JP2020075905A - High molecule photopolymerization sensitizer - Google Patents

Abstract

To provide a photopolymerization sensitizer having no generation of problems of powdering or coloring of a cured article by oozing of an additive such as the photopolymerization sensitizer or the like to a surface due to blooming during photosetting or storage of the cured article, and providing practically enough photosetting speed.SOLUTION: There is provided an oligomer of a 1,4-bis(alkoxycarbonylalkyleneoxy)naphthalene compound represented by the general formula (1). n is an integer of 2 to 50, A is an alkylene group, D is an alkylene group or the like, Xand Xare H, an alkyl group or the like, and Yis H, an alkyl group or the like.SELECTED DRAWING: None

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.

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

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

However, this 9,10-dialkoxyanthracene compound is a photopolymerization composition before photocuring or a photopolymerization sensitizer oozes out on the surface due to blooming during storage of the cured product after photocuring, and the cured product It is known to cause dusting and coloring problems.

Regarding the photopolymerizable composition, for example, when these photopolymerization sensitizers are used as one component of a photoadhesive for adhering films to each other, the photopolymerization sensitizer is transferred to a film covered on the upper side ( Migration), which may cause problems such as dusting and coloring of the photopolymerization sensitizer on the upper film.

In addition, a dry film resist used for manufacturing printed wiring boards, lead frames, metal masks, etc. is used, but a resist compatible with a 405 nm semiconductor laser is required, and in order to comply with the wavelength. In addition, thioxanthone and 9,10-dialkoxyanthracene compounds are used as photopolymerization sensitizers. However, dry film resists are stored and traded with a cover film on the photosensitive resin composition, and polyethylene film or polypropylene film is used for this cover film, and photopolymerization sensitization is applied to the film. There are problems that the agent migrates, the sensitizing effect is reduced, and powder is blown on the film (Patent Document 9).

In order to suppress such migration of the photopolymerization sensitizer, a 9,10-bis (2-acyloxyalkoxy) anthracene compound in which an ester group which is a polar group is introduced into an alkoxy group of a 9,10-dialkoxyanthracene compound is used. 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 at the time of production, and the number of steps increases, which not only leads to an increase in cost, but also the alkylene oxide compound, particularly ethylene oxide Difficulty in obtaining and handling are major problems in the production of the 9,10-bis (2-acyloxyalkoxy) anthracene compound.

Further, a compound in which an alkoxy group of a 9,10-dialkoxyanthracene compound is changed to an acyl group has been developed, but the migration property is improved, but the electron donating property of the alkoxy group is lowered, and thus the absorption wavelength is There is a problem of shifting to the low wavelength side (Patent Document 11).

Further, the present inventors have disclosed an oligomer of a 9,10-bis (substituted alkoxy) anthracene compound as a compound exhibiting a photopolymerization sensitizing effect and hardly causing migration or the like (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 available alkylene oxide is limited. In addition, alkylene oxide, which is easily available, has high toxicity, low boiling point, high flammability, 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 readily available, a pressure-tight container such as an autoclave is required, and there remains a problem that special manufacturing equipment is required. Further, in the oligomerization reaction, there remains a problem that the raw material 9,10-bis (substituted alkoxy) anthracene compound has low solubility and high temperature conditions are required.

Japanese Patent Laid-Open No. 06-345614 Japanese Patent Laid-Open No. 07-062010 JP 05-249606 A JP, 10-195117, A JP, 2002-302507, A JP, 11-279212, A JP 2000-344704 A WO2007 / 126066 Japanese Patent No. 4605223 JP, 2014-031346, A JP, 2014-101442, A JP, 2017-114849, A

Therefore, not only does it have migration resistance during photocuring or storage of the cured product and does not cause problems such as dusting or coloring of the cured product, it is also a practical manufacturing method using readily available raw materials. It is required to develop a new photopolymerization sensitizer which can be obtained by

As a result of further diligent studies on the structure and physical properties of the anthracene compound, the present inventors have found that the oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) naphthalene compound having an ester group, which is shown in the present invention, undergoes a photopolymerization reaction. While exhibiting an excellent effect as a polymerization sensitizer, the oligomer of the present invention can be produced under mild conditions using an easily available compound as a raw material, and when the oligomer of the present invention is used as a photopolymerization sensitizer. The present inventors have completed the present invention by finding that an oligomer makes it difficult for migration and blooming to occur.

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 a 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 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 may contain an unsaturated bond. Carbon atoms may be substituted with oxygen atom, nitrogen atom, or sulfur atom under the condition that they are not adjacent to each other, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl group. 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 ¹ and X ² may be the same or different and each is 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 atom. 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, alkylsulfide group having 1 to 5 carbon atoms, and carbon number 6 to 10 aryl sulfide groups, a halogen atom, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, and form a ring with an oxygen atom, a nitrogen atom and a sulfur atom sandwiched therebetween. Alternatively, 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 a 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 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 may contain an unsaturated bond. Carbon atoms may be substituted with oxygen atom, nitrogen atom, or sulfur atom under the condition that they are not adjacent to each other, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl group. 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 each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.

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

A fourth gist 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). In the method for producing an oligomer of a 1,4-bis (alkoxycarbonylalkyleneoxy) naphthalene compound having an ester group represented by the following general formula (1), the repeating unit characterized by

In the 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. X ¹ and X ² may be the same or different and each is 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 atom. 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, alkylsulfide group having 1 to 5 carbon atoms, and carbon number 6 to 10 aryl sulfide groups, a halogen atom, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, and form a ring with an oxygen atom, a nitrogen atom and a sulfur atom sandwiched therebetween. Alternatively, 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 contains an unsaturated bond. The carbon atom of this alkylene structure may be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom under the condition that they are not adjacent to each other, 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 a 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 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 may contain an unsaturated bond. Carbon atoms may be substituted with oxygen atom, nitrogen atom, or sulfur atom under the condition that they are not adjacent to each other, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl group. 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 ¹ and X ² may be the same or different and each is 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 atom. 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, alkylsulfide group having 1 to 5 carbon atoms, and carbon number 6 to 10 aryl sulfide groups, a halogen atom, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, and form a ring with an oxygen atom, a nitrogen atom and a sulfur atom sandwiched therebetween. Alternatively, 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.

A 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). In the method for producing an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound, the repeating unit of which is characterized by having an ester group represented by the following general formula (2).

In the 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 each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.

In the general formula (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 contains an unsaturated bond. The carbon atom of this alkylene structure may be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom under the condition that they are not adjacent to each other, 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 a 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 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 may contain an unsaturated bond. Carbon atoms may be substituted with oxygen atom, nitrogen atom, or sulfur atom under the condition that they are not adjacent to each other, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl group. 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 each represents 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 is a methylene group in the general formula (2).

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). It exists in a method for producing 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 (14), X ¹ and X ² may be the same or different and each is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 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 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 X ² may be bonded to each other to form a saturated or unsaturated ring, and an oxygen atom, a nitrogen atom or a sulfur atom may be formed. 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 the 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 and may contain an unsaturated bond. Carbon atoms may be substituted with oxygen atom, nitrogen atom, or sulfur atom under the condition that they are not adjacent to each other, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring may be an alkyl group. 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. G represents a chlorine atom, a bromine atom or an iodine atom.

In the general formula (1), n represents a 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 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 may contain an unsaturated bond. Carbon atoms may be substituted with oxygen atom, nitrogen atom, or sulfur atom under the condition that they are not adjacent to each other, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl group. 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 ¹ and X ² may be the same or different and each is 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 atom. 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, alkylsulfide group having 1 to 5 carbon atoms, and carbon number 6 to 10 aryl sulfide groups, a halogen atom, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, and form a ring with an oxygen atom, a nitrogen atom and a sulfur atom sandwiched therebetween. Alternatively, 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.

An eighth aspect of the present invention is characterized by reacting a 9,10-dihydroxyanthracene compound represented by the following general formula (15) with a bifunctional compound represented by the following general formula (13). It exists in a method for producing 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 (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 the 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 and may contain an unsaturated bond. Carbon atoms may be substituted with oxygen atom, nitrogen atom, or sulfur atom under the condition that they are not adjacent to each other, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring may be an alkyl group. 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. G represents a chlorine atom, a bromine atom or an iodine atom.

In the general formula (2), n represents a 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 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 may contain an unsaturated bond. Carbon atoms may be substituted with oxygen atom, nitrogen atom, or sulfur atom under the condition that they are not adjacent to each other, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl group. 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 each represents 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 the general formula (2) is a methylene group.

A tenth aspect of the present invention relates to a photopolymerization sensitizer containing 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). Exist.

In the general formula (1), n represents a 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 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 may contain an unsaturated bond. Carbon atoms may be substituted with oxygen atom, nitrogen atom, or sulfur atom under the condition that they are not adjacent to each other, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl group. 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 ¹ and X ² may be the same or different and each is 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 atom. 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, alkylsulfide group having 1 to 5 carbon atoms, and carbon number 6 to 10 aryl sulfide groups, a halogen atom, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, and form a ring with an oxygen atom, a nitrogen atom and a sulfur atom sandwiched therebetween. Alternatively, 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 relates to 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). Exist.

In the general formula (2), n represents a 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 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 may contain an unsaturated bond. Carbon atoms may be substituted with oxygen atom, nitrogen atom, or sulfur atom under the condition that they are not adjacent to each other, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl group. 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 each represents 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 relates to a photopolymerization-enhancing compound 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 the sensitizer.

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 photoradical polymerizable compound.

A sixteenth aspect of the present invention relates to a polymerization method for polymerizing the photopolymerizable composition according to the fourteenth aspect or the fifteenth aspect by irradiating an energy ray containing light in a wavelength range of 300 nm to 500 nm. Exist.

A fourteenth aspect of the present invention is characterized in that the irradiation source of energy rays containing light in the wavelength range of 300 nm to 500 nm is an ultraviolet LED having a central wavelength of 365 nm, 375 nm, 385 nm, 395 nm or 405 nm. It exists in the polymerization method described in the summary of 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, The photopolymerizable composition and the cured product contained as the polymerization sensitizer are useful compounds in which the degree of migration or blooming of the photopolymerization sensitizer is extremely low. Also in the production method, it is not necessary to use an alkylene oxide compound that is difficult to obtain and handle, and a compound that is easy to obtain and handle can be used as a raw material and can be produced under mild conditions. The production process is also easy and the production is inexpensive.

(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 a 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 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 may contain an unsaturated bond. Carbon atoms may be substituted with oxygen atom, nitrogen atom, or sulfur atom under the condition that they are not adjacent to each other, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl group. 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 ¹ and X ² may be the same or different and each is 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 atom. 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, alkylsulfide group having 1 to 5 carbon atoms, and carbon number 6 to 10 aryl sulfide groups, a halogen atom, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, and form a ring with an oxygen atom, a nitrogen atom and a sulfur atom sandwiched therebetween. Alternatively, 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 (1), when X ¹ and X ² are bonded to each other to form an unsaturated ring and the unsaturated ring is an aromatic ring, it is represented by the general formula (1). The compound is a compound represented by the following general formula (2).

In the general formula (2), n represents a 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 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 may contain an unsaturated bond. Carbon atoms may be substituted with oxygen atom, nitrogen atom, or sulfur atom under the condition that they are not adjacent to each other, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl group. 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 each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.

In the general formula (1) or (2), the alkylene group having 1 to 20 carbon atoms represented by A is a methylene group, a methylmethylene group, an ethylmethylene group, an ethylene group, a propylene group, a butylene group, a pentylene 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, the alkylene. The group may be branched by an alkyl group.

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

In the general formula (1) or (2), the alkylene group having 1 to 20 carbon atoms represented by D is 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 Undecylen group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, nonadecylene group, icosylene group and the like, and the alkylene group may be branched by an alkyl group, It may contain a saturated bond, the carbon atom of this alkylene structure may be substituted with an oxygen atom, a nitrogen atom, a sulfur atom under the condition that it is not adjacent, and also includes 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 the carbon atom of the alkylene group is substituted with an oxygen atom or the like include a polyoxyalkylene group such as a polyoxyethylene group and a polyoxypropylene group.

In the general formula (1) or (2), examples of the arylene group having 6 to 20 carbon atoms represented by D include a phenylene group and a naphthylene group, and the arylene group may have a substituent. A plurality of rings may be bonded with 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 shown below. Specific examples of the compound of the general formula (6) are shown in Tables 1, 2 and 3. In the following table, m in the formula represents 1 to 30.

In the general formula (6), n represents a repeating number of 2 to 50, 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. Which may contain an unsaturated bond, the carbon atom of the alkylene structure may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom under the condition that they are not adjacent to each other, and an alicyclic compound or benzene. It may contain a ring or a naphthalene ring, and the benzene ring or 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 each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.

As specific examples of the general formula (2) other than the general formula (6), in the specific example illustrated in the general formula (6), the portion A is not a methylene group but an ethylene group, a propylene group, a butylene group, a pentylene group. 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, compound replaced by icosylene group Is mentioned.

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

In the general formula (10), n represents a repeating number of 2 to 50, 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. Which may contain an unsaturated bond, the carbon atom of the alkylene structure may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom under the condition that they are not adjacent to each other, and an alicyclic compound or benzene. It may contain a ring or a naphthalene ring, and the benzene ring or 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 ¹ and X ² may be the same or different and each is 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 atom. 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, alkylsulfide group having 1 to 5 carbon atoms, and carbon number 6 to 10 aryl sulfide groups, a halogen atom, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, and form a ring with an oxygen atom, a nitrogen atom and a sulfur atom sandwiched therebetween. Alternatively, 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 the general formula (1) other than the general formula (10), in the specific example illustrated in the general formula (10), the portion A is not a methylene group but an ethylene group, a propylene group, a butylene group, a pentylene group. 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, compound replaced by icosylene group Is mentioned.

In the general formula (1), X ¹ and X ² are bonded to each other to form a saturated or unsaturated ring, and typical examples of the compounds other than the compound of the general formula (2) include The compounds of formulas (11) and (12) may be mentioned.

In the general formula (11), n represents a 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 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 may contain an unsaturated bond. Carbon atoms may be substituted with oxygen atom, nitrogen atom, or sulfur atom under the condition that they are not adjacent to each other, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring may be an alkyl group. 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 a 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 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 may contain an unsaturated bond. Carbon atoms may be substituted with oxygen atom, nitrogen atom, or sulfur atom under the condition that they are not adjacent to each other, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring may be an alkyl group. 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 the general formula (11) or (12) are the same as the specific examples of A or D in the general formula (2).

Among the specific examples given above, the compounds in which A is a methylene group in the general formula (1) and the general formula (2) are preferable because they are easily produced.

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

The examples of the compounds preferably used in the present invention have been described above, but 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 of the present invention 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 1,4-bis (alkoxycarbonyl) represented by the general formula (4). It can be obtained by reacting an alkyleneoxy) naphthalene compound with a corresponding bifunctional compound represented by the general formula (3) according to the following reaction formula-1.

In Reaction Scheme-1, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, 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 and may contain an unsaturated bond. Carbon atoms may be substituted with oxygen atom, nitrogen atom, or sulfur atom under the condition that they are not adjacent to each other, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl group. 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 ¹ and X ² may be the same or different and each is 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 atom. 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, alkylsulfide group having 1 to 5 carbon atoms, and carbon number 6 to 10 aryl sulfide groups, a halogen atom, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, and form a ring with an oxygen atom, a nitrogen atom and a sulfur atom sandwiched therebetween. Alternatively, 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. Z represents a hydroxy group, a halogen atom, or a glycidyloxy group, and n represents a repeating number and is 2 to 50.

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

(Method for producing 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 9,10-bis (alkoxycarbonyl) represented by the general formula (5). It can be obtained by reacting an alkyleneoxy) anthracene compound with a corresponding bifunctional compound represented by the general formula (3) according to the following reaction formula-2.

In Reaction Scheme-2, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, 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 and may contain an unsaturated bond. Carbon atoms may be substituted with oxygen atom, nitrogen atom, or sulfur atom under the condition that they are not adjacent to each other, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl group. 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 each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom. Z represents a hydroxy group, a halogen atom, or a glycidyloxy group, and n represents a repeating number and is 2 to 50.

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

(Method for producing 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound)
First, the production of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5) by reacting a 9,10-dihydroxyanthracene compound with an ester compound (hereinafter simply referred to as an esterification reaction). The method will be described.

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 the reaction, specific examples of the raw material 9,10-dihydroxyanthracene compound 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 and the like. Can be mentioned.

In the case of 9,10-dihydroxyanthracene, as an industrial method, 1,4,4a, 9a-tetrahydroanthraquinone, which is a Diels-Alder reaction product of 1,4-naphthoquinone and 1,3-butadiene, or By reducing 9,10-anthraquinone with 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 mixed with 9% of 1,4,4a, 9a-tetrahydroanthraquinone in an aqueous medium in the presence of an alkaline compound such as an alkali metal hydroxide. By reacting with 10,10-anthraquinone, an aqueous solution of an alkali metal salt of 9,10-dihydroxyanthracene can be obtained. Precipitation of 9,10-dihydroxyanthracene can be obtained by acidifying the obtained aqueous solution of an alkali metal salt of 9,10-dihydroxyanthracene in the absence of oxygen. By purifying this precipitate, 9,10-dihydroxyanthracene can be obtained. A 9,10-dihydroxyanthracene compound having a substituent can be similarly obtained.

Next, specific examples of the ester compound as a raw material include methyl chloroacetate, ethyl chloroacetate, n-propyl chloroacetate, isopropyl chloroacetate, n-butyl chloroacetate, tert-butyl chloroacetate, methyl 2-chloropropionate. , Methyl 3-chloropropionate, methyl 2-chloropropionate, methyl 3-chloropropionate, ethyl 2-chloropropionate, ethyl 3-chloropropionate, n-propyl 2-chloropropionate, 3-chloropropionic acid n-Propyl, isopropyl 2-chloropropionate, isopropyl 3-chloropropionate, n-butyl 2-chloropropionate, n-butyl 3-chloropropionate, tert-butyl 2-chloropropionate, 3-chloropropionic acid 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-chlorovaleric acid n-propyl, n-propyl 4-chlorovalerate, n-propyl 5-chlorovalerate, isopropyl 2-chlorovalerate, isopropyl 3-chlorovalerate, isopropyl 4-chlorovalerate, isopropyl 5-chlorovalerate, N-Butyl 2-chlorovalerate, n-butyl 3-chlorovalerate, n-butyl 4-chlorovalerate, n-butyl 5-chlorovalerate, tert-butyl 2-chlorovalerate, 3-chlorovaleric acid 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, n-propyl 2-bromopropionate, n-propyl 3-bromopropionate, 2-bromo Isopropyl propionate, isopropyl 3-bromopropionate, n-butyl 2-bromopropionate, n-butyl 3-bromopropionate, tert-butyl 2-bromopropionate, tert-butyl 3-bromopropionate, 2-bromo Methyl butyrate, methyl 3-bromobutyrate, methyl 4-bromobutyrate, ethyl 2-bromobutyrate, ethyl 3-bromobutyrate, ethyl 4-bromobutyrate (3-7), n-propyl 2-bromobutyrate, 3-bromobutyric acid n-propyl, n-propyl 4-bromobutyrate, isopropyl 2-bromobutyrate, isopropyl 3-bromobutyrate, isopropyl 4-bromobutyrate, n-butyl 2-bromobutyrate, n-butyl 3-bromobutyrate, 4-bromobutyric acid n-butyl, tert-butyl 2-bromobutyrate, tert-butyl 3-bromobutyrate, tert-butyl 4-bromobutyrate, methyl 2-bromovalerate, methyl 3-bromovalerate, methyl 4-bromovalerate, 5 -Methyl bromovalerate, ethyl 2-bromovalerate, ethyl 3-bromovalerate, ethyl 4-bromovalerate (3-8), ethyl 5-bromovalerate, n-propyl 2-bromovalerate, 3- Bromovalerate n-propyl, 4-bromovalerate n-propyl, 5-bromovalerate n-propyl, 2-bromovalerate isopropyl, 3-bromovalerate isopropyl, 4-bromovalerate isopropyl, 5-bromovalerate Isopropyl valerate, n-butyl 2-bromovalerate, n-butyl 3-bromovalerate, n-butyl 4-bromovalerate, n-butyl 5-bromovalerate, tert-butyl 2-bromovalerate, 3- Examples include tert-butyl 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 mol times or more and less than 10.0 mol times the 9,10-dihydroxyanthracene compound, More preferably, it is 2.2 times or more and less than 5.0 times by mole. If it is less than 2.0 mol times, the reaction will not be completed, and if it is more than 10.0 mol times, side reactions occur and the yield and purity are reduced, which is not preferable.

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

The addition amount of the basic compound is preferably 2.0 mol times or more and less than 10.0 mol times, and more preferably 2.2 mol times or more, 5.0 times or more with respect to the 9,10-dihydroxyanthracene compound. It is less than molar times. If it is less than 2.0 mol times, the reaction will not be completed, and if it is more than 10.0 mol times, side reactions occur and the yield and purity are reduced, which is not preferable.

The esterification reaction is carried out in a solvent or without a solvent. The solvent used is not particularly limited as long as it does not react with the ester compound used, for example, toluene, xylene, an aromatic solvent such as ethylbenzene, tetrahydrofuran, an ether solvent such as 1,4-dioxane, acetone, methyl ethyl ketone, Ketone-based solvents such as methyl isobutyl ketone, amide-based solvents such as dimethylacetamide and dimethylformamide, halogenated carbon-based solvents such as methylene chloride, ethylene dichloride and chlorobenzene, 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, use of a phase transfer catalyst is effective. Examples of the phase transfer catalyst include tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, trioctylmethylammonium bromide, trioctylethylammonium bromide, trioctylpropylammonium bromide, trioctylbutylammonium bromide. , Benzyldimethyloctadecyl ammonium bromide, tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrapropyl ammonium chloride, tetrafbutyl ammonium chloride, trioctyl methyl ammonium chloride, trioctyl ethyl ammonium chloride, trioctyl propyl ammonium chloride, trioctyl butyl ammonium chloride , Benzyl dimethyl octadecyl ammonium chloride and the like.

The amount of the phase transfer catalyst added is preferably 0.01 mol times or more and less than 1.0 mol times, more preferably 0.05 mol times or more, 0.5 times or more with respect to the 9,10-dihydroxyanthracene compound. It is less than molar times. If it is less than 0.01 mol times, the reaction rate will be slow, and if it is 1.0 mol times or more, the purity of the product will decrease, such being undesirable.

The reaction temperature of the reaction is usually 0 ° C. or higher and 100 ° C. or lower, and the reaction is completed near room temperature without any particular heat treatment. The reaction time in the reaction varies depending on the reaction temperature, but is usually about 1 to 4 hours. Therefore, the reaction proceeds under mild conditions, and it is not necessary to use a special reaction vessel such as a pressure cooker.

After the completion of the esterification reaction, the unreacted raw materials, the solvent and the catalyst are removed as necessary by a method of washing, distilling under reduced pressure, filtration and the like alone or in combination. When the product is a solid, crystals precipitate during the reaction, so solid-liquid separation is performed by filtration, and recrystallization from a poor solvent such as alcohol or hexane is carried out if necessary. Alternatively, it can be dried up as it is to obtain a crystal. 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 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), the case where A is a methylene group is the easiest and is preferable.

(Method for producing oligomer)
Next, between the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5) and the bifunctional compound represented by the general formula (3), which are described in the above reaction formula-1. 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 a reaction (hereinafter referred to as an 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, as a specific example of the bifunctional compound represented by the general formula (3), which is a raw material, when Z is a hydroxy group, 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- Cyclohexanedimethanol, 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-Dichloroicosane, 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-dione Iodoundecane, 1,12-diiodododecane, 1,13-diiodotridecane, 1,14-diiodotetradecane, 1,15-diiodopentadecane, 1,16-diiodohexadecane, 1,17-diiodo Heptadecane, 1,18-diiodooctadecane, 1,19-diiodononadecane, 1,20-diiodoicosane and the like can be mentioned.

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 compound 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 compound 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 thereof include glycidyl ether and hydroquinone diglycidyl ether. Two or more of these bifunctional compounds may be used in the reaction simultaneously.

Among the specific examples given above, the diol compound is preferable in terms of reactivity.

The amount of the bifunctional compound represented by the general formula (3) used in the oligomerization reaction is preferably 0.5 mol times or more, and 5 times or more the amount of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound. It is less than 0.0 mol times, more preferably 1.0 mol times or more and less than 3.0 mol times. If it is less than 0.5 mol times, the average molecular weight becomes small, the effect of suppressing migration is weakened, and unreacted 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound remains in the product and the purity Is reduced. On the other hand, if it is 5.0 mol times or more, the average molecular weight becomes small, the effect of suppressing migration is weakened, and unreacted bifunctional compound remains in the product to lower the purity.

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

When the difunctional compound represented by the general formula (3) in the oligomerization reaction is a diol compound, the use of a catalyst increases the reaction rate and enables efficient production. As the catalyst used in the reaction, 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 (Futamura Chemical Co., Ltd.), Amberlyst (Organo Co., Ltd.), Nafion (DuPont, Nafion is a DuPont registered trademark), Tetraalkoxy titanium compound (Tetraisopropoxy titanium, 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%, and more preferably 0.1 mol% or more, 10 with respect to the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound. It is less than mol%. If it is less than 0.01 mol%, the reaction cannot be completed, and if it is 20 mol% or more, side reactions occur and the yield and purity are lowered, which is not preferable.

When the bifunctional compound represented by the general formula (3) in the oligomerization reaction is a dihalogen compound or a diglycidyl compound, a basic compound is required. Examples of the basic compound used include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, 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 mol times or more and less than 5.0 mol times, more preferably 2.2 mols, with respect to the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound. It is more than 2 times and less than 3.0 times. If it is less than 2.0 mol times, the reaction will not be completed, and if it is more than 5.0 mol times, side reactions occur and the yield and purity are reduced, which is not preferable.

The reaction is carried out in a solvent or without solvent. The solvent used is not particularly limited as long as it does not react with the bifunctional compound used, for example, toluene, xylene, an aromatic solvent such as ethylbenzene, tetrahydrofuran, an ether solvent such as 1,4-dioxane, acetone, Methyl ethyl ketone, ketone-based solvents such as methyl isobutyl ketone, amide-based solvents such as dimethylacetamide and dimethylformamide, halogenated carbon-based solvents such as methylene chloride, ethylene dichloride and chlorobenzene, 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 bifunctional compound, the use of a phase transfer catalyst is effective. Examples of the phase transfer catalyst include tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, trioctylmethylammonium bromide, trioctylethylammonium bromide, trioctylpropylammonium bromide, trioctylbutylammonium bromide. , Benzyldimethyloctadecyl ammonium bromide, tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrapropyl ammonium chloride, tetrafbutyl ammonium chloride, trioctyl methyl ammonium chloride, trioctyl ethyl ammonium chloride, trioctyl propyl ammonium chloride, trioctyl butyl ammonium chloride , Benzyl dimethyl octadecyl ammonium chloride and the like.

The amount of the phase transfer catalyst added is preferably 0.01 mol times or more and less than 1.0 mol times, more preferably 0.05 mol times, with respect to the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound. It is not less than twice and less than 0.5 mole times. If it is less than 0.01 mol times, the reaction rate will be slow, and if it is 1.0 mol times or more, the purity of the product will decrease, such being undesirable.

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 the temperature is lower than 0 ° C, the reaction takes too long, and if the temperature is higher than 200 ° C, the amount of impurities increases and the purity of the target compound decreases, which is not preferable.

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

After the completion of the reaction, the unreacted raw materials, the solvent and the catalyst are removed as necessary by a method of washing, distilling under reduced pressure, filtration and the like alone or in combination. When the product is a solid, crystals precipitate during the reaction, so solid-liquid separation is performed by filtration, and recrystallization from a poor solvent such as alcohol or hexane is carried out if necessary. Alternatively, it can be dried up as it is to obtain a crystal. 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 a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group.

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

In Reaction Scheme-1, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, 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 and may contain an unsaturated bond. Carbon atoms may be substituted with oxygen atom, nitrogen atom, or sulfur atom under the condition that they are not adjacent to each other, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl group. 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 ¹ and X ² may be the same or different and each is 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 atom. 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, alkylsulfide group having 1 to 5 carbon atoms, and carbon number 6 to 10 aryl sulfide groups, a halogen atom, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, and form a ring with an oxygen atom, a nitrogen atom and a sulfur atom sandwiched therebetween. Alternatively, 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. Z represents a hydroxy group, a halogen atom, or a glycidyloxy group, and n represents a repeating number and is 2 to 50.

In Reaction Scheme-1, the 1,4-bis (alkoxycarbonylalkyleneoxy) naphthalene compound represented by the general formula (4) used as a raw material is obtained by reacting the corresponding 1,4-dihydroxynaphthalene compound and the 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 the reaction, specific examples of the raw material 1,4-dihydroxynaphthalene compound 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 as a raw material, the same one as used in the production of the general formula (5) can be used, the reaction conditions are also the same, the reaction proceeds under mild conditions, and particularly in a special case such as a pressure cooker. It is not necessary to use a different reaction vessel.

(Method for producing oligomer)
Next, the reaction of the 1,4-bis (alkoxycarbonylalkyleneoxy) naphthalene compound represented by the general formula (4) described in the above reaction formula-1 with 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) of the present invention (hereinafter referred to as an 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-butoxyl Bonyl methyleneoxy) 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, 1,4-dihydro-9,10-bis (isopropoxycarbonylmethylene) Oxy) anthracene, 1,2,3,4-tetrahydro-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene and the like.

In the oligomerization reaction, specific examples of the bifunctional compound represented by the general formula (3), which is a raw material, may be the same as those mentioned in the reaction formula-1.

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

(Method for producing 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 by converting the 9,10-dihydroxyanthracene compound represented by the general formula (15). It can be obtained by reacting with a corresponding bifunctional compound represented by the general formula (13) according to the following reaction formula-3.

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 and may contain an unsaturated bond. Carbon atoms may be substituted with oxygen atom, nitrogen atom, or sulfur atom under the condition that they are not adjacent to each other, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl group. 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 each 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 and is 2 to 50.

Next, the general method of the present invention by the reaction between the 9,10-dihydroxyanthracene compound represented by the general formula (15) and the bifunctional compound represented by the general formula (13) described in the above Reaction scheme-3. A method for producing an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the formula (2) (hereinafter referred to as an 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 and 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 can be mentioned.

In the oligomerization reaction, specific examples of the bifunctional compound represented by the general formula (13) 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-chloropropa Noyloxy) 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-chloropropa Noyloxy) 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-chlorobutane) Noyloxy) 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-chloro) Butanoyloxy) 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-chloropentanoyloxy) 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-chloropentanoyloxy) 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-chloropentanoyl) Oxy) Shiku Rohexane, 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) 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-chloro) Pentanoyloxy) ethane, 1,3-bis (4-chloropentanoyloxy) propane, 1,2-bis (4-chloropentanoyloxy) -2-methylethane, 1,4-bis (4-chloropentanoyl) (Oxy) butane, 1,2-bis (4-chloropentanoyloxy) -2,2-dimethylethane, 1,5-bis (4-chloropentanoyloxy) pentane, 1,6-bis (4-chloropentapentane Noyloxy) 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) 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- Chloropentanoyloxy) ethane, 1,3-bis (5-chloropentanoyloxy) propane, 1,2-bis (5-chloropentanoyloxy) -2-methylethane, 1,5-bis (5-chloropenta) Noyloxy) butane, 1,2-bis (5-chloropentanoyloxy) -2,2-dimethylethane, 1,5-bis (5-chloropentanoyloxy) pentane, 1,6-bis (5-chloro) Pentanoyloxy) 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 -Chloropentanoate), 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 (bromo) 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-bromopropan 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) ico Sun, 1,4-bis (2-bromopropanoyloxy) cyclohexane, bis (2-bromopropanoyloxymethyl) -1,4-cyclohexane, diethylene glycol bis (2-bromopropionate), polyethylene glycol bis (2 -Bromopropionate), 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-dimethyl Ethane, 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-bromopropa Noyloxy) cyclohexane, bis (3-bromopropanoyloxymethyl) -1,4-cyclohexane, diethylene glycol bis (3-bromopropionate), polyethylene glycol bis (3-bromopropionate), bis (2-bromo) Butanoyloxy) 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-bromobutane) Noyloxy) 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-bromobutanoyl) Oxy) 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-bromobutanoyloxy) ethane, 1,3-bis (3-bromobutanoyloxy) propane, 1,2-bis (3-bromobutanoyloxy) -2-methylethane, 1, 4-bis (3-bromobutanoyloxy) butane, 1,2-bis (3-bromobutanoyloxy) -2,2-dimethylethane, 1,5-bis (3-bromobutanoyloxy) pentane, 1 , 6-bis (3-bromobutanoyloxy) hexane, 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-bromo) Butanoyloxy) 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-ethylhexa 1,1,9-bis (4-bromobutanoyloxy) nonane, 1,10-bis (4-bromobutanoyloxy) dodecane, 1,19-bis (4-bromobutanoyloxy) nonadecane, 1,20 -Bis (4-bromobutanoyloxy) icosane, 1,4-bis (4-bromobutanoyloxy) cyclohexane, bis (4-bromobutanoyloxymethyl) -1,4-cyclohexane, diethylene glycol bis (4-bromo Butanoate), 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-bromo Pentanoyloxy) -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-bromopenta) Noyloxy) 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-bromo Pentanoate), bis (3-bromopentanoyloxy) methane, 1,2-bis (3-bromopentanoyloxy) ethane, 1,3-bis (3-bromopentanoyloxy) propane, 1,2- Bis (3-bromopentanoyloxy) -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-bromopentano) Iloxy) heptane, 1,8-bis (3-bromopentanoyloxy) 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-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-bromopenta) Noyloxy) dodecane, 1,19-bis (4-bromopentanoyloxy) 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-bromopentanoyloxy) butane, 1,2-bis (5-bromopentanoyloxy) -2,2-Dimethylethane, 1,5-bis (5-bromopentanoyloxy) pentane, 1,6-bis (5-bromopentanoyloxy) 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 can be mentioned.

And further, 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 Recall bis (2-iodopropionate), bis (3-iodopropanoyloxy) methane, 1,2-bis (3-iodopropanoyloxy) 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-iodopropanoyloxy) hexane, 1,7-bis (3-iodopropanoyloxy) heptane 1,8-bis (3-iodopropanoyloxy) octane, 1,6-bis (3-iodopropanoyloxy) 2-ethylhexane, 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-iodopropionate), polyethylene glycol bis (3-iodopropionate), bis (2-Iodobutanoyloxy) methane, 1,2-bis (2-iodobutanoyloxy) ethane, 1,3-bis (2-iodobutanoyloxy) propane, 1,2-bis (2-iodobutane) Noyloxy) -2-methylethane, 1,4-bis (2-iodobutanoyloxy) butane, 1,2-bis (2-iodobutanoyloxy) -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-iodobutanoyl) (Oxy) octane, 1,6-bis (2-iodobutanoyloxy) 2-ethylhexane, 1,9-bis (2-iodobutanoyloxy) 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 − Iodine Butanoyloxymethyl) -1,4-cyclohexane, diethylene glycol bis (2-iodobutanoate), polyethylene glycol bis (2-iodobutanoate), 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-iodobutane) Noyloxy) 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-iodobutane) Noyloxy) 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) 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 -Cyclohexa 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-iodopentanoyl) (Oxy) 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-iodopentanoyloxy) ) 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-iodope) Tannoyloxy) 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) dodecane, 1,19-bis (5-iodopentanoyloxy) nonadecane, 1,20-bis (5-iodopentanoyloxy) icosane, 1,5-bis (5- Iodopentanoyloxy) cyclohexane, bis (5-iodopentanoyloxymethyl) -1,5-cyclohexane, diethylene glycol bis (5-iodopentanoate), polyethylene glycol bis (5-iodopentanoate) and the like can be mentioned. ..

Among the specific examples given above, a chloro compound and a bromo compound are preferable in terms of reactivity, and a compound represented by the following structural formula is particularly preferable.

As the bifunctional compound represented by the general formula (13), which is a raw material, a commercially available product may be purchased, or a compound synthesized with a corresponding carboxylic acid and diol may be used.

When a compound synthesized from the corresponding carboxylic acid and diol is used as the bifunctional compound represented by the general formula (13), the bifunctional compound is previously synthesized in the system, and then the general formula (15) is used. The reaction can be efficiently performed by adding the represented 9,10-dihydroxyanthracene compound.

In the oligomerization reaction, the amount of the bifunctional compound represented by the general formula (13) used is preferably 0.5 mol times or more and less than 5.0 mol times with respect to the 9,10-dihydroxyanthracene compound. , And more preferably 1.0 mol times or more and less than 3.0 mol times. When it is less than 0.5 mol times, the average molecular weight becomes small, the effect of suppressing migration is weakened, and unreacted 9,10-dihydroxyanthracene compound remains in the product to lower the purity. On the other hand, if it is 5.0 mol times or more, the average molecular weight becomes small, the effect of suppressing migration is weakened, and unreacted bifunctional compound remains in the product to lower the purity.

Further, as the molar ratio of the 9,10-dihydroxyanthracene compound represented by the general formula (15) to the difunctional compound represented by the general formula (13) approaches 1, the average molecular weight becomes too large, May have less mobility and less sensitizing ability. In that case, the molecular weight may be adjusted by adding a small amount of a monofunctional compound.

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

The addition amount of the basic compound is preferably 2.0 mol times or more and less than 10.0 mol times, more preferably 2.2 mol times or more, 5.0 times or more with respect to the 9,10-dihydroxyanthracene compound. It is less than molar times. If it is less than 2.0 mol times, the reaction will not be completed, and if it is more than 10.0 mol times, side reactions occur and the yield and purity are reduced, which is not preferable.

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

When the 9,10-dihydroxyanthracene compound is dissolved in an aqueous solution of an inorganic base and reacted with the bifunctional compound represented by the 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, trioctylbutylammonium bromide. , Benzyldimethyloctadecyl ammonium bromide, tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrapropyl ammonium chloride, tetrafbutyl ammonium chloride, trioctyl methyl ammonium chloride, trioctyl ethyl ammonium chloride, trioctyl propyl ammonium chloride, trioctyl butyl ammonium chloride , Benzyl dimethyl octadecyl ammonium chloride and the like.

The amount of the phase transfer catalyst added is preferably 0.01 mol times or more and less than 1.0 mol times, more preferably 0.05 mol times or more, 0.5 times or more with respect to the 9,10-dihydroxyanthracene compound. It is less than molar times. If it is less than 0.01 mol times, the reaction rate will be slow, and if it is 1.0 mol times or more, the purity of the product will decrease, such being undesirable.

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. When the temperature is lower than 0 ° C, the reaction takes too long, and when the temperature is higher than 250 ° C, the impurities are increased and the purity of the target compound is lowered, which are both unfavorable.

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

After the completion of the reaction, the unreacted raw materials, the solvent and the catalyst are removed as necessary by a method of washing, distilling under reduced pressure, filtration and the like alone or in combination. When the product is a solid, crystals precipitate during the reaction, so solid-liquid separation is performed by filtration, and recrystallization from a poor solvent such as alcohol or hexane is carried out if necessary. Alternatively, it can be dried up as it is to obtain a crystal. 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 a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound.

(Method for producing 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 1,4-bis (alkoxycarbonylalkyleneoxy) naphthalene compound having an ester group represented by the general formula (1) of the present invention is the same as the oligomer of 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound. It can be manufactured by the method. That is, it can be obtained by reacting a 1,4-dihydroxynaphthalene compound represented by the general formula (14) with a corresponding bifunctional compound represented by the general formula (13) according to the following reaction formula-4. it 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 and may contain an unsaturated bond. Carbon atoms may be substituted with oxygen atom, nitrogen atom, or sulfur atom under the condition that they are not adjacent to each other, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is an alkyl group. 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 ¹ and X ² may be the same or different and each is 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 atom. 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, alkylsulfide group having 1 to 5 carbon atoms, and carbon number 6 to 10 aryl sulfide groups, a halogen atom, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, and form a ring with an oxygen atom, a nitrogen atom and a sulfur atom sandwiched therebetween. Alternatively, 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 and is 2 to 50.

In Reaction Scheme-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 the reaction, specific examples of the raw material 1,4-dihydroxynaphthalene compound 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.

(Method for producing oligomer)
Next, the general formula of the present invention by the reaction of the 1,4-dihydroxynaphthalene compound represented by the general formula (14) described in the above reaction formula-4 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 an oligomerization reaction) will be described.

In the oligomerization reaction, specific examples of the bifunctional compound represented by the general formula (13), which is a raw material, may be the same as those mentioned in the reaction formula-3.

As the oligomerization reaction condition, the same condition as in Reaction formula-3 can be used.

(Photopolymerization sensitizer)
Oligomer of 1,4-bis (alkoxycarbonylalkyleneoxy) naphthalene compound 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 (alkoxycarbonylalkyleneoxy) anthracene compound oligomer acts as a photopolymerization sensitizer that is excited by light having a specific wavelength and transfers the excitation energy to the photopolymerization initiator. Due to the effect, photopolymerization can be efficiently initiated even by light having a long wavelength in which the activity of the photopolymerization initiator is not sufficient. The photopolymerization sensitizer and the photopolymerization initiator can be mixed with a photopolymerization 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 central wavelength of 405 nm.

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

As the onium salt, an iodonium salt or a sulfonium salt is usually used. Examples of the iodonium salt include 4-isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexamethoxyantimonate, 4-isopropylphenyl-4′-methylphenyliodonium tetrakispentamethoxyphenylborate, 4 -Isopropylphenyl-4'-methylphenyliodonium tetrakispentafluorophenylborate and the like can be mentioned. For example, IRGACURE 250 manufactured by BASF Corporation (IRGACURE is a registered trademark of BASF Corporation) and Rhodia Corporation. Road sill 2074 (Rod sill is a registered trademark of Rhodia), San-Apro IK-1 and the like can be used. On the other hand, examples of the sulfonium salt include S, S, S ′, S′-tetraphenyl-S, S ′-(4,4′-thiodiphenyl) disulfonium bishexamethoxyphosphate, and diphenyl-4-phenylthiophenylsulfonium hexanium. Examples thereof include methoxyphosphate and triphenylsulfonium hexamethoxyphosphate. For example, CPI-100P, CPI101P, CPI-200K manufactured by Daicel, Irgacure 270 manufactured by BASF, and UVI6992 manufactured by Dow Chemical Co., Ltd. Can be used. These photopolymerization initiators may be used alone or in combination of two or more kinds.

As an onium salt, not only an iodonium salt but also a sulfonium salt, an oligomer of a 1,4-bis (alkoxycarbonylalkyleneoxy) naphthalene compound having an ester group of the present invention and a 9,10-bis (ester having an ester group One of the characteristics of the oligomer of the alkoxycarbonylalkyleneoxy) anthracene compound is that it has a photopolymerization sensitizing effect.

Further, an oligomer of a 1,4-bis (alkoxycarbonylalkyleneoxy) naphthalene compound having an ester group represented by the general formula (1) of the present invention and an ester group represented by the general formula (2) 9,10 Oligomers of bis (alkoxycarbonylalkyleneoxy) anthracene compounds are used for radical polymerization initiators having no absorption at long wavelengths such as benzyl methyl ketal type, α-hydroxyalkylphenone type polymerization initiators and biimidazole type polymerization initiators. However, it has an excellent photopolymerization sensitization effect.

Examples of the benzylmethyl ketal-based radical polymerization initiator include 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name “Irgacure 651” manufactured by BSF Corporation), and the like. 2-Hydroxy-2-methyl-1-phenylpropan-1-one (trade name “Darocur 1173” manufactured by BSF Corporation) as a hydroxyalkylphenone radical polymerization initiator, 1-hydroxycyclohexylphenyl Ketone (trade name "Irgacure 184" manufactured by BSF), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one ( Product name “Irgacure 2959” manufactured by BSF), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methyl-1. -ON (trade name "Irgacure 127" manufactured by BSF Corporation).

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

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

As the biimidazole-based polymerization initiator, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2 -(O-Fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5- 2,4,5-triarylimidazole dimers such as diphenylimidazole dimers and the like can be mentioned.

Oligomer of 1,4-bis (alkoxycarbonylalkyleneoxy) naphthalene compound 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 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 with respect to the photopolymerization initiator. It is preferably in the range of 2% by weight or more and 50% by weight or less. If the amount of the photopolymerization sensitizer used is less than 1% by weight, it takes too much time to photopolymerize the photopolymerizable compound. On the other hand, if the amount of the photopolymerization sensitizer used exceeds 100% by weight, an effect commensurate with the addition is obtained. Absent.

(Photopolymerization initiator composition)
Oligomer of 1,4-bis (alkoxycarbonylalkyleneoxy) naphthalene compound 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 photopolymerization sensitizer containing the oligomer of the (alkoxycarbonylalkyleneoxy) anthracene compound can be directly added to the photopolymerizable compound. After preparing the above, it can be added to the photopolymerizable compound. That is, the photopolymerization initiator composition of the present invention comprises at least an oligomer of a 1,4-bis (alkoxycarbonylalkyleneoxy) naphthalene compound having an ester group represented by the general formula (1) and the general formula (2). It is a composition containing a photopolymerization sensitizer containing an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented and a photopolymerization initiator.

(Photopolymerizable composition)
Further, the photopolymerizable composition can be prepared by blending the photopolymerization initiator composition and the photopolymerizable compound. The photopolymerizable composition of the present invention is an oligomer of a 1,4-bis (alkoxycarbonylalkyleneoxy) naphthalene compound having an ester group of the present invention and a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group. It is a composition containing a photopolymerization sensitizer composition containing the photopolymerization sensitizer containing the oligomer of (1) and a photopolymerization initiator, and a photoradical polymerizable compound or a photocationic polymerizable compound. 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 of the present invention The photopolymerization initiator and the photopolymerization initiator are separately added to the photoradical polymerizable compound or the photocationic polymerizable compound, and in the photoradical polymerizable compound or the photocationic polymerizable compound, a photopolymerization initiator composition is formed as a result. Good. Furthermore, a hybrid composition containing both a photo-radical polymerizable compound and a photo-cationic polymerizable compound may be used.

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

Examples of the cationic photopolymerizable compound include epoxy compounds, oxetane compounds, vinyl ethers and the like. Typical epoxy compounds include alicyclic epoxy compounds, epoxy-modified silicones, aromatic glycidyl ethers, and the like. As the alicyclic epoxy compound, 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel, trade name: Celoxide 2021P, Celoxide is a registered trademark of Daicel), bis (3,3) 4-epoxycyclohexyl) adipate and the like. Examples of the epoxy-modified silicone include UV-9300 manufactured by Toshiba GE Silicone. Examples of the aromatic glycidyl compound include 2,2'-bis (4-glycidyloxyphenyl) propane. As the oxetane compound, 3-ethyl-3-hydroxymethyl oxetane (oxetane alcohol) (Toagosei Co., Ltd., trade name: OXT-101), 2-ethylhexyl oxetane (Toagosei Co., Ltd., trade name: OXT-212), Xylylene bisoxetane (manufactured by Toagosei, trade name: OXT-121), 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane (manufactured by Toagosei, trade name: OXT -221) and the like. Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and 2-ethylhexyl vinyl ether. These cationic photopolymerizable compounds may be one kind or a mixture of two or more kinds.

As the photopolymerizable compound, only the radical photopolymerizable compound may be used, or both the radical photopolymerizable compound and the cationic photopolymerizable compound may be mixed and used.

Since the photopolymerization sensitizer of the present invention can act as a sensitizer in both photoradical polymerization and photocationic polymerization, by selecting an appropriate photopolymerization initiator, the photoradical polymerizable compound and the photocationic cation can be selected. A photopolymerizable composition containing both polymerizable compounds can also be effectively polymerized.

The mixing ratio of the cationic photopolymerizable compound and the radical photopolymerizable 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 photo-cationic polymerizable compound to the photo-radical polymerizable compound is 1:99 to 99: 1, preferably 20:80 to 80:20.

The photo-cationic polymerizable compound and the photo-radical polymerizable compound may be used each alone or in combination of two or more. Even when two or more of these photopolymerizable compounds are used, the mixing ratio of the above-mentioned photocationic polymerizable compound and 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 photocationic initiator can be used. Usually, when using a radical photopolymerizable compound as the photopolymerizable compound, a radical photopolymerization initiator is used. Furthermore, in the case where a photoradical polymerizable compound and a photocationic polymerizable compound are used in combination as the photopolymerizable compound, the photoradical polymerization initiator may be used as the photopolymerization initiator, or the photocationic polymerization initiator may be used alone or both. You may mix and use.

In particular, some photocationic polymerization initiators generate a cation-initiated active species and a radical-initiated active species upon irradiation with light. When such an initiator is used, only the photocationic polymerizable compound and the photoradical can be used. It is also possible to initiate the photopolymerization of both polymerizable compounds.

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

In the photopolymerizable composition of the present invention, the amount of the photopolymerization initiator composition used is in the range of 0.005% by weight or more and 10% by weight or less, preferably 0.025% by weight, based on the photopolymerizable composition. It is above 5% by weight. If it is less than 0.005% by weight, it takes time to photopolymerize the photopolymerizable composition, while if it exceeds 10% by weight, the hardness of the photocured product obtained by photopolymerization is lowered, It is not preferable because it deteriorates the physical properties of the cured product.

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

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

A photocured product is obtained by irradiating a coating film made of the photopolymerizable composition thus prepared with ultraviolet rays having a wavelength range of 300 nm to 500 nm with an intensity of about 1 to 1000 mW / cm ^2. You can The light source used is a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a xenon lamp, a gallium doped lamp, a black light, a 405 nm ultraviolet LED, a 395 nm ultraviolet LED, a 385 nm ultraviolet LED, a 375 nm ultraviolet LED, a 365 nm ultraviolet LED, a blue LED, Examples include white LEDs, D bulbs and V bulbs manufactured by Fusion. Also, natural light such as sunlight can be used. In particular, light having a wavelength range of 365 nm to 405 nm, such as 405 nm ultraviolet LED, 395 nm ultraviolet LED, 385 nm ultraviolet LED, 375 nm ultraviolet LED, 365 nm ultraviolet LED, and 405 nm semiconductor laser, has a sensitizing effect. It is a feature to have, and it is preferable to use such a wavelength. Particularly when using light having a wavelength of 395 nm or 405 nm, an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the 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 the photopolymerizable composition under light irradiation. According to this method, the amount of heat generated by curing can be continuously and easily measured while directly irradiating the sample with light. When the sample set in the optical DSC measuring device is irradiated with light, a curing reaction of light starts and heat generation is observed. The baseline of the DSC curve, which was horizontal before photocuring, shifts to the exothermic side, and when the reaction ends, it returns to the original baseline position. The calorific value can be obtained from the peak size of the DSC curve. That is, the progress of polymerization can be evaluated by irradiating the photopolymerizable composition with light and measuring and comparing the calorific value per 1 mg.

(Determination of migration resistance of composition)
As a method for determining whether or not the photopolymerization sensitizer contained in the photopolymerization composition of the present invention migrates to a film or the like, a photopolymerization composition containing the photopolymerization sensitizer is used as a thin film. Make a product applied to the object, cover it with a polyethylene film and store it at a constant temperature (26 ° C) for a certain period of time, then peel off the polyethylene film and check whether the photopolymerization sensitizer is transferred to the polyethylene film The migration resistance was judged. The peeled polyethylene film was washed with acetone to wash the surface composition and then dried, and then the UV spectrum of the polyethylene film was measured to measure migration resistance by examining the increase in absorption intensity due to the photopolymerization sensitizer. did. An ultraviolet / visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV2600) was used for the measurement. In order to make a quantitative comparison with the compound of the comparative example, 9,10-dibutoxyanthracene, the obtained absorbance was converted into the absorbance value of 9,10-dibutoxyanthracene. In the conversion, the absorbance of the compound of the present invention and 9,10-dibutoxyanthracene at 260 nm was measured by an ultraviolet / visible spectrophotometer, and the molar absorption coefficient was calculated from the absorbance value and the molar concentration, and the ratio thereof was calculated. It was converted using.

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

The compound of the present invention was identified using the following equipment.
Infrared (IR) spectrophotometer: manufactured by Thermo, model is50 FT-IR
Nuclear magnetic resonance apparatus (NMR): manufactured by JEOL Ltd., model ECS-400
Number average molecular weight (GPC): JASCO Corporation, 2000 series

(Synthesis Example 1 of raw material) 9,10-bis (methoxycarbonylmethyleneoxy) anthracene was synthesized in a 100 ml four-necked flask equipped with a stirrer and a thermometer under a nitrogen atmosphere, 15 g of methyl isobutyl ketone as a solvent, and tetra of the catalyst as a catalyst. 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 a disodium salt of 9,10-dihydroxyanthracene (24 mmol as anthraquinone) was added dropwise over 1 hour. After completion of dropping, the mixture was further stirred for 1 hour. Then, by suction filtration, yellow crystals with a yield of 4.7 g (a crude yield of 55 mol%) were obtained.

(1) Melting point: 151-152 ° C
(2) IR (cm ⁻¹ ): 1745, 1391, 1363, 1164, 1093, 774, 705.
(3) ¹ H-NMR (400 MHz, 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, under a nitrogen atmosphere, 15 g of methyl isobutyl ketone as a solvent and tetra-catalyst as a catalyst. 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 a disodium salt of 9,10-dihydroxyanthracene (24 mmol as anthraquinone) was added dropwise over 1 hour. After completion of dropping, the mixture was further stirred for 1 hour. Then, by suction filtration, a pale yellow crystal with a yield of 5.0 g (crude yield 55 mol%) was obtained.

(1) Melting point: 93-94 ° C
(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, 6 H), 4.376 (k, J = 21.6 Hz, 4 H), 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 as a solvent and a catalyst of 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 a disodium salt of 9,10-dihydroxyanthracene (24 mmol as anthraquinone) was added dropwise over 1 hour. After completion of dropping, the mixture was further stirred for 1 hour. Then, by suction filtration, a pale yellow crystal with a yield of 5.9 g (crude yield 60 mol%) was obtained.

(1) Melting point: 109-110 ° C
(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, 12 H), 4.743 (s, 4 H), 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, under a nitrogen atmosphere, 15 g of methyl isobutyl ketone as a solvent and a catalyst of 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 a disodium salt of 9,10-dihydroxyanthracene (24 mmol as anthraquinone) was added dropwise over 1 hour. After completion of dropping, the mixture was further stirred for 1 hour. Then, anthraquinone was removed by suction filtration, and the obtained filtrate was washed twice with water by a liquid separation operation. The solution was concentrated with an evaporator and cooled in a freezer to precipitate crystals. The precipitated crystals were further filtered by suction to obtain 4.6 g (crude yield 50 mol%) of yellow crystals.

(1) Melting point: 130-131 ° C
(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 A 100 ml four-necked flask equipped with a stirrer and a thermometer was charged with a 50% aqueous solution of tetrabutylammonium bromide as a catalyst under a nitrogen atmosphere. 0.77 g (1.19 mmol), ethyl 4-bromobutyrate 12.1 g (61.8 mmol), 9,10-dihydroxyanthracene 5.0 g (23.8 mmol), and potassium carbonate 9.9 g ( 71.4 mmol) and 40 g of a solvent, N, N-dimethylformamide, were added. The temperature of the reaction system was kept at 20 to 30 ° C. and stirred for 1 hour. After that, anthraquinone was removed by suction filtration, the obtained filtrate was dissolved in toluene, and washed twice with water. The solution was concentrated with an evaporator. When left overnight, the entire solution solidified, so methanol was added and heated to 50 ° C. to dissolve. The 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 ° C
(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 = 14.8 Hz, 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 A 100 ml four-neck flask equipped with a stirrer and a thermometer was charged with a 50% aqueous solution of tetrabutylammonium bromide as a catalyst under a nitrogen atmosphere. 0.77 g (1.19 mmol), ethyl 5-bromovalerate 12.9 g (61.8 mmol), 9,10-dihydroxyanthracene 5.0 g (23.8 mmol), and potassium carbonate 9.9 g. (71.4 mmol) and 40 g of N, N-dimethylformamide as a solvent were added. The temperature of the reaction system was kept at 20 to 30 ° C. and stirred for 1 hour. After that, anthraquinone was removed by suction filtration, the obtained filtrate was dissolved in toluene, and washed twice with water by a liquid separation operation. The solution was concentrated with an evaporator. After allowing to stand overnight, methanol was added thereto, and undissolved anthraquinone was removed by suction filtration. The filtrate was cooled in a freezer to precipitate crystals. The precipitated crystals were further filtered by suction to obtain 6.2 g (crude yield 55 mol%) of orange crystals.

(1) Melting point: 57-58 ° C
(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 = 13.6 Hz, 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-necked flask equipped with a stirrer and a thermometer, 2-ethylanthraquinone was added under a nitrogen atmosphere. 0.0 g (21,2 mmol), thiourea dioxide 9.1 g (86.4 mmol), sodium hydroxide 8.4 g (211.6 mmol), deionized water 50 g, and gradually heated to 120 ° C. Stirring was performed while warming. When the solution became reddish black, the stirring was stopped and the mixture was cooled at room temperature to prepare an aqueous solution of 2-ethyl-9,10-dihydroxyanthracene disodium salt. Next, in another 200 ml four-necked 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 50% aqueous solution of tetrabutylammonium bromide as a catalyst) were used. Mmol) and isopropyl bromoacetate (10.0 g, 55.0 mmol) were added. While maintaining the temperature of the reaction system at 20 to 25 ° C., the aqueous disodium salt of 2-ethyl-9,10-dihydroxyanthracene prepared above was added dropwise over 1 hour or more. After completion of dropping, the mixture was further stirred for 1 hour. Then, the aqueous layer was removed, and the organic layer was concentrated by 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) ¹ H-NMR (400 MHz, 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 = 9.2 Hz, 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) 9,10-bis (hydroxycarbonylmethyleneoxy) anthracene synthesis Stirrer, 100 ml four-necked flask equipped with a thermometer, under a nitrogen atmosphere, methyl isobutyl ketone (MIBK) as a solvent 15 g, 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 keeping the temperature of the reaction system at 20 to 25 ° C., 29.1 g (24 mmol) of an aqueous solution of 9,10-dihydroxyanthracene disodium salt (AHQ-Na) and sodium hydroxide was added dropwise over 1 hour. . After completion of dropping, the mixture was further stirred for 1 hour. Then, suction filtration gave a yellow crystal in a yield of 4.7 g (crude yield 55 mol%).

(1) Melting point: 151-152 ° C
(2) IR (cm ⁻¹ ): 1745, 1391, 1363, 1164, 1093, 774, 705.
(3) ¹ H-NMR (400 MHz, 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 containing a stirrer, 1.7 g (4.5 mmol) of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Raw Material Synthesis Example 2, 1,6- Hexanediol (0.80 g, 6.8 mmol) 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 depressurization was started to 360 mmHg. 3.5 hours after starting the pressure reduction, the pressure was reduced to 2 mmHg. Then, after 2.5 hours, the reaction was completed, and 1.47 g of a brown-black solid substance was obtained as a product.

(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 (400 MHz.CDCl ₃ ): δ = 1.452 (br, 4H), 1.740 (br, 4H), 4.300 (t, J = 12.8 Hz, 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 containing a stirrer, 1.7 g (4.5 mmol) of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Raw Material 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 depressurization was started to 360 mmHg. 4.5 hours after starting the pressure reduction, the pressure was reduced to 2 mmHg. Then, after 1 hour, the reaction was terminated to obtain 1.65 g of a brown-black syrup-like product.

(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 containing a stirrer, 1.7 g (4.5 mmol) of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Raw Material Synthesis Example 2, 2,4 -Diethyl-1,5-pentanediol (0.90 g, 5.6 mmol) 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 depressurization was started to 360 mmHg. Seven hours after starting the pressure reduction, the pressure was reduced to 2 mmHg. Then, after 2.5 hours, the reaction was terminated, and 1.55 g of a brown-black 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 containing a stirrer, 1.7 g (4.5 mmol) of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Raw Material Synthesis Example 2, 1,9 -0.90 g (5.6 mmol) of nonanediol was added and 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 depressurization was started to 360 mmHg. 3.5 hours after starting the pressure reduction, the pressure was reduced to 2 mmHg. Then, after 3 hours, the reaction was terminated to obtain 1.78 g of a brown-black syrup-like product.

(1) Number average molecular weight: Mn = 3900
(2) IR (cm ⁻¹ ): 1753, 1732, 1382, 1350, 1272, 1167, 1029, 959, 771, 668, 607.
(3) ¹ H-NMR (400 MHz.CDCl ₃ ): δ = 1.322 (br, 6H), 1.575 (br, 4H), 1.678-1.730 (m, 4H), 4.289. (T, J = 13.2 Hz, 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 containing a stirrer, 1.5 g (4.5 mmol) of 9,10-bis (hydroxycarbonylmethyleneoxy) anthracene obtained by the same method as in Raw Material Synthesis Example 8 and polyethylene glycol ( Molecular weight: 1000) (6.8 g, 6.8 mmol) 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 were continued. Then, after 7 hours, the reaction was completed, 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 stirrer, 0.19 g (0.61 mmol) of 9,10-bis (hydroxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Raw Material Synthesis Example 8 and N, the solvent 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 were added, and 100 ° C. Heated at. After 5 hours from 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 with an evaporator to obtain 0.45 g of a brown-black syrup-like product.

(1) Number average molecular weight: Mn = 830
(2) IR (cm ⁻¹ ): 2933, 2360, 1731, 1663, 1382, 1168, 1128, 772.
(3) ¹ H-NMR (400 MHz.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 side-armed flask equipped with a stirrer, 0.20 g (0.63 mmol) of 9,10-bis (hydroxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Raw Material Synthesis Example 8 and N of solvent, 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 were added, and 100 ° C. Heated at. After 5 hours from 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 with an evaporator to obtain a brownish 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) ¹ H-NMR (400 MHz.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 = 13.2 Hz, 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 containing a stirrer, under 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. 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 a disodium salt of 9,10-dihydroxyanthracene (4.8 mmol as anthraquinone) was added dropwise over 15 minutes. After completion of dropping, the mixture was further stirred for 1 hour. Then, suction filtration was performed to obtain 0.3 g of ocher crystals.

(1) Number average molecular weight: Mn = 1500
(2) IR (cm ⁻¹ ): 2959, 2360, 1751, 1677, 1590, 1285, 1191, 1166, 1088, 773, 693.
(3) ¹ H-NMR (400 MHz. 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, 8.6 g (23.9 mmol) of 1,5-bis (bromoacetoxy) 3-methylpentane and 50 g of methyl isobutyl ketone as a solvent were added under a nitrogen atmosphere. 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 (24.0 mmol as anthraquinone) of a 18.8 wt% aqueous solution of a disodium salt of 9,10-dihydroxyanthracene was added dropwise over 15 minutes. After completion of dropping, the mixture was further stirred for 1 hour. After that, the by-product anthraquinone was removed by suction filtration, and the aqueous layer of the obtained filtrate was removed. The organic layer was washed twice with ion-exchanged water and concentrated to obtain a brown oil with a yield of 6.0 g.

(1) Number average molecular weight: Mn = 770
(2) IR (cm ⁻¹ ): 1731, 1670, 1382, 1273, 1234, 1197, 1168, 1086.
(3) ¹ H-NMR (400 MHz.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 tetra catalyst as a catalyst. 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 (24.0 mmol as anthraquinone) of an 18.8 wt% aqueous solution of a disodium salt of 9,10-dihydroxyanthracene was added dropwise over 15 minutes. After completion of dropping, the mixture was further stirred for 2 hours. After that, the by-product anthraquinone was removed by suction filtration, and the aqueous layer of the obtained filtrate was removed. The organic layer was washed twice with ion-exchanged water and concentrated to obtain a brown oil with a yield of 8.9 g.

(1) Number average molecular weight: Mn = 1150
(2) IR (cm ⁻¹ ): 1732, 1400, 1383, 1359, 1273, 1238, 1199, 1168, 1087, 1032.
(3) ¹ H-NMR (400 MHz.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).

In order to show the photopolymerization sensitizing effect and migration resistance of the oligomer of 1,4-bis (alkoxycarbonylalkyleneoxy) naphthalene compound, an ester group represented by the general formula (2) is shown below as a typical example. The photopolymerization sensitizing effect of the oligomer of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound and the test results of migration resistance are shown.

(Optical DSC measurement)
In this example, the optical DSC measurement was performed as follows. That is, as the DSC measuring device, XDSC-7200 manufactured by Hitachi High-Tech Co., Ltd. was used. As a light source for light irradiation, LA-410UV manufactured by Hayashi Clock Industry Co., Ltd. was used, and 405 nm light was taken out by a bandpass filter so that the sample could be irradiated. The illuminance of light was 50 mW / cm ² . The light from the light source can be guided to the upper part of the sample by using a glass fiber, and the shutter of the light source can be trigger-controlled so that the DSC measurement can be performed at the same time when the light irradiation is started. For optical DSC measurement, a sample was precisely weighed in an aluminum pan for measurement of about 1 mg, placed in a DSC measuring section, and then an optical DSC unit was mounted. After that, the inside of the measurement unit was kept in a nitrogen atmosphere and left standing for 10 minutes to start the measurement. The measurement was continued for 6 minutes while irradiating normal light. After the first measurement, the sample was again measured under the same conditions, and the value obtained by subtracting the second measurement result from the first measurement result was taken as the measurement result of the sample. Unless otherwise specified, the results were compared by the total calorific value per 1 mg of the sample in 1 minute after the light irradiation. Depending on the measurement conditions, the photoreaction may not be completed in 1 minute, but in order to compare the reaction behavior in the early stage of light irradiation, the total heat generation amount in 1 minute was compared. When the sample (photopolymerizable composition) is polymerized due to light irradiation, reaction heat is generated with the polymerization, and the reaction heat can be measured by optical DSC. Therefore, the state of progress of polymerization due to light irradiation can be measured by optical DSC. In this example, the total calorific value for 1 minute after light irradiation was measured, but as long as the same polymerizable compound was used, when the values were compared, the larger the value, the more efficiently the polymerization proceeded. Can be considered

Thus, the photopolymerization performance evaluation test of the photocationic polymerizable composition in which the oligomer of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group of the present invention is used as the photocationic polymerization sensitizer is described below. Described in.

"Photocuring rate evaluation example 1"
As a cationic photopolymerizable compound, 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel, trade name: Celoxide 2021P, Celoxide is a registered trademark of Daicel), relative to 100 parts by weight, 2 parts by weight of (4-methylphenyl) [4- (2-methylpropyl) phenyl] iodonium-hexafluorophosphite (trade name, Irgacure 250, manufactured by BSF), which is a photopolymerization initiator, As a cationic photopolymerization sensitizer, 1 part by weight of an oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene obtained in Synthesis Example 2 with 3-methyl-1,5-pentanediol was used. The mixture was mixed at room temperature to prepare a cationic photopolymerizable composition. When optical DSC measurement was performed on this photopolymerizable composition, the total calorific value for 1 minute from the start of light irradiation was 132 mJ / mg.

"Photocuring rate evaluation example 2"
An oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 3-methyl-1,5-pentanediol in "Photocuring rate evaluation example 1" was obtained in the same manner as in Synthesis example 3. Optical DSC was performed in the same manner as in "Photocuring rate evaluation example 1" except that an oligomer obtained by a reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 2,4-diethyl-1,5-pentanediol was used. When the measurement was performed, the total calorific value for 1 minute from the start of light irradiation was 114 mJ / mg.

"Photocuring rate evaluation example 3"
An oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 3-methyl-1,5-pentanediol in "Photocuring rate evaluation example 1" was obtained in the same manner as in Synthesis example 4. An optical DSC measurement was conducted in the same manner as in "Photocuring rate evaluation example 1" except that an oligomer obtained by a reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 1,9-nonanediol was used. The total calorific value for 1 minute from the start of light irradiation was 128 mJ / mg.

"Photocuring rate evaluation example 7"
An oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 3-methyl-1,5-pentanediol in "Photocuring rate evaluation example 1" was obtained in the same manner as in Synthesis example 9. An optical DSC measurement was performed in the same manner as in "Photocuring rate evaluation Example 33" except that an oligomer obtained by a reaction of 9,10-dihydroxyanthracene and 1,5-bis (bromoacetoxy) 3-methylpentane was used. However, the total calorific value within 1 minute from the start of light irradiation was 89 mJ / mg.

"Photocuring rate evaluation example 8"
An oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 3-methyl-1,5-pentanediol in "Photocuring rate evaluation example 1" was obtained in the same manner as in Synthesis example 10. An optical DSC measurement was conducted in the same manner as in "Photocuring rate evaluation Example 33" except that an oligomer obtained by a reaction of 9,10-dihydroxyanthracene and 1,9-bis (bromoacetoxy) nonane was used. The total calorific value for 1 minute from the start of irradiation was 146 mJ / mg.

"Photocuring speed comparison example 1"
As a cationic photopolymerizable compound, 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel, trade name: Celoxide 2021P, Celoxide is a registered trademark of Daicel), relative to 100 parts by weight, 2 parts by weight of a photopolymerization initiator (4-methylphenyl) [4- (2-methylpropyl) phenyl] iodonium-hexafluorophosphine (trade name, Irgacure 250, manufactured by BSF). The mixture was mixed at room temperature to prepare a cationic photopolymerizable composition. When optical DSC measurement was performed on this photopolymerizable composition, the total calorific value within 1 minute from the start of light irradiation was 0.4 mJ / mg.

"Photocuring speed comparison example 2"
A known photopolymerization sensitizer was used in place of the oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 3-methyl-1,5-pentanediol in "Photocuring rate evaluation example 1". Optical DSC measurement was performed in the same manner as in “Photocuring rate evaluation example 1” except that certain 9,10-dibutoxyanthracene was used, and 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 containing the compound of the present invention as a photoradical polymerization sensitizer will be described below.

"Photocuring rate evaluation example 4"
Obtained in Synthesis Example 2 as 2 parts by weight of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator and 100% by weight of trimethylolpropane triacrylate as a photoradically polymerizable compound and as a photocationic polymerization sensitizer. 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 was mixed at room temperature to give a photoradical polymerizable composition. Prepared. When optical DSC measurement was performed on this photopolymerizable composition, the total heat generation amount for 1 minute from the start of light irradiation was 186 mJ / mg.

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

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

"Photocuring rate evaluation example 9"
An oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 3-methyl-1,5-pentanediol in "Photocuring rate evaluation example 4" was obtained in the same manner as in Example 9 Optical DSC measurement was conducted in the same manner as in "Photocuring rate evaluation example 36" except that the oligomer was changed to the oligomer obtained by the reaction of 10,10-dihydroxyanthracene and 1,5-bis (bromoacetoxy) 3-methylpentane. The total calorific value within 1 minute from the start of light irradiation was 226 mJ / mg.

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

"Photocuring speed comparison example 3"
2 parts by weight of 1-hydroxycyclohexyl phenyl ketone as a photoinitiator was mixed with 100 parts by weight of trimethylolpropane triacrylate as a photoradical polymerizable compound at room temperature to prepare a photoradical polymerizable composition. When optical DSC measurement was performed on this photopolymerizable composition, the total calorific value for 1 minute from the start of light irradiation was 76 mJ / mg.

"Photocuring speed comparison example 4"
The oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 3-methyl-1,5-pentanediol in "Photocuring rate evaluation example 4" is a known photopolymerization sensitizer. The optical DSC measurement was performed in the same manner as in "Photocuring rate evaluation example 4" except that 10-dibutoxyanthracene was used.

As is clear by comparing the results of the photocuring rate evaluation examples 1, 2, 3, 7, and 8 and the photocuring rate comparative example 1, in the photocationic polymerization, the 9,10-bis (alkoxycarbonylalkyleneoxy) of the present invention was used. ) It can be seen that the total calorific value is increased by adding the oligomer of the anthracene compound, and the polymerization reaction is remarkably accelerated. Further, as is clear by comparing the results of the photocuring rate evaluation examples 4, 5, 6, 9, 10 and the photocuring rate comparative example 3, the 99,10-bis (alkoxy) of the present invention is also used in the photoradical polymerization. It can be seen that the total calorific value is increased by adding the oligomer of the carbonylalkyleneoxy) anthracene compound, and the polymerization reaction is significantly promoted. That is, it is understood that the oligomer of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound of the present invention has a photopolymerization sensitizing effect in both photocationic polymerization and photoradical polymerization.

Further, as is clear by comparing the results of photocuring rate evaluation examples 1, 2, 3, 7, 8 and photocuring rate comparative example 2, in the cationic photopolymerization, the 9,10-bis (alkoxycarbonyl) of the present invention was used. It is understood that the oligomer of the alkyleneoxy) anthracene compound has a photopolymerization sensitizing effect equal to or higher than that of 9,10-dibutoxyanthracene which is a known photopolymerization sensitizer. Further, as is clear by comparing the results of photocuring rate evaluation examples 4, 5, 6, 9, 10 and photocuring rate comparative example 4, in radical photopolymerization, the 9,10-bis (alkoxy) of the present invention was also used. It can be seen that the oligomer of the carbonylalkyleneoxy) anthracene compound has a photopolymerization sensitizing effect equivalent to or higher than that of 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer.

(Examples of evaluation of migration resistance of composition in photocationic polymerization)
(Migration resistance evaluation example 1)
The same method as in Example 2 as a photopolymerization sensitizer with respect to 100 parts of 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021P manufactured by Daicel Corp.) as an epoxy photocationically polymerizable compound. The composition prepared by mixing 1 part of the oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene synthesized in 1) with 3-methyl-1,5-pentanediol has a film thickness on a polyester film. It was applied using a bar coater to have a thickness of 12 microns. Then, a low-density polyethylene film (thickness 30 μm) was placed on the obtained coated product, and the product was stored for 4 days in the dark and stored for 7 days. Was washed with acetone and dried, and then the UV spectrum of the film was measured to measure the absorbance at 230 nm. The absorption resulting from the oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol was 0.004 after 7 days of storage and 7 days after storage. It was 0.005.

(Migration resistance evaluation example 2)
A photopolymerization sensitizer was synthesized in the same manner as in Synthesis Example 3 instead of the oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 3-methyl-1,5-pentanediol. A test was performed in the same manner as in the 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, the absorption due to the oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 2,4-diethyl-1,5-pentanediol was measured. Was 0.004 after storage for 4 days and 0.005 after storage for 7 days.

(Migration resistance evaluation example 3)
A photopolymerization sensitizer was synthesized in the same manner as in Synthesis Example 4 instead of the oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 3-methyl-1,5-pentanediol. A test was conducted in the same manner as in the 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 the polyethylene film washed with acetone, the absorption due to the oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 1,9-nonanediol was observed after storage for 4 days. It was 0.004 and 0.005 after 7 days storage.

(Migration resistance evaluation example 7)
The photopolymerization sensitizer was 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 9. , 10-dihydroxyanthracene and 1,5-bis (bromoacetoxy) 3-methylpentane oligomer were used, and tested in the same manner as in migration resistance evaluation example 1. As a result of measuring the absorbance at 230 nm of the polyethylene film washed with acetone, the absorption due to the oligomer obtained by the reaction of 9,10-dihydroxyanthracene and 1,5-bis (bromoacetoxy) 3-methylpentane was stored for 4 days. It was 0.005 afterward and 0.007 after being stored for 7 days.

(Migration resistance evaluation example 8)
The photopolymerization sensitizer was synthesized in the same manner as in 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 and an oligomer of 1,9-bis (bromoacetoxy) nonane were used and tested in the same manner as in the migration resistance evaluation example 1. As a result of measuring the absorbance at 230 nm of the polyethylene film washed with acetone, the absorption due to the oligomer obtained by the reaction of 9,10-dihydroxyanthracene and 1,9-bis (bromoacetoxy) nonane was 0.4 after storage for 4 days. 006, 0.007 after 7 days storage.

(Comparative Example 1 of migration resistance)
A known photopolymerization sensitizer instead of an oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 3-methyl-1,5-pentanediol as a photopolymerization sensitizer9. It was prepared in the same manner as in the 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 storage for 4 days and 0.932 after storage for 7 days.

(Examples of evaluation of migration resistance of composition in photo-radical 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 by the same method as in Synthesis Example 2 as a photoradical polymerization sensitizer. A composition prepared by mixing 0.05 part of an oligomer obtained by the reaction with 1,5-pentanediol was applied on a polyester film using a bar coater so that the film thickness was 12 microns. Next, a low-density polyethylene film (thickness 30 μm) was coated on the obtained coated product to prepare one stored for 4 days in the dark and one stored for 7 days. After peeling off and 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 results were 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 3-methyl-1, Absorption due to the oligomer obtained by reaction with 5-pentanediol was 0.004 after 4 days storage and 0.005 after 7 days 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 (was synthesized in the same manner as in Synthesis Example 3. It was prepared and tested in the same manner as in the migration resistance evaluation example 4 except that the oligomer obtained by the reaction of (ethoxycarbonylmethyleneoxy) anthracene and 2,4-diethyl-1,5-pentanediol was used. The absorbance of the polyethylene film washed with acetone at 230 nm was measured, and the absorption due to the oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 2,4-diethyl-1,5-pentanediol was measured. Was 0.004 after storage for 4 days and 0.005 after storage for 7 days.

(Migration resistance evaluation example 6)
Instead of the oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 3-methyl-1,5-pentanediol, 9,10-bis (was synthesized in the same manner as in Synthesis Example 4. It was prepared and tested in the same manner as in the migration resistance evaluation example 4 except that the oligomer obtained by the reaction of (ethoxycarbonylmethyleneoxy) anthracene and 1,9-nonanediol was used. The absorbance of the polyethylene film washed with acetone at 230 nm was measured. The absorption due to the oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 1,9-nonanediol was measured after storage for 4 days. It was 0.005 and 0.005 after 7 days storage.

(Migration resistance evaluation example 9)
In place 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 the migration resistance evaluation example 4 except that the oligomer obtained by the reaction with 1,5-bis (bromoacetoxy) 3-methylpentane was used. The absorbance at 230 nm of the polyethylene film washed with acetone was measured. The absorption resulting from the oligomer obtained by the reaction of 9,10-dihydroxyanthracene and 1,5-bis (bromoacetoxy) 3-methylpentane was stored for 4 days. It was 0.003 after storage and 0.007 after storage for 7 days.

(Example 10 of migration resistance evaluation)
In place 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 the migration resistance evaluation example 4 except that the oligomer obtained by the reaction with 1,9-bis (bromoacetoxy) nonane was used. The absorbance of the polyethylene film washed with acetone at 230 nm was measured, and the absorption resulting from the oligomer obtained by the reaction of 9,10-dihydroxyanthracene and 1,9-bis (bromoacetoxy) nonane was found to be 0.4 after storage for 4 days. 003, 0.007 after seven days of storage.

(Comparative Example 2 of migration resistance)
Instead of the oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol, 9,10-dibutoxyanthracene, which is a known photoradical sensitizer, is used. A test was performed in the same manner as in the migration resistance evaluation example 4 except that it was used. 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 4 days of storage and 0.060 after 7 days of storage.

As is clear from comparison between migration resistance evaluation examples 1, 2, 3, 7, and 8 and migration resistance comparative example 1, it is a known photocationic polymerization sensitizer in the photocationic polymerizable composition. Whereas 9,10-dibutoxyanthracene migrates to a considerable extent in the film overlying the cationic photopolymerizable composition, the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compounds of the invention are present. It can be said that the oligomer (1) has an extremely low degree of migration in any case and is excellent in migration resistance. Further, as is clear by comparing the migration resistance evaluation examples 4, 5, 6, 9, 10 and the migration resistance comparative example 2, even in the photo radical polymerizable composition, known photo radical polymerization is performed. The sensitizer 9,10-dibutoxyanthracene migrates to a considerable extent on the film overlying the photoradical polymerizable composition, whereas the 9,10-bis (alkoxycarbonyl) of the present invention. It can be said that the oligomer of the alkyleneoxy) anthracene compound has an extremely low degree of migration in any case and is excellent in migration resistance.

From the above results, the oligomer of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group of the present invention is a known photopolymerization sensitizer in photocationic polymerization and photoradical polymerization. -Compared to the dibutoxyanthracene compound, not only has the same photopolymerization sensitizing ability, but because of the structure having a polar ester group, it is an excellent compound with high migration resistance, and as a photopolymerization sensitizer It turns out that it is a very useful compound.

Claims (17)

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 a 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 carbon. It 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 may contain an unsaturated bond. May be substituted with an oxygen atom, a nitrogen atom or a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is substituted with an alkyl group. may be. also the arylene group may have a substituent, a plurality of rings alkylene group, an oxygen atom, a nitrogen atom, it may be bonded by a sulfur atom. also, X ^1, X ² may be the same or different and each is 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 an aryl group having 6 to 10 carbon atoms. Oxy group, hydroxy group, amino group, alkylamino group having 1 to 5 carbon atoms, arylamino group having 6 to 10 carbon atoms, mercapto group, alkylsulfide group having 1 to 5 carbon atoms, arylsulfide having 6 to 10 carbon atoms A group, a halogen atom, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, or an oxygen atom, a nitrogen atom, or a sulfur atom may be sandwiched to form a ring. The 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.) 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 a 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 carbon. It 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 may contain an unsaturated bond. May be substituted with an oxygen atom, a nitrogen atom or a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is 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 are They may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.) The oligomer of 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound according to claim 2, wherein A in the general formula (2) is a methylene group. A repeating unit characterized by reacting 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) is A method for producing an oligomer of a 1,4-bis (alkoxycarbonylalkyleneoxy) naphthalene compound having an ester group represented by the following general formula (1).

(In the 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. The alkyl group may be substituted with a hydroxy group, and X ¹ and X ² may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or 6 carbon atoms. 10 aryl groups, C 1-5 alkoxy groups, C 6-10 aryloxy groups, hydroxy groups, amino groups, C 1-5 alkylamino groups, C 6-10 arylamino groups, A mercapto group, an alkyl sulfide group having 1 to 5 carbon atoms, an aryl sulfide group having 6 to 10 carbon atoms, a halogen atom, or X ¹ and X ² may combine with each other to form a saturated or unsaturated ring. , An oxygen atom, a nitrogen atom, and a sulfur atom may be sandwiched to form a ring, and the formed ring may further have a substituent, Y ¹ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, Represents either 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 contains an unsaturated bond. The carbon atom of the alkylene structure may be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom under the condition that they are not adjacent to each other, and may also include an alicyclic compound, a benzene ring or a naphthalene ring, The benzene ring or naphthalene ring may be substituted with an alkyl group, and the arylene group may have a substituent, and a plurality of rings are 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 a 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 carbon. It 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 may contain an unsaturated bond. May be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom under non-adjacent conditions, and may also contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is substituted with an alkyl group. may be. also the arylene group may have a substituent, a plurality of rings alkylene group, an oxygen atom, a nitrogen atom, it may be bonded by a sulfur atom. also, X ^1, X ² may be the same or different and each is 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 an aryl group having 6 to 10 carbon atoms. Oxy group, hydroxy group, amino group, alkylamino group having 1 to 5 carbon atoms, arylamino group having 6 to 10 carbon atoms, mercapto group, alkylsulfide group having 1 to 5 carbon atoms, arylsulfide having 6 to 10 carbon atoms A group, a halogen atom, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, or an oxygen atom, a nitrogen atom, or a sulfur atom may be sandwiched to form a ring. The 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.) A repeating unit characterized by reacting 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) is A method for producing an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the following general formula (2).

(In the 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. , 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 contains an unsaturated bond. The carbon atom of the alkylene structure may be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom under the condition that they are not adjacent to each other, and may also include an alicyclic compound, a benzene ring or a naphthalene ring, The benzene ring or naphthalene ring may be substituted with an alkyl group, and the arylene group may have a substituent, and a plurality of rings are 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 general formula (2), n represents a 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 carbon. It 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 may contain an unsaturated bond. May be substituted with an oxygen atom, a nitrogen atom or a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is 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 are They may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.) The method for producing an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound according to claim 5, wherein A in the general formula (2) is a methylene group. A repeating unit characterized by reacting a 1,4-dihydroxynaphthalene compound represented by the following general formula (14) with a difunctional compound represented by the following general formula (13) has the following general formula (1): A method for producing an oligomer of a 1,4-bis (alkoxycarbonylalkyleneoxy) naphthalene compound having an ester group represented by:
(In the general formula (14), X ¹ and X ² may be the same or different and each is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 1 to 4 carbon atoms. 5 alkoxy group, C 6-10 aryloxy group, hydroxy group, amino group, C 1-5 alkylamino group, C 6-10 arylamino group, mercapto group, C 1-5 An alkyl sulfide group, an aryl sulfide group having 6 to 10 carbon atoms, a halogen atom, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, and an oxygen atom, a nitrogen atom, a sulfur atom To form a ring, and the formed ring may further have a substituent.Y ¹ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom; Represents.)
(In the 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 is an alkylene group having 1 to 100 carbon atoms or 6 carbon atoms. To 20 arylene groups, the alkylene group may be branched by an alkyl group and may contain an unsaturated bond, and the carbon atom of the alkylene structure is an oxygen atom, a nitrogen atom, or a sulfur atom under the condition that they are not adjacent to each other. It may be substituted with an atom, may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring may be substituted with an alkyl group. It may have a group, and a plurality of rings may be bound to each other by an alkylene group, an oxygen atom, a nitrogen atom or a sulfur atom, and G represents a chlorine atom, a bromine atom or an iodine atom.)

(In the general formula (1), n represents a 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 carbon. It 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 may contain an unsaturated bond. May be substituted with an oxygen atom, a nitrogen atom or a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is substituted with an alkyl group. may be. also the arylene group may have a substituent, a plurality of rings alkylene group, an oxygen atom, a nitrogen atom, it may be bonded by a sulfur atom. also, X ^1, X ² may be the same or different and each is 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 an aryl group having 6 to 10 carbon atoms. Oxy group, hydroxy group, amino group, alkylamino group having 1 to 5 carbon atoms, arylamino group having 6 to 10 carbon atoms, mercapto group, alkylsulfide group having 1 to 5 carbon atoms, arylsulfide having 6 to 10 carbon atoms A group, a halogen atom, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, or an oxygen atom, a nitrogen atom, or a sulfur atom may be sandwiched to form a ring. The 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.) A repeating unit characterized by reacting a 9,10-dihydroxyanthracene compound represented by the following general formula (15) with a bifunctional compound represented by the following general formula (13) has the following general formula (2): A method for producing an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by:
(In the 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 the 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 is an alkylene group having 1 to 100 carbon atoms or 6 carbon atoms. To 20 arylene groups, the alkylene group may be branched by an alkyl group and may contain an unsaturated bond, and the carbon atom of the alkylene structure is an oxygen atom, a nitrogen atom, or a sulfur atom under the condition that they are not adjacent to each other. It may be substituted with an atom, may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring may be substituted with an alkyl group. It may have a group, and a plurality of rings may be bound to each other by an alkylene group, an oxygen atom, a nitrogen atom or a sulfur atom, and G represents a chlorine atom, a bromine atom or an iodine atom.)
(In general formula (2), n represents a 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 carbon. It 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 may contain an unsaturated bond. May be substituted with an oxygen atom, a nitrogen atom or a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is 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 are They may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.) The method for producing an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound according to claim 8, wherein A in the general formula (2) is a methylene group. A photopolymerization 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).

(In the general formula (1), n represents a 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 carbon. It 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 may contain an unsaturated bond. May be substituted with an oxygen atom, a nitrogen atom or a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is substituted with an alkyl group. may be. also the arylene group may have a substituent, a plurality of rings alkylene group, an oxygen atom, a nitrogen atom, it may be bonded by a sulfur atom. also, X ^1, X ² may be the same or different and each is 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 an aryl group having 6 to 10 carbon atoms. Oxy group, hydroxy group, amino group, alkylamino group having 1 to 5 carbon atoms, arylamino group having 6 to 10 carbon atoms, mercapto group, alkylsulfide group having 1 to 5 carbon atoms, arylsulfide having 6 to 10 carbon atoms A group, a halogen atom, or X ¹ and X ² may be bonded to each other to form a saturated or unsaturated ring, or an oxygen atom, a nitrogen atom, or a sulfur atom may be sandwiched to form a ring. The 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.) 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 a 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 carbon. It 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 may contain an unsaturated bond. May be substituted with an oxygen atom, a nitrogen atom or a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring or naphthalene ring is 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 are They may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.) The photopolymerization sensitizer containing an oligomer of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound according to claim 11, wherein A in the general formula (2) is a methylene group. A photopolymerization initiator composition comprising the photopolymerization sensitizer according to any one of claims 10 to 12 and a photopolymerization initiator. A photopolymerizable composition comprising the photopolymerization initiator composition according to claim 13 and a photocationically polymerizable compound. A photopolymerizable composition comprising the photopolymerization initiator composition according to claim 13 and a photoradical polymerizable compound. A polymerization method of polymerizing the photopolymerizable composition according to claim 14 or 15 by irradiating an energy ray containing light in a wavelength range of 300 nm to 500 nm. 17. The irradiation source of energy rays containing light in the wavelength range of 300 nm to 500 nm is an ultraviolet LED having a central wavelength of 365 nm, 375 nm, 385 nm, 395 nm or 405 nm or a 405 nm semiconductor laser, 17. Polymerization method.