 9,10-bis (hydroxyalkoxy) anthracene compound in the photoradical polymerization composition Compared to 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer, it can be said that migration resistance is extremely excellent.

That is, it can be said that the 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention is excellent in migration resistance of the composition in both photocationic polymerization and photoradical polymerization.

(Example 11 for evaluating migration resistance of photocured product)
As a photocationically polymerizable compound, 3 parts by weight of 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021P manufactured by Daicel), and as a photopolymerization initiator, (4-methylphenyl) [4 -(2-Methylpropyl) phenyl] iodonium-hexafluorophosphor (manufactured by BASF, trade name Irgacure 250) 2.0 parts by weight as a photopolymerization sensitizer, Synthesis Example 2 and A photopolymerizable composition was prepared by mixing 1 part by weight of 9,10-bis (4-hydroxybutoxy) anthracene synthesized by the same method. The composition thus prepared was applied on a polyester film using a bar coater so that the film thickness was 30 microns. Next, the surface of the polyester film coated with the composition was irradiated with light for 6 minutes using a UV LED manufactured by Foseon. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 50 mW / cm ² .

Next, the photocured product was cut into 2 cm square, dipped in acetone as a solvent at 25 ° C. for 16 hours, dried, and the UV spectrum of the cured product was measured. Inclusion of 9,10-bis (4-hydroxybutoxy) anthracene before and after immersion in a solvent by measuring UV absorption intensity at 405 nm due to 9,10-bis (4-hydroxybutoxy) anthracene used as a photopolymerization sensitizer The amount was calculated. As a result, the UV absorption intensity of 9,10-bis (4-hydroxybutoxy) anthracene added as a photopolymerization sensitizer after immersion in the solvent was 91% of the UV absorption intensity before immersion in the solvent. Bis (4-hydroxybutoxy) anthracene was found to elute 9%.

(Example 12 for evaluating migration resistance of photocured product)
As a photopolymerization sensitizer, 9,10-bis [(2-hydroxyethoxy) ethoxy] anthracene synthesized in the same manner as in Synthesis Example 5 was used instead of 9,10-bis (4-hydroxybutoxy) anthracene. A photopolymerizable composition was prepared in the same manner as in Example 11 except that the photocured product was evaluated for migration resistance, and the film thickness was adjusted to 30 microns using a bar coater on a polyester film. Applied. Next, the surface of the polyester film coated with the composition was irradiated with light for 6 minutes using a UV LED manufactured by Foseon. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 50 mW / cm ² . Next, the photocured product was cut into 2 cm square, dipped in acetone as a solvent at 25 ° C. for 16 hours, dried, and the UV spectrum of the cured product was measured. The UV absorption intensity at 405 nm due to 9,10-bis [(2-hydroxyethoxy) ethoxy] anthracene used as a photopolymerization sensitizer was measured, and 9,10-bis ((2-hydroxyethoxy) before and after solvent immersion was measured. The content of) ethoxy) anthracene was calculated. As a result, the UV absorption intensity of 9,10-bis [(2-hydroxyethoxy) ethoxy] anthracene added as a photopolymerization sensitizer after immersion in the solvent is 90% of the UV absorption intensity before immersion in the solvent, It was found that 10-bis [(2-hydroxyethoxy) ethoxy] anthracene eluted at 10%.

(Migration resistance comparative example 3 for photocured product)
Migration resistance of photocured material, except that 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer, is used instead of 9,10-bis (4-hydroxybutoxy) anthracene as the photopolymerization sensitizer. A photopolymerizable composition was prepared in the same manner as in Evaluation Example 11, and the composition was applied on a polyester film using a bar coater so as to have a film thickness of 30 microns. Next, the surface of the polyester film coated with the composition was irradiated with light for 6 minutes using a UV LED manufactured by Foseon. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 50 mW / cm ² . Next, the photocured product was cut into 2 cm square, dipped in acetone as a solvent at 25 ° C. for 16 hours, dried, and the UV spectrum of the cured product was measured. The UV absorption intensity at 405 nm due to 9,10-dibutoxyanthracene used as the photopolymerization sensitizer was measured, and the content of 9,10-dibutoxyanthracene before and after immersion in the solvent was calculated. As a result, the UV absorption intensity of 9,10-dibutoxyanthracene added as a photopolymerization sensitizer after solvent immersion was 36% before solvent immersion, and 64% of 9,10-dibutoxyanthracene was eluted. It has been found.

Evaluation of migration resistance of photocured product Examples 11 and 12 and Comparative Example 3 of evaluation of migration resistance of photocured product are apparent in photocured products obtained by polymerizing a photopolymerizable composition. When 9,10-dibutoxyanthracene, which is a photopolymerization sensitizer, is eluted in acetone, more than half of it is eluted with 9,10-bis (hydroxy) having the primary hydroxyl group of the present invention. When an alkoxy) anthracene compound is used as a photopolymerization sensitizer, the elution amount of the 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group can be kept low even if the photocured product is immersed in a solvent for a long time. Therefore, the 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group as a photopolymerization sensitizer also causes a photopolymerization reaction. And it is presumed to be incorporated into the polymer resin skeleton produced in the polymerization reaction.

(Sublimation resistance evaluation example 1)
The 9,10-bis (6-hydroxyhexyloxy) anthracene synthesized in Synthesis Example 4 was heated in an air atmosphere (flow rate: 100 ml / min), and the weight loss was measured by a differential calorimeter (TG / DTA7200 manufactured by Hitachi High-Tech Science Co., Ltd.). ). As heating conditions, the temperature was raised from room temperature to 180 ° C. (10 ° C./min) and then held for 60 minutes. The weight loss before and after heating was 2.8%.

(Sublimation resistance evaluation comparative example 1)
Evaluation of sublimation resistance was performed except that 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer, was used instead of 9,10-bis (6-hydroxyhexyloxy) anthracene as the photopolymerization sensitizer. Tested as in Example 1. As a result, the weight loss before and after heating was 8.5%.

As is clear by comparing the sublimation resistance evaluation example 1 and the sublimation resistance evaluation comparative example 1, the 9,10-bis (hydroxyalkoxy) anthracene compound of the present invention is a known photopolymerization sensitizer. Compared with 9,10-dibutoxyanthracene, the weight loss upon heating is small, indicating that the compound has low sublimation properties, that is, excellent sublimation resistance.

From the above results, the 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention is a known photopolymerization sensitizer in photocationic polymerization and photoradical polymerization, and 9,10-dibutoxy. Compared to anthracene compounds, it not only has the same photopolymerization sensitizing ability, but also has a primary hydroxyl group, so it is an excellent compound with high migration resistance and sublimation resistance, and is extremely useful as a photopolymerization sensitizer. It turns out to be a useful compound.

Claims (11)

A 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the following general formula (1).

(In the general formula (1), A represents an alkylene group having 2 to 20 carbon atoms, and the alkylene group may be branched and contains an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring. X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom.) A 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the following general formula (2).

(In General Formula (2), n represents an integer of 2 to 20, X and Y may be the same or different, and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom. Represents.) The 9,10-dihydroxyanthracene compound represented by the following general formula (3) is reacted with the halogenated alcohol compound represented by the following general formula (4). A process for producing a 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group.

(In general formula (3), X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom.)
(In the general formula (4), A represents an alkylene group having 2 to 20 carbon atoms, and the alkylene group may be branched and contains an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring. Z represents a halogen atom.)
(In the general formula (1), A represents an alkylene group having 2 to 20 carbon atoms, and the alkylene group may be branched and contains an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring. X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom.) A 9,10-dihydroxyanthracene compound represented by the following general formula (3) is reacted with a halogenated alcohol compound represented by the following structural formula (5). A process for producing a 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group.
(In general formula (3), X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom.)
(In general formula (5), n represents an integer of 2 to 20, and Z represents a halogen atom.)
(In General Formula (2), n represents an integer of 2 to 20, X and Y may be the same or different, and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom. Represents.) A photopolymerization sensitizer containing a 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the following general formula (1).

(In the general formula (1), A represents an alkylene group having 2 to 20 carbon atoms, and the alkylene group may be branched and contains an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring. X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom.) A photopolymerization sensitizer containing a 9,10-bis (hydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the following general formula (2).

(In General Formula (2), n represents an integer of 2 to 20, X and Y may be the same or different, and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom. Represents.) A photopolymerization initiator composition comprising the photopolymerization sensitizer according to claim 5 and a photopolymerization initiator. A photopolymerizable composition comprising the photopolymerization initiator composition according to claim 7 and a photocationically polymerizable compound. A photopolymerizable composition comprising the photopolymerization initiator composition according to claim 7 and a photoradical polymerizable compound. The polymerization method which superposes | polymerizes the photopolymerizable composition of Claim 8 or 9 by irradiating the energy ray containing the light of the wavelength range of 300 nm to 500 nm. The irradiation source of energy rays including light in a wavelength range of 300 nm to 500 nm is an ultraviolet LED having a central wavelength of 365 nm, 375 nm, 385 nm, 395 nm, or 405 nm or a semiconductor laser having a wavelength of 405 nm. Polymerization method.