JP7356644B2 - Polymer photopolymerization sensitizer - Google Patents

Description

The present invention contains an oligomer of a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group, a method for producing the same, and an oligomer of a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group. It relates to a photopolymerization sensitizer.

Photocurable resins, which are polymerized by active energy rays such as ultraviolet rays and visible light, cure quickly and can significantly reduce the amount of organic solvent used compared to thermosetting resins, improving the working environment and reducing environmental impact. It is excellent in that it can be reduced. Conventional photocurable resins by themselves have poor polymerization initiation function, and usually require the use of a photopolymerization initiator for curing. As the photopolymerization initiator, alkylphenone polymerization initiators such as hydroxyacetophenone and benzophenone, acylphosphine oxide photopolymerization initiators, onium salts, and the like are used (Patent Documents 1, 2, and 3). When using an onium salt initiator among these photopolymerization initiators, the light absorption of the onium salt is around 225 nm to 350 nm, and it does not have absorption above 350 nm, so a lamp with a long wavelength of 350 nm or above is used as the light source. In this case, there are problems such as the photocuring reaction being difficult to proceed, and it is common to add a photopolymerization sensitizer. Similarly, many photopolymerization initiators such as alkylphenone polymerization initiators do not have 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 in particular due to color problems (Patent Document 4).

As anthracene-based photopolymerization sensitizers, 9,10-dialkoxyanthracene compounds are used. For example, 9,10-dialkoxyanthracene compounds such as 9,10-dibutoxyanthracene and 9,10-diethoxyanthracene are used as photopolymerization sensitizers for iodonium salts, which are photopolymerization initiators in photopolymerization. (Patent Documents 5, 6, 7, 8).

However, when this 9,10-dialkoxyanthracene compound is stored in the photopolymerizable composition before photocuring or the cured product after photocuring, the photopolymerization sensitizer etc. ooze out onto the surface of the cured product due to blooming. Known to cause dusting and staining problems.

Regarding photopolymerizable compositions, for example, when these photopolymerizable sensitizers are used as a component of a photoadhesive for bonding films together, the photopolymerizable sensitizers migrate to the film covered on top ( Migration) may cause problems with powdering and coloring of the photopolymerized sensitizer on the top film.

In addition, dry film resists are used for processing such as manufacturing printed wiring boards, lead frames, and metal masks, but there is a demand for resists that can be used with 405 nm semiconductor lasers. Thioxanthone and 9,10-dialkoxyanthracene compounds are used as photopolymerization sensitizers. However, dry film resists are stored and traded with a cover film covering the photosensitive resin composition, but polyethylene film or polypropylene film is used for this cover film, and the film is photopolymerized and sensitized. There are problems in that the agent migrates, reducing the sensitizing effect and causing dusting on the film (Patent Document 9).

In order to suppress such migration of photopolymerization sensitizers, 9,10-bis(2-acyloxyalkoxy)anthracene compounds, in which an ester group, which is a polar group, is introduced into the alkoxy group of a 9,10-dialkoxyanthracene compound, have been developed. It has been reported (Patent Document 10). However, the 9,10-bis(2-acyloxyalkoxy)anthracene compound has a step of using an alkylene oxide compound during production, which not only increases the number of steps but also increases the cost of the alkylene oxide compound, especially ethylene oxide. Difficulty in obtaining and handling is a major problem in the production of the 9,10-bis(2-acyloxyalkoxy)anthracene compound.

In addition, compounds have been developed in which the alkoxy group of the 9,10-dialkoxyanthracene compound is changed to an acyl group, but although the migration property is improved, the electron donating property of the alkoxy group is reduced, so the absorption wavelength is There is a problem that the wavelength is shifted to the lower wavelength side (Patent Document 11).

Furthermore, the present inventors have disclosed an oligomer of a 9,10-bis(substituted alkoxy)anthracene compound as a compound that exhibits a photopolymerization sensitizing effect and does not easily cause migration (Patent Document 12). However, the oligomer of the 9,10-bis(substituted alkoxy)anthracene compound uses alkylene oxide in addition to the 9,10-dihydroxyanthracene compound as a raw material for oligomer synthesis, but the available alkylene oxide is limited. Moreover, alkylene oxide, which is easily available, is highly toxic, has a low boiling point, is highly flammable, and is difficult to handle, and requires heat treatment in the 9,10-bis(substituted alkoxy)anthracene compound synthesis reaction. In the case of using ethylene oxide, which is the most easily available, a pressurized sealed container such as an autoclave is required, and there remains the problem that special manufacturing equipment is required. Further, in the oligomerization reaction, there still remained problems such as the low solubility of the 9,10-bis(substituted alkoxy)anthracene compound serving as a raw material and the need for high temperature conditions.

Japanese Patent Application Publication No. 06-345614 Japanese Patent Application Publication No. 07-062010 Japanese Patent Application Publication No. 05-249606 Japanese Patent Application Publication No. 10-195117 Japanese Patent Application Publication No. 2002-302507 Japanese Patent Application Publication No. 11-279212 Japanese Patent Application Publication No. 2000-344704 WO2007/126066 publication Patent No. 4605223 Japanese Patent Application Publication No. 2014-031346 Japanese Patent Application Publication No. 2014-101442 Unexamined Japanese Patent Publication No. 2017-114849

Therefore, we developed a practical manufacturing method that not only has migration resistance during photocuring or during storage of the cured product and does not cause problems with powdering or coloring of the cured product, but also uses easily available raw materials. There is a need for the development of new photopolymerizable sensitizers that can be obtained by

As a result of further intensive studies regarding the structure and physical properties of anthracene compounds, the present inventors found that the oligomer of the 9,10-bis(alkoxycarbonylalkyleneoxy)naphthalene compound having an ester group shown in the present invention is In addition to exhibiting excellent effects as a polymerization sensitizer, the oligomer of the present invention can be produced using readily available compounds as raw materials and under mild conditions, and furthermore, when the oligomer of the present invention is used as a photopolymerization sensitizer, The present invention was completed based on the discovery that migration and blooming are less likely to occur due to the presence of oligomers.

That is, the first gist of the present invention resides in an oligomer of a 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound whose repeating unit has an ester group represented by the following general formula (1).

In the general formula (1), n represents the repeating number and is from 2 to 50, and A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond, and this alkylene structure The carbon atoms of may be substituted with oxygen atoms, nitrogen atoms, or sulfur atoms on the condition that they are not adjacent, and may also contain an alicyclic compound, a benzene ring, or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl It may be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. Furthermore, X ¹ and X ² may be the same or different, and may be a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a carbon Aryloxy group having 6 to 10 carbon atoms, hydroxy group, amino group, alkylamino group having 1 to 5 carbon atoms, arylamino group having 6 to 10 carbon atoms, mercapto group, alkyl sulfide group having 1 to 5 carbon atoms, carbon number 6 to 10 aryl sulfide groups, halogen atoms, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, forming a ring with an oxygen atom, nitrogen atom, or sulfur atom in between. The formed ring may further have a substituent. Y ¹ 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 an oligomer of a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound whose repeating unit has an ester group represented by the following general formula (2).

In the general formula (2), n represents the repeating number and is from 2 to 50, and A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond, and this alkylene structure The carbon atoms of may be substituted with oxygen atoms, nitrogen atoms, or sulfur atoms on the condition that they are not adjacent, and may also contain an alicyclic compound, a benzene ring, or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl It may be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. X ³ and Y ³ 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.

The third gist of the present invention resides in the oligomer of the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound according to the second gist, wherein A in the general formula (2) is a methylene group.

The fourth aspect of the present invention is to react a 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound represented by the following general formula (4) with a bifunctional compound represented by the following general formula (3). A method for producing an oligomer of a 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound having a repeating unit having an ester group represented by the following general formula (1) is provided.

In general formula (4), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be substituted with a hydroxy group. Furthermore, X ¹ and X ² may be the same or different, and may be a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a carbon Aryloxy group having 6 to 10 carbon atoms, hydroxy group, amino group, alkylamino group having 1 to 5 carbon atoms, arylamino group having 6 to 10 carbon atoms, mercapto group, alkyl sulfide group having 1 to 5 carbon atoms, carbon number 6 to 10 aryl sulfide groups, halogen atoms, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, forming a ring with an oxygen atom, nitrogen atom, or sulfur atom in between. The formed ring may further have a substituent. Y ¹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom.

In the general formula (3), D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group and contain an unsaturated bond. The carbon atoms of this alkylene structure may be substituted with an oxygen atom, nitrogen atom, or sulfur atom on the condition that they are not adjacent, and may also contain an alicyclic compound, a benzene ring, or a naphthalene ring. The benzene ring and naphthalene ring may be substituted with an alkyl group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. Z represents a hydroxy group, a halogen atom, or a glycidyloxy group.

In the general formula (1), n represents the repeating number and is from 2 to 50, and A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond, and this alkylene structure The carbon atoms of may be substituted with oxygen atoms, nitrogen atoms, or sulfur atoms on the condition that they are not adjacent, and may also contain an alicyclic compound, a benzene ring, or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl It may be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. Furthermore, X ¹ and X ² may be the same or different, and may be a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a carbon Aryloxy group having 6 to 10 carbon atoms, hydroxy group, amino group, alkylamino group having 1 to 5 carbon atoms, arylamino group having 6 to 10 carbon atoms, mercapto group, alkyl sulfide group having 1 to 5 carbon atoms, carbon number 6 to 10 aryl sulfide groups, halogen atoms, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, forming a ring with an oxygen atom, nitrogen atom, or sulfur atom in between. The formed ring may further have a substituent. Y ¹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom.

The fifth aspect of the present invention is to react a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound represented by the following general formula (5) with a bifunctional compound represented by the following general formula (3). The present invention relates to a method for producing an oligomer of a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having a repeating unit having an ester group represented by the following general formula (2).

In general formula (5), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be substituted with a hydroxy group. X ³ and Y ³ 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.

In the general formula (3), D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group and contain an unsaturated bond. The carbon atoms of this alkylene structure may be substituted with an oxygen atom, nitrogen atom, or sulfur atom on the condition that they are not adjacent, and may also contain an alicyclic compound, a benzene ring, or a naphthalene ring. The benzene ring and naphthalene ring may be substituted with an alkyl group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. Z represents a hydroxy group, a halogen atom, or a glycidyloxy group.

In the general formula (2), n represents the repeating number and is from 2 to 50, and A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond, and this alkylene structure The carbon atoms of may be substituted with oxygen atoms, nitrogen atoms, or sulfur atoms on the condition that they are not adjacent, and may also contain an alicyclic compound, a benzene ring, or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl It may be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. X ³ and Y ³ 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.

A sixth aspect of the present invention resides in a method for producing an oligomer of a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound according to the fifth aspect, wherein A in general formula (2) is a methylene group.

A seventh aspect of the present invention is characterized in that a 1,4-dihydroxynaphthalene compound represented by the following general formula (14) is reacted with a bifunctional compound represented by the following general formula (13). The present invention relates to a method for producing an oligomer of a 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound having an ester group whose repeating unit is represented by the following general formula (1).

In the general formula (14), X ¹ and X ² may be the same or different, and include a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryl group having 1 to 5 carbon atoms. alkoxy group, aryloxy group having 6 to 10 carbon atoms, hydroxy group, amino group, alkylamino group having 1 to 5 carbon atoms, arylamino group having 6 to 10 carbon atoms, mercapto group, alkyl group having 1 to 5 carbon atoms ^A sulfide group, an aryl sulfide group having 6 to 10 carbon atoms, a halogen atom, or X ¹ and They may be sandwiched to form a ring, and the formed ring may further have a substituent. Y ¹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom.

In general formula (13), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond, and this alkylene structure The carbon atoms of may be substituted with oxygen atoms, nitrogen atoms, or sulfur atoms on the condition that they are not adjacent, and may also contain an alicyclic compound, a benzene ring, or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl It may be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. Further, G represents a chlorine atom, a bromine atom, or an iodine atom.

In the general formula (1), n represents the repeating number and is from 2 to 50, and A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond, and this alkylene structure The carbon atoms of may be substituted with oxygen atoms, nitrogen atoms, or sulfur atoms on the condition that they are not adjacent, and may also contain an alicyclic compound, a benzene ring, or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl It may be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. Furthermore, X ¹ and X ² may be the same or different, and may be a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a carbon Aryloxy group having 6 to 10 carbon atoms, hydroxy group, amino group, alkylamino group having 1 to 5 carbon atoms, arylamino group having 6 to 10 carbon atoms, mercapto group, alkyl sulfide group having 1 to 5 carbon atoms, carbon number 6 to 10 aryl sulfide groups, halogen atoms, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, forming a ring with an oxygen atom, nitrogen atom, or sulfur atom in between. The formed ring may further have a substituent. Y ¹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom.

The eighth aspect of the present invention is characterized in that a 9,10-dihydroxyanthracene compound represented by the following general formula (15) is reacted with a bifunctional compound represented by the following general formula (13). The present invention relates to a method for producing an oligomer of a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having a repeating unit having an ester group represented by the following general formula (2).

In general formula (15), X ³ and Y ³ 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.

In general formula (13), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond, and this alkylene structure The carbon atoms of may be substituted with oxygen atoms, nitrogen atoms, or sulfur atoms on the condition that they are not adjacent, and may also contain an alicyclic compound, a benzene ring, or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl It may be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. Further, G represents a chlorine atom, a bromine atom, or an iodine atom.

In the general formula (2), n represents the repeating number and is from 2 to 50, and A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond, and this alkylene structure The carbon atoms of may be substituted with oxygen atoms, nitrogen atoms, or sulfur atoms on the condition that they are not adjacent, and may also contain an alicyclic compound, a benzene ring, or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl It may be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. X ³ and Y ³ 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.

A ninth aspect of the present invention resides in a method for producing an oligomer of a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound according to the eighth invention, wherein A in general formula (2) is a methylene group.

The tenth aspect of the present invention is to provide a photopolymerizable sensitizer containing an oligomer of a 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound whose repeating unit has an ester group represented by the following general formula (1). Exists.

In the general formula (1), n represents the repeating number and is from 2 to 50, and A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond, and this alkylene structure The carbon atoms of may be substituted with oxygen atoms, nitrogen atoms, or sulfur atoms on the condition that they are not adjacent, and may also contain an alicyclic compound, a benzene ring, or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl It may be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. Furthermore, X ¹ and X ² may be the same or different, and may be a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a carbon Aryloxy group having 6 to 10 carbon atoms, hydroxy group, amino group, alkylamino group having 1 to 5 carbon atoms, arylamino group having 6 to 10 carbon atoms, mercapto group, alkyl sulfide group having 1 to 5 carbon atoms, carbon number 6 to 10 aryl sulfide groups, halogen atoms, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, forming a ring with an oxygen atom, nitrogen atom, or sulfur atom in between. The formed ring may further have a substituent. Y ¹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom.

The eleventh aspect of the present invention is to provide a photopolymerizable sensitizer containing an oligomer of a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound whose repeating unit has an ester group represented by the following general formula (2). Exists.

In the general formula (2), n represents the repeating number and is from 2 to 50, and A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond, and this alkylene structure The carbon atoms of may be substituted with oxygen atoms, nitrogen atoms, or sulfur atoms on the condition that they are not adjacent, and may also contain an alicyclic compound, a benzene ring, or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl It may be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. X ³ and Y ³ 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.

A twelfth aspect of the present invention is a photopolymerized polymer containing an oligomer of the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound according to the seventh aspect, wherein A is a methylene group in the general formula (2). Exists in sensitizers.

A thirteenth aspect of the present invention resides in a photopolymerization initiator composition containing the photopolymerization sensitizer according to any one of the tenth to twelfth aspects and a photopolymerization initiator.

A fourteenth aspect of the present invention resides in a photopolymerizable composition containing the photopolymerization initiator composition according to the thirteenth aspect and a photocationically polymerizable compound.

A fifteenth aspect of the present invention resides in a photopolymerizable composition containing the photopolymerization initiator composition according to the thirteenth aspect and a photoradically polymerizable compound.

A sixteenth aspect of the present invention provides a polymerization method for polymerizing the photopolymerizable composition according to the fourteenth aspect or the fifteenth aspect by irradiating the photopolymerizable composition with energy rays containing light in a wavelength range of 300 nm to 500 nm. Exists.

A fourteenth aspect of the present invention is that the irradiation source of energy rays containing light in a wavelength range of 300 nm to 500 nm is an ultraviolet LED having a center wavelength of 365 nm, 375 nm, 385 nm, 395 nm or 405 nm. The present invention is based on the polymerization method described in the gist of No. 13.

The oligomer of the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group of the present invention not only has a high effect as a photopolymerization sensitizer in a photopolymerization reaction, but also has a high effect on the photopolymerization of the compound of the present invention. It is a useful compound in that the degree of migration or blooming of the photopolymerization sensitizer is extremely low in photopolymerizable compositions and cured products containing it as a polymerization sensitizer. In addition, in the manufacturing method, there is no need to use alkylene oxide compounds that are difficult to obtain and handle, and compounds that are easy to obtain and handle are used as raw materials, and it can be manufactured under mild conditions, the manufacturing process is easy, and it can be manufactured at low cost.

(Compound)
The oligomer of the 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound having an ester group of the present invention is a compound whose repeating unit is represented by the following general formula (1).

In the general formula (1), n represents the repeating number and is from 2 to 50, and A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond, and this alkylene structure The carbon atoms of may be substituted with oxygen atoms, nitrogen atoms, or sulfur atoms on the condition that they are not adjacent, and may also contain an alicyclic compound, a benzene ring, or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl It may be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. Furthermore, X ¹ and X ² may be the same or different, and may be a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a carbon Aryloxy group having 6 to 10 carbon atoms, hydroxy group, amino group, alkylamino group having 1 to 5 carbon atoms, arylamino group having 6 to 10 carbon atoms, mercapto group, alkyl sulfide group having 1 to 5 carbon atoms, carbon number 6 to 10 aryl sulfide groups, halogen atoms, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, forming a ring with an oxygen atom, nitrogen atom, or sulfur atom in between. The formed ring may further have a substituent. Y ¹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom.

In the above general formula (1), when X ¹ and X ² combine with each other to form an unsaturated ring, and the unsaturated ring is an aromatic ring, it is represented by the above general formula (1). The compound is represented by the following general formula (2).

In the general formula (2), n represents the repeating number and is from 2 to 50, and A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond, and this alkylene structure The carbon atoms of may be substituted with oxygen atoms, nitrogen atoms, or sulfur atoms on the condition that they are not adjacent, and may also contain an alicyclic compound, a benzene ring, or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl It may be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. X ³ and Y ³ 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.

In general formula (1) or (2), the alkylene group having 1 to 20 carbon atoms represented by A includes a methylene group, a methylmethylene group, an ethylmethylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, Examples include hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, nonadecylene group, and icosylene group, and the alkylene group The group may be branched by an alkyl group.

In general formula (1), the alkyl group or alkenyl group having 1 to 8 carbon atoms represented by X ¹ , X ² or Y ¹ and in general formula (2) by X ³ or Y ³ includes a 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- Examples include ethylhexyl group and 4-methyl-3-pentenyl group, and examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, and iodine atom.

In general formula (1) or (2), the alkylene group having 1 to 20 carbon atoms represented by D includes a methylene group, an ethylene group, a methylethylene group, an ethylethylene group, a propylene group, a 1-methylpropylene group, 2-methylpropylene group, 2,2-dimethylpropylene group, butylene group, pentylene group, 3-methylpentylene group, 2,4-diethylpentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group , undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, nonadecylene group, icosylene group, etc., and the alkylene group may be branched by an alkyl group, It may contain a saturated bond, the carbon atoms of this alkylene structure may be substituted with oxygen, nitrogen, or sulfur atoms on non-adjacent conditions, and it may contain an alicyclic compound, a benzene ring, or a naphthalene ring. The benzene ring and naphthalene ring may be substituted with an alkyl group. Examples of the alkylene group in which a carbon atom of the alkylene group is substituted with an oxygen atom or the like include polyoxyalkylene groups such as a polyoxyethylene group and a polyoxypropylene group.

In general formula (1) or (2), the arylene group having 6 to 20 carbon atoms represented by D includes a phenylene group, a naphthylene group, etc., and the arylene group may have a substituent. , a plurality of rings may be bonded via an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom.

As a specific example of the oligomer of the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group represented by the general formula (2) of the present invention, first, in the general formula (2), A is a methylene group. Specific examples of the compound of general formula (6) are shown in Tables 1, 2 and 3. In the table below, m in the formula represents 1 to 30.

In the general formula (6), n represents the repeating number and is from 2 to 50, and D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group is branched by an alkyl group. The carbon atoms of this alkylene structure may be substituted with oxygen atoms, nitrogen atoms, or sulfur atoms under the condition that they are not adjacent to each other.Also, alicyclic compounds, benzene ring or naphthalene ring, and the benzene ring and naphthalene ring may be substituted with an alkyl group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. X ³ and Y ³ 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.

As specific examples of general formula (2) other than general formula (6), in the specific examples illustrated in general formula (6), the part A is not a methylene group, but an ethylene group, a propylene group, a butylene group, a pentylene group, etc. Compounds substituted by a group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, nonadecylene group, icosylene group can be mentioned.

Furthermore, as specific examples of general formula (1) other than general formula (2), specific examples of compounds of the following general formula (10) where A is a methylene group in general formula (1) are shown in Tables 4, 5 and 6. Shown below.

In the general formula (10), n represents the repeating number and is from 2 to 50, and D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group is branched by an alkyl group. The carbon atoms of this alkylene structure may be substituted with oxygen atoms, nitrogen atoms, or sulfur atoms under the condition that they are not adjacent to each other.Also, alicyclic compounds, benzene ring or naphthalene ring, and the benzene ring and naphthalene ring may be substituted with an alkyl group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. Further, X ¹ and X ² may be the same or different, and may be a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a carbon Aryloxy group having 6 to 10 carbon atoms, hydroxy group, amino group, alkylamino group having 1 to 5 carbon atoms, arylamino group having 6 to 10 carbon atoms, mercapto group, alkyl sulfide group having 1 to 5 carbon atoms, carbon number 6 to 10 aryl sulfide groups, halogen atoms, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, forming a ring with an oxygen atom, nitrogen atom, or sulfur atom in between. The formed ring may further have a substituent. Y ¹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom.

As specific examples of general formula (1) other than general formula (10), in the specific examples illustrated in general formula (10), the part A is not a methylene group, but an ethylene group, a propylene group, a butylene group, a pentylene group, etc. Compounds substituted by a group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, nonadecylene group, icosylene group can be mentioned.

In addition, in general formula (1), it ^is a compound in which X ¹ and Examples include compounds of formulas (11) and (12).

In the general formula (11), n represents the repeating number and is from 2 to 50, and A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond, and this alkylene structure The carbon atoms of may be substituted with oxygen atoms, nitrogen atoms, or sulfur atoms on the condition that they are not adjacent, and may also contain an alicyclic compound, a benzene ring, or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl It may be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom.

In the general formula (12), n represents the repeating number and is from 2 to 50, and A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond, and this alkylene structure The carbon atoms of may be substituted with oxygen atoms, nitrogen atoms, or sulfur atoms on the condition that they are not adjacent, and may also contain an alicyclic compound, a benzene ring, or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl It may be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom.

Specific examples of A or D in general formula (11) or (12) are the same as those of A or D in general formula (2).

Among the specific examples listed above, compounds in which A is a methylene group in general formula (1) and general formula (2) are preferred because they are easy to manufacture.

From the viewpoint of ease of production and high sensitizing ability, the structural formulas (6-5), (6-6), (6-7), (6-9), and (6-11) are listed below. , (6-14) are preferred.

Although examples of compounds suitably used in the present invention have been shown above, the present invention is not limited to the compounds exemplified above.

(Manufacturing method)
Next, a method for producing an oligomer of a 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound having an ester group according to the present invention will be explained. The oligomer of the 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound having an ester group represented by the general formula (1) of the present invention is a 1,4-bis(alkoxycarbonyl It can be obtained by reacting an alkyleneoxy)naphthalene compound with a difunctional compound represented by the corresponding general formula (3) according to Reaction Formula-1 below.

In Reaction Formula-1, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond, and this alkylene structure The carbon atoms of may be substituted with oxygen atoms, nitrogen atoms, or sulfur atoms on the condition that they are not adjacent, and may also contain an alicyclic compound, a benzene ring, or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl It may be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. Furthermore, X ¹ and X ² may be the same or different, and may be a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a carbon Aryloxy group having 6 to 10 carbon atoms, hydroxy group, amino group, alkylamino group having 1 to 5 carbon atoms, arylamino group having 6 to 10 carbon atoms, mercapto group, alkyl sulfide group having 1 to 5 carbon atoms, carbon number 6 to 10 aryl sulfide groups, halogen atoms, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, forming a ring with an oxygen atom, nitrogen atom, or sulfur atom in between. The formed ring may further have a substituent. Y ¹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom. Further, Z represents a hydroxy group, a halogen atom, or a glycidyloxy group, and n represents the repeating number and is from 2 to 50.

In the above general formula (1), when X ¹ and X ² combine with each other to form an unsaturated ring, and the unsaturated ring is an aromatic ring, it is represented by the above general formula (1). Since the compound is a compound represented by general formula (2), first, a method for producing the compound of general formula (2) will be explained.

(Production method of oligomer of 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound-1)
The oligomer of the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group represented by the general formula (2) of the present invention is a 9,10-bis(alkoxycarbonyl) compound represented by the general formula (5). It can be obtained by reacting an alkyleneoxy)anthracene compound with a difunctional compound represented by the corresponding general formula (3) according to Reaction Formula-2 below.

In Reaction Formula-2, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond, and this alkylene structure The carbon atoms of may be substituted with oxygen atoms, nitrogen atoms, or sulfur atoms on the condition that they are not adjacent, and may also contain an alicyclic compound, a benzene ring, or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl It may be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. Moreover, X ³ and Y ³ 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. Further, Z represents a hydroxy group, a halogen atom, or a glycidyloxy group, and n represents the number of repeats and is from 2 to 50.

In Reaction Formula-2, the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound represented by the general formula (5) used as a raw material is reacted with the corresponding 9,10-dihydroxyanthracene compound and an ester compound. It can be obtained by

(Method for producing 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound)
First, a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound represented by general formula (5) is produced by a reaction between a 9,10-dihydroxyanthracene compound and an ester compound (hereinafter simply referred to as esterification reaction). Explain the method.

The 9,10-dihydroxyanthracene compound used as a raw material in the esterification reaction is obtained by reducing the corresponding 9,10-anthraquinone compound. In this reaction, specific examples of the 9,10-dihydroxyanthracene compounds used as raw materials include 9,10-dihydroxyanthracene, 2-methyl-9,10-dihydroxyanthracene, and 2-ethyl-9,10-dihydroxyanthracene. , 2-t-pentyl-9,10-dihydroxyanthracene, 2,6-dimethyl-9,10-dihydroxyanthracene, 2-chloro-9,10-dihydroxyanthracene, 2-bromo-9,10-dihydroxyanthracene, etc. Can be mentioned.

In the case of 9,10-dihydroxyanthracene, 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 its isomer, 1,4-dihydro-9,10-dihydroxyanthracene, 9,10-dihydroxyanthracene can be obtained more easily. That is, 1,4,4a,9a-tetrahydroanthraquinone obtained by the reaction of 1,4-naphthoquinone and 1,3-butadiene is 9 , 10-anthraquinone, an aqueous solution of an alkali metal salt of 9,10-dihydroxyanthracene can be obtained. By acidifying the obtained aqueous solution of the alkali metal salt of 9,10-dihydroxyanthracene in the absence of oxygen, 9,10-dihydroxyanthracene can be precipitated. By purifying this precipitate, 9,10-dihydroxyanthracene can be obtained. A 9,10-dihydroxyanthracene compound having a substituent can also be obtained in the same manner.

Next, specific examples of the ester compounds used as raw materials include methyl chloroacetate, ethyl chloroacetate, n-propyl chloroacetate, isopropyl chloroacetate, n-butyl chloroacetate, tert-butyl chloroacetate, and methyl 2-chloropropionate. , methyl 3-chloropropionate, methyl 2-chloropropionate, methyl 3-chloropropionate, ethyl 2-chloropropionate, ethyl 3-chloropropionate, n-propyl 2-chloropropionate, 3-chloropropionate n-propyl, isopropyl 2-chloropropionate, isopropyl 3-chloropropionate, n-butyl 2-chloropropionate, n-butyl 3-chloropropionate, tert-butyl 2-chloropropionate, 3-chloropropionate tert-butyl, methyl 2-chlorobutyrate, methyl 3-chlorobutyrate, methyl 4-chlorobutyrate, ethyl 2-chlorobutyrate, ethyl 3-chlorobutyrate, ethyl 4-chlorobutyrate, n-propyl 2-chlorobutyrate, 3- n-propyl chlorobutyrate, n-propyl 4-chlorobutyrate, isopropyl 2-chlorobutyrate, isopropyl 3-chlorobutyrate, isopropyl 4-chlorobutyrate, n-butyl 2-chlorobutyrate, n-butyl 3-chlorobutyrate, 4- n-butyl chlorobutyrate, tert-butyl 2-chlorobutyrate, tert-butyl 3-chlorobutyrate, tert-butyl 4-chlorobutyrate, methyl 2-chlorovalerate, methyl 3-chlorovalerate, methyl 4-chlorovalerate , methyl 5-chlorovalerate, ethyl 2-chlorovalerate, ethyl 3-chlorovalerate, ethyl 4-chlorovalerate, ethyl 5-chlorovalerate, n-propyl 2-chlorovalerate, 3-chlorovalerate n-propyl, 4-chlorovalerate n-propyl, 5-chlorovalerate n-propyl, 2-chlorovalerate isopropyl, 3-chlorovalerate isopropyl, 4-chlorovalerate isopropyl, 5-chlorovalerate isopropyl, n-butyl 2-chlorovalerate, n-butyl 3-chlorovalerate, n-butyl 4-chlorovalerate, n-butyl 5-chlorovalerate, tert-butyl 2-chlorovalerate, 3-chlorovalerate tert-butyl, tert-butyl 4-chlorovalerate, tert-butyl 5-chlorovalerate, methyl bromoacetate, ethyl bromoacetate, n-propyl bromoacetate, isopropyl bromoacetate, n-butyl bromoacetate, tert- bromoacetate Butyl, methyl 2-bromopropionate, methyl 3-bromopropionate, methyl 2-bromopropionate, methyl 3-bromopropionate, ethyl 2-bromopropionate, ethyl 3-bromopropionate, 2-bromopropionate n -propyl, n-propyl 3-bromopropionate, isopropyl 2-bromopropionate, isopropyl 3-bromopropionate, n-butyl 2-bromopropionate, n-butyl 3-bromopropionate, tert 2-bromopropionate -butyl, tert-butyl 3-bromopropionate, methyl 2-bromobutyrate, methyl 3-bromobutyrate, methyl 4-bromobutyrate, ethyl 2-bromobutyrate, ethyl 3-bromobutyrate, ethyl 4-bromobutyrate (3- 7), n-propyl 2-bromobutyrate, n-propyl 3-bromobutyrate, n-propyl 4-bromobutyrate, isopropyl 2-bromobutyrate, isopropyl 3-bromobutyrate, isopropyl 4-bromobutyrate, n-bromobutyrate -butyl, n-butyl 3-bromobutyrate, n-butyl 4-bromobutyrate, tert-butyl 2-bromobutyrate, tert-butyl 3-bromobutyrate, tert-butyl 4-bromobutyrate, methyl 2-bromovalerate, Methyl 3-bromovalerate, methyl 4-bromovalerate, methyl 5-bromovalerate, ethyl 2-bromovalerate, ethyl 3-bromovalerate, ethyl 4-bromovalerate (3-8), 5-bromo Ethyl valerate, n-propyl 2-bromovalerate, n-propyl 3-bromovalerate, n-propyl 4-bromovalerate, n-propyl 5-bromovalerate, isopropyl 2-bromovalerate, 3-bromo Isopropyl valerate, isopropyl 4-bromovalerate, isopropyl 5-bromovalerate, n-butyl 2-bromovalerate, n-butyl 3-bromovalerate, n-butyl 4-bromovalerate, 5-bromovalerate Examples include n-butyl, tert-butyl 2-bromovalerate, and tert-butyl 3-bromovalerate.

In the reaction between the 9,10-dihydroxyanthracene compound and the ester compound, the amount of the ester compound used is preferably 2.0 times or more and less than 10.0 times by mole relative to the 9,10-dihydroxyanthracene compound. More preferably, it is 2.2 times or more and less than 5.0 times by mole. If the amount is less than 2.0 times by mole, the reaction will not be completed, and if it is more than 10.0 times by mole, side reactions will occur and the yield and purity will decrease, which is not preferable.

Basic compounds used in the esterification reaction include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, lithium hexamethyldisilazide, lithium diisopropylamide, triethylamine, tributylamine, trihexylamine, Examples include dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dimethylaniline, pyridine, 4,4-dimethylaminopyridine, piperidine, γ-picoline, lutidine, and the like.

The amount of the basic compound added is preferably 2.0 times or more and less than 10.0 times by mole, more preferably 2.2 times or more and 5.0 times by mole, relative to the 9,10-dihydroxyanthracene compound. less than twice the mole. If the amount is less than 2.0 times by mole, the reaction will not be completed, and if it is more than 10.0 times by mole, side reactions will occur and the yield and purity will decrease, which is not preferable.

The esterification reaction is carried out in a solvent or without a solvent. The type of solvent used is not particularly limited as long as it does not react with the ester compound used, and examples include aromatic solvents such as toluene, xylene, and ethylbenzene, ether solvents such as tetrahydrofuran and 1,4-dioxane, acetone, methyl ethyl ketone, Ketone solvents such as 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 are used. .

When a 9,10-dihydroxyanthracene compound is dissolved in an aqueous solution of an inorganic base and reacted with an ester, it is effective to use a phase transfer catalyst. Examples of the phase transfer catalyst include tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, trioctylmethylammonium bromide, trioctylethylammonium bromide, trioctylpropylammonium bromide, and trioctylbutylammonium bromide. , benzyldimethyloctadecylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrafbutylammonium chloride, trioctylmethylammonium chloride, trioctylethylammonium chloride, trioctylpropylammonium chloride, trioctylbutylammonium chloride , benzyldimethyloctadecylammonium chloride, and the like.

The amount of the phase transfer catalyst added is preferably 0.01 mole or more and less than 1.0 mole times, more preferably 0.05 mole times or more and 0.5 mole times, relative to the 9,10-dihydroxyanthracene compound. less than twice the mole. If the amount is less than 0.01 times by mole, the reaction rate is slow, and if it is more than 1.0 times by mole, the purity of the product decreases, which is not preferable.

The reaction temperature of the reaction is usually 0° C. or higher and 100° C. or lower, and the reaction is completed at around room temperature without any particular heat treatment. The reaction time in this reaction varies depending on the reaction temperature, but is usually about 1 hour to 4 hours. Therefore, the reaction proceeds under mild conditions, and there is no need to use a special reaction vessel such as a pressure cooker.

After the esterification reaction is completed, unreacted raw materials, solvents, and catalysts are removed, if necessary, by washing, distillation under reduced pressure, filtration, or other operations singly or in combination. If the product is solid, crystals will precipitate during the reaction, so solid-liquid separation is performed by filtration, and if necessary, recrystallization is performed from a poor solvent such as alcohol or hexane. Alternatively, it can be dried up as it is to obtain crystals. When the product is a liquid, it can be dried up as it is and, if necessary, purified by distillation to obtain a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound.

In the method for producing the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound represented by the general formula (5), it is preferable that A is a methylene group because it is easiest to produce.

(Production method of oligomer)
Next, the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound represented by the general formula (5) and the bifunctional compound represented by the general formula (3) described in the above reaction formula-1 are combined. A method for producing an oligomer of a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group represented by the general formula (2) of the present invention by reaction (hereinafter referred to as oligomerization reaction) will be described.

In the oligomerization reaction, a specific example of the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound represented by the general formula (5) as a raw material is 9,10-bis(hydroxycarbonylmethyleneoxy). Anthracene, 9,10-bis(methoxycarbonylmethyleneoxy)anthracene, 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene, 9,10-bis(isopropoxycarbonylmethyleneoxy)anthracene, 9,10-bis(tert- Butoxycarbonylmethyleneoxy)anthracene, 9,10-bis(n-butoxycarbonylmethyleneoxy)anthracene, 9,10-bis(methoxycarbonylmethylmethyleneoxy)anthracene, 9,10-bis(ethoxycarbonylpropyleneoxy)anthracene, 9 , 10-bis(ethoxycarbonylbutyleneoxy)anthracene, 2-ethyl-9,10-bis(isopropoxycarbonylmethyleneoxy)anthracene, 9,10-bis(ethoxycarbonylethylmethyleneoxy)anthracene, and the like.

In the oligomerization reaction, specific examples of the bifunctional compound represented by general formula (3) as a raw material include ethylene glycol, propylene glycol, 1,2-butanediol, 1, 3-propanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-Methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol , 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,16-hexadecanediol , 1,17-heptadecanediol, 1,18-octadecanediol, 1,19-nonadecanediol, 1,20-icosanediol, polyethylene glycol, polypropylene glycol, 1,1-cyclohexanedimethanol, 1,4- Cyclohexane dimethanol, tricyclodecanedimethanol, isosorbide, xylylene glycol, bis(p-hydroxy)diphenyl, bis(p-hydroxyphenyl)propane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane , bis[4-(2-hydroxyethoxy)phenyl]sulfone, 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, and the like.

When Z is a halogen atom, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane, 1,7-dichloroheptane, 1 , 8-dichlorooctane, 1,9-dichlorononane, 1,10-dichlorodecane, 1,11-dichloroundecane, 1,12-dichlorododecane, 1,13-dichlorotridecane, 1,14-dichlorotetradecane, 1 , 15-dichloropentadecane, 1,16-dichlorohexadecane, 1,17-dichloroheptadecane, 1,18-dichlorooctadecane, 1,19-dichlorononadecane, 1,20-dichloroleucosan, 1,2-dibromoethane , 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane, 1,7-dibromoheptane, 1,8-dibromooctane, 1,9-dibromononane, 1,10-dibromodecane, 1,11-dibromoundecane, 1,12-dibromododecane, 1,13-dibromotridecane, 1,14-dibromotetradecane, 1,15-dibromopentadecane, 1,16-dibromohexadecane, 1,17-dibromoheptadecane, 1,18-dibromooctadecane, 1,19-dibromononadecane, 1,20-dibromoicosane, 1,2-diiodoethane, 1,3-diiodopropane, 1,4-diiodobutane , 1,5-diiodopentane, 1,6-diiodohexane, 1,7-diiodoheptane, 1,8-diiodooctane, 1,9-diiodononane, 1,10-diiododecane, 1,11-diiododecane Iodoundecane, 1,12-diiodododecane, 1,13-diiodotridecane, 1,14-diiodotetradecane, 1,15-diiodopentadecane, 1,16-diiodohexadecane, 1,17-diiodo Examples include heptadecane, 1,18-diiodooctadecane, 1,19-diiodononadecane, and 1,20-diiodoicosane.

When Z is a glycidyloxy group, it may be any of an aliphatic diglycidyl ether compound, an alicyclic glycidyl ether compound, and an aromatic diglycidyl ether compound. Examples of the aliphatic diglycidyl ether compounds include ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, diethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1,6-hexanediol diglycidyl ether. Examples of the alicyclic diglycidyl ether compounds include hydrogenated bisphenol-A diglycidyl ether and hydrogenated bisphenol-F diglycidyl ether, and examples of the aromatic diglycidyl ether include bisphenol A diglycidyl ether and bisphenol F diglycidyl ether. Examples include glycidyl ether and hydroquinone diglycidyl ether. Two or more of these bifunctional compounds may be used simultaneously in the reaction.

Among the specific examples listed above, diol compounds are preferred in terms of reactivity.

In the oligomerization reaction, the amount of the bifunctional compound represented by the general formula (3) to be used is preferably 0.5 times or more by mole, 5 times the amount of the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound. It is less than .0 mole times, more preferably 1.0 mole times or more and less than 3.0 mole times. If the amount is less than 0.5 times by mole, the average molecular weight becomes small, the effect of suppressing migration becomes weak, and unreacted 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound remains in the product, resulting in poor purity. decreases. Moreover, if it is 5.0 moles or more, the average molecular weight becomes small, the effect of suppressing migration becomes weak, and unreacted bifunctional compounds remain in the product, resulting in a decrease in purity.

Furthermore, as the molar ratio of the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound represented by general formula (5) and the bifunctional compound represented by general formula (3) approaches 1, the average molecular weight increases. If it becomes too large, the molecular mobility may become small and the sensitizing ability may decrease. In that case, the molecular weight may be adjusted by adding a small amount of a monofunctional compound.

When the bifunctional compound represented by general formula (3) in the oligomerization reaction is a diol compound, use of a catalyst increases the reaction rate and enables efficient production. Catalysts used in the reaction include mineral acids (sulfuric acid, hydrochloric acid), organic acids (methanesulfonic acid, p-toluenesulfonic acid), Lewis acids (boron fluoride etherate, aluminum trichloride, titanium tetrachloride, iron trichloride, zinc dichloride) solid acid catalyst (manufactured by Futamura Chemical), Amberlyst (manufactured by Organo), Nafion (manufactured by DuPont, Nafion is a registered trademark of DuPont), tetraalkoxytitanium compounds (tetraisopropoxytitanium, tetra n-butoxy titanium, tetramethoxytitanium), organic tin compounds (dibutyltin dilaurate, dibutyltin oxide), and the like.

The amount of the catalyst added is preferably 0.01 mol% or more and less than 20 mol%, more preferably 0.1 mol% or more, 10 to 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound. Less than mol%. If it is less than 0.01 mol%, the reaction will not be completed, and if it is more than 20 mol%, side reactions will occur and the yield and purity will decrease, which is not preferable.

When the bifunctional compound represented by general formula (3) in the oligomerization reaction is a dihalogen compound or diglycidyl compound, a basic compound is required. Basic compounds used include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, sodium bicarbonate, lithium hexamethyldisilazide, lithium diisopropylamide, triethylamine, tributylamine. , trihexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dimethylaniline, pyridine, 4,4-dimethylaminopyridine, piperidine, γ-picoline, lutidine and the like.

The amount of the basic compound added is preferably 2.0 moles or more and less than 5.0 moles, more preferably 2.2 moles, relative to the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound. 3.0 times or more, but less than 3.0 times. If the amount is less than 2.0 times by mole, the reaction will not be completed, and if it is more than 5.0 times by mole, side reactions will occur and the yield and purity will decrease, which is not preferable.

The reaction is carried out in a solvent or without a solvent. The type of solvent used is not particularly limited as long as it does not react with the difunctional compound used, and examples include aromatic solvents such as toluene, xylene, and ethylbenzene, ether solvents 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-bis(alkoxycarbonylalkyleneoxy)anthracene compound is dissolved in an aqueous solution of an inorganic base and reacted with a difunctional compound, it is effective to use a phase transfer catalyst. Examples of the phase transfer catalyst include tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, trioctylmethylammonium bromide, trioctylethylammonium bromide, trioctylpropylammonium bromide, and trioctylbutylammonium bromide. , benzyldimethyloctadecylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrafbutylammonium chloride, trioctylmethylammonium chloride, trioctylethylammonium chloride, trioctylpropylammonium chloride, trioctylbutylammonium chloride , benzyldimethyloctadecylammonium chloride, and the like.

The amount of the phase transfer catalyst added is preferably 0.01 mole or more and less than 1.0 mole times, more preferably 0.05 mole times, relative to the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound. It is more than twice as much, but less than 0.5 times by mole. If the amount is less than 0.01 times by mole, the reaction rate is slow, and if it is more than 1.0 times by mole, the purity of the product decreases, which is not preferable.

The reaction temperature of the reaction is usually 0°C or higher and 200°C or lower, preferably 20°C or higher and 150°C or lower. If it is less than 0°C, the reaction time will be too long, and if it is heated above 200°C, impurities will increase and the purity of the target compound will decrease, both of which are not preferred.

The reaction time in this reaction varies depending on the reaction temperature, but is usually about 1 hour to 30 hours. More preferably, the time is from 2 hours to 20 hours.

After the reaction is completed, unreacted raw materials, solvents, and catalysts are removed, if necessary, by washing, distillation under reduced pressure, filtration, or other operations singly or in combination. If the product is solid, crystals will precipitate during the reaction, so solid-liquid separation is performed by filtration, and if necessary, recrystallization is performed from a poor solvent such as alcohol or hexane. Alternatively, it can be dried up as it is to obtain crystals. When the product is a liquid, it can be dried up as it is and, if necessary, purified by distillation to obtain an oligomer of a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group.

(Production method of oligomer of 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound)
Next, a method for producing an oligomer of a 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound will be described. The oligomer of the 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound having an ester group represented by the general formula (1) of the present invention is similar to the oligomer of the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound. It can be manufactured by the following method. That is, a 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound represented by general formula (4) is reacted with a corresponding bifunctional compound represented by general formula (3) according to reaction formula-1 below. It can be obtained by

In Reaction Formula-1, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond, and this alkylene structure The carbon atoms of may be substituted with oxygen atoms, nitrogen atoms, or sulfur atoms on the condition that they are not adjacent, and may also contain an alicyclic compound, a benzene ring, or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl It may be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. Furthermore, X ¹ and X ² may be the same or different, and may be a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a carbon Aryloxy group having 6 to 10 carbon atoms, hydroxy group, amino group, alkylamino group having 1 to 5 carbon atoms, arylamino group having 6 to 10 carbon atoms, mercapto group, alkyl sulfide group having 1 to 5 carbon atoms, carbon number 6 to 10 aryl sulfide groups, halogen atoms, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, forming a ring with an oxygen atom, nitrogen atom, or sulfur atom in between. The formed ring may further have a substituent. Y ¹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom. Further, Z represents a hydroxy group, a halogen atom, or a glycidyloxy group, and n represents the repeating number and is from 2 to 50.

In Reaction Formula-1, the 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound represented by the general formula (4) used as a raw material is prepared by combining the corresponding 1,4-dihydroxynaphthalene compound and ester compound with the general formula ( It can be obtained by reacting in the same manner as in the production of 5).

The 1,4-dihydroxynaphthalene compound used as a raw material in the esterification reaction is obtained by reducing the corresponding 1,4-naphthoquinone compound. In this reaction, specific examples of 1,4-dihydroxynaphthalene compounds used as raw materials include 1,4-dihydroxynaphthalene, 2-methyl-1,4-dihydroxynaphthalene, and 2,3-dimethyl-1,4- Dihydroxynaphthalene, 2-chloro-1,4-dihydroxynaphthalene, 2,3-dichloro-1,4-dihydroxynaphthalene, 2-hydroxy-1,4-dihydroxynaphthalene, 1,4-dihydro-9,10-dihydroxyanthracene , 1,2,3,4-tetrahydro-9,10-dihydroxyanthracene and the like.

As a specific example of the ester compound used as a raw material, those similar to those used in the production of general formula (5) can be used, and the reaction conditions are also the same, and the reaction proceeds under mild conditions, especially in a special pressure cooker etc. There is no need to use a special reaction vessel.

(Oligomer manufacturing method)
Next, a reaction between the 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound represented by the general formula (4) described in Reaction Formula-1 above and the bifunctional compound represented by the general formula (3) A method for producing an oligomer of a 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound having an ester group represented by the general formula (1) according to the present invention (hereinafter referred to as oligomerization reaction) will be described.

In the oligomerization reaction, a specific example of the 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound represented by the general formula (4) as a raw material is 1,4-bis(hydroxycarbonylmethyleneoxy). Naphthalene, 1,4-bis(methoxycarbonylmethyleneoxy)naphthalene, 1,4-bis(ethoxycarbonylmethyleneoxy)naphthalene, 1,4-bis(isopropoxycarbonylmethyleneoxy)naphthalene, 1,4-bis(tert- butoxycarbonylmethyleneoxy)naphthalene, 1,4-bis(n-butoxycarbonylmethyleneoxy)naphthalene, 1,4-bis(methoxycarbonylmethylmethyleneoxy)naphthalene, 1,4-bis(ethoxycarbonylpropyleneoxy)naphthalene, 1 ,4-bis(ethoxycarbonylbutyleneoxy)naphthalene, 1,4-bis(ethoxycarbonylethylmethyleneoxy)naphthalene, 2-methyl-1,4-bis(hydroxycarbonylmethyleneoxy)naphthalene, 2-methyl-1,4 -bis(methoxycarbonylmethyleneoxy)naphthalene, 2-methyl-1,4-bis(ethoxycarbonylmethyleneoxy)naphthalene, 2-methyl-1,4-bis(isopropoxycarbonylmethyleneoxy)naphthalene, 2-methyl-1 , 4-bis(tert-butoxycarbonylmethyleneoxy)naphthalene, 2-methyl-1,4-bis(n-butoxycarbonylmethyleneoxy)naphthalene, 2-methyl-1,4-bis(methoxycarbonylmethylmethyleneoxy)naphthalene , 2-methyl-1,4-bis(ethoxycarbonylpropyleneoxy)naphthalene, 2-methyl-1,4-bis(ethoxycarbonylbutyleneoxy)naphthalene, 2-methyl-1,4-bis(ethoxycarbonylethylmethyleneoxy) ) Naphthalene, 2,3-dichloro-1,4-bis(hydroxycarbonylmethyleneoxy)naphthalene, 2,3-dichloro-1,4-bis(methoxycarbonylmethyleneoxy)naphthalene, 2,3-dichloro-1,4 -bis(ethoxycarbonylmethyleneoxy)naphthalene, 2,3-dichloro-1,4-bis(isopropoxycarbonylmethyleneoxy)naphthalene, 2,3-dichloro-1,4-bis(tert-butoxycarbonylmethyleneoxy)naphthalene , 2,3-dichloro-1,4-bis(n-butoxycarbonylmethyleneoxy)naphthalene, 2,3-dichloro-1,4-bis(methoxycarbonylmethylmethyleneoxy)naphthalene, 2,3-dichloro-1, 4-bis(ethoxycarbonylpropyleneoxy)naphthalene, 2,3-dichloro-1,4-bis(ethoxycarbonylbutyleneoxy)naphthalene, 2,3-dichloro-1,4-bis(ethoxycarbonylethylmethyleneoxy)naphthalene, Examples include 1,4-dihydro-9,10-bis(isopropoxycarbonylmethyleneoxy)anthracene and 1,2,3,4-tetrahydro-9,10-bis(isopropoxycarbonylmethyleneoxy)anthracene.

In the oligomerization reaction, specific examples of the bifunctional compound represented by the general formula (3) as a raw material can be the same as those listed in Reaction Formula-1.

As the oligomerization reaction conditions, the same conditions as in Reaction Formula-1 can be used.

(Production method of oligomer of 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound-2)
The oligomer of the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group represented by the general formula (2) of the present invention is obtained from the 9,10-dihydroxyanthracene compound represented by the general formula (15). It can be obtained by reacting with a difunctional compound represented by the corresponding general formula (13) according to Reaction Formula-3 below.

In Reaction Formula-3, A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond, and this alkylene structure The carbon atoms of may be substituted with oxygen atoms, nitrogen atoms, or sulfur atoms on the condition that they are not adjacent, and may also contain an alicyclic compound, a benzene ring, or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl It may be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. Moreover, X ³ and Y ³ 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. Further, G represents a chlorine atom, a bromine atom, or an iodine atom, and n represents a repeating number of 2 to 50.

Next, the general compound of the present invention is prepared by reacting the 9,10-dihydroxyanthracene compound represented by the general formula (15) with the bifunctional compound represented by the general formula (13) described in Reaction Formula-3 above. A method for producing an oligomer of a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group represented by formula (2) (hereinafter referred to as oligomerization reaction) will be described.

In the oligomerization reaction, specific examples of the 9,10-dihydroxyanthracene compound represented by the general formula (15) as a raw material include 9,10-dihydroxyanthracene, 2-methyl-9,10-dihydroxyanthracene, , 2-ethyl-9,10-dihydroxyanthracene, 2-t-pentyl-9,10-dihydroxyanthracene, 2,6-dimethyl-9,10-dihydroxyanthracene, 2-chloro-9,10-dihydroxyanthracene, 2 -bromo-9,10-dihydroxyanthracene and the like.

In the oligomerization reaction, specific examples of the bifunctional compound represented by the general formula (13) used as a raw material include bis(chloroacetoxy)methane, 1,2-bis(chloroacetoxy)ethane (13-13), 1,3-bis(chloroacetoxy)propane, 1,2-bis(chloroacetoxy)-2-methylethane, 1,4-bis(chloroacetoxy)butane (13-14), 1,2-bis(chloroacetoxy) -2,2-dimethylethane, 1,5-bis(chloroacetoxy)pentane, 1,6-bis(chloroacetoxy)hexane, 1,5-bis(chloroacetoxy)3-methylpentane, 1,7-bis( chloroacetoxy)heptane, 1,8-bis(chloroacetoxy)octane, 1,6-bis(chloroacetoxy)2-ethylhexane, 1,9-bis(chloroacetoxy)nonane, 1,5-bis(chloroacetoxy) 2,4-diethylpentane, 1,10-bis(chloroacetoxy)dodecane, 1,19-bis(chloroacetoxy)nonadecane, 1,20-bis(chloroacetoxy)icosane, 1,4-bis(chloroacetoxy)cyclohexane , bis(chloroacetoxymethyl)-1,4-cyclohexane, diethylene glycol dichloroacetate, polyethylene glycol dichloroacetate,
Bis(2-chloropropanoyloxy)methane, 1,2-bis(2-chloropropanoyloxy)ethane, 1,3-bis(2-chloropropanoyloxy)propane, 1,2-bis(2-chloro propanoyloxy)-2-methylethane, 1,4-bis(2-chloropropanoyloxy)butane, 1,2-bis(2-chloropropanoyloxy)-2,2-dimethylethane, 1,5-bis (2-chloropropanoyloxy)pentane, 1,6-bis(2-chloropropanoyloxy)hexane, 1,7-bis(2-chloropropanoyloxy)heptane, 1,8-bis(2-chloropropanoyloxy)heptane, octane, 1,6-bis(2-chloropropanoyloxy)2-ethylhexane, 1,9-bis(2-chloropropanoyloxy)nonane, 1,10-bis(2-chloropropanoyloxy) ) dodecane, 1,19-bis(2-chloropropanoyloxy)nonadecane, 1,20-bis(2-chloropropanoyloxy)icosane, 1,4-bis(2-chloropropanoyloxy)cyclohexane, bis( 2-chloropropanoyloxymethyl)-1,4-cyclohexane, diethylene glycol bis(2-chloropropionate), polyethylene glycol bis(2-chloropropionate),
Bis(3-chloropropanoyloxy)methane, 1,2-bis(3-chloropropanoyloxy)ethane, 1,3-bis(3-chloropropanoyloxy)propane, 1,2-bis(3-chloro propanoyloxy)-2-methylethane, 1,4-bis(3-chloropropanoyloxy)butane, 1,2-bis(3-chloropropanoyloxy)-2,2-dimethylethane, 1,5-bis (3-chloropropanoyloxy)pentane, 1,6-bis(3-chloropropanoyloxy)hexane, 1,7-bis(3-chloropropanoyloxy)heptane, 1,8-bis(3-chloropropanoyloxy)heptane, octane, 1,6-bis(3-chloropropanoyloxy)2-ethylhexane, 1,9-bis(3-chloropropanoyloxy)nonane, 1,10-bis(3-chloropropanoyloxy) ) dodecane, 1,19-bis(3-chloropropanoyloxy)nonadecane, 1,20-bis(3-chloropropanoyloxy)icosane, 1,4-bis(3-chloropropanoyloxy)cyclohexane, bis( 3-chloropropanoyloxymethyl)-1,4-cyclohexane, diethylene glycol bis(3-chloropropionate), polyethylene glycol bis(3-chloropropionate),
Bis(2-chlorobutanoyloxy)methane, 1,2-bis(2-chlorobutanoyloxy)ethane, 1,3-bis(2-chlorobutanoyloxy)propane, 1,2-bis(2-chloro butanoyloxy)-2-methylethane, 1,4-bis(2-chlorobutanoyloxy)butane, 1,2-bis(2-chlorobutanoyloxy)-2,2-dimethylethane, 1,5-bis (2-chlorobutanoyloxy)pentane, 1,6-bis(2-chlorobutanoyloxy)hexane, 1,7-bis(2-chlorobutanoyloxy)heptane, 1,8-bis(2-chlorobutanoyloxy)hexane octane, 1,6-bis(2-chlorobutanoyloxy)2-ethylhexane, 1,9-bis(2-chlorobutanoyloxy)nonane, 1,10-bis(2-chlorobutanoyloxy) ) dodecane, 1,19-bis(2-chlorobutanoyloxy)nonadecane, 1,20-bis(2-chlorobutanoyloxy)icosane, 1,4-bis(2-chlorobutanoyloxy)cyclohexane, bis( 2-chlorobutanoyloxymethyl)-1,4-cyclohexane, diethylene glycol bis(2-chlorobutanoate), polyethylene glycol bis(2-chlorobutanoate), bis(3-chlorobutanoyloxy)methane, 1 , 2-bis(3-chlorobutanoyloxy)ethane, 1,3-bis(3-chlorobutanoyloxy)propane, 1,2-bis(3-chlorobutanoyloxy)-2-methylethane, 1,4 -bis(3-chlorobutanoyloxy)butane, 1,2-bis(3-chlorobutanoyloxy)-2,2-dimethylethane, 1,5-bis(3-chlorobutanoyloxy)pentane, 1, 6-bis(3-chlorobutanoyloxy)hexane, 1,7-bis(3-chlorobutanoyloxy)heptane, 1,8-bis(3-chlorobutanoyloxy)octane, 1,6-bis(3 -Chlorobutanoyloxy)2-ethylhexane, 1,9-bis(3-chlorobutanoyloxy)nonane, 1,10-bis(3-chlorobutanoyloxy)dodecane, 1,19-bis(3-chloro butanoyloxy)nonadecane, 1,20-bis(3-chlorobutanoyloxy)icosane, 1,4-bis(3-chlorobutanoyloxy)cyclohexane, bis(3-chlorobutanoyloxymethyl)-1,4 -Cyclohexane, diethylene glycol bis(3-chlorobutanoate), polyethylene glycol bis(3-chlorobutanoate), bis(4-chlorobutanoyloxy)methane, 1,2-bis(4-chlorobutanoyloxy) Ethane, 1,3-bis(4-chlorobutanoyloxy)propane, 1,2-bis(4-chlorobutanoyloxy)-2-methylethane, 1,4-bis(4-chlorobutanoyloxy)butane, 1,2-bis(4-chlorobutanoyloxy)-2,2-dimethylethane, 1,5-bis(4-chlorobutanoyloxy)pentane, 1,6-bis(4-chlorobutanoyloxy)hexane , 1,7-bis(4-chlorobutanoyloxy)heptane, 1,8-bis(4-chlorobutanoyloxy)octane, 1,6-bis(4-chlorobutanoyloxy)2-ethylhexane, 1 , 9-bis(4-chlorobutanoyloxy)nonane, 1,10-bis(4-chlorobutanoyloxy)dodecane, 1,19-bis(4-chlorobutanoyloxy)nonadecane, 1,20-bis( 4-chlorobutanoyloxy)icosane, 1,4-bis(4-chlorobutanoyloxy)cyclohexane, bis(4-chlorobutanoyloxymethyl)-1,4-cyclohexane, diethylene glycol bis(4-chlorobutanoate) ), polyethylene glycol bis(4-chlorobutanoate), bis(2-chloropentanoyloxy)methane, 1,2-bis(2-chloropentanoyloxy)ethane, 1,3-bis(2-chloropentanoate), Noyloxy)propane, 1,2-bis(2-chloropentanoyloxy)-2-methylethane, 1,4-bis(2-chloropentanoyloxy)butane, 1,2-bis(2-chloropentanoyloxy) )-2,2-dimethylethane, 1,5-bis(2-chloropentanoyloxy)pentane, 1,6-bis(2-chloropentanoyloxy)hexane, 1,7-bis(2-chloropentanoyl) oxy)heptane, 1,8-bis(2-chloropentanoyloxy)octane, 1,6-bis(2-chloropentanoyloxy)2-ethylhexane, 1,9-bis(2-chloropentanoyloxy) Nonane, 1,10-bis(2-chloropentanoyloxy)dodecane, 1,19-bis(2-chloropentanoyloxy)nonadecane, 1,20-bis(2-chloropentanoyloxy)icosane, 1,4 -Bis(2-chloropentanoyloxy)cyclohexane, bis(2-chloropentanoyloxymethyl)-1,4-cyclohexane, diethylene glycol bis(2-chloropentanoate), polyethylene glycol bis(2-chloropentanoate) ), bis(3-chloropentanoyloxy)methane, 1,2-bis(3-chloropentanoyloxy)ethane, 1,3-bis(3-chloropentanoyloxy)propane, 1,2-bis(3 -chloropentanoyloxy)-2-methylethane, 1,4-bis(3-chloropentanoyloxy)butane, 1,2-bis(3-chloropentanoyloxy)-2,2-dimethylethane, 1,5 -Bis(3-chloropentanoyloxy)pentane, 1,6-bis(3-chloropentanoyloxy)hexane, 1,7-bis(3-chloropentanoyloxy)heptane, 1,8-bis(3- Chloropentanoyloxy)octane, 1,6-bis(3-chloropentanoyloxy)2-ethylhexane, 1,9-bis(3-chloropentanoyloxy)nonane, 1,10-bis(3-chloropentanoyloxy) noyloxy)dodecane, 1,19-bis(3-chloropentanoyloxy)nonadecane, 1,20-bis(3-chloropentanoyloxy)icosane, 1,4-bis(3-chloropentanoyloxy)cyclohexane, Bis(3-chloropentanoyloxymethyl)-1,4-cyclohexane, diethylene glycol bis(3-chloropentanoate), polyethylene glycol bis(3-chloropentanoate), bis(4-chloropentanoyloxy)methane , 1,2-bis(4-chloropentanoyloxy)ethane, 1,3-bis(4-chloropentanoyloxy)propane, 1,2-bis(4-chloropentanoyloxy)-2-methylethane, 1 , 4-bis(4-chloropentanoyloxy)butane, 1,2-bis(4-chloropentanoyloxy)-2,2-dimethylethane, 1,5-bis(4-chloropentanoyloxy)pentane, 1,6-bis(4-chloropentanoyloxy)hexane, 1,7-bis(4-chloropentanoyloxy)heptane, 1,8-bis(4-chloropentanoyloxy)octane, 1,6-bis (4-chloropentanoyloxy)2-ethylhexane, 1,9-bis(4-chloropentanoyloxy)nonane, 1,10-bis(4-chloropentanoyloxy)dodecane, 1,19-bis(4-chloropentanoyloxy)dodecane, -chloropentanoyloxy)nonadecane, 1,20-bis(4-chloropentanoyloxy)icosane, 1,4-bis(4-chloropentanoyloxy)cyclohexane, bis(4-chloropentanoyloxymethyl)-1 , 4-cyclohexane, diethylene glycol bis(4-chloropentanoate), polyethylene glycol bis(4-chloropentanoate), bis(5-chloropentanoyloxy)methane, 1,2-bis(5-chloropentanoyl) oxy)ethane, 1,3-bis(5-chloropentanoyloxy)propane, 1,2-bis(5-chloropentanoyloxy)-2-methylethane, 1,5-bis(5-chloropentanoyloxy) Butane, 1,2-bis(5-chloropentanoyloxy)-2,2-dimethylethane, 1,5-bis(5-chloropentanoyloxy)pentane, 1,6-bis(5-chloropentanoyloxy) ) hexane, 1,7-bis(5-chloropentanoyloxy)heptane, 1,8-bis(5-chloropentanoyloxy)octane, 1,6-bis(5-chloropentanoyloxy)2-ethylhexane , 1,9-bis(5-chloropentanoyloxy)nonane, 1,10-bis(5-chloropentanoyloxy)dodecane, 1,19-bis(5-chloropentanoyloxy)nonadecane, 1,20- Bis(5-chloropentanoyloxy)icosane, 1,5-bis(5-chloropentanoyloxy)cyclohexane, bis(5-chloropentanoyloxymethyl)-1,5-cyclohexane, diethylene glycol bis(5-chloropentanoyloxy) polyethylene glycol bis(5-chloropentanoate), and the like.

Furthermore, bis(bromoacetoxy)methane, 1,2-bis(bromoacetoxy)ethane (13-1), 1,3-bis(bromoacetoxy)propane (13-2), 1,2-bis(bromoacetoxy) -2-methylethane (13-3), 1,4-bis(bromoacetoxy)butane (13-4), 1,4-bis(bromoacetoxy)2-butene, 1,2-bis(bromoacetoxy)-2 ,2-dimethylethane, 1,5-bis(bromoacetoxy)pentane (13-5), 1,6-bis(bromoacetoxy)hexane (13-6), 1,5-bis(bromoacetoxy)3-methyl Pentane (13-7), 1,7-bis(bromoacetoxy)heptane, 1,8-bis(bromoacetoxy)octane, 1,6-bis(bromoacetoxy)2-ethylhexane, 1,9-bis(bromoacetoxy)heptane acetoxy)nonane (13-8), 1,5-bis(bromoacetoxy)2,4-diethylpentane(13-9), 1,10-bis(bromoacetoxy)dodecane, 1,19-bis(bromoacetoxy) Nonadecane, 1,20-bis(bromoacetoxy)icosane, 1,4-bis(bromoacetoxy)cyclohexane (13-10), bis(bromoacetoxymethyl)-1,4-cyclohexane, diethylene glycol dibromoacetate (13-11) , polyethylene glycol dibromoacetate (13-12), bis(2-bromopropanoyloxy)methane, 1,2-bis(2-bromopropanoyloxy)ethane (13-15), 1,3-bis(2- Bromopropanoyloxy)propane, 1,2-bis(2-bromopropanoyloxy)-2-methylethane, 1,4-bis(2-bromopropanoyloxy)butane, 1,2-bis(2-bromopropanoyloxy)propane Noyloxy)-2,2-dimethylethane, 1,5-bis(2-bromopropanoyloxy)pentane, 1,6-bis(2-bromopropanoyloxy)hexane, 1,7-bis(2-bromo propanoyloxy)heptane, 1,8-bis(2-bromopropanoyloxy)octane, 1,6-bis(2-bromopropanoyloxy)2-ethylhexane, 1,9-bis(2-bromopropanoyl) oxy)nonane, 1,10-bis(2-bromopropanoyloxy)dodecane, 1,19-bis(2-bromopropanoyloxy)nonadecane, 1,20-bis(2-bromopropanoyloxy)icosane, 1 , 4-bis(2-bromopropanoyloxy)cyclohexane, bis(2-bromopropanoyloxymethyl)-1,4-cyclohexane, diethylene glycol bis(2-bromopropionate), polyethylene glycol bis(2-bromopropionate), pionate), bis(3-bromopropanoyloxy)methane, 1,2-bis(3-bromopropanoyloxy)ethane, 1,3-bis(3-bromopropanoyloxy)propane, 1,2-bis (3-bromopropanoyloxy)-2-methylethane, 1,4-bis(3-bromopropanoyloxy)butane, 1,2-bis(3-bromopropanoyloxy)-2,2-dimethylethane, 1 , 5-bis(3-bromopropanoyloxy)pentane, 1,6-bis(3-bromopropanoyloxy)hexane, 1,7-bis(3-bromopropanoyloxy)heptane, 1,8-bis( 3-bromopropanoyloxy)octane, 1,6-bis(3-bromopropanoyloxy)2-ethylhexane, 1,9-bis(3-bromopropanoyloxy)nonane, 1,10-bis(3- Bromopropanoyloxy)dodecane, 1,19-bis(3-bromopropanoyloxy)nonadecane, 1,20-bis(3-bromopropanoyloxy)icosane, 1,4-bis(3-bromopropanoyloxy) Cyclohexane, bis(3-bromopropanoyloxymethyl)-1,4-cyclohexane, diethylene glycol bis(3-bromopropionate), polyethylene glycol bis(3-bromopropionate), bis(2-bromobutanoyloxy) ) Methane, 1,2-bis(2-bromobutanoyloxy)ethane, 1,3-bis(2-bromobutanoyloxy)propane, 1,2-bis(2-bromobutanoyloxy)-2-methylethane , 1,4-bis(2-bromobutanoyloxy)butane, 1,2-bis(2-bromobutanoyloxy)-2,2-dimethylethane, 1,5-bis(2-bromobutanoyloxy) Pentane, 1,6-bis(2-bromobutanoyloxy)hexane, 1,7-bis(2-bromobutanoyloxy)heptane, 1,8-bis(2-bromobutanoyloxy)octane, 1,6 -Bis(2-bromobutanoyloxy)2-ethylhexane, 1,9-bis(2-bromobutanoyloxy)nonane, 1,10-bis(2-bromobutanoyloxy)dodecane, 1,19-bis (2-bromobutanoyloxy)nonadecane, 1,20-bis(2-bromobutanoyloxy)icosane, 1,4-bis(2-bromobutanoyloxy)cyclohexane, bis(2-bromobutanoyloxymethyl) -1,4-cyclohexane, diethylene glycol bis(2-bromobutanoate), polyethylene glycol bis(2-bromobutanoate), bis(3-bromobutanoyloxy)methane, 1,2-bis(3-bromobutanoate) butanoyloxy)ethane, 1,3-bis(3-bromobutanoyloxy)propane, 1,2-bis(3-bromobutanoyloxy)-2-methylethane, 1,4-bis(3-bromobutanoyl) oxy)butane, 1,2-bis(3-bromobutanoyloxy)-2,2-dimethylethane, 1,5-bis(3-bromobutanoyloxy)pentane, 1,6-bis(3-bromobutanoyloxy) 1,7-bis(3-bromobutanoyloxy)heptane, 1,8-bis(3-bromobutanoyloxy)octane, 1,6-bis(3-bromobutanoyloxy)2- Ethylhexane, 1,9-bis(3-bromobutanoyloxy)nonane, 1,10-bis(3-bromobutanoyloxy)dodecane, 1,19-bis(3-bromobutanoyloxy)nonadecane, 1, 20-bis(3-bromobutanoyloxy)icosane, 1,4-bis(3-bromobutanoyloxy)cyclohexane, bis(3-bromobutanoyloxymethyl)-1,4-cyclohexane, diethylene glycol bis(3- bromobutanoate), polyethylene glycol bis(3-bromobutanoate), bis(4-bromobutanoyloxy)methane, 1,2-bis(4-bromobutanoyloxy)ethane (13-16), 1 , 3-bis(4-bromobutanoyloxy)propane, 1,2-bis(4-bromobutanoyloxy)-2-methylethane, 1,4-bis(4-bromobutanoyloxy)butane, 1,2 -bis(4-bromobutanoyloxy)-2,2-dimethylethane, 1,5-bis(4-bromobutanoyloxy)pentane, 1,6-bis(4-bromobutanoyloxy)hexane, 1, 7-bis(4-bromobutanoyloxy)heptane, 1,8-bis(4-bromobutanoyloxy)octane, 1,6-bis(4-bromobutanoyloxy)2-ethylhexane, 1,9- Bis(4-bromobutanoyloxy)nonane, 1,10-bis(4-bromobutanoyloxy)dodecane, 1,19-bis(4-bromobutanoyloxy)nonadecane, 1,20-bis(4-bromobutanoyloxy)nonane butanoyloxy)icosane, 1,4-bis(4-bromobutanoyloxy)cyclohexane, bis(4-bromobutanoyloxymethyl)-1,4-cyclohexane, diethylene glycol bis(4-bromobutanoate), polyethylene Glycol bis(4-bromobutanoate), bis(2-bromopentanoyloxy)methane, 1,2-bis(2-bromopentanoyloxy)ethane, 1,3-bis(2-bromopentanoyloxy) Propane, 1,2-bis(2-bromopentanoyloxy)-2-methylethane, 1,4-bis(2-bromopentanoyloxy)butane, 1,2-bis(2-bromopentanoyloxy)-2 , 2-dimethylethane, 1,5-bis(2-bromopentanoyloxy)pentane, 1,6-bis(2-bromopentanoyloxy)hexane, 1,7-bis(2-bromopentanoyloxy)heptane , 1,8-bis(2-bromopentanoyloxy)octane, 1,6-bis(2-bromopentanoyloxy)2-ethylhexane, 1,9-bis(2-bromopentanoyloxy)nonane, 1 , 10-bis(2-bromopentanoyloxy)dodecane, 1,19-bis(2-bromopentanoyloxy)nonadecane, 1,20-bis(2-bromopentanoyloxy)icosane, 1,4-bis( 2-bromopentanoyloxy)cyclohexane, bis(2-bromopentanoyloxymethyl)-1,4-cyclohexane, diethylene glycol bis(2-bromopentanoate), polyethylene glycol bis(2-bromopentanoate), bis (3-bromopentanoyloxy)methane, 1,2-bis(3-bromopentanoyloxy)ethane, 1,3-bis(3-bromopentanoyloxy)propane, 1,2-bis(3-bromopentanoyloxy) Noyloxy)-2-methylethane, 1,4-bis(3-bromopentanoyloxy)butane, 1,2-bis(3-bromopentanoyloxy)-2,2-dimethylethane, 1,5-bis( 3-Bromopentanoyloxy)pentane, 1,6-bis(3-bromopentanoyloxy)hexane, 1,7-bis(3-bromopentanoyloxy)heptane, 1,8-bis(3-bromopentanoyl) oxy)octane, 1,6-bis(3-bromopentanoyloxy)2-ethylhexane, 1,9-bis(3-bromopentanoyloxy)nonane, 1,10-bis(3-bromopentanoyloxy) Dodecane, 1,19-bis(3-bromopentanoyloxy)nonadecane, 1,20-bis(3-bromopentanoyloxy)icosane, 1,4-bis(3-bromopentanoyloxy)cyclohexane, bis(3-bromopentanoyloxy)cyclohexane, -bromopentanoyloxymethyl)-1,4-cyclohexane, diethylene glycol bis(3-bromopentanoate), polyethylene glycol bis(3-bromopentanoate), bis(4-bromopentanoyloxy)methane, 1, 2-bis(4-bromopentanoyloxy)ethane, 1,3-bis(4-bromopentanoyloxy)propane, 1,2-bis(4-bromopentanoyloxy)-2-methylethane, 1,4- Bis(4-bromopentanoyloxy)butane, 1,2-bis(4-bromopentanoyloxy)-2,2-dimethylethane, 1,5-bis(4-bromopentanoyloxy)pentane, 1,6 -bis(4-bromopentanoyloxy)hexane, 1,7-bis(4-bromopentanoyloxy)heptane, 1,8-bis(4-bromopentanoyloxy)octane, 1,6-bis(4- bromopentanoyloxy)2-ethylhexane, 1,9-bis(4-bromopentanoyloxy)nonane, 1,10-bis(4-bromopentanoyloxy)dodecane, 1,19-bis(4-bromopentanoyloxy) Noyloxy)nonadecane, 1,20-bis(4-bromopentanoyloxy)icosane, 1,4-bis(4-bromopentanoyloxy)cyclohexane, bis(4-bromopentanoyloxymethyl)-1,4- Cyclohexane, diethylene glycol bis(4-bromopentanoate), polyethylene glycol bis(4-bromopentanoate), bis(5-bromopentanoyloxy)methane, 1,2-bis(5-bromopentanoyloxy)ethane (13-17), 1,3-bis(5-bromopentanoyloxy)propane, 1,2-bis(5-bromopentanoyloxy)-2-methylethane, 1,5-bis(5-bromopentanoyl) oxy)butane, 1,2-bis(5-bromopentanoyloxy)-2,2-dimethylethane, 1,5-bis(5-bromopentanoyloxy)pentane, 1,6-bis(5-bromopentanoyloxy) noyloxy)hexane, 1,7-bis(5-bromopentanoyloxy)heptane, 1,8-bis(5-bromopentanoyloxy)octane,
1,6-bis(5-bromopentanoyloxy)2-ethylhexane, 1,9-bis(5-bromopentanoyloxy)nonane, 1,10-bis(5-bromopentanoyloxy)dodecane, 1, 19-bis(5-bromopentanoyloxy)nonadecane, 1,20-bis(5-bromopentanoyloxy)icosane, 1,5-bis(5-bromopentanoyloxy)cyclohexane, bis(5-bromopentanoyl) (oxymethyl)-1,5-cyclohexane, diethylene glycol bis(5-bromopentanoate), polyethylene glycol bis(5-bromopentanoate), and the like.

Furthermore, bis(iodoacetoxy)methane, 1,2-bis(iodoacetoxy)ethane, 1,3-bis(iodoacetoxy)propane, 1,2-bis(iodoacetoxy)-2-methylethane, 1,4- Bis(iodoacetoxy)butane, 1,2-bis(iodoacetoxy)-2,2-dimethylethane, 1,5-bis(iodoacetoxy)pentane, 1,6-bis(iodoacetoxy)hexane, 1,5- Bis(iodoacetoxy)3-methylpentane, 1,7-bis(iodoacetoxy)heptane, 1,8-bis(iodoacetoxy)octane, 1,6-bis(iodoacetoxy)2-ethylhexane, 1,9- Bis(iodoacetoxy)nonane, 1,5-bis(iodoacetoxy)2,4-diethylpentane, 1,10-bis(iodoacetoxy)dodecane, 1,19-bis(iodoacetoxy)nonadecane, 1,20-bis (iodoacetoxy)icosane, 1,4-bis(iodoacetoxy)cyclohexane, bis(iodoacetoxymethyl)-1,4-cyclohexane, diethylene glycol diiodoacetate, polyethylene glycol diiodoacetate, bis(2-iodopropanoyloxy) Methane, 1,2-bis(2-iodopropanoyloxy)ethane, 1,3-bis(2-iodopropanoyloxy)propane, 1,2-bis(2-iodopropanoyloxy)-2-methylethane, 1,4-bis(2-iodopropanoyloxy)butane, 1,2-bis(2-iodopropanoyloxy)-2,2-dimethylethane, 1,5-bis(2-iodopropanoyloxy)pentane , 1,6-bis(2-iodopropanoyloxy)hexane, 1,7-bis(2-iodopropanoyloxy)heptane, 1,8-bis(2-iodopropanoyloxy)octane, 1,6- Bis(2-iodopropanoyloxy)2-ethylhexane, 1,9-bis(2-iodopropanoyloxy)nonane, 1,10-bis(2-iodopropanoyloxy)dodecane, 1,19-bis( 2-iodopropanoyloxy)nonadecane, 1,20-bis(2-iodopropanoyloxy)icosane, 1,4-bis(2-iodopropanoyloxy)cyclohexane, bis(2-iodopropanoyloxymethyl)- 1,4-cyclohexane, diethylene glycol bis(2-iodopropionate), polyethylene glycol bis(2-iodopropionate), bis(3-iodopropanoyloxy)methane, 1,2-bis(3-iodopropionate) Noyloxy)ethane, 1,3-bis(3-iodopropanoyloxy)propane, 1,2-bis(3-iodopropanoyloxy)-2-methylethane, 1,4-bis(3-iodopropanoyloxy) ) butane, 1,2-bis(3-iodopropanoyloxy)-2,2-dimethylethane, 1,5-bis(3-iodopropanoyloxy)pentane, 1,6-bis(3-iodopropanoyl) oxy)hexane, 1,7-bis(3-iodopropanoyloxy)heptane, 1,8-bis(3-iodopropanoyloxy)octane, 1,6-bis(3-iodopropanoyloxy)2-ethyl Hexane, 1,9-bis(3-iodopropanoyloxy)nonane, 1,10-bis(3-iodopropanoyloxy)dodecane, 1,19-bis(3-iodopropanoyloxy)nonadecane, 1,20 -bis(3-iodopropanoyloxy)icosane, 1,4-bis(3-iodopropanoyloxy)cyclohexane, bis(3-iodopropanoyloxymethyl)-1,4-cyclohexane, diethylene glycol bis(3-iodo propionate), polyethylene glycol bis(3-iodopropionate), bis(2-iodobutanoyloxy)methane, 1,2-bis(2-iodobutanoyloxy)ethane, 1,3-bis(2-iodobutanoyloxy)ethane, -iodobutanoyloxy)propane, 1,2-bis(2-iodobutanoyloxy)-2-methylethane, 1,4-bis(2-iodobutanoyloxy)butane, 1,2-bis(2-iodo butanoyloxy)-2,2-dimethylethane, 1,5-bis(2-iodobutanoyloxy)pentane, 1,6-bis(2-iodobutanoyloxy)hexane, 1,7-bis(2- iodobutanoyloxy)heptane, 1,8-bis(2-iodobutanoyloxy)octane, 1,6-bis(2-iodobutanoyloxy)2-ethylhexane, 1,9-bis(2-iodobutanoyloxy) noyloxy)nonane, 1,10-bis(2-iodobutanoyloxy)dodecane, 1,19-bis(2-iodobutanoyloxy)nonadecane, 1,20-bis(2-iodobutanoyloxy)icosane, 1,4-bis(2-iodobutanoyloxy)cyclohexane, bis(2-iodobutanoyloxymethyl)-1,4-cyclohexane, diethylene glycol bis(2-iodobutanoate), polyethylene glycol bis(2-iodobutanoate) butanoate), bis(3-iodobutanoyloxy)methane, 1,2-bis(3-iodobutanoyloxy)ethane, 1,3-bis(3-iodobutanoyloxy)propane, 1,2- Bis(3-iodobutanoyloxy)-2-methylethane, 1,4-bis(3-iodobutanoyloxy)butane, 1,2-bis(3-iodobutanoyloxy)-2,2-dimethylethane, 1,5-bis(3-iodobutanoyloxy)pentane, 1,6-bis(3-iodobutanoyloxy)hexane, 1,7-bis(3-iodobutanoyloxy)heptane, 1,8-bis (3-iodobutanoyloxy)octane, 1,6-bis(3-iodobutanoyloxy)2-ethylhexane, 1,9-bis(3-iodobutanoyloxy)nonane, 1,10-bis(3 -iodobutanoyloxy)dodecane, 1,19-bis(3-iodobutanoyloxy)nonadecane, 1,20-bis(3-iodobutanoyloxy)icosane, 1,4-bis(3-iodobutanoyloxy) ) cyclohexane, bis(3-iodobutanoyloxymethyl)-1,4-cyclohexane, diethylene glycol bis(3-iodobutanoate), polyethylene glycol bis(3-iodobutanoate),
Bis(4-iodobutanoyloxy)methane, 1,2-bis(4-iodobutanoyloxy)ethane, 1,3-bis(4-iodobutanoyloxy)propane, 1,2-bis(4-iodo butanoyloxy)-2-methylethane, 1,4-bis(4-iodobutanoyloxy)butane, 1,2-bis(4-iodobutanoyloxy)-2,2-dimethylethane, 1,5-bis (4-iodobutanoyloxy)pentane, 1,6-bis(4-iodobutanoyloxy)hexane, 1,7-bis(4-iodobutanoyloxy)heptane, 1,8-bis(4-iodobutanoyloxy) octane, 1,6-bis(4-iodobutanoyloxy)2-ethylhexane, 1,9-bis(4-iodobutanoyloxy)nonane, 1,10-bis(4-iodobutanoyloxy) ) dodecane, 1,19-bis(4-iodobutanoyloxy)nonadecane, 1,20-bis(4-iodobutanoyloxy)icosane, 1,4-bis(4-iodobutanoyloxy)cyclohexane, bis( 4-iodobutanoyloxymethyl)-1,4-cyclohexane, diethylene glycol bis(4-iodobutanoate), polyethylene glycol bis(4-iodobutanoate), bis(2-iodopentanoyloxy)methane, 1 , 2-bis(2-iodopentanoyloxy)ethane, 1,3-bis(2-iodopentanoyloxy)propane, 1,2-bis(2-iodopentanoyloxy)-2-methylethane, 1,4 -bis(2-iodopentanoyloxy)butane, 1,2-bis(2-iodopentanoyloxy)-2,2-dimethylethane, 1,5-bis(2-iodopentanoyloxy)pentane, 1, 6-bis(2-iodopentanoyloxy)hexane, 1,7-bis(2-iodopentanoyloxy)heptane, 1,8-bis(2-iodopentanoyloxy)octane, 1,6-bis(2-iodopentanoyloxy)octane -iodopentanoyloxy)2-ethylhexane, 1,9-bis(2-iodopentanoyloxy)nonane, 1,10-bis(2-iodopentanoyloxy)dodecane, 1,19-bis(2-iodo Pentanoyloxy)nonadecane, 1,20-bis(2-iodopentanoyloxy)icosane, 1,4-bis(2-iodopentanoyloxy)cyclohexane, bis(2-iodopentanoyloxymethyl)-1,4 -Cyclohexane, diethylene glycol bis(2-iodopentanoate), polyethylene glycol bis(2-iodopentanoate), bis(3-iodopentanoyloxy)methane, 1,2-bis(3-iodopentanoyloxy) Ethane, 1,3-bis(3-iodopentanoyloxy)propane, 1,2-bis(3-iodopentanoyloxy)-2-methylethane, 1,4-bis(3-iodopentanoyloxy)butane, 1,2-bis(3-iodopentanoyloxy)-2,2-dimethylethane, 1,5-bis(3-iodopentanoyloxy)pentane, 1,6-bis(3-iodopentanoyloxy)hexane , 1,7-bis(3-iodopentanoyloxy)heptane, 1,8-bis(3-iodopentanoyloxy)octane, 1,6-bis(3-iodopentanoyloxy)2-ethylhexane, 1 , 9-bis(3-iodopentanoyloxy)nonane, 1,10-bis(3-iodopentanoyloxy)dodecane, 1,19-bis(3-iodopentanoyloxy)nonadecane, 1,20-bis( 3-iodopentanoyloxy)icosane, 1,4-bis(3-iodopentanoyloxy)cyclohexane, bis(3-iodopentanoyloxymethyl)-1,4-cyclohexane, diethylene glycol bis(3-iodopentanoate) ), polyethylene glycol bis(3-iodopentanoate), bis(4-iodopentanoyloxy)methane, 1,2-bis(4-iodopentanoyloxy)ethane, 1,3-bis(4-iodopentanoate), Noyloxy)propane, 1,2-bis(4-iodopentanoyloxy)-2-methylethane, 1,4-bis(4-iodopentanoyloxy)butane, 1,2-bis(4-iodopentanoyloxy) )-2,2-dimethylethane, 1,5-bis(4-iodopentanoyloxy)pentane, 1,6-bis(4-iodopentanoyloxy)hexane, 1,7-bis(4-iodopentanoyl) oxy)heptane, 1,8-bis(4-iodopentanoyloxy)octane, 1,6-bis(4-iodopentanoyloxy)2-ethylhexane, 1,9-bis(4-iodopentanoyloxy) Nonane, 1,10-bis(4-iodopentanoyloxy)dodecane, 1,19-bis(4-iodopentanoyloxy)nonadecane, 1,20-bis(4-iodopentanoyloxy)icosane, 1,4 -Bis(4-iodopentanoyloxy)cyclohexane, bis(4-iodopentanoyloxymethyl)-1,4-cyclohexane, diethylene glycol bis(4-iodopentanoate), polyethylene glycol bis(4-iodopentanoate) ), bis(5-iodopentanoyloxy)methane, 1,2-bis(5-iodopentanoyloxy)ethane, 1,3-bis(5-iodopentanoyloxy)propane, 1,2-bis(5 -iodopentanoyloxy)-2-methylethane, 1,5-bis(5-iodopentanoyloxy)butane, 1,2-bis(5-iodopentanoyloxy)-2,2-dimethylethane, 1,5 -Bis(5-iodopentanoyloxy)pentane, 1,6-bis(5-iodopentanoyloxy)hexane, 1,7-bis(5-iodopentanoyloxy)heptane, 1,8-bis(5- iodopentanoyloxy)octane, 1,6-bis(5-iodopentanoyloxy)2-ethylhexane, 1,9-bis(5-iodopentanoyloxy)nonane, 1,10-bis(5-iodopentanoyloxy) noyloxy)dodecane, 1,19-bis(5-iodopentanoyloxy)nonadecane, 1,20-bis(5-iodopentanoyloxy)icosane, 1,5-bis(5-iodopentanoyloxy)cyclohexane, Examples include bis(5-iodopentanoyloxymethyl)-1,5-cyclohexane, diethylene glycol bis(5-iodopentanoate), polyethylene glycol bis(5-iodopentanoate), and the like.

Among the specific examples listed above, chloro compounds and bromo compounds are preferred in terms of reactivity, and compounds of the following structural formulas are particularly preferred.

The bifunctional compound represented by the general formula (13) serving as a raw material may be purchased commercially, or may be synthesized from the corresponding carboxylic acid and diol.

When using a bifunctional compound represented by the general formula (13) synthesized from the corresponding carboxylic acid and diol, the bifunctional compound is synthesized in advance in the system, and then the difunctional compound represented by the general formula (15) is used. By introducing the 9,10-dihydroxyanthracene compound shown below, the reaction can be carried out efficiently.

In the oligomerization reaction, the amount of the bifunctional compound represented by general formula (13) to be used is preferably 0.5 times or more and less than 5.0 times by mole relative to the 9,10-dihydroxyanthracene compound. , more preferably 1.0 times or more and less than 3.0 times by mole. When the amount is less than 0.5 times by mole, the average molecular weight becomes small, the effect of suppressing migration becomes weak, and unreacted 9,10-dihydroxyanthracene compound remains in the product, resulting in a decrease in purity. Moreover, if it is 5.0 moles or more, the average molecular weight becomes small, the effect of suppressing migration becomes weak, and unreacted bifunctional compounds remain in the product, resulting in a decrease in purity.

Furthermore, as the molar ratio of the 9,10-dihydroxyanthracene compound represented by the general formula (15) and the bifunctional compound represented by the general formula (13) approaches 1, the average molecular weight becomes too large. mobility may become smaller and the sensitizing ability may decrease. In that case, the molecular weight may be adjusted by adding a small amount of a monofunctional compound.

Basic compounds used in Reaction Formula-3 include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, lithium hexamethyldisilazide, lithium diisopropylamide, triethylamine, tributylamine, trihexylamine, Examples include dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dimethylaniline, pyridine, 4,4-dimethylaminopyridine, piperidine, γ-picoline, lutidine, and the like.

The amount of the basic compound added is preferably 2.0 times or more and less than 10.0 times by mole, more preferably 2.2 times or more and 5.0 times by mole, relative to the 9,10-dihydroxyanthracene compound. less than twice the mole. If the amount is less than 2.0 times by mole, the reaction will not be completed, and if it is more than 10.0 times by mole, side reactions will occur and the yield and purity will decrease, which is not preferable.

The reaction is carried out in a solvent or without a solvent. The type of solvent used is not particularly limited as long as it does not react with the ester compound used, and examples include aromatic solvents such as toluene, xylene, and ethylbenzene, ether solvents such as tetrahydrofuran and 1,4-dioxane, acetone, methyl ethyl ketone, Ketone solvents such as 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 are used. .

When a 9,10-dihydroxyanthracene compound is dissolved in an aqueous solution of an inorganic base and reacted with a difunctional compound represented by general formula (13), it is effective to use a phase transfer catalyst. Examples of the phase transfer catalyst include tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, trioctylmethylammonium bromide, trioctylethylammonium bromide, trioctylpropylammonium bromide, and trioctylbutylammonium bromide. , benzyldimethyloctadecylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrafubutylammonium chloride, trioctylmethylammonium chloride, trioctylethylammonium chloride, trioctylpropylammonium chloride, trioctylbutylammonium chloride , benzyldimethyloctadecylammonium chloride, and the like.

The amount of the phase transfer catalyst added is preferably 0.01 mole or more and less than 1.0 mole times, more preferably 0.05 mole times or more and 0.5 mole times, relative to the 9,10-dihydroxyanthracene compound. less than twice the mole. If the amount is less than 0.01 times by mole, the reaction rate is slow, and if it is more than 1.0 times by mole, the purity of the product decreases, which is not preferable.

The reaction temperature of the reaction is usually 0°C or higher and 250°C or lower, preferably 10°C or higher and 200°C or lower. If it is less than 0°C, the reaction time will be too long, and if it is heated above 250°C, impurities will increase and the purity of the target compound will decrease, both of which are not preferred.

The reaction time in this reaction varies depending on the reaction temperature, but is usually about 1 hour to 40 hours. More preferably, the time is from 2 hours to 20 hours.

After the reaction is completed, unreacted raw materials, solvents, and catalysts are removed, if necessary, by washing, distillation under reduced pressure, filtration, or other operations singly or in combination. If the product is solid, crystals will precipitate during the reaction, so solid-liquid separation is performed by filtration, and if necessary, recrystallization is performed from a poor solvent such as alcohol or hexane. Alternatively, it can be dried up as it is to obtain crystals. When the product is a liquid, it can be dried up as it is and, if necessary, purified by distillation or the like to obtain an oligomer of the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound.

(Production method of oligomer of 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound-2)
Next, a method for producing an oligomer of a 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound will be described. The oligomer of the 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound having an ester group represented by the general formula (1) of the present invention is similar to the oligomer of the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound. It can be manufactured by the following method. That is, it can be obtained by reacting a 1,4-dihydroxynaphthalene compound represented by general formula (14) with a corresponding difunctional compound represented by general formula (13) according to reaction formula-4 below. can.

In Reaction Formula-4, A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond, and this alkylene structure The carbon atoms of may be substituted with oxygen atoms, nitrogen atoms, or sulfur atoms on the condition that they are not adjacent, and may also contain an alicyclic compound, a benzene ring, or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl It may be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded with an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. Further, X ¹ and X ² may be the same or different, and may be a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a carbon Aryloxy group having 6 to 10 carbon atoms, hydroxy group, amino group, alkylamino group having 1 to 5 carbon atoms, arylamino group having 6 to 10 carbon atoms, mercapto group, alkyl sulfide group having 1 to 5 carbon atoms, carbon number 6 to 10 aryl sulfide groups, halogen atoms, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, forming a ring with an oxygen atom, nitrogen atom, or sulfur atom in between. The formed ring may further have a substituent. Y ¹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom. Further, G represents a chlorine atom, a bromine atom, or an iodine atom, and n represents a repeating number of 2 to 50.

In Reaction Formula-4, the 1,4-dihydroxynaphthalene compound represented by the general formula (14) used as a raw material is obtained by reducing the corresponding 1,4-naphthoquinone compound. In this reaction, specific examples of 1,4-dihydroxynaphthalene compounds used as raw materials include 1,4-dihydroxynaphthalene, 2-methyl-1,4-dihydroxynaphthalene, and 2,3-dimethyl-1,4- Dihydroxynaphthalene, 2-chloro-1,4-dihydroxynaphthalene, 2,3-dichloro-1,4-dihydroxynaphthalene, 2-hydroxy-1,4-dihydroxynaphthalene, 1,4-dihydro-9,10-dihydroxyanthracene , 1,2,3,4-tetrahydro-9,10-dihydroxyanthracene and the like.

(Oligomer manufacturing method)
Next, the general formula of the present invention is obtained by reacting the 1,4-dihydroxynaphthalene compound represented by the general formula (14) described in Reaction Formula-4 above with the bifunctional compound represented by the general formula (13). A method for producing an oligomer of a 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound having an ester group represented by (1) (hereinafter referred to as oligomerization reaction) will be described.

In the oligomerization reaction, as a specific example of the bifunctional compound represented by the general formula (13) as a raw material, the same ones as those listed in Reaction Formula-3 can be used.

As the oligomerization reaction conditions, the same conditions as in Reaction Formula-3 can be used.

(Photopolymerization sensitizer)
Oligomers of 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compounds having an ester group represented by the general formula (1) of the present invention and 9,10-bis having an ester group represented by the general formula (2) The oligomer of the (alkoxycarbonylalkyleneoxy) anthracene compound is excited by light of a specific wavelength and acts as a photopolymerization sensitizer that transfers the excitation energy to the photopolymerization initiator. Due to this effect, it becomes possible to efficiently initiate photopolymerization even with long wavelength light for which the activity of the photopolymerization initiator is insufficient. The photopolymerization sensitizer and photopolymerization initiator can be mixed with a photopolymerizable compound to form a photopolymerizable composition. The photopolymerizable composition can be easily photocured by irradiation with long wavelength light such as ultraviolet LED light having a center wavelength of 405 nm.

(Photopolymerization initiator)
Examples of the photopolymerization initiators used in the present invention include onium salts, benzyl methyl ketal-based polymerization initiators, α-hydroxyalkylphenone-based polymerization initiators, oxime ester-based photopolymerization initiators, α-aminoacetophenone-based photopolymerization initiators, and acylphosphine oxide. A photopolymerization initiator, a biimidazole initiator, and the like can be used.

As the onium salt, an iodonium salt or a sulfonium salt is usually used. Iodonium salts include 4-isobutylphenyl-4'-methylphenyliodonium hexafluorophosphate, bis(dodecylphenyl)iodonium hexamethoxyantimonate, 4-isopropylphenyl-4'-methylphenyliodonium tetrakis pentamethoxyphenylborate, -isopropylphenyl-4'-methylphenyliodonium tetrakis pentafluorophenylborate, etc., such as Irgacure 250 manufactured by B.A.S.F. (Irgacure is a registered trademark of B.A.S.F.), Rhodia Co., Ltd. Roadsill 2074 manufactured by Rhodia Corporation (Lodsill is a registered trademark of Rhodia Corporation), IK-1 manufactured by Sun-Apro Corporation, etc. can be used. On the other hand, examples of sulfonium salts include S,S,S',S'-tetraphenyl-S,S'-(4,4'-thiodiphenyl)disulfonium bishexamethoxyphosphate, diphenyl-4-phenylthiophenylsulfonium hexa Examples include methoxyphosphate, triphenylsulfonium hexamethoxyphosphate, etc., such as CPI-100P, CPI101P, CPI-200K manufactured by Daicel, Irgacure 270 manufactured by BASF, UVI6992 manufactured by Dow Chemical, etc. Can be used. These photopolymerization initiators may be used alone or in combination of two or more.

As onium salts, not only iodonium salts but also sulfonium salts can be used as oligomers of 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compounds having ester groups and 9,10-bis( One of the characteristics of oligomers of alkoxycarbonylalkyleneoxy)anthracene compounds is that they have a photopolymerization sensitizing effect.

Furthermore, oligomers of 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compounds having an ester group represented by the general formula (1) of the present invention and 9,10-bis(alkoxycarbonylalkyleneoxy)naphthalene compounds having an ester group represented by the general formula (2) - Oligomers of bis(alkoxycarbonylalkyleneoxy) anthracene compounds are effective against radical polymerization initiators that do not absorb at long wavelengths, such as benzyl methyl ketal, α-hydroxyalkylphenone, and biimidazole polymerization initiators. It has an excellent photopolymerization sensitizing effect.

Examples of the benzyl methyl ketal radical polymerization initiator include 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name "Irgacure 651" manufactured by B.A.S.F.), etc. -Hydroxyalkylphenone-based radical polymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name "Darocur 1173" manufactured by B.A.S.F.), 1-hydroxycyclohexylphenyl Ketone (trade name "Irgacure 184" manufactured by B.A.S.F.), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one ( Product name: "Irgacure 2959" manufactured by B.A.S.F.), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methyl-1 -on (trade name "Irgacure 127" manufactured by BASAF).

In particular, 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name "Irgacure 651" manufactured by B.A.S.F.), which is a benzyl methyl ketal radical polymerization initiator, and α-hydroxyalkyl Phenone radical polymerization initiator 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name "Darocure 1173" manufactured by BASAF), 1-hydroxycyclohexylphenyl ketone (trade name) ``Irgacure 184'' manufactured by BASA F. Co., Ltd.) is preferred.

In addition, acetophenone radical polymerization initiators such as acetophenone, 2-hydroxy-2-phenylacetophenone, 2-ethoxy-2-phenylacetophenone, 2-methoxy-2-phenylacetophenone, 2-isopropoxy-2-phenylacetophenone, -isobutoxy-2-phenylacetophenone, benzyl radical polymerization initiator, 4,4'-dimethoxybenzyl, anthraquinone radical polymerization initiator 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-phenoxyanthraquinone , 2-(phenylthio)anthraquinone, 2-(hydroxyethylthio)anthraquinone, etc. can also be used.

Examples of the biimidazole polymerization initiator include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, -(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5- Examples include 2,4,5-triarylimidazole dimers such as diphenylimidazole dimers.

Oligomers of 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compounds having an ester group represented by the general formula (1) of the present invention and 9,10-bis having an ester group represented by the general formula (2) The amount of the photopolymerization sensitizer containing the (alkoxycarbonylalkyleneoxy) anthracene compound to be used relative to the photopolymerization initiator is not particularly limited, but is usually in the range of 1% by weight or more and 100% by weight or less based on the photopolymerization initiator. , preferably in the range of 2% by weight or more and 50% by weight or less. If the amount of photopolymerizable sensitizer used is less than 1% by weight, it will take too much time to photopolymerize the photopolymerizable compound, while if it is used in excess of 100% by weight, no effect commensurate with the addition will be obtained. do not have.

(Photopolymerization initiator composition)
Oligomers of 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compounds having an ester group represented by the general formula (1) of the present invention and 9,10-bis having an ester group represented by the general formula (2) A photopolymerization sensitizer containing an oligomer of an (alkoxycarbonylalkyleneoxy) anthracene compound can be added directly to a photopolymerizable compound, but it can be added to a photopolymerization initiator composition in advance by blending it with a photopolymerization initiator. It can also be added to the photopolymerizable compound after it has been prepared. That is, the photoinitiator composition of the present invention comprises at least an oligomer of a 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound having an ester group represented by general formula (1) and a general formula (2). This is a composition containing a photopolymerization sensitizer containing an oligomer of a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group as shown above, and a photopolymerization 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 an oligomer of a 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound having an ester group and a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group of the present invention. This is a composition containing a photopolymerization sensitizer containing an oligomer, a photopolymerization initiator composition containing a photopolymerization initiator, and a photoradical polymerizable compound or a photocationic polymerizable compound. A photopolymerization sensitizer containing an oligomer of a 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound having an ester group and an oligomer of a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group according to the present invention and the photoinitiator are separately added to the photoradical polymerizable compound or the photocationic polymerizable compound to form a photoinitiator composition in the photoradical polymerizable compound or the photocationic polymerizable compound. Good too. Furthermore, it may be a hybrid composition containing both a photo-radical polymerizable compound and a photo-cationic polymerizable compound.

As the photoradically polymerizable compound, for example, an organic compound having a double bond such as styrene, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, acrylic ester, methacrylic ester, etc. can be used. . Among these radically polymerizable compounds, acrylic esters and methacrylic esters (hereinafter, both are collectively referred to as (meth)acrylic esters) are preferred 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, and methacrylic acid. Cyclohexyl, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tricyclo[5,2,1,02,6]decane dimethanol diacrylate, isobornyl methacrylate, epoxy acrylate, urethane acrylate, polyester acrylate, Examples include polybutadiene acrylate, polyol acrylate, polyether acrylate, silicone resin acrylate, and imide acrylate. These photoradically polymerizable compounds may be used alone or in a mixture of two or more.

Examples of the photocationically polymerizable compound include epoxy compounds, oxetane compounds, vinyl ethers, and the like. Common epoxy compounds include alicyclic epoxy compounds, epoxy-modified silicones, and aromatic glycidyl ethers. Examples of the alicyclic epoxy compounds include 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel, trade name: Celloxide 2021P, Celloxide is a registered trademark of Daicel), bis(3, Examples include 4-epoxycyclohexyl) adipate. Examples of the epoxy-modified silicone include UV-9300 manufactured by Toshiba GE Silicone. Examples of aromatic glycidyl compounds include 2,2'-bis(4-glycidyloxyphenyl)propane and the like. Examples of oxetane compounds include 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol) (manufactured by Toagosei Co., Ltd., trade name: OXT-101), 2-ethylhexyloxetane (manufactured by Toagosei Co., Ltd., trade name: OXT-212), Xylylene bisoxetane (manufactured by Toagosei Co., Ltd., trade name: OXT-121), 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane (manufactured by Toagosei Co., Ltd., trade name: OXT) -221), etc. Examples of the vinyl ether include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and 2-ethylhexyl vinyl ether. These photocationic polymerizable compounds may be used alone or in a mixture of two or more.

As the photopolymerizable compound, only a photoradical polymerizable compound may be used, or a mixture of both a photoradical polymerizable compound and a photocationic polymerizable compound may be used.

The photopolymerization sensitizer of the present invention can act as a sensitizer in both photoradical polymerization and photocationic polymerization. Photopolymerizable compositions containing both polymerizable compounds can also be effectively polymerized.

The mixing ratio of the photocationic polymerizable compound and the photoradical polymerizable compound is not particularly limited, and is appropriately selected depending on the physical properties of the coating film or molded product obtained by photopolymerizing and curing the composition. Usually, the composition ratio is determined so that the weight ratio of the photocationic polymerizable compound to the photoradical polymerizable compound is in the range of 1:99 to 99:1, preferably 20:80 to 80:20.

One type of each of the photocationic polymerizable compound and the photoradical polymerizable compound may be used, or two or more types of each may be used in combination. Even when two or more of these photopolymerizable compounds are used, the mixing ratio of the photocationic polymerizable compound and the photoradical polymerizable compound is considered as the ratio of the total amount of each photopolymerizable compound.

As the photopolymerization initiator used in the photopolymerizable composition of the present invention, the above-mentioned photoradical initiator or photocation initiator can be used. Usually, when using a photoradical polymerizable compound as a photopolymerizable compound, a photoradical polymerization initiator is used. Furthermore, when a radical photopolymerizable compound and a cationic photopolymerizable compound are used together as the photopolymerizable compound, the radical photopolymerization initiator or the cationic photopolymerization initiator alone may be used as the photopolymerization initiator, or both may be used. You may use a mixture of them.

In particular, some photo-cationic polymerization initiators generate cation-initiating active species and radical-initiating active species when irradiated with light, and when such initiators are used, they alone can generate photo-cationic polymerizable compounds and photo-radicals. It is also possible to initiate photopolymerization of both polymerizable compounds.

Furthermore, the photopolymerizable composition of the present invention may contain a binder polymer such as an acrylic resin, a styrene resin, or an epoxy resin. Moreover, an alkali-soluble resin may be included.

In the photopolymerizable composition of the present invention, the amount of the photopolymerization initiator composition used is in the range of 0.005% by weight or more and 10% by weight or less, preferably 0.025% by weight based on the photopolymerizable composition. The content is 5% by weight or less. If it is less than 0.005% by weight, it will take time to photopolymerize the photopolymerizable composition, while if it is added in excess of 10% by weight, the hardness of the photocured product obtained by photopolymerization will decrease, This is not preferable because it deteriorates the physical properties of the cured product.

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

(Photocured product)
A photocured product can be obtained by irradiating the photopolymerizable composition of the present invention with light and polymerizing it. When a photopolymerizable composition is irradiated with light to polymerize and photocure, the photopolymerizable composition can be formed into a film and photocured, or it can be formed into a block and photocured. When molded into a film and photocured, the liquid photopolymerizable composition is applied to a base material such as a polyester film using a bar coater or the like to a thickness of 5 to 300 microns. On the other hand, it is also possible to apply the coating to a thinner or thicker layer by spin coating or screen printing.

A photocured product is obtained by irradiating the coating film made of the photopolymerizable composition thus prepared with ultraviolet light having a wavelength range of 300 nm to 500 nm at an intensity of about 1 to 1000 mW/cm ² . I can do it. The light sources used include high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, xenon lamps, gallium-doped lamps, black lights, 405nm ultraviolet LEDs, 395nm ultraviolet LEDs, 385nm ultraviolet LEDs, 375nm ultraviolet LEDs, 365nm ultraviolet LEDs, blue LEDs, Examples include white LED, D bulb and V bulb manufactured by Fusion. Moreover, natural light such as sunlight can also be used. In particular, 405nm ultraviolet LED, 395nm ultraviolet LED, 385nm ultraviolet LED, 375nm ultraviolet LED, 365nm ultraviolet LED, and 405nm semiconductor laser have a sensitizing effect even with light in the long wavelength range from 365nm to 405nm. It is preferable to use such a wavelength. In particular, when using light with a wavelength of 395 nm or 405 nm, an oligomer of a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group represented by general formula (2) is preferable.

(Optical DSC measurement)
In the present invention, an optical DSC measurement method can be used as a method for quantitatively evaluating the photopolymerization rate of a photopolymerizable composition under light irradiation. According to this method, the amount of heat generated during curing can be continuously and easily measured while directly irradiating the sample with light. When a sample set in an optical DSC measurement device is irradiated with light, a light curing reaction begins and heat generation is observed. The baseline of the DSC curve, which was horizontal before photocuring, shifts to the exothermic side and returns to the original baseline position when the reaction is completed. The amount of heat generated can be determined from the size of the peak of this 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 composition)
As a method for determining whether the photopolymerizable sensitizer contained in the photopolymerizable composition of the present invention migrates to a film, etc., the photopolymerizable composition containing the photopolymerizable sensitizer is transferred into a thin film. Create a coating on an 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 check whether the photopolymerized sensitizer has migrated to the polyethylene film. , migration resistance was determined. After washing the composition on the surface of the peeled polyethylene film with acetone, it is dried, the UV spectrum of the polyethylene film is measured, and the migration resistance is measured by examining the increase in absorption intensity caused by the photopolymerization sensitizer. did. Note that an ultraviolet/visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV2600) was used for the measurement. For quantitative comparison with 9,10-dibutoxyanthracene, which is a compound of comparative example, the obtained absorbance was converted to the absorbance value of 9,10-dibutoxyanthracene. For conversion, measure the absorbance of the compound of the present invention and 9,10-dibutoxyanthracene at 260 nm using an ultraviolet/visible spectrophotometer, calculate the molar extinction coefficient of each from the absorbance value and molar concentration, and calculate the ratio. It was converted using

The invention is illustrated by the following examples, but these examples are not intended to limit the scope of the invention. Also, unless otherwise specified, all parts are parts by weight. Confirmation of the product was performed based on measurement using the following equipment.

Identification of the compounds of the present invention was performed 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
Number average molecular weight (GPC): JASCO Corporation, 2000 series

(Raw material synthesis example 1) Synthesis of 9,10-bis(methoxycarbonylmethyleneoxy)anthracene In a 100 ml four-necked flask equipped with a stirrer and a thermometer, 15 g of methyl isobutyl ketone as a solvent was added to tetracene as a catalyst under a nitrogen atmosphere. 0.8 g (1.2 mmol) of a 50% aqueous solution of butylammonium bromide and 9.5 g (62.1 mmol) of methyl bromoacetate were added. While maintaining the temperature of the reaction system at 20 to 25° C., 29.1 g of a 17 wt % aqueous solution of disodium salt of 9,10-dihydroxyanthracene (24 mmol as anthraquinone) was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was further stirred for 1 hour. Thereafter, 4.7 g (crude yield 55 mol%) of yellow crystals were obtained by suction filtration.

(1) Melting point: 151-152℃
(2) IR (cm ⁻¹ ): 1745, 1391, 1363, 1164, 1093, 774, 705.
(3) ^1H -NMR (400MHz, CDCl ₃ ): δ = 3.914 (s, 6H), 4.792 (s, 4H), 7.261-7.545 (m, 4H), 8.319 -8.366 (m, 4H).

(Raw material synthesis example 2) Synthesis of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene In a 100 ml four-necked flask equipped with a stirrer and a thermometer, 15 g of methyl isobutyl ketone as a solvent was added to tetracene as a catalyst under a nitrogen atmosphere. 0.8 g (1.2 mmol) of a 50% aqueous solution of butylammonium bromide and 10.4 g (62.5 mmol) of ethyl bromoacetate were added. While maintaining the temperature of the reaction system at 20 to 25° C., 29.1 g of a 17 wt % aqueous solution of disodium salt of 9,10-dihydroxyanthracene (24 mmol as anthraquinone) was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was further stirred for 1 hour. Thereafter, 5.0 g (crude yield 55 mol%) of pale yellow crystals were obtained by suction filtration.

(1) Melting point: 93-94℃
(2) IR (cm ^-1 ): 1754, 1742, 1382, 1367, 1241, 1212, 1168, 1087, 1034, 1004, 936, 809, 768, 720, 691, 669, 585.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 1.370 (t, J = 14 Hz, 6H), 4.376 (k, J = 21.6 Hz, 4H), 4.777 (s, 4H), 7.261-7.540 (m, 4H).

(Raw material synthesis example 3) Synthesis of 9,10-bis(isopropoxycarbonylmethyleneoxy)anthracene In a 100 ml four-necked flask equipped with a stirrer and a thermometer, 15 g of methyl isobutyl ketone was added as a solvent, and 15 g of methyl isobutyl ketone was added as a catalyst. 0.8 g (1.2 mmol) of a 50% aqueous solution of tetrabutylammonium bromide and 11.3 g (62.5 mmol) of isopropyl bromoacetate were added. While maintaining the temperature of the reaction system at 20 to 25° C., 29.1 g of a 17 wt % aqueous solution of disodium salt of 9,10-dihydroxyanthracene (24 mmol as anthraquinone) was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was further stirred for 1 hour. Thereafter, 5.9 g (crude yield 60 mol%) of pale yellow crystals were obtained by suction filtration.

(1) Melting point: 109-110℃
(2) IR (cm ⁻¹ ): 1744, 1360, 1210, 1163, 1086, 1018, 1004, 776, 768, 671.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 1.347 (d, J = 6.4 Hz, 12H), 4.743 (s, 4H), 5.246-5.277 (m, 2H), 7.504-7.529 (m, 4H), 8.356-8.398 (m, 4H).

(Raw material synthesis example 4) Synthesis of 9,10-bis(methoxycarbonylmethylmethyleneoxy)anthracene In a 100 ml four-necked flask equipped with a stirrer and a thermometer, 15 g of methyl isobutyl ketone was added as a solvent, and 15 g of methyl isobutyl ketone was added as a catalyst. 0.8 g (1.2 mmol) of a 50% aqueous solution of tetrabutylammonium bromide and 10.4 g (62.5 mmol) of methyl 2-bromopropionate were added. While maintaining the temperature of the reaction system at 20 to 25° C., 29.1 g of a 17 wt % aqueous solution of disodium salt of 9,10-dihydroxyanthracene (24 mmol as anthraquinone) was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was further stirred for 1 hour. Thereafter, anthraquinone was removed by suction filtration, and the resulting filtrate was washed twice with water by a liquid separation operation. The solution was concentrated using an evaporator and cooled in a freezer to precipitate crystals. The precipitated crystals were further suction-filtered to obtain 4.6 g (crude yield: 50 mol%) of yellow crystals.

(1) Melting point: 130-131℃
(2) IR (cm ⁻¹ ): 1737, 1366, 1207, 1134, 1078, 1061, 1020, 970, 748, 681.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 1.644 (d, J = 6.4 Hz, 6H), 3.770 (s, 6H), 4.904 (k, J = 20. 4Hz, 2H), 7.464-7.489 (m, 4H), 8.292-8.332 (m, 4H).

(Raw material synthesis example 5) Synthesis of 9,10-bis(ethoxycarbonylpropyleneoxy)anthracene In a 100 ml four-necked flask equipped with a stirrer and a thermometer, a 50% aqueous solution of tetrabutylammonium bromide as a catalyst was added under a nitrogen atmosphere. 0.77 g (1.19 mmol), 12.1 g (61.8 mmol) of ethyl 4-bromobutyrate, 5.0 g (23.8 mmol) of 9,10-dihydroxyanthracene, and 9.9 g (23.8 mmol) of potassium carbonate. 71.4 mmol) and 40 g of N,N-dimethylformamide as a solvent were added. The reaction system was stirred for 1 hour while maintaining the temperature at 20 to 30°C. Thereafter, anthraquinone was removed by suction filtration, and the resulting filtrate was dissolved in toluene and washed twice with water. The solution was concentrated using an evaporator. When left overnight, the entire solution solidified, so methanol was added and heated to 50°C to dissolve it. Undissolved anthraquinone was removed by suction filtration, and the filtrate was cooled in a freezer to precipitate crystals. The precipitated crystals were further suction-filtered to obtain 5.4 g (crude yield: 51 mol%) of yellow crystals.

(1) Melting point: 95-96℃
(2) IR (cm ⁻¹ ): 1721, 1351, 1312, 1239, 1183, 1164, 1081, 1024, 1015, 913, 767, 742, 669.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 1.307 (t, J = 14.0 Hz, 6H), 2.340-2.408 (m, 4H), 2.776 (t, J=14.8Hz, 4H), 4.171-4.235 (m, 8H), 7.456-7.494 (m, 4H), 8.230-8.256 (m, 4H).

(Raw material synthesis example 6) Synthesis of 9,10-bis(ethoxycarbonylbutyleneoxy)anthracene In a 100 ml four-necked flask equipped with a stirrer and a thermometer, a 50% aqueous solution of tetrabutylammonium bromide as a catalyst was added under a nitrogen atmosphere. 0.77 g (1.19 mmol), 12.9 g (61.8 mmol) of ethyl 5-bromovalerate, 5.0 g (23.8 mmol) of 9,10-dihydroxyanthracene, 9.9 g of potassium carbonate. (71.4 mmol) and 40 g of N,N-dimethylformamide as a solvent were added. The reaction system was stirred for 1 hour while maintaining the temperature at 20 to 30°C. Thereafter, anthraquinone was removed by suction filtration, and the resulting filtrate was dissolved in toluene and washed twice with water by a liquid separation operation. The solution was concentrated using an evaporator. After standing overnight, methanol was added and undissolved anthraquinone was removed by suction filtration. The filtrate was cooled in a freezer to precipitate crystals. The precipitated crystals were further suction-filtered to obtain 6.2 g (crude yield 55 mol%) of orange crystals.

(1) Melting point: 57-58℃
(2) IR (cm ⁻¹ ): 1722, 1403, 1337, 1284, 1269, 1229, 1178, 1167, 1068, 1021, 934, 763, 675.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 1.286 (t, J = 14.4 Hz, 6H), 2.018-2.103 (m, 8H), 2.496 (t, J=13.6Hz, 4H), 4.151-4.205 (m, 8H), 7.463-7.487 (m, 4H), 8.243-8.268 (m, 4H).

(Raw material synthesis example 7) Synthesis of 2-ethyl-9,10-bis(isopropoxycarbonylmethyleneoxy)anthracene In a 200 ml four-neck flask equipped with a stirrer and a thermometer, 55% of 2-ethyl anthraquinone was added under a nitrogen atmosphere. .0 g (21.2 mmol), 9.1 g (86.4 mmol) of thiourea dioxide, 8.4 g (211.6 mmol) of sodium hydroxide, and 50 g of ion-exchanged water were added, and the temperature was gradually raised to 120°C. Stirring was performed while heating. When the solution turned reddish-black, stirring was stopped and cooled to room temperature to prepare an aqueous disodium salt solution of 2-ethyl-9,10-dihydroxyanthracene. Next, in another 200 ml four-neck flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 15 g of methyl isobutyl ketone as a solvent and 2.7 g (4.23 g) of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst were added. 10.0 g (55.0 mmol) of isopropyl bromoacetate were added. While maintaining the temperature of the reaction system at 20 to 25°C, the disodium salt aqueous solution of 2-ethyl-9,10-dihydroxyanthracene prepared above was added dropwise over one hour or more. After the dropwise addition was completed, the mixture was further stirred for 1 hour. Thereafter, the aqueous layer was removed, and the organic layer was concentrated using an evaporator to obtain 4.5 g (crude yield: 48 mol%) of an orange oil.

(1) Melting point: liquid at room temperature (2) IR (cm ^-1 ): 1728, 1673, 1454, 1385, 1373, 1324, 1286, 1206, 1085, 962, 931, 901, 825, 772, 750, 712.
(3) ^1H -NMR (400MHz, CDCl ₃ ): δ = 1.237-1.371 (m, 15H), 2.816-2.899 (m, 2H), 4.731 (s, 4H) , 5.014-5.123 (m, 1H), 5.225-5.301 (m, 1H), 7.391 (d, J = 9.2Hz, 1H), 7.461-7.512 ( m, 2H), 7.766-7.790 (m, 1H), 8.119 (d, J=7.6Hz, 1H), 8.284-8.368 (m, 2H).

(Raw material synthesis example 8) Synthesis of 9,10-bis(hydroxycarbonylmethyleneoxy)anthracene In a 100 ml four-necked flask equipped with a stirrer and a thermometer, 15 g of the solvent methyl isobutyl ketone (MIBK) was added under a nitrogen atmosphere. 0.8 g (1.2 mmol) of a 50% aqueous solution of tetrabutylammonium bromide (TBAB) as a catalyst and 9.5 g (62.1 mmol) of bromoacetic acid were added. While maintaining the temperature of the reaction system at 20 to 25°C, 29.1 g (24 mmol) of an aqueous solution of disodium salt of 9,10-dihydroxyanthracene (AHQ-Na) and sodium hydroxide was added dropwise over 1 hour. . After the dropwise addition was completed, the mixture was further stirred for 1 hour. Thereafter, 4.7 g (crude yield 55 mol%) of yellow crystals were obtained by suction filtration.

(1) Melting point: 151-152℃
(2) IR (cm ⁻¹ ): 1745, 1391, 1363, 1164, 1093, 774, 705.
(3) ^1H -NMR (400MHz, CDCl ₃ ): δ = 3.914 (s, 6H), 4.792 (s, 4H), 7.261-7.545 (m, 4H), 8.319 -8.366 (m, 4H).

(Synthesis Example 1) Synthesis of oligomer obtained by reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 1,6-hexanediol (6-6)
In a 50 ml three-necked flask equipped with a stirrer, 1.7 g (4.5 mmol) of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene, obtained in the same manner as in Raw Materials Synthesis Example 2, and 1,6- 0.80 g (6.8 mmol) of hexanediol was added, and the mixture was heated to 130° C. in an oil bath. Stirring was started after the raw materials were melted, and when the temperature reached 130°C, 0.064 g (0.225 mmol) of tetra-i-propoxy titanium (TPT) as a catalyst was added, and pressure reduction to 360 mmHg was started. 3.5 hours after the start of pressure reduction, the pressure was reduced to 2 mmHg. Thereafter, the reaction was completed after 2.5 hours, and 1.47 g of a brown-black solid product was obtained.

(1) Number average molecular weight: Mn=3600
(2) IR (cm ^-1 ): 1750, 1731, 1401, 1382, 1350, 1272, 1167, 1082, 1020, 771, 695, 667, 607, 581.
(3) ¹ H-NMR (400MHz. CDCl ₃ ): δ = 1.452 (br, 4H), 1.740 (br, 4H), 4.300 (t, J = 12.8Hz, 4H), 4 .764 (s, 4H), 7.480-7.504 (m, 4H), 8.329-8.354 (m, 4H).

(Synthesis Example 2) Synthesis of oligomer obtained by reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl-1,5-pentanediol (6-7)
In a 50 ml three-necked flask equipped with a stirring bar, 1.7 g (4.5 mmol) of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene, obtained in the same manner as in Raw Materials Synthesis Example 2, and 3-methyl 0.66 g (5.6 mmol) of -1,5-pentanediol was added, and the mixture was heated to 130° C. in an oil bath. Stirring was started after the raw materials were melted, and when the temperature reached 130°C, 0.064 g (0.225 mmol) of tetra-i-propoxy titanium (TPT) as a catalyst was added, and pressure reduction to 360 mmHg was started. 4.5 hours after the start of pressure reduction, the pressure was reduced to 2 mmHg. Thereafter, the reaction was terminated after 1 hour, and 1.65 g of a brown-black starch syrup-like product was obtained.

(1) Number average molecular weight: Mn=5500
(2) IR (cm ⁻¹ ): 1751, 1382, 1350, 1272, 1167, 1127, 957, 770, 700, 667, 607.
(3) ¹ H-NMR (400 MHz. CDCl ₃ ): δ = 0.936-1.013 (m, 3H), 1.590-1.636 (m, 4H), 1.786-1.844 ( m, 1H), 4.304-4.368 (m, 4H), 4.734-4.778 (m, 4H), 7.261-7.488 (m, 4H), 8.291-8. 339 (m, 4H).

(Synthesis Example 3) Synthesis of oligomer obtained by reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 2,4-diethyl-1,5-pentanediol (6-9)
In a 50 ml three-necked flask equipped with a stirrer, 1.7 g (4.5 mmol) of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene obtained in the same manner as in Raw Materials Synthesis Example 2, and 2,4 0.90 g (5.6 mmol) of -diethyl-1,5-pentanediol was added, and the mixture was heated to 130° C. in an oil bath. Stirring was started after the raw materials were melted, and when the temperature reached 130°C, 0.064 g (0.225 mmol) of tetra-i-propoxy titanium (TPT) as a catalyst was added, and pressure reduction to 360 mmHg was started. Seven hours after the start of pressure reduction, the pressure was reduced to 2 mmHg. Thereafter, the reaction was terminated after 2.5 hours, and 1.55 g of a brown-black starch syrup-like product was obtained.

(1) Number average molecular weight: Mn=3800
(2) IR (cm ^-1 ): 1754, 1735, 1400, 1380, 1350, 1272, 1167, 1127, 1031, 771, 669, 607.
(3) ¹ H-NMR (400 MHz. CDCl ₃ ): δ = 0.826-0.955 (m, 6H), 1.294-1.470 (m, 6H), 1.575-1.696 ( m, 1H), 1.763-1.818 (m, 1H), 4.190-4.261 (m, 4H), 4.719-4.754 (m, 4H), 7.424-7. 493 (m, 4H), 8.284-8.314 (m, 4H).

(Synthesis Example 4) Synthesis of oligomer obtained by reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 1,9-nonanediol (6-11)
In a 50 ml three-necked flask equipped with a stirrer, 1.7 g (4.5 mmol) of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene obtained in the same manner as in Raw Materials Synthesis Example 2, 1,9 -0.90 g (5.6 mmol) of nonanediol was added, and the mixture was heated to 130°C in an oil bath. Stirring was started after the raw materials were melted, and when the temperature reached 130°C, 0.064 g (0.225 mmol) of tetra-i-propoxy titanium (TPT) as a catalyst was added, and pressure reduction to 360 mmHg was started. 3.5 hours after the start of pressure reduction, the pressure was reduced to 2 mmHg. Thereafter, the reaction was terminated after 3 hours, and 1.78 g of a brown-black starch syrup-like product was obtained.

(1) Number average molecular weight: Mn=3900
(2) IR (cm ^-1 ): 1753, 1732, 1382, 1350, 1272, 1167, 1029, 959, 771, 668, 607.
(3) ^1H -NMR (400MHz. CDCl ₃ ): δ = 1.322 (br, 6H), 1.575 (br, 4H), 1.678-1.730 (m, 4H), 4.289 (t, J=13.2Hz, 4H), 4.765 (s, 4H), 7.261-7.521 (m, 4H), 8.340-8.370 (m, 4H).

(Synthesis Example 5) Synthesis of oligomer obtained by reaction of 9,10-bis(hydroxycarbonylmethyleneoxy)anthracene and polyethylene glycol (molecular weight: 1000) (6-14)
In a 50 ml three-necked flask equipped with a stirring bar, 1.5 g (4.5 mmol) of 9,10-bis(hydroxycarbonylmethyleneoxy)anthracene obtained in the same manner as in Raw Materials Synthesis Example 8, and polyethylene glycol ( 6.8 g (6.8 mmol) of molecular weight: 1000) was added, and the mixture was heated to 160° C. in an oil bath. Stirring was started after the raw materials were melted, and when the temperature reached 160°C, 0.02 g (0.225 mmol) of sulfuric acid as a catalyst was added, and heating and stirring was continued. Thereafter, the reaction was completed after 7 hours, and a brown-black solid product was obtained at room temperature.

(1) Number average molecular weight: Mn=1500
(2) IR (cm ⁻¹ ): 2871, 1749, 1456, 1342, 1279, 1240, 1088, 954, 840, 777, 692, 526.
(3) ¹ H-NMR (400 MHz. CDCl ₃ ): δ = 3.546-3.800 (m), 4.445-4.467 (m, 2H), 7.505-7.529 (m, 4H), 8.317-8.368 (m, 4H).

(Synthesis Example 6) Synthesis of oligomer obtained by reaction of 9,10-bis(hydroxycarbonylmethyleneoxy)anthracene and 1,5-dibromopentane (6-5)
In a 50 ml side-armed flask containing a stirring bar, 0.19 g (0.61 mmol) of 9,10-bis(hydroxycarbonylmethyleneoxy)anthracene obtained in the same manner as in Raw Materials Synthesis Example 8, N as a solvent, Add 5 ml of N'-dimethylformamide (DMF), 0.09 g (0.64 mmol) of potassium carbonate (K ₂ CO ₃ ), and 0.15 g (0.66 mmol) of 1,5-dibromopentane, and heat at 100°C. heated with. Five hours after the start of heating, the mixture was cooled to room temperature, and the residue containing potassium carbonate was removed by suction filtration. The obtained filtrate was concentrated under reduced pressure using an evaporator to obtain a brown-black syrup-like product in a yield of 0.45 g.

(1) Number average molecular weight: Mn=830
(2) IR (cm ⁻¹ ): 2933, 2360, 1731, 1663, 1382, 1168, 1128, 772.
(3) ^1H -NMR (400MHz. CDCl ₃ ): δ = 1.322-1.930 (m, 8H), 2.857 (s, 4H), 2.934 (s, 4H), 4.292 (br, 3H), 4.765 (s, 4H), 7.32-7.521 (m, 4H), 8.340-8.370 (m, 4H).

(Synthesis Example 7) Synthesis of oligomer obtained by reaction of 9,10-bis(hydroxycarbonylmethyleneoxy)anthracene and 1,9-dibromononane (6-11)
In a 50 ml branched flask containing a stirring bar, 0.20 g (0.63 mmol) of 9,10-bis(hydroxycarbonylmethyleneoxy)anthracene obtained in the same manner as in Raw Materials Synthesis Example 8, N as a solvent, Add 5 ml of N'-dimethylformamide (DMF), 0.09 g (0.64 mmol) of potassium carbonate (K ₂ CO ₃ ), and 0.18 g (0.63 mmol) of 1,9-dibromononane, and heat at 100°C. heated with. Five hours after the start of heating, the mixture was cooled to room temperature, and the residue containing potassium carbonate was removed by suction filtration. The obtained filtrate was concentrated under reduced pressure using an evaporator to obtain a brown-black syrup-like product in a yield of 0.26 g.

(1) Number average molecular weight: Mn=960
(2) IR (cm ⁻¹ ): 2926, 2854, 1731, 1664, 1200, 1085, 773.
(3) ^1H -NMR (400MHz. CDCl ₃ ): δ = 1.322 (br, 8H), 1.687 (br, 8H), 2.857 (s, 4H), 2.934 (s, 4H ), 4.265 (br, 3H), 4.742 (t, J = 13.2Hz, 4H), 7.41-7.521 (m, 4H), 8.340-8.370 (m, 4H ).

(Synthesis Example 8) Synthesis of oligomer obtained by reaction of 9,10-dihydroxyanthracene and 1,2-bis(bromoacetoxy)ethane (6-1)
In a 30 ml side-armed flask equipped with a stirring bar, under a nitrogen atmosphere, 1.6 g (5.3 mmol) of 1,2-bis(bromoacetoxy)ethane, 10 g of methyl isobutyl ketone as a solvent, and tetrabutylammonium as a catalyst were added. 0.15 g (0.2 mmol) of a 50% aqueous solution of bromide was added. While maintaining the temperature of the reaction system at 20 to 25° C., 5.3 g of an 18.8 wt % aqueous solution of disodium salt of 9,10-dihydroxyanthracene (4.8 mmol as anthraquinone) was added dropwise over 15 minutes. After the dropwise addition was completed, the mixture was further stirred for 1 hour. Thereafter, 0.3 g of ocher crystals were obtained by suction filtration.

(1) Number average molecular weight: Mn=1500
(2) IR (cm ^-1 ): 2959, 2360, 1751, 1677, 1590, 1285, 1191, 1166, 1088, 773, 693.
(3) ^1H -NMR (400MHz. CDCl ₃ ): 1.652 (s, 4H) 4.771 (br, 4H) 7.403-7.520 (m, 4H), 8.311-8.333 (m, 4H).

(Synthesis Example 9) Synthesis of oligomer obtained by reaction of 9,10-dihydroxyanthracene and 1,5-bis(bromoacetoxy)3-methylpentane (6-7)
In a 200 ml four-necked flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, add 8.6 g (23.9 mmol) of 1,5-bis(bromoacetoxy)3-methylpentane, 50 g of methyl isobutyl ketone as a solvent, 0.77 g (1.2 mmol) of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst was added. While maintaining the temperature of the reaction system at 25 to 30° C., 26.6 g of an 18.8 wt % aqueous solution of disodium salt of 9,10-dihydroxyanthracene (24.0 mmol as anthraquinone) was added dropwise over 15 minutes. After the dropwise addition was completed, the mixture was further stirred for 1 hour. Thereafter, the by-product anthraquinone was removed by suction filtration, and the aqueous layer of the resulting filtrate was removed. The organic layer was washed twice with ion-exchanged water and concentrated to obtain 6.0 g of brown oil.

(1) Number average molecular weight: Mn=770
(2) IR (cm ^-1 ): 1731, 1670, 1382, 1273, 1234, 1197, 1168, 1086.
(3) ^1H -NMR (400MHz. CDCl ₃ ): δ = 1.295 (br, 6H), 1.594 (br, 4H), 1.680-1.689 (m, 4H), 7.247 -7.510 (m, 4H), 8.235-8.324 (m, 4H)

(Synthesis Example 10) Synthesis of oligomer obtained by reaction of 9,10-dihydroxyanthracene and 1,9-bis(bromoacetoxy)nonane (6-11)
In a 200 ml four-necked flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 9.7 g (24.0 mmol) of 1,9-bis(bromoacetoxy)nonane, 50 g of methyl isobutyl ketone as a solvent, and tetrafluoride as a catalyst were placed. 0.77 g (1.2 mmol) of a 50% aqueous solution of butylammonium bromide was added. While maintaining the temperature of the reaction system at 20 to 25° C., 26.6 g of an 18.8 wt% aqueous solution of disodium salt of 9,10-dihydroxyanthracene (24.0 mmol as anthraquinone) was added dropwise over 15 minutes. After the dropwise addition was completed, the mixture was further stirred for 2 hours. Thereafter, the by-product anthraquinone was removed by suction filtration, and the aqueous layer of the resulting filtrate was removed. The organic layer was washed twice with ion-exchanged water and concentrated to obtain 8.9 g of brown oil.

(1) Number average molecular weight: Mn=1150
(2) IR (cm ^-1 ): 1732, 1400, 1383, 1359, 1273, 1238, 1199, 1168, 1087, 1032.
(3) ^1H -NMR (400MHz. CDCl ₃ ): δ = 1.316 (br, 6H), 1.717 (br, 4H), 4,294 (s, 4H), 4.774 (s, 4H) ), 7.461-7,530 (m, 4H), 8.305-8.368 (m, 4H).

Below, in order to show the photopolymerization sensitizing effect and migration resistance of oligomers of 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compounds, we will use the ester group represented by general formula (2) as a representative example. The results of tests on the photopolymerization sensitization effect and migration resistance of oligomers of 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compounds are shown.

(Optical DSC measurement)
In this example, optical DSC measurement was performed as follows. That is, the DSC measurement device used was XDSC-7200 manufactured by Hitachi High-Tech Corporation, and an optical DSC measurement unit was attached to it so that DSC measurement could be performed while irradiating light. LA-410UV manufactured by Hayashi Watch Industry Co., Ltd. was used as a light source for light irradiation, and a bandpass filter was used to extract 405 nm light so that it could be irradiated onto the sample. The illuminance of the light was 50 mW/cm ² . The light from the light source was guided to the top of the sample using a glass fiber, and the shutter of the light source could be triggered to perform DSC measurements at the same time the light irradiation started. For optical DSC measurement, approximately 1 mg of the sample was accurately weighed in an aluminum measuring pan, placed in the DSC measuring section, and then the optical DSC unit was attached. Thereafter, the inside of the measurement section was kept in a nitrogen atmosphere and left to stand for 10 minutes, and measurement was started. The measurement continued for 6 minutes with normal light irradiation. After the first measurement, the sample was measured again under the same conditions as it was, and the value obtained by subtracting the second measurement result from the first measurement result was taken as the measurement result of the sample. Unless otherwise specified, the results were compared based on the total calorific value per 1 mg of sample in 1 minute after irradiation with light. Depending on the measurement conditions, the photoreaction may not be completed within 1 minute, but in order to compare the reaction behavior at the initial stage of light irradiation, the total calorific value per minute was compared. When polymerization of a sample (photopolymerizable composition) occurs due to light irradiation, reaction heat is generated due to the polymerization, and optical DSC can measure the reaction heat. Therefore, the progress of polymerization due to light irradiation can be measured by optical DSC. In this example, the total calorific value was measured for 1 minute after light irradiation, but as long as the same polymerizable compounds are used, the larger the value, the more efficiently the polymerization progresses. You can think that there is.

In this way, the photopolymerization performance evaluation test of the photocationic polymerizable composition using the oligomer of the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group of the present invention as the photocationic polymerization sensitizer is as follows. Describe it in

“Photocuring speed evaluation example 1”
As a photocationically polymerizable compound, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel, trade name: Celloxide 2021P, Celloxide is a registered trademark of Daicel) 100 parts by weight, 2 parts by weight of (4-methylphenyl)[4-(2-methylpropyl)phenyl]iodonium-hexafluorophosphate (manufactured by BASF, trade name Irgacure 250), which is a photopolymerization initiator; As a photocationic polymerization sensitizer, 1 part by weight of an oligomer obtained by reacting 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene obtained in Synthesis Example 2 with 3-methyl-1,5-pentanediol was used. A photocationically polymerizable composition was prepared by mixing at room temperature. When this photopolymerizable composition was subjected to optical DSC measurement, the total calorific value for 1 minute from the start of light irradiation was 132 mJ/mg.

“Photocuring speed evaluation example 2”
The oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl-1,5-pentanediol in "Photocuring Speed Evaluation Example 1" was obtained in the same manner as in Synthesis Example 3. Photo-DSC was carried out in the same manner as in "Photo-curing rate evaluation example 1" except that the oligomer was changed to the one obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 2,4-diethyl-1,5-pentanediol. When measured, the total calorific value for 1 minute from the start of light irradiation was 114 mJ/mg.

“Photo-curing speed evaluation example 3”
The oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl-1,5-pentanediol in "Photocuring Speed Evaluation Example 1" was obtained in the same manner as in Synthesis Example 4. Optical DSC measurement was performed in the same manner as in "Photocuring rate evaluation example 1" except that the oligomer was changed to the one obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 1,9-nonanediol. The total calorific value for 1 minute from the start of light irradiation was 128 mJ/mg.

“Photo-curing speed evaluation example 7”
The oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl-1,5-pentanediol in "Photocuring Speed Evaluation Example 1" was obtained in the same manner as in Synthesis Example 9. Optical DSC measurement was performed in the same manner as in "Photocuring rate evaluation example 33" except that the oligomer obtained by the reaction of 9,10-dihydroxyanthracene and 1,5-bis(bromoacetoxy)3-methylpentane was used. However, the total calorific value for one minute from the start of light irradiation was 89 mJ/mg.

“Photo-curing speed evaluation example 8”
The oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl-1,5-pentanediol in "Photocuring Speed Evaluation Example 1" was obtained in the same manner as in Synthesis Example 10. Optical DSC measurement was performed in the same manner as in "Photocuring rate evaluation example 33" except that the oligomer was changed to the one obtained by the reaction of 9,10-dihydroxyanthracene and 1,9-bis(bromoacetoxy)nonane. The total calorific value for 1 minute from the start of irradiation was 146 mJ/mg.

"Photo-curing speed comparison example 1"
Per 100 parts by weight of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, trade name: Celloxide 2021P, Celloxide is a registered trademark of Daicel Corporation) as a photocationically polymerizable compound, 2 parts by weight of (4-methylphenyl)[4-(2-methylpropyl)phenyl]iodonium-hexafluorophosphate (manufactured by BASF, trade name Irgacure 250) as a photopolymerization initiator. A photocationically polymerizable composition was prepared by mixing at room temperature. When this photopolymerizable composition was subjected to optical DSC measurement, the total calorific value for 1 minute from the start of light irradiation was 0.4 mJ/mg.

“Light curing speed comparison example 2”
A known photopolymerization sensitizer was used instead of the oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl-1,5-pentanediol in "Photocuring speed evaluation example 1". When optical DSC measurement was performed in the same manner as in "Photo-curing speed evaluation example 1" except for using a certain 9,10-dibutoxyanthracene, the total calorific value for 1 minute from the start of light irradiation was 99 mJ/mg. .

Next, a photopolymerization performance evaluation test of a radically polymerizable composition using the compound of the present invention as a photoradical polymerization sensitizer will be described below.

“Photo-curing speed evaluation example 4”
To 100 parts by weight of trimethylolpropane triacrylate as a photoradical polymerizable compound, 2 parts by weight of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator, and 2 parts by weight of 1-hydroxycyclohexyl phenyl ketone as a photocationic polymerization sensitizer obtained in Synthesis Example 2. 0.05 parts by weight of the oligomer obtained by the reaction of the obtained 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl-1,5-pentanediol were mixed at room temperature to form a photoradically polymerizable composition. Prepared. When this photopolymerizable composition was subjected to optical DSC measurement, the total calorific value for 1 minute from the start of light irradiation was 186 mJ/mg.

"Photo-curing speed evaluation example 5"
The oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl-1,5-pentanediol in "Photocuring speed evaluation example 4" was obtained in the same manner as in Example 3. , 10-bis(ethoxycarbonylmethyleneoxy)anthracene and 2,4-diethyl-1,5-pentanediol except that the oligomer was used. Photo-DSC measurement was carried out in the same manner as in "Photo-curing rate evaluation example 4". As a result, the total calorific value for 1 minute from the start of light irradiation was 213 mJ/mg.

“Photo-curing speed evaluation example 6”
The oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl-1,5-pentanediol in "Photocuring Speed Evaluation Example 4" was obtained in the same manner as in Example 4. , 10-bis(ethoxycarbonylmethyleneoxy)anthracene and 1,9-nonanediol was used, but optical DSC measurement was performed in the same manner as in "Photocuring rate evaluation example 4". The total calorific value for 1 minute from the start of irradiation was 196 mJ/mg.

“Photo-curing speed evaluation example 9”
The oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl-1,5-pentanediol in "Photocuring speed evaluation example 4" was obtained in the same manner as in Example 9. , 10-dihydroxyanthracene and 1,5-bis(bromoacetoxy)3-methylpentane, except that the oligomer obtained by the reaction was used. Photo-DSC measurement was carried out in the same manner as in "Photo-curing rate evaluation example 36". The total calorific value for 1 minute from the start of light irradiation was 226 mJ/mg.

“Photo-curing speed evaluation example 10”
The oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl-1,5-pentanediol in "Photocuring speed evaluation example 4" was obtained in the same manner as in Example 10. , 10-dihydroxyanthracene and 1,9-bis(bromoacetoxy)nonane except that the oligomer was used as the oligomer obtained by the reaction. When optical DSC measurement was performed in the same manner as in "Photocuring rate evaluation example 36", light irradiation. The total calorific value for 1 minute from the start was 199 mJ/mg.

“Light curing speed comparison example 3”
A photoradical polymerizable composition was prepared by mixing 100 parts by weight of trimethylolpropane triacrylate as a photoradical polymerizable compound with 2 parts by weight of 1-hydroxycyclohexylphenyl ketone as a photoinitiator at room temperature. When this photopolymerizable composition was subjected to optical DSC measurement, the total calorific value for 1 minute from the start of light irradiation was 76 mJ/mg.

“Photo-curing speed comparison example 4”
The oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl-1,5-pentanediol in "Photocuring Speed Evaluation Example 4" is a known photopolymerization sensitizer 9 , 10-dibutoxyanthracene was used, but optical DSC measurement was performed in the same manner as in "Photocuring speed evaluation example 4", and the total calorific value for 1 minute from the start of light irradiation was 125 mJ/mg.

As is clear from comparing the results of Photocuring Speed Evaluation Examples 1, 2, 3, 7, and 8 with Photocuring Speed Comparative Example 1, the 9,10-bis(alkoxycarbonylalkyleneoxy) of the present invention was ) It can be seen that the addition of the oligomer of anthracene compound increases the total calorific value and significantly accelerates the polymerization reaction. In addition, as is clear by comparing the results of Photocuring Speed Evaluation Examples 4, 5, 6, 9, and 10 with Photocuring Speed Comparative Example 3, the 99,10-bis(alkoxy It can be seen that by adding the oligomer of the carbonylalkyleneoxy)anthracene compound, the total calorific value increases and the polymerization reaction is significantly promoted. That is, it can be seen that the oligomer of the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound of the present invention has a photopolymerization sensitizing effect in both cationic photopolymerization and radical photopolymerization.

Furthermore, as is clear from comparing the results of Photocuring Speed Evaluation Examples 1, 2, 3, 7, and 8 with Photocuring Speed Comparative Example 2, the 9,10-bis(alkoxycarbonyl It can be seen that the oligomer of the alkyleneoxy)anthracene compound has a photopolymerization sensitizing effect equal to or greater than that of 9,10-dibutoxyanthracene, a known photopolymerization sensitizer. Furthermore, as is clear from comparing the results of Photocuring Speed Evaluation Examples 4, 5, 6, 9, and 10 with Photocuring Speed Comparative Example 4, the 9,10-bis(alkoxy It can be seen that the oligomer of the carbonylalkyleneoxy)anthracene compound has a photopolymerization sensitizing effect equal to or greater than that of 9,10-dibutoxyanthracene, a known photopolymerization sensitizer.

(Evaluation example of migration resistance of composition in photocationic polymerization)
(Migration resistance evaluation example 1)
The same method as in Example 2 was carried out as a photopolymerization sensitizer using 100 parts of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021P manufactured by Daicel Corporation) as an epoxy photocationically polymerizable compound. A composition prepared by mixing one part of the oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene synthesized with 3-methyl-1,5-pentanediol was placed on a polyester film in a film thickness of It was applied using a bar coater to a thickness of 12 microns. Next, a low-density polyethylene film (thickness: 30 microns) was placed on the obtained coated product and stored in a dark place for 4 days and 7 days. After storage, the polyethylene film was peeled off and the polyethylene film was After washing with acetone and drying, the UV spectrum of the film was measured, and the absorbance at 230 nm was measured. The absorption caused by the oligomer obtained by the reaction of the obtained 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene with 3-methyl-1,5-pentanediol was 0.004 after 4 days of storage, and 0.004 after 7 days of storage. It was 0.005.

(Migration resistance evaluation example 2)
Synthesized in the same manner as in Synthesis Example 3 in place of the oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl-1,5-pentanediol as a photopolymerization sensitizer. The test was conducted in the same manner as in Migration Resistance Evaluation Example 1, except that a polymer of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 2,4-diethyl-1,5-pentanediol was used. As a result of measuring the absorbance at 230 nm of the polyethylene film washed with acetone, it was found that the absorption was caused by the oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 2,4-diethyl-1,5-pentanediol. was 0.004 after four days of storage and 0.005 after seven days of storage.

(Migration resistance evaluation example 3)
Synthesized in the same manner as in Synthesis Example 4 in place of the oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl-1,5-pentanediol as a photopolymerization sensitizer. The test was conducted in the same manner as in Migration Resistance Evaluation Example 1, except that a polymer of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 1,9-nonanediol was used. As a result of measuring the absorbance at 230 nm of a polyethylene film washed with acetone, it was found that the absorption caused by the oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 1,9-nonanediol was observed after four days of storage. 0.004, and 0.005 after 7 days of storage.

(Migration resistance evaluation example 7)
9 synthesized in the same manner as in Example 9 instead of the oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl-1,5-pentanediol as a photopolymerization sensitizer. , 10-dihydroxyanthracene and 1,5-bis(bromoacetoxy)3-methylpentane were used in the same manner as in Migration Resistance Evaluation Example 1. As a result of measuring the absorbance at 230 nm of a polyethylene film washed with acetone, it was found that the absorption caused by the oligomer obtained by the reaction of 9,10-dihydroxyanthracene and 1,5-bis(bromoacetoxy)3-methylpentane was due to the absorption after 4 days of storage. It was 0.005 after storage, and 0.007 after 7 days of storage.

(Migration resistance evaluation example 8)
9 synthesized in the same manner as in Example 10 in place of the oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl-1,5-pentanediol as a photopolymerization sensitizer. , 10-dihydroxyanthracene and 1,9-bis(bromoacetoxy)nonane oligomers were used, but the test was carried out in the same manner as in Migration Resistance Evaluation Example 1. As a result of measuring the absorbance at 230 nm of a polyethylene film washed with acetone, it was found that the absorption caused by the oligomer obtained by the reaction of 9,10-dihydroxyanthracene and 1,9-bis(bromoacetoxy)nonane was 0.0 nm after storage for 4 days. 006, and 0.007 after 7 days of storage.

(Migration resistance comparative example 1)
As a photopolymerization sensitizer, 9, which is a known photopolymerization sensitizer, can be used instead of the oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl-1,5-pentanediol. It was prepared in the same manner as in Migration Resistance Evaluation Example 1 except that 10-dibutoxyanthracene was used. As a result of measuring the absorbance at 230 nm of the polyethylene film washed with acetone, the absorbance of 9,10-dibutoxyanthracene was 0.860 after four days of storage and 0.932 after seven days of storage.

(Evaluation example of migration resistance of composition in photoradical polymerization)
(Migration resistance evaluation example 4)
100 parts of trimethylolpropane triacrylate as a photoradical polymerizable compound, and 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl- synthesized in the same manner as in Synthesis Example 2 as a photoradical polymerization sensitizer. A composition prepared by mixing 0.05 part of an oligomer obtained by reaction with 1,5-pentanediol was coated on a polyester film using a bar coater to a thickness of 12 microns. Next, a low-density polyethylene film (thickness: 30 microns) was placed on the obtained coating material, and one was stored in a dark place for four days, and another was stored for seven days. After storage, the covered polyethylene film was removed. After peeling off, washing the polyethylene film with acetone and drying, the UV spectrum of the polyethylene film was measured, and the absorbance at 230 nm was measured. The absorption due to the oligomer obtained by reaction with 5-pentanediol was 0.004 after 4 days of storage and 0.005 after 7 days of storage.

(Migration resistance evaluation example 5)
Instead of the oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl-1,5-pentanediol, 9,10-bis( It was prepared and tested in the same manner as in Migration Resistance Evaluation Example 4, except that an oligomer obtained by the reaction of ethoxycarbonylmethyleneoxy)anthracene and 2,4-diethyl-1,5-pentanediol was used. The absorbance at 230 nm of the polyethylene film washed with acetone was measured, but the absorption was due to the oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 2,4-diethyl-1,5-pentanediol. was 0.004 after four days of storage and 0.005 after seven days of storage.

(Migration resistance evaluation example 6)
In place of the oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl-1,5-pentanediol, 9,10-bis( It was prepared and tested in the same manner as in Migration Resistance Evaluation Example 4, except that an oligomer obtained by the reaction of ethoxycarbonylmethyleneoxy)anthracene and 1,9-nonanediol was used. The absorbance at 230 nm of the polyethylene film washed with acetone was measured, but the absorption caused by the oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 1,9-nonanediol was observed after four days of storage. 0.005, and 0.005 after storage for 7 days.

(Migration resistance evaluation example 9)
Instead of the oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl-1,5-pentanediol, 9,10-dihydroxyanthracene synthesized in the same manner as in Example 9 was used. It was prepared and tested in the same manner as in Migration Resistance Evaluation Example 4, except that an oligomer obtained by reaction with 1,5-bis(bromoacetoxy)3-methylpentane was used. The absorbance at 230 nm of the polyethylene film washed with acetone was measured, but the absorption caused by the oligomer obtained by the reaction of 9,10-dihydroxyanthracene and 1,5-bis(bromoacetoxy)3-methylpentane was observed after four days of storage. It was 0.003 after storage for 7 days, and 0.007 after storage for 7 days.

(Migration resistance evaluation example 10)
Instead of the oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl-1,5-pentanediol, 9,10-dihydroxyanthracene synthesized in the same manner as in Example 10 was used. It was prepared and tested in the same manner as in Migration Resistance Evaluation Example 4, except that an oligomer obtained by reaction with 1,9-bis(bromoacetoxy)nonane was used. The absorbance at 230 nm of the polyethylene film washed with acetone was measured, and the absorption caused by the oligomer obtained by the reaction of 9,10-dihydroxyanthracene and 1,9-bis(bromoacetoxy)nonane was 0.0 nm after storage for 4 days. 003, and 0.007 after seven days of storage.

(Migration resistance comparative example 2)
9,10-dibutoxyanthracene, a known photoradical sensitizer, was used instead of the oligomer obtained by the reaction of 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene and 3-methyl-1,5-pentanediol. The test was carried out in the same manner as in Migration Resistance Evaluation Example 4 except for using the same method. As a result of measuring the absorbance at 230 nm of the polyethylene film washed with acetone, the absorbance of the obtained 9,10-dibutoxyanthracene was 0.049 after four days of storage and 0.060 after seven days.

As is clear by comparing migration resistance evaluation examples 1, 2, 3, 7, and 8 with migration resistance comparative example 1, it is a known photocationic polymerization sensitizer in the photocationic polymerizable composition. While 9,10-dibutoxyanthracene migrates to a considerable extent into the film placed over the photocationically polymerizable composition, the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound of the present invention In all cases, the degree of migration of these oligomers is extremely low, and it can be said that they have excellent migration resistance. Further, as is clear from comparing Migration Resistance Evaluation Examples 4, 5, 6, 9, and 10 with Migration Resistance Comparative Example 2, even in the photoradical polymerizable composition, known photoradical polymerization 9,10-dibutoxyanthracene, which is a sensitizer, migrates to a considerable extent into the film covered on the photoradical polymerizable composition, whereas the 9,10-bis(alkoxycarbonyl) of the present invention In any case, the degree of migration of the oligomer of the alkyleneoxy)anthracene compound is extremely low, and it can be said that the oligomer has excellent migration resistance.

From the above results, the oligomer of the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group of the present invention can be used as a known photopolymerization sensitizer in cationic photopolymerization and radical photopolymerization. -Compared to dibutoxyanthracene compounds, it not only has the same photopolymerization sensitizing ability, but also has a structure with a polar ester group, making it an excellent compound with high migration resistance, making it suitable as a photopolymerization sensitizer. It turns out that it is an extremely useful compound.

Claims (7)

A photopolymerization sensitizer containing an oligomer of a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound whose repeating unit has an ester group represented by the following general formula (2).

(In general formula (2), n represents the repeating number and is 2 to 50, A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D is a carbon Represents an alkylene group of number 1 to 100, the alkylene group may be branched by an alkyl group, and the carbon atoms of this alkylene structure may be substituted with oxygen atoms on the condition that ^they are not adjacent . , ^Y3 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.) A photopolymerization sensitizer containing an oligomer of a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound according to claim 1 , wherein A in general formula (2) is a methylene group. A photopolymerization initiator composition comprising the photopolymerization sensitizer according to claim 1 or 2 and a photopolymerization initiator. A photopolymerizable composition comprising the photopolymerization initiator composition according to claim 3 and a photocationic polymerizable compound. A photopolymerizable composition comprising the photopolymerization initiator composition according to claim 3 and a photoradical polymerizable compound. A polymerization method comprising irradiating the photopolymerizable composition according to claim 4 or 5 with energy rays containing light in a wavelength range of 300 nm to 500 nm. 7. The irradiation source of energy rays containing light in the wavelength range of 300 nm to 500 nm is an ultraviolet LED or a 405 nm semiconductor laser with a center wavelength of 365 nm, 375 nm, 385 nm, 395 nm, or 405 nm, according to claim 6 . Polymerization method.