WO2020054874A1 - Photopolymerization sensitizer - Google Patents

Abstract

[Problem] To provide a photopolymerization sensitizer which exhibits sufficient photocuring speed during practical use, without causing problems such as staining or powder on the cured article or the appearance of an additive such as the photopolymerization sensitizer on the surface thereof due to blooming or the like at the time of photocuring or during storage of the cured article. [Solution] An oligomer of: a 9,10-bis (alkoxycarbonyl alkyleneoxy) anthracene compound which has an ester group and is represented by general formula (1), or a 9,10-bis (alkoxycarbonyl alkyleneoxy) anthracene compound which has an ester group and is represented by general formula (10). (In the general formulas, A represents a C1-20 alkylene group, and the alkylene group may be bifurcated by an alkyl group.)

Description

Photopolymerization sensitizer

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

Photocurable resins that are polymerized by active energy rays such as ultraviolet rays and visible light cure quickly and can significantly reduce the amount of organic solvents used compared to thermosetting resins. It is excellent in that it can be reduced. The conventional photocurable resin itself has a poor polymerization initiation function, and usually requires the use of a photopolymerization initiator for curing. Examples of the photopolymerization initiator include alkylphenone-based polymerization initiators such as hydroxyacetophenone and benzophenone, acylphosphine oxide-based photopolymerization initiators, and onium salts (Patent Documents 1, 2, and 3). When an onium salt-based initiator is used among these photopolymerization initiators, the onium salt absorbs light at about 225 nm to about 350 nm and has no absorption above 350 nm. In this case, there is a problem that the photocuring reaction does not easily proceed, and a photopolymerization sensitizer is generally added. Similarly, many photopolymerization initiators such as alkylphenone-based polymerization initiators have no absorption at 350 nm or more. Anthracene compounds and thioxanthone compounds are known as photopolymerization sensitizers for these photopolymerization initiators, and in particular, anthracene compounds are often used due to the problem of coloration (Patent Document 4).

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

However, the 9,10-dialkoxyanthracene compound blooms during storage of the photopolymerizable composition before photocuring or the cured product after photocuring, so that the photopolymerization sensitizer or the like oozes out on the surface, and the cured product is cured. It is known to cause dusting and coloring problems.

With respect to the photopolymerizable composition, for example, when these photopolymerization sensitizers are used as one component of a photoadhesive for bonding a film to a film, the photopolymerization sensitizer migrates to the film covered on the top ( Migration), which may cause a problem of powder blowing or coloring of the photopolymerization sensitizer on the upper film.

In addition, dry film resists used for processes such as printed wiring board manufacturing, lead frame manufacturing, and metal mask manufacturing are used. However, resists corresponding to 405 nm semiconductor lasers are required, and in order to cope with such wavelengths. As photopolymerization sensitizers, thioxanthone and 9,10-dialkoxyanthracene compounds are used. However, dry film resists are stored and traded with a cover film over the photosensitive resin composition, and a polyethylene film or a polypropylene film is used for the cover film or the like, and the film is subjected to photopolymerization sensitization. There is a problem that the agent migrates and the sensitizing effect is reduced, or 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 a polar ester 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, which not only increases the number of steps but leads to an increase in cost, but also increases the cost of the alkylene oxide compound, particularly ethylene oxide. The difficulty in availability and handling is a major problem in producing the 9,10-bis (2-acyloxyalkoxy) anthracene compound.

Further, compounds in which the alkoxy group of the 9,10-dialkoxyanthracene compound is changed to an acyl group have been developed. However, although the migration property is improved, the electron donating property of the alkoxy group is reduced, so that the absorption wavelength is reduced. There is a problem of shifting to a lower 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 which exhibits a photopolymerization sensitizing effect and hardly causes migration or the like (Patent Document 12). However, the oligomer of the 9,10-bis (substituted alkoxy) anthracene compound uses an alkylene oxide in addition to the 9,10-dihydroxyanthracene compound as a raw material for oligomer synthesis, but available alkylene oxide is limited. Moreover, alkylene oxide, which is easily available, has high toxicity, low boiling point, high flammability and is difficult to handle, and requires heat treatment in the synthesis reaction of 9,10-bis (substituted alkoxy) anthracene compound. When using ethylene oxide, which is most easily available, a pressurized hermetically sealed container such as an autoclave is required, and a problem that a special production facility is required remains. Further, in the oligomerization reaction, there remains a problem that the 9,10-bis (substituted alkoxy) anthracene compound as a raw material has low solubility and requires high-temperature conditions.

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

Therefore, during light curing or during storage of the cured product, it has migration resistance and does not cause problems such as dusting or coloring of the cured product, and also uses a readily available raw material and a practical manufacturing method. There is a demand for the development of a new photopolymerization sensitizer that can be obtained by the above method.

The present inventors have conducted further intensive studies on the structure and physical properties of the anthracene compound. As a result, the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group and the oligomer thereof shown in the present invention can be used in the photopolymerization reaction. While exhibiting excellent effects as a photopolymerization sensitizer, the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound and its oligomer of the present invention can be produced from easily available compounds as raw materials under mild conditions. Further, they have found that when the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound or an oligomer thereof of the present invention is used as a photopolymerization sensitizer, migration and blooming are unlikely to occur, thereby completing the present invention. Was.

A first gist of the present invention resides in a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the following general formula (1).

 

In the general formula (1), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, and may be a cycloalkyl group or a cycloalkylalkyl group. However, the alkyl group does not contain an oxygen atom. X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.

A second aspect of the present invention resides in the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound according to the first aspect, wherein A in the general formula (1) is a methylene group.

A third aspect of the present invention resides in an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having a repeating unit represented by the following general formula (10).

In the general formula (10), n represents the number of repetitions 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 or may contain an unsaturated bond; May be substituted with an oxygen atom, a nitrogen atom, and a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring and the naphthalene ring are alkyl. May be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.

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

A fifth gist of the present invention is to provide a method of reacting a 9,10-dihydroxyanthracene compound represented by the following general formula (2) with an ester compound represented by the following general formula (3). The present invention relates to a method for producing a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the formula (1).

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

In the general formula (3), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, may be substituted with a hydroxy group, Some of the atoms may be replaced by oxygen atoms (except when peroxides are formed). G represents a chlorine atom, a bromine atom or an iodine atom.

In the general formula (1), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, may be substituted with a hydroxy group, Some of the atoms may be replaced by oxygen atoms (except when peroxides are formed). X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.

The sixth gist of the present invention is to react a 9,10-dihydroxyanthracene compound represented by the following general formula (2) with a carboxylic acid compound represented by the following general formula (4), 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5) is synthesized with a 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5). 6), a 9,10-bis (alkoxy) having an ester group represented by the following general formula (1), characterized by reacting an esterifying agent represented by the general formula (7) or (8). Carbonylalkyleneoxy) anthracene compound.

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

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. G represents a chlorine atom, a bromine atom or an iodine atom.

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. X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.

In the general formula (6), R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, and may be substituted with a hydroxy group. And some of the carbon atoms may be replaced by oxygen atoms (except when peroxides are formed).

In the general formula (7), R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, and may be substituted with a hydroxy group. And some of the carbon atoms may be replaced by oxygen atoms (except when peroxides are formed). G represents a chlorine atom, a bromine atom, or an iodine atom.

In the general formula (8), R ¹ represents a hydrogen atom or an alkyl group having 1 to 17 carbon atoms, and the alkyl group may be branched by an alkyl group, and may be a cycloalkyl group or a cycloalkylalkyl group. , May be substituted with a hydroxy group, and a part of carbon atoms may be replaced by an oxygen atom (except when peroxide is formed). However, if R ¹ is an alkyl group having a carbon number of 1 to 17 carbon atoms of R ¹ is the formula number of carbon atoms of R in (1) except in the case of the 1 3, only 3 for the number of carbon atoms in R It will be a small number.

In the general formula (1), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, may be substituted with a hydroxy group, Some of the atoms may be replaced by oxygen atoms (except when peroxides are formed). X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.

A seventh gist of the present invention is to react a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound represented by the following general formula (1) with a bifunctional compound represented by the following general formula (11). A method for producing an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the following general formula (10), wherein the repeating unit is characterized in that:

In the general formula (1), 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 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, or may be substituted with a hydroxy group. Often, some of the carbon atoms may be replaced by oxygen atoms (except when forming peroxides). X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.

In the general formula (11), 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 non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring. The benzene ring and naphthalene ring may be substituted with an alkyl group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded by 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 (10), n represents the number of repetitions 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 or may contain an unsaturated bond; May be substituted with an oxygen atom, a nitrogen atom, and a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring and the naphthalene ring are alkyl. May be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.

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

In the general formula (2), X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms 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 or may contain an unsaturated bond; May be substituted with an oxygen atom, a nitrogen atom, and a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring and the naphthalene ring are alkyl. May be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded by 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 (10), n represents the number of repetitions 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 or may contain an unsaturated bond; May be substituted with an oxygen atom, a nitrogen atom, and a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring and the naphthalene ring are alkyl. May be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.

A ninth aspect of the present invention resides in a photopolymerization sensitizer containing a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the following general formula (1).

In the general formula (1), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, may be substituted with a hydroxy group, Some of the atoms may be replaced by oxygen atoms (except when peroxides are formed). X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.

A tenth aspect of the present invention resides in a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1), wherein A is a methylene group and R is substituted with a hydroxy group. The photopolymerization sensitizer according to the ninth aspect, wherein the photopolymerization sensitizer is a C1 to C20 alkyl group which is not substituted and a part of carbon atoms is not replaced by an oxygen atom.

An eleventh aspect of the present invention is directed to a photopolymerization sensitizer containing an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having a repeating unit having an ester group represented by the following general formula (10). Exist.

In the general formula (10), n represents the number of repetitions 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 or may contain an unsaturated bond; May be substituted with an oxygen atom, a nitrogen atom, and a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring and the naphthalene ring are alkyl. May be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.

A twelfth aspect of the present invention is a photopolymerization-enhancing method comprising an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound according to the eleventh aspect, wherein A in the general formula (10) is a methylene group. It 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 ninth 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 cationic photopolymerizable 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 is directed to a polymerization method of 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 seventeenth aspect of the present invention is characterized in that the irradiation source of energy rays containing light in a wavelength range of 300 nm to 500 nm is an ultraviolet LED or a 405 nm semiconductor laser having a center wavelength of 365 nm, 375 nm, 385 nm, 395 nm or 405 nm. In the polymerization method according to the sixteenth aspect.

The 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group and the oligomer thereof according to the present invention not only have a high effect as a photopolymerization sensitizer in a photopolymerization reaction, but also have the compound of the present invention. It is a useful compound in which the degree of migration or blooming of the photopolymerizable sensitizer is extremely low with respect to the photopolymerizable composition and the cured product contained as the photopolymerization sensitizer. Also in the production method, there is no need to use an alkylene oxide compound which is difficult to obtain and handle, and the compound can be produced under mild conditions using a compound which is easy to obtain and handle, and the production process is easy and inexpensive.

The objects, features and advantages of the present invention will become more apparent from the following detailed description.

(9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having ester group)
The 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group of the present invention is a compound represented by the following general formula (1).

In the general formula (1), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, may be substituted with a hydroxy group, Some of the atoms may be replaced by oxygen atoms (except when peroxides are formed). X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.

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

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

In the general formula (1), as the alkyl group having 1 to 20 carbon atoms represented by R, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t- -Butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n -Dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group or n-icosyl group; When the group is substituted with a hydroxy group, examples thereof include a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 2-hydroxybutyl group, and a 3-hydropropyl group. Cibutyl group, 4-hydroxybutyl group, 5-hydroxypentyl group, 6-hydroxyhexyl group, 7-hydroxyheptyl group, 8-hydroxyoctyl group, 6-hydroxy-2-ethylhexyl group, 9-hydroxynonyl group, 10- Hydroxydecyl, 11-hydroxyundecyl, 12-hydroxydodecyl, 2-hydroxy-3-methoxypropyl, 2-hydroxy-3-ethoxypropyl, 2-hydroxy-3-propoxypropyl, 2-hydroxy -3-butoxypropyl group, 2-hydroxy-3-pentyloxypropyl group, 2-hydroxy-3-hexyloxypropyl group, 2-hydroxy-3-octyloxypropyl group, 2-hydroxy-3- (2-ethylhexyl Oxy) propyl group, 2,3-dihydroxy Propyl, 2-hydroxy-3-allyloxy propyl, and 2-hydroxy-3-methallyl propyl group. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, adamantyl, 4-n-dodecylcyclohexyl, decahydronaphthyl, hydroxycyclohexyl, etc. Examples of the cycloalkylalkyl group include a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cycloheptylmethyl group, a cyclooctylmethyl group, a cyclononylmethyl group, a cyclodecylmethyl group, and -Cyclobutylethyl group, 2-cyclopentylethyl group, 2-cyclohexylethyl group, 2-cycloheptylethyl group, 2-cyclooctylethyl group, 2-cyclononylethyl group, 2-cyclodecylethyl , 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 3-cyclooctylpropyl, 3-cyclononylpropyl, 3-cyclodecylpropyl, 4- Cyclobutylbutyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl, 4-cycloheptylbutyl, 4-cyclooctylbutyl, 4-cyclononylbutyl, 4-cyclodecylbutyl, 3-3-adamantyl And a propyl group and a decahydronaphthylpropyl group.

Specific examples of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention include, for example, 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene, 9,10-bis (n-propoxycarbonylmethyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene, 9,10-bis (tert- Butoxycarbonylmethyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene, 9,10-bis (n-pentyloxycarbonylmethyleneoxy) anthracene, 9,10-bis (methoxycarbonyl) Pyreneoxy) anthracene, 9,10-bis (ethoxycarbonylpropyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylpropyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylpropyleneoxy) anthracene, 9,10- Bis (n-butoxycarbonylpropyleneoxy) anthracene, 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonylmethylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonylethylmethyleneoxy) ) Anthracene, 9,10-bis (isopropoxycarbonylmethylmethyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylmethylmethyleneoxy) Anthracene, 9,10-bis (n-butoxycarbonylmethylmethyleneoxy) anthracene, 9,10-bis (methoxycarbonylbutyleneoxy) anthracene, 9,10-bis (ethoxycarbonylbutyleneoxy) anthracene, 9,10-bis ( Isopropoxycarbonylbutyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylbutyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylbutyleneoxy) anthracene, 9,10-bis (2-hydroxyethoxycarbonylmethylene Oxy) anthracene, 9,10-bis (cyclohexyloxycarbonylmethyleneoxy) anthracene, 9,10-bis (cyclohexylmethyloxycarbonylmethyleneoxy) anthracene, 10-bis (norbornyloxycarbonylmethyleneoxy) anthracene and the like.

Further, for example, 9,10-bis (methoxycarbonylpentyleneoxy) anthracene, 9,10-bis (ethoxycarbonylpentyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylpentyleneoxy) anthracene, 9,10- Bis (tert-butoxycarbonylpentyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylpentyleneoxy) anthracene, 9,10-bis (methoxycarbonylhexyleneoxy) anthracene, 9,10-bis (ethoxycarbonyl) Hexyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylhexyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylhexyleneoxy) anthracene, 9,10-bis (n-butene) (Cicarbonylhexyleneoxy) anthracene, 9,10-bis (methoxycarbonylheptyleneoxy) anthracene, 9,10-bis (ethoxycarbonylheptyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylheptylene) Oxy) anthracene, 9,10-bis (tert-butoxycarbonylheptyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylheptyleneoxy) anthracene, 9,10-bis (methoxycarbonyloctyleneoxy) Anthracene, 9,10-bis (ethoxycarbonyloctyleneoxy) anthracene, 9,10-bis (isopropoxycarbonyloctyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonyloctyleneoxy) anthracene Helix, 9,10-bis (n-butoxycarbonyloctyleneoxy) anthracene, 9,10-bis (methoxycarbonylnonyleneoxy) anthracene, 9,10-bis (ethoxycarbonylnonyleneoxy) anthracene, 9,10- Bis (isopropoxycarbonylnonyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylnonyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylnonyleneoxy) anthracene, 9,10-bis (methoxy) Carbonyldecyleneoxy) anthracene, 9,10-bis (ethoxycarbonyldecyleneoxy) anthracene, 9,10-bis (isopropoxycarbonyldecyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonyldecyl) Oxy) anthracene, 9,10-bis (n-butoxycarbonyldecyleneoxy) anthracene, 9,10-bis (methoxycarbonylundecyleneoxy) anthracene, 9,10-bis (ethoxycarbonylundecyleneoxy) anthracene, 9,10- Bis (isopropoxycarbonylundecyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylundecyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylundecylenoxy) anthracene, 9,10-bis (methoxycarbonyldodecane) (Syleneoxy) anthracene, 9,10-bis (ethoxycarbonyldodecyleneoxy) anthracene, 9,10-bis (isopropoxycarbonyldodecyleneoxy) anthracene, 9,10- (Tert-butoxycarbonyldodecyleneoxy) anthracene, 9,10-bis (n-butoxycarbonyldodecyleneoxy) anthracene, 9,10-bis (methoxycarbonyltridecyleneoxy) anthracene, 9,10-bis ( Ethoxycarbonyltridecyleneoxy) anthracene, 9,10-bis (isopropoxycarbonyltridecyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonyltridecyleneoxy) anthracene, 9,10-bis (n-butoxycarbonyltride) (Sileneoxy) anthracene, 9,10-bis (methoxycarbonyltetradecyleneoxy) anthracene, 9,10-bis (ethoxycarbonyltetradecyleneoxy) anthracene, 9,10-bis (isopropoxy) Rubonyltetradecyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonyltetradecyleneoxy) anthracene, 9,10-bis (n-butoxycarbonyltetradecyleneoxy) anthracene, 9,10-bis (methoxycarbonyl) Pentadecyleneoxy) anthracene, 9,10-bis (ethoxycarbonylpentadecyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylpentadecyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylpentade) (Syleneoxy) anthracene, 9,10-bis (n-butoxycarbonylpentadecyleneoxy) anthracene, 9,10-bis (methoxycarbonylhexadecyleneoxy) anthracene, 9,10-bis (ethoxycal Bonylhexadecyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylhexadecyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylhexadecyleneoxy) anthracene, 9,10-bis (n-butoxy) Carbonylhexadecyleneoxy) anthracene, 9,10-bis (methoxycarbonylheptadecyleneoxy) anthracene, 9,10-bis (ethoxycarbonylheptadecyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylheptadecylene) Oxy) anthracene, 9,10-bis (tert-butoxycarbonylheptadecyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylheptadecyleneoxy) anthracene, 9,10-bis (methoxy) Rubonyl octadecyleneoxy) anthracene, 9,10-bis (ethoxycarbonyloctadecyleneoxy) anthracene, 9,10-bis (isopropoxycarbonyloctadecyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylocta) Decyleneoxy) anthracene, 9,10-bis (n-butoxycarbonyloctadecyleneoxy) anthracene, 9,10-bis (methoxycarbonylnonadecyleneoxy) anthracene, 9,10-bis (ethoxycarbonylnonadecyleneoxy) ) Anthracene, 9,10-bis (isopropoxycarbonylnonadecylenoxy) anthracene, 9,10-bis (tert-butoxycarbonylnonadecylenoxy) anthracene, 9,10-bis (n-butoxycal Nilnonadecyleneoxy) anthracene, 9,10-bis (methoxycarbonylicosyleneoxy) anthracene, 9,10-bis (ethoxycarbonylicosyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylicosyleneoxy) anthracene , 9,10-bis (tert-butoxycarbonylicosyleneoxy) anthracene and 9,10-bis (n-butoxycarbonylicosyleneoxy) anthracene.

Further, specific examples of X and / or Y as an alkyl group include, for example, 2-ethyl-9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (ethoxycarbonylmethyleneoxy) Anthracene, 2-ethyl-9,10-bis (n-propoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (tert -Butoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (n-pentyloxycarbonylmethyleneoxy) anthracene, 2-ethyl -9,10-bis (methoxycal Nylpropyleneoxy) anthracene, 2-ethyl-9,10-bis (ethoxycarbonylpropyleneoxy) anthracene, 2-ethyl-9,10-bis (isopropoxycarbonylpropyleneoxy) anthracene, 2-ethyl-9,10-bis (Tert-butoxycarbonylpropyleneoxy) anthracene, 2-ethyl-9,10-bis (n-butoxycarbonylpropyleneoxy) anthracene, 2-ethyl-9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene, 2-ethyl -9,10-bis (ethoxycarbonylmethylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (ethoxycarbonylethylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (isopropoxycarbonyl) Methylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (tert-butoxycarbonylmethylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (n-butoxycarbonylmethylmethyleneoxy) anthracene, 2-ethyl- 9,10-bis (methoxycarbonylbutyleneoxy) anthracene, 2-ethyl-9,10-bis (ethoxycarbonylbutyleneoxy) anthracene, 2-ethyl-9,10-bis (isopropoxycarbonylbutyleneoxy) anthracene, 2- Ethyl-9,10-bis (tert-butoxycarbonylbutyleneoxy) anthracene, 2-ethyl-9,10-bis (n-butoxycarbonylbutyleneoxy) anthracene, 2-ethyl-9,10-bis (methoxycarbonyloctyl) Lenoxy) anthracene, 2-ethyl-9,10-bis (ethoxycarbonyloctyleneoxy) anthracene, 2-ethyl-9,10-bis (isopropoxycarbonyloctyleneoxy) anthracene, 2-ethyl-9,10-bis (Tert-butoxycarbonyloctyleneoxy) anthracene, 2-ethyl-9,10-bis (n-butoxycarbonyloctyleneoxy) anthracene, 2-ethyl-9,10-bis (methoxycarbonylhexadecyleneoxy) anthracene, 2-ethyl-9,10-bis (ethoxycarbonylhexadecyleneoxy) anthracene, 2-ethyl-9,10-bis (isopropoxycarbonylhexadecyleneoxy) anthracene, 2-ethyl-9,10-bis (tert -Butoxycarbonyl Xadecylenoxy) anthracene, 2-ethyl-9,10-bis (n-butoxycarbonylhexadecyleneoxy) anthracene, 2-ethyl-9,10-bis (methoxycarbonylicosilenoxy) anthracene, 2-ethyl- 9,10-bis (ethoxycarbonylicosyleneoxy) anthracene, 2-ethyl-9,10-bis (isopropoxycarbonylicosyleneoxy) anthracene, 2-ethyl-9,10-bis (tert-butoxycarbonylicosyleneoxy) ) Anthracene, 2-ethyl-9,10-bis (n-butoxycarbonylicosyleneoxy) anthracene, 2-ethyl-9,10-bis (2-hydroxyethoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10 -Bis (cyclohexylo Aryloxycarbonyl methyleneoxy) anthracene, 2-ethyl-9,10-bis (cyclohexylmethyl oxycarbonyl methyleneoxy) anthracene, 2-ethyl-9,10-bis (norbornyloxy oxycarbonyl methyleneoxy) anthracene, and the like.

Further, for example, 2-amyl-9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (ethoxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (n- Propoxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene, 2-amyl-9, 10-bis (n-butoxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (n-pentyloxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (methoxycarbonylpropyleneoxy) anthracene, 2-A Ru-9,10-bis (ethoxycarbonylpropyleneoxy) anthracene, 2-amyl-9,10-bis (isopropoxycarbonylpropyleneoxy) anthracene, 2-amyl-9,10-bis (tert-butoxycarbonylpropyleneoxy) Anthracene, 2-amyl-9,10-bis (n-butoxycarbonylpropyleneoxy) anthracene, 2-amyl-9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene, 2-amyl-9,10-bis (ethoxy) Carbonylmethylmethyleneoxy) anthracene, 2-amyl-9,10-bis (ethoxycarbonylethylmethyleneoxy) anthracene, 2-amyl-9,10-bis (isopropoxycarbonylmethylmethyleneoxy) anthracene, 2-a -9,10-bis (tert-butoxycarbonylmethylmethyleneoxy) anthracene, 2-amyl-9,10-bis (n-butoxycarbonylmethylmethyleneoxy) anthracene, 2-amyl-9,10-bis (methoxycarbonyl) (Butyleneoxy) anthracene, 2-amyl-9,10-bis (ethoxycarbonylbutyleneoxy) anthracene, 2-amyl-9,10-bis (isopropoxycarbonylbutyleneoxy) anthracene, 2-amyl-9,10-bis ( tert-butoxycarbonylbutyleneoxy) anthracene, 2-amyl-9,10-bis (n-butoxycarbonylbutyleneoxy) anthracene, 2-amyl-9,10-bis (2-hydroxyethoxycarbonylmethyleneoxy) anthracene, 2- A Mill-9,10-bis (cyclohexyloxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (cyclohexylmethyloxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (norbornyloxycarbonyl) Methyleneoxy) anthracene and the like.

Specific examples of X and / or Y as a halogen atom include, for example, 2-chloro-9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10-bis (ethoxycarbonylmethyleneoxy) Anthracene, 2-chloro-9,10-bis (n-propoxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10-bis (tert -Butoxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10-bis (methoxycarbonylpropyleneoxy) anthracene, 2-chloro-9, 10-bis (ethoxycarbonyl Ropyleneoxy) anthracene, 2-chloro-9,10-bis (isopropoxycarbonylpropyleneoxy) anthracene, 2-chloro-9,10-bis (tert-butoxycarbonylpropyleneoxy) anthracene, 2-chloro-9,10- Bis (n-butoxycarbonylpropyleneoxy) anthracene, 2-chloro-9,10-bis (n-pentyloxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene, -Chloro-9,10-bis (ethoxycarbonylmethylmethyleneoxy) anthracene, 2-chloro-9,10-bis (ethoxycarbonylethylmethyleneoxy) anthracene, 2-chloro-9,10-bis (isopropoxycarbo) 2-methyl-9,10-bis (tert-butoxycarbonylmethylmethyleneoxy) anthracene, 2-chloro-9,10-bis (n-butoxycarbonylmethylmethyleneoxy) anthracene, 2-chloro -9,10-bis (methoxycarbonylbutyleneoxy) anthracene, 2-chloro-9,10-bis (ethoxycarbonylbutyleneoxy) anthracene, 2-chloro-9,10-bis (isopropoxycarbonylbutyleneoxy) anthracene, -Chloro-9,10-bis (tert-butoxycarbonylbutyleneoxy) anthracene, 2-chloro-9,10-bis (n-butoxycarbonylbutyleneoxy) anthracene, 2-chloro-9,10-bis (methoxycarbonyloctane) (Tyleneoxy) anthracene, 2-chloro-9,10-bis (ethoxycarbonyloctyleneoxy) anthracene, 2-chloro-9,10-bis (isopropoxycarbonyloctyleneoxy) anthracene, 2-chloro-9,10-bis (Tert-butoxycarbonyloctyleneoxy) anthracene, 2-chloro-9,10-bis (n-butoxycarbonyloctyleneoxy) anthracene, 2-chloro-9,10-bis (methoxycarbonylhexadecyleneoxy) anthracene, 2-chloro-9,10-bis (ethoxycarbonylhexadecyleneoxy) anthracene, 2-chloro-9,10-bis (isopropoxycarbonylhexadecyleneoxy) anthracene, 2-chloro-9,10-bis (tert -Butoxycarboni Hexadecyleneoxy) anthracene, 2-chloro-9,10-bis (n-butoxycarbonylhexadecyleneoxy) anthracene, 2-chloro-9,10-bis (methoxycarbonylicosilenoxy) anthracene, 2-chloro- 9,10-bis (ethoxycarbonylicosyleneoxy) anthracene, 2-chloro-9,10-bis (isopropoxycarbonylicosyleneoxy) anthracene, 2-chloro-9,10-bis (tert-butoxycarbonylicosyleneoxy) ) Anthracene, 2-chloro-9,10-bis (n-butoxycarbonylicosyleneoxy) anthracene, 2-chloro-9,10-bis (2-hydroxyethoxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10 -Bis (cyclohexyl Alkoxycarbonyl methyleneoxy) anthracene, 2-chloro-9,10-bis (cyclohexylmethyl oxycarbonyl methyleneoxy) anthracene, 2-chloro-9,10-bis (norbornyloxy oxycarbonyl methyleneoxy) anthracene, and the like.

Among the specific examples described above, 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene, and 9,10-bis (n-propoxycarbonyl) are preferred for ease of production. Methyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene, 9 9,10-bis (n-pentyloxycarbonylmethyleneoxy) anthracene, 9,10-bis (cyclohexyloxycarbonylmethyleneoxy) anthracene, 9,10-bis (methoxycarbonylpropyleneoxy) anthracene , 9,10-bis (ethoxycarbonylpropyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylpropyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylpropyleneoxy) anthracene, 9,10-bis (n -Butoxycarbonylpropyleneoxy) anthracene, 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonylmethylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonylethylmethyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylmethylmethyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylmethylmethyleneoxy) anthracene, 9,10-bi (N-butoxycarbonylmethylmethyleneoxy) anthracene, 9,10-bis (methoxycarbonylbutyleneoxy) anthracene, 9,10-bis (ethoxycarbonylbutyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylbutyleneoxy) anthracene 9,10-bis (tert-butoxycarbonylbutyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylbutyleneoxy) anthracene, 9,10-bis (2-hydroxyethoxycarbonylmethyleneoxy) anthracene, 2-ethyl -9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (ethoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (n-pro Poxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9, 10-bis (n-butoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (methoxycarbonylpropyleneoxy) anthracene, 2-ethyl-9,10-bis (ethoxycarbonylpropyleneoxy) anthracene, 2-ethyl -9,10-bis (isopropoxycarbonylpropyleneoxy) anthracene, 2-ethyl-9,10-bis (tert-butoxycarbonylpropyleneoxy) anthracene, 2-ethyl-9,10-bis (n-butoxycal Nylpropyleneoxy) anthracene, 2-ethyl-9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (ethoxycarbonylmethylmethyleneoxy) anthracene, 2-ethyl-9,10- Bis (ethoxycarbonylethylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (isopropoxycarbonylmethylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (tert-butoxycarbonylmethylmethyleneoxy) anthracene, -Ethyl-9,10-bis (n-butoxycarbonylmethylmethyleneoxy) anthracene and 2-ethyl-9,10-bis (2-hydroxyethoxycarbonylmethyleneoxy) anthracene are preferred, and are exemplified by the following structural formulas. 9,10-bis (methoxycarbonylmethyleneoxy) anthracene (1-1), 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene (1-2), 9,10-bis (n-propoxycarbonylmethyleneoxy) anthracene (1-10), 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene (1-3), 9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene (1-4), 9,10-bis (N-butoxycarbonylmethyleneoxy) anthracene (1-5), 9,10-bis (n-pentyloxycarbonylmethyleneoxy) anthracene (1-11), 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene ( 1-6), 9,10-bis (ethoxycal Bonylpropyleneoxy) anthracene (1-7), 9,10-bis (ethoxycarbonylbutyleneoxy) anthracene (1-8), 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene (1-9) ) And 9,10-bis (cyclohexyloxycarbonylmethyleneoxy) anthracene (1-12) are particularly preferred.

Comprehensively judging the ease of production, the availability of raw materials, and the ease of handling, it is preferable that R in the general formula (1) is an alkyl group containing no oxygen atom and having 1 to 20 carbon atoms. A in the general formula (1) is preferably a methylene group having 1 carbon atom. In view of various physical properties such as migration resistance and hydrophobicity, an alkyl group having 3 or more carbon atoms of R is preferable, and 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene (1-3), 9,10 -Bis (n-pentyloxycarbonylmethyleneoxy) anthracene (1-11) and 9,10-bis (cyclohexyloxycarbonylmethyleneoxy) anthracene (1-12) are particularly preferred.

(Oligomer of 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having ester group)
The oligomer of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group according to the present invention is a compound having a repeating unit represented by the following general formula (10).

In the general formula (10), n represents the number of repetitions 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 or may contain an unsaturated bond; May be substituted with an oxygen atom, a nitrogen atom, and a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring and the naphthalene ring are alkyl. May be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.

In the general formula (10), examples of the alkylene group having 1 to 20 carbon atoms represented by A include a methylene group, a methylmethylene group, an ethylmethylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a 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, and the alkylene group is an alkyl group. May be branched.

In the general formula (10), examples of the alkyl or alkenyl group having 1 to 8 carbon atoms represented by X or Y include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group. -Butyl group, n-pentyl group, i-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, 4-methyl-3-pentenyl group and the like. Represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the general formula (1) or (10), the alkylene group having 1 to 20 carbon atoms represented by D includes a methylene group, an ethylene group, a methylethylene group, an ethylethylene group, a propylene group, a 1-methylpropylene group, 2-methylpropylene group, 2,2-dimethylpropylene group, butylene group, pentylene group, 3-methylpentylene group, 2,4-diethylpentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group An undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, an octadecylene group, a nonadecylene group, an icosylene group, and the like.The alkylene group may be branched by an alkyl group. The alkylene structure may contain a saturated bond. An element atom 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 and the naphthalene ring are alkyl groups. May be substituted. Examples of the alkylene group in which the carbon atom of the alkylene group is substituted by an oxygen atom and the like include polyoxyalkylene groups such as a polyoxyethylene group and a polyoxypropylene group.

In the general formula (10), 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, and May be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom.

As specific examples of the oligomer of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (10) of the present invention, first, in the general formula (10), A is a methylene group. Tables 1, 2 and 3 show specific examples of the compound of the general formula (12). In the following tables, m in the formula represents 1 to 30.

In the general formula (12), n represents the number of repetitions and is 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. May contain 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 non-adjacent conditions, or an alicyclic compound, benzene It may contain a ring or a naphthalene ring, and the benzene ring and the 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 by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.

As specific examples of the general formula (10) other than the general formula (12), in the specific examples exemplified in the general formula (12), A is not a methylene group but an ethylene group, a propylene group, a butylene group, and 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, compound replaced by icosylene group Is mentioned.

Among the specific examples described above, a compound in which A is a methylene group in the general formula (10) is preferable because of easy production.

From the viewpoint of ease of production and high sensitizing ability, the following structural formulas (12-5), (12-6), (12-7), (12-9), and (12-11) , (12-14) are preferred.

As described above, examples of the compound suitably used in the present invention have been described, but the present invention is not limited to the compounds exemplified above.

(Method for producing 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound)
Next, a method for producing the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group according to the present invention will be described. The 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention is obtained by using a 9,10-dihydroxyanthracene compound represented by the following general formula (2) as a raw material. Are synthesized in a one-step reaction using a 9,10-dihydroxyanthracene compound as a raw material (one-step production method) and a two-step reaction through an intermediate (two-step production method). There is.

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

(Single-step manufacturing method)
First, a one-step method for producing a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group according to the present invention will be described. The 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention is obtained by converting the 9,10-dihydroxyanthracene compound represented by the general formula (2) into the following. According to Reaction Scheme-1, it can be obtained by reacting with a corresponding ester compound represented by the general formula (3) in the presence or absence of a basic compound.

In Reaction Scheme-1, A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, may be substituted with a hydroxy group, Some of the atoms may be replaced by oxygen atoms (except when peroxides are formed). X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom. G represents a chlorine atom, a bromine atom or an iodine atom.

In Reaction Scheme-1, the 9,10-dihydroxyanthracene compound represented by the general formula (2) used as a raw material is obtained by reducing the corresponding 9,10-anthraquinone compound.

In the reaction, the 9,10-dihydroxyanthracene compound used as a raw material is obtained by reducing the corresponding 9,10-anthraquinone compound. Specific examples of the 9,10-dihydroxyanthracene compound serving as a raw material in the reaction include 9,10-dihydroxyanthracene, 2-methyl-9,10-dihydroxyanthracene, 2-ethyl-9,10-dihydroxyanthracene , 2-t-pentyl-9,10-dihydroxyanthracene, 2,6-dimethyl-9,10-dihydroxyanthracene, 2-chloro-9,10-dihydroxyanthracene, 2-bromo-9,10-dihydroxyanthracene and the like. No.

Since the 9,10-dihydroxyanthracene compound is unstable to oxygen, the hydroxyl group may be used in a form protected by a known protecting group.

Further, in the case of 9,10-dihydroxyanthracene, an industrial method such as 1,4,4a, 9a-tetrahydroanthraquinone which is a Diels-Alder reaction product of 1,4-naphthoquinone and 1,3-butadiene or By reducing 9,10-anthraquinone using an alkali metal salt of 1,4-dihydro9,10-dihydroxyanthracene as its isomer, 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 converted into 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. The resulting aqueous solution of the alkali metal salt of 9,10-dihydroxyanthracene is acidified in the absence of oxygen, whereby a precipitate of 9,10-dihydroxyanthracene can be obtained. By purifying the precipitate, 9,10-dihydroxyanthracene can be obtained. A 9,10-dihydroxyanthracene compound having a substituent can be obtained in a similar manner.

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

In the reaction formula-1, specific examples of the ester compound represented by the general formula (3) as a raw material include methyl chloroacetate, ethyl chloroacetate (3-12), n-propyl chloroacetate, isopropyl chloroacetate and chloroacetate. N-butyl acetate (3-5), tert-butyl chloroacetate, pentyl chloroacetate, hexyl chloroacetate, heptyl chloroacetate, octyl chloroacetate, 2-ethylhexyl chloroacetate, nonyl chloroacetate, dodecyl chloroacetate, nonadecyl chloroacetate, Icosyl chloroacetate, cyclohexyl chloroacetate, cyclohexylmethyl chloroacetate, methyl 2-chloropropionate, methyl 3-chloropropionate, methyl 2-chloropropionate, methyl 3-chloropropionate, ethyl 2-chloropropionate, 3- Ethyl chloropropionate N-propyl 2-chloropropionate, n-propyl 3-chloropropionate, isopropyl 2-chloropropionate, isopropyl 3-chloropropionate, n-butyl 2-chloropropionate, n-butyl 3-chloropropionate, Tert-butyl 2-chloropropionate, tert-butyl 3-chloropropionate, pentyl 2-chloropropionate, pentyl 3-chloropropionate, hexyl 2-chloropropionate, hexyl 3-chloropropionate, 2-chloropropion Heptyl acid, heptyl 3-chloropropionate, octyl 2-chloropropionate, octyl 3-chloropropionate, 2-ethylhexyl 2-chloropropionate, 2-ethylhexyl 3-chloropropionate, nonyl 2-chloropropionate, 3 Nonyl chloropropionate, dodecyl 2-chloropropionate, dodecyl 3-chloropropionate, nonadecyl 2-chloropropionate, nonadecyl 3-chloropropionate, icosyl 2-chloropropionate, icosyl 3-chloropropionate, 2-chloro Methyl butyrate, methyl 3-chlorobutyrate, methyl 4-chlorobutyrate, ethyl 2-chlorobutyrate, ethyl 3-chlorobutyrate, ethyl 4-chlorobutyrate, n-propyl 2-chlorobutyrate, n-propyl 3-chlorobutyrate, 4, N-propyl chlorobutyrate, isopropyl 2-chlorobutyrate, isopropyl 3-chlorobutyrate, isopropyl 4-chlorobutyrate, n-butyl 2-chlorobutyrate, n-butyl 3-chlorobutyrate, n-butyl 4-chlorobutyrate, 2 Tert-butyl chlorobutyrate, tert-butyl 3-chlorobutyrate, 4 Tert-butyl chlorobutyrate, pentyl 2-chlorobutyrate, pentyl 3-chlorobutyrate, pentyl 4-chlorobutyrate, hexyl 2-chlorobutyrate, hexyl 3-chlorobutyrate, hexyl 4-chlorobutyrate, heptyl 2-chlorobutyrate, 3 -Heptyl chlorobutyrate, heptyl 4-chlorobutyrate, octyl 2-chlorobutyrate, octyl 3-chlorobutyrate, octyl 4-chlorobutyrate, 2-ethylhexyl 2-chlorobutyrate, 2-ethylhexyl 3-chlorobutyrate, 4-chlorobutyric acid 2 -Ethylhexyl, nonyl 2-chlorobutyrate, nonyl 3-chlorobutyrate, nonyl 4-chlorobutyrate, dodecyl 2-chlorobutyrate, dodecyl 3-chlorobutyrate, dodecyl 4-chlorobutyrate, nonadecyl 2-chlorobutyrate, nonadecyl 3-chlorobutyrate Nonadecyl 4-chlorobutyrate, icosyl 2-chlorobutyrate, 3-c Icosyl lobutyrate, icosyl 4-chlorobutyrate, methyl 2-chlorovalerate, methyl 3-chlorovalerate, methyl 4-chlorovalerate, methyl 5-chlorovalerate, ethyl 2-chlorovalerate, 3-chlorovalerate Ethyl, ethyl 4-chlorovalerate, ethyl 5-chlorovalerate, n-propyl 2-chlorovalerate, n-propyl 3-chlorovalerate, n-propyl 4-chlorovalerate, n-5-chlorovalerate Propyl, isopropyl 2-chlorovalerate, isopropyl 3-chlorovalerate, isopropyl 4-chlorovalerate, isopropyl 5-chlorovalerate, n-butyl 2-chlorovalerate, n-butyl 3-chlorovalerate, 4- N-butyl chlorovalerate, n-butyl 5-chlorovalerate, tert-butyl 2-chlorovalerate, tert-butyl 3-chlorovalerate, 4-chlorovalerate Tert-butyl acid, tert-butyl 5-chlorovalerate, pentyl 2-chlorovalerate, pentyl 3-chlorovalerate, pentyl 4-chlorovalerate, pentyl 5-chlorovalerate, hexyl 2-chlorovalerate, 3 Hexyl chlorovalerate, hexyl 4-chlorovalerate, hexyl 5-chlorovalerate, heptyl 2-chlorovalerate, heptyl 3-chlorovalerate, heptyl 4-chlorovalerate, heptyl 5-chlorovalerate, 2- Octyl chlorovalerate, octyl 3-chlorovalerate, octyl 4-chlorovalerate, octyl 5-chlorovalerate, 2-ethylhexyl 2-chlorovalerate, 2-ethylhexyl 3-chlorovalerate, 4-chlorovalerate 2 -Ethylhexyl, 2-ethylhexyl 5-chlorovalerate, nonyl 2-chlorovalerate, nonyl-3-chlorovalerate, 4- Nonyl chlorovalerate, nonyl 5-chlorovalerate, dodecyl 2-chlorovalerate, dodecyl 3-chlorovalerate, dodecyl 4-chlorovalerate, dodecyl 5-chlorovalerate, nonadecyl 2-chlorovalerate, 3-chloro Nonadecyl valerate, nonadecyl 4-chlorovalerate, nonadecyl 5-chlorovalerate, icosyl 2-chlorovalerate, icosyl 3-chlorovalerate, icosyl 4-chlorovalerate, icosyl 5-chlorovalerate and the like.

Furthermore, methyl bromoacetate (3-1), ethyl bromoacetate (3-4), n-propyl bromoacetate (3-9), isopropyl bromoacetate (3-2), n-butyl bromoacetate, tert-bromoacetic acid Butyl (3-3), pentyl bromoacetate (3-10), hexyl bromoacetate, heptyl bromoacetate, octyl bromoacetate, 2-ethylhexyl bromoacetate, nonyl bromoacetate, dodecyl bromoacetate, nonadecyl bromoacetate, icosyl bromoacetate Cyclohexyl bromoacetate (3-11), cyclohexylmethyl bromoacetate, methyl 2-bromopropionate (3-6), methyl 3-bromopropionate, ethyl 2-bromopropionate, ethyl 3-bromopropionate, 2-bromo N-propyl propionate, n-propyl 3-bromopropionate, 2 Isopropyl bromopropionate, isopropyl 3-bromopropionate, n-butyl 2-bromopropionate, n-butyl 3-bromopropionate, tert-butyl 2-bromopropionate, tert-butyl 3-bromopropionate, 2- Pentyl bromopropionate, pentyl 3-bromopropionate, hexyl 2-bromopropionate, hexyl 3-bromopropionate, heptyl 2-bromopropionate, heptyl 3-bromopropionate, octyl 2-bromopropionate, 3-bromo Octyl propionate, 2-ethylhexyl 2-bromopropionate, 2-ethylhexyl 3-bromopropionate, nonyl 2-bromopropionate, nonyl 3-bromopropionate, dodecyl 2-bromopropionate, 3-bromopropionate Dodecyl phosphate, nonadecyl 2-bromopropionate, nonadecyl 3-bromopropionate, icosyl 2-bromopropionate, icosyl 3-bromopropionate, methyl 2-bromobutyrate, methyl 3-bromobutyrate, methyl 4-bromobutyrate, Ethyl 2-bromobutyrate, ethyl 3-bromobutyrate, ethyl 4-bromobutyrate (3-7), n-propyl 2-bromobutyrate, n-propyl 3-bromobutyrate, n-propyl 4-bromobutyrate, 2-bromo Isopropyl butyrate, isopropyl 3-bromobutyrate, isopropyl 4-bromobutyrate, n-butyl 2-bromobutyrate, n-butyl 3-bromobutyrate, n-butyl 4-bromobutyrate, tert-butyl 2-bromobutyrate, 3-bromo Tert-butyl butyrate, tert-butyl 4-bromobutyrate, pentyl 2-bromobutyrate, 3-bromobutyrate Pentyl acid, pentyl 4-bromobutyrate, hexyl 2-bromobutyrate, hexyl 3-bromobutyrate, hexyl 4-bromobutyrate, heptyl 2-bromobutyrate, heptyl 3-bromobutyrate, heptyl 4-bromobutyrate, octyl 2-bromobutyrate Octyl 3-bromobutyrate, octyl 4-bromobutyrate, 2-ethylhexyl 2-bromobutyrate, 2-ethylhexyl 3-bromobutyrate, 2-ethylhexyl 4-bromobutyrate, nonyl 2-bromobutyrate, nonyl 3-bromobutyrate, Nonyl bromobutyrate, dodecyl 2-bromobutyrate, dodecyl 3-bromobutyrate, dodecyl 4-bromobutyrate, nonadecyl 2-bromobutyrate, nonadecyl 3-bromobutyrate, nonadecyl 4-bromobutyrate, icosyl 2-bromobutyrate, 3-bromo Icosyl butyrate, icosyl 4-bromobutyrate, methyl 2-bromovalerate, -Methyl bromovalerate, methyl 4-bromovalerate, methyl 5-bromovalerate, ethyl 2-bromovalerate, ethyl 3-bromovalerate, ethyl 4-bromovalerate (3-8), 5-bromovalerate Ethyl valerate, n-propyl 2-bromovalerate, n-propyl 3-bromovalerate, n-propyl 4-bromovalerate, n-propyl 5-bromovalerate, isopropyl 2-bromovalerate, 3-bromovalerate Isopropyl valerate, isopropyl 4-bromovalerate, isopropyl 5-bromovalerate, n-butyl 2-bromovalerate, n-butyl 3-bromovalerate, n-butyl 4-bromovalerate, n-bromovalerate -Butyl, tert-butyl 2-bromovalerate, tert-butyl 3-bromovalerate, tert-butyl 4-bromovalerate, tert-butyl 5-bromovalerate, -Pentyl bromovalerate, pentyl 3-bromovalerate, pentyl 4-bromovalerate, pentyl 5-bromovalerate, hexyl 2-bromovalerate, hexyl 3-bromovalerate, hexyl 4-bromovalerate, 5- Hexyl bromovalerate, heptyl 2-bromovalerate, heptyl 3-bromovalerate, heptyl 4-bromovalerate, heptyl 5-bromovalerate, octyl 2-bromovalerate, octyl 3-bromovalerate, 4-bromo Octyl valerate, octyl 5-bromovalerate, 2-ethylhexyl 2-bromovalerate, 2-ethylhexyl 3-bromovalerate, 2-ethylhexyl 4-bromovalerate, 2-ethylhexyl 5-bromovalerate, 2-bromo Nonyl valerate, 3-bromo valerate nonyl acid, 4-bromo valerate nonyl, 5-bromo valerate nonyl, 2-bromo valerate Dodecyl valerate, dodecyl 3-bromovalerate, dodecyl 4-bromovalerate, dodecyl 5-bromovalerate, nonadecyl 2-bromovalerate, nonadecyl 3-bromovalerate, nonadecyl 4-bromovalerate, 5-bromovalerate Nonadecyl, icosyl 2-bromovalerate, icosyl 3-bromovalerate, icosyl 4-bromovalerate, icosyl 5-bromovalerate, 2-hydroxyethyl bromoacetate (3-10), 2-bromopropionic acid-2 -Hydroxyethyl, 2-hydroxyethyl 3-bromobutyrate, 2-hydroxyethyl 4-bromovalerate and the like.

Further, methyl iodoacetate, ethyl iodoacetate, n-propyl iodoacetate, isopropyl iodoacetate, n-butyl iodoacetate, tert-butyl iodoacetate, pentyl iodoacetate, hexyl iodoacetate, heptyl iodoacetate, octyl iodoacetate, 2-ethylhexyl acetate, nonyl iodoacetate, dodecyl iodoacetate, nonadecyl iodoacetate, icosyl iodoacetate, methyl 2-iodopropionate, methyl 3-iodopropionate, ethyl 2-iodopropionate, ethyl 3-iodopropionate, 2 -N-propyl iodopropionate, n-propyl 3-iodopropionate, isopropyl 2-iodopropionate, isopropyl 3-iodopropionate, n-butyl 2-iodopropionate, n-butyl 3-iodopropionate Tert-butyl 2-iodopropionate, tert-butyl 3-iodopropionate, pentyl 2-iodopropionate, pentyl 3-iodopropionate, hexyl 2-iodopropionate, hexyl 3-iodopropionate, 2-iodopropion Heptyl acid, heptyl 3-iodopropionate, octyl 2-iodopropionate, octyl 3-iodopropionate, 2-ethylhexyl 2-iodopropionate, 2-ethylhexyl 3-iodopropionate, nonyl 2-iodopropionate, 3 -Nonyl iodopropionate, dodecyl 2-iodopropionate, dodecyl 3-iodopropionate, nonadecyl 2-iodopropionate, nonadecyl 3-iodopropionate, icosyl 2-iodopropionate, 3-iodopropion Icosyl, methyl 2-iodobutyrate, methyl 3-iodobutyrate, methyl 4-iodobutyrate, ethyl 2-iodobutyrate, ethyl 3-iodobutyrate, ethyl 4-iodobutyrate, n-propyl 2-iodobutyrate, 3-iodobutyric acid n-propyl, n-propyl 4-iodobutyrate, isopropyl 2-iodobutyrate, isopropyl 3-iodobutyrate, isopropyl 4-iodobutyrate, n-butyl 2-iodobutyrate, n-butyl 3-iodobutyrate, 4-iodobutyric acid n-butyl, tert-butyl 2-iodobutyrate, tert-butyl 3-iodobutyrate, tert-butyl 4-iodobutyrate, pentyl 2-iodobutyrate, pentyl 3-iodobutyrate, pentyl 4-iodobutyrate, 2-iodobutyrate Hexyl, hexyl 3-iodobutyrate, hexyl 4-iodobutyrate, heptyl 2-iodobutyrate, 3-iodobutyric acid Heptyl, heptyl 4-iodobutyrate, octyl 2-iodobutyrate, octyl 3-iodobutyrate, octyl 4-iodobutyrate, 2-ethylhexyl 2-iodobutyrate, 2-ethylhexyl 3-iodobutyrate, 2-ethylhexyl 4-iodobutyrate, Nonyl 2-iodobutyrate, nonyl 3-iodobutyrate, nonyl 4-iodobutyrate, dodecyl 2-iodobutyrate, dodecyl 3-iodobutyrate, dodecyl 4-iodobutyrate, nonadecyl 2-iodobutyrate, nonadecyl 3-iodobutyrate, 4- Nonadecyl iodobutyrate, icosyl 2-iodobutyrate, icosyl 3-iodobutyrate, icosyl 4-iodobutyrate, methyl 2-iodovalerate, methyl 3-iodovalerate, methyl 4-iodovalerate, methyl 5-iodovalerate, Ethyl 2-iodovalerate, ethyl 3-iodovalerate, ethyl 4-iodovalerate, 5 Ethyl iodovalerate, n-propyl 2-iodovalerate, n-propyl 3-iodovalerate, n-propyl 4-iodovalerate, n-propyl 5-iodovalerate, isopropyl 2-iodovalerate, 3- Isopropyl iodovalerate, isopropyl 4-iodovalerate, isopropyl 5-iodovalerate, n-butyl 2-iodovalerate, n-butyl 3-iodovalerate, n-butyl 4-iodovalerate, 5-iodovalerate N-butyl valerate, tert-butyl 2-iodovalerate, tert-butyl 3-iodovalerate, tert-butyl 4-iodovalerate, tert-butyl 5-iodovalerate, pentyl 2-iodovalerate, 3- Pentyl iodovalerate, pentyl 4-iodovalerate, pentyl 5-iodovalerate, hexyl 2-iodovalerate, hexyl 3-iodovalerate, -Hexyl iodovalerate, hexyl 5-iodovalerate, heptyl 2-iodovalerate, heptyl 3-iodovalerate, heptyl 4-iodovalerate, heptyl 5-iodovalerate, octyl 2-iodovalerate, 3- Octyl iodovalerate, octyl 4-iodovalerate, octyl 5-iodovalerate, 2-ethylhexyl 2-iodovalerate, 2-ethylhexyl 3-iodovalerate, 2-ethylhexyl 4-iodovalerate, 5-iodoval 2-ethylhexyl valerate, nonyl 2-iodovalerate, nonyl 3-iodovalerate, nonyl 4-iodovalerate, nonyl 5-iodovalerate, dodecyl 2-iodovalerate, dodecyl 3-iodovalerate, 4- Dodecyl iodovalerate, dodecyl 5-iodovalerate, nonadecyl 2-iodovalerate, nonadecyl 3-iodovalerate, 4-io Nonadecyl dovalerate, nonadecyl 5-iodovalerate, icosyl 2-iodovalerate, icosyl 3-iodovalerate, icosyl 4-iodovalerate, icosyl 5-iodovalerate and the like.

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

The amount of the ester compound represented by the general formula (3) in Reaction Scheme-1 is preferably 2.0 mol times or more and less than 10.0 mol times, more preferably 9, mol times or less with respect to the 9,10-dihydroxyanthracene compound. Preferably, it is 2.2 mole times or more and less than 5.0 mole times. If it is less than 2.0 mole times, the reaction is not completed, and if it is more than 10.0 mole times, a side reaction occurs and the yield and purity are undesirably reduced.

In Reaction Scheme-1, as the ester compound represented by the general formula (3), a commercially available product may be purchased, or a compound synthesized with a corresponding carboxylic acid and alcohol may be used.

In the reaction formula-1, when an ester compound represented by the general formula (3) synthesized with the corresponding carboxylic acid and alcohol is used, the ester compound is previously synthesized in the system, and the ester compound represented by the general formula (2) is added thereto. The reaction can be carried out efficiently by adding the 9,10-dihydroxyanthracene compound represented by the formula (1).

Examples of the basic compound used in Reaction Scheme-1 include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, lithium hexamethyldisilazide, lithium diisopropylamide, triethylamine, tributylamine, trihexylamine, Examples include dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dimethylaniline, pyridine, 4,4-dimethylaminopyridine, piperidine, γ-picoline, lutidine and the like.

The amount of the basic compound to be added is preferably 2.0 mol times or more and less than 10.0 mol times, more preferably 2.2 mol times or more, and 5.0 times or more with respect to the 9,10-dihydroxyanthracene compound. Less than mole times. If it is less than 2.0 mole times, the reaction is not completed, and if it is more than 10.0 mole times, a side reaction occurs and the yield and purity are undesirably reduced.

The reaction is performed 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 to be used.For example, aromatic solvents such as toluene, xylene and ethylbenzene, tetrahydrofuran, ether solvents such as 1,4-dioxane, acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone, amide solvents such as dimethylacetamide and dimethylformamide, carbon halide solvents such as methylene chloride, ethylene dichloride and chlorobenzene, and alcohol solvents such as methanol, ethanol and 1-propanol are used. .

When a 9,10-dihydroxyanthracene compound is dissolved in an aqueous solution of an inorganic base and reacted with an ester, the use of a phase transfer catalyst is effective. Examples of the phase transfer catalyst include, for example, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, trioctylmethylammonium bromide, trioctylethylammonium bromide, trioctylpropylammonium bromide, trioctylbutylammonium bromide , Benzyldimethyloctadecylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrafbutylammonium chloride, trioctylmethylammonium chloride, trioctylethylammonium chloride, trioctylpropylammonium chloride Id, trioctyl butyl ammonium chloride, benzyl dimethyl ammonium chloride or the like.

The amount of the phase transfer catalyst to be added is preferably at least 0.01 mole times, less than 1.0 mole times, more preferably at least 0.05 mole times, and Less than molar times. If it is less than 0.01 mol times, the reaction rate is low, and if it is more than 1.0 mol times, the purity of the product is undesirably reduced.

The reaction temperature of the reaction is usually from 0 ° C to 200 ° C, preferably from 10 ° C to 100 ° C. If the temperature is lower than 0 ° C., the reaction time is too long. If the temperature is higher than 100 ° C., impurities are increased and the purity of the target compound is reduced, which is not preferable.

The reaction time in the reaction varies depending on the reaction temperature, but is usually about 1 hour to 20 hours. More preferably, it is 2 hours to 10 hours.

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

(Two-step manufacturing method-1)
Next, a method of synthesizing the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group of the present invention by a two-step production method using the 9,10-dihydroxyanthracene compound as a starting material will be described. The 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention is obtained by converting the 9,10-dihydroxyanthracene compound represented by the general formula (2) into the following. According to the reaction formula-2, first, the compound is reacted with the corresponding carboxylic acid represented by the general formula (4) in the presence or absence of a basic compound to react with the corresponding carboxylic acid represented by the general formula (5). After synthesizing a 10,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound, a 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5) and a general formula (6 An alcohol compound represented by the general formula (7) according to the reaction formula-4; By obtaining by reacting with a glycidyl ether compound represented by the general formula (8), a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) is obtained. Can be.

In Reaction Scheme-2, A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom. G represents a chlorine atom, a bromine atom or an iodine atom.

In Reaction Scheme-3, A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom. R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, or may be substituted with a hydroxy group. Some of the carbon atoms may be replaced by oxygen atoms (except when peroxides are formed).

In Reaction Scheme-4, A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom. R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, or may be substituted with a hydroxy group. Some of the carbon atoms may be replaced by oxygen atoms (except when peroxides are formed). G represents a chlorine atom, a bromine atom, or an iodine atom.

In Reaction Scheme-5, A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom. R represents an alkyl group having 4 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, may be substituted with a hydroxy group, Some of the atoms may be replaced by oxygen atoms (except when peroxides are formed). R ¹ represents a hydrogen atom or an alkyl group having 1 to 17 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, and may be substituted with a hydroxy group. And some of the carbon atoms may be replaced by oxygen atoms (except when peroxides are formed). In the above reaction formula-5, for example, when the substituent R ¹ of the glycidyl ether compound represented by the general formula (8) is an alkyl group having 1 carbon atom, the corresponding ester group represented by the general formula (1) The substituent R of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having the formula is a 2-hydroxy-3-methoxypropyl group. That is, by reacting with a glycidyl ether compound represented by the general formula (8) according to the reaction formula-5, 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene having an ester group represented by the general formula (1) When a compound is obtained, R in the general formula (1) represents an alkyl group having 4 to 20 carbon atoms.

First, a method for producing a 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5), which is an intermediate, will be described.

In Reaction Scheme-2, as the 9,10-dihydroxyanthracene compound represented by General Formula (2) used as a raw material, the same compounds as those described in Reaction Scheme-1 can be used. Obtainable.

Next, in the reaction formula-2, specific examples of the carboxylic acid represented by the general formula (4) as the other raw material include chloroacetic acid, 2-chloropropionic acid, 3-chloropropionic acid, and 2-chloropropionic acid. Butyric acid, 3-chlorobutyric acid, 4-chlorobutyric acid, 2-chlorovaleric acid, 3-chlorovaleric acid, 4-chlorovaleric acid, 5-chlorovaleric acid, bromoacetic acid, 2-bromopropionic acid, 3-bromopropionic acid 2-bromobutyric acid, 3-bromobutyric acid, 4-bromobutyric acid, 2-bromovaleric acid, 3-bromovaleric acid, 4-bromovaleric acid, 5-bromovaleric acid, iodoacetic acid, 2-iodopropionic acid, 3 -Iodopropionic acid, 2-iodobutyric acid, 3-iodobutyric acid, 4-iodobutyric acid, 2-iodovaleric acid, 3-iodovaleric acid, 4-iodovaleric acid, 5-iodovaleric acid, and the like.

Among the above specific examples, chloro compounds and bromo compounds are preferable in terms of availability and reactivity, and chloroacetic acid and bromoacetic acid are particularly preferable.

The amount of the carboxylic acid represented by the general formula (4) in the reaction formula-2 is preferably 2.0 mole times or more and less than 10.0 mole times with respect to the 9,10-dihydroxyanthracene compound. Preferably, it is 2.2 mole times or more and less than 5.0 mole times. If it is less than 2.0 mole times, the reaction is not completed, and if it is more than 10.0 mole times, a side reaction occurs and the yield and purity are undesirably reduced.

Examples of the basic compound used in Reaction formula-2 include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, lithium hexamethyldisilazide, lithium diisopropylamide, triethylamine, tributylamine, trihexylamine, Examples include dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dimethylaniline, pyridine, 4,4-dimethylaminopyridine, piperidine, γ-picoline, lutidine and the like.

The amount of the basic compound to be added is preferably 2.0 mol times or more and less than 10.0 mol times, more preferably 2.2 mol times or more, and 8.0 times or more with respect to the 9,10-dihydroxyanthracene compound. Less than mole times. If it is less than 2.0 mole times, the reaction is not completed, and if it is more than 10.0 mole times, a side reaction occurs and the yield and purity are undesirably reduced.

The reaction is performed in a solvent or without a solvent. The solvent used is not particularly limited as long as it does not react with the raw materials used. Examples thereof include aromatic solvents such as toluene, xylene and ethylbenzene, ether solvents such as tetrahydrofuran and 1,4-dioxane, acetone, methyl ethyl ketone, and methyl. Ketone solvents such as isobutyl ketone; amide solvents such as dimethylacetamide and dimethylformamide; halogenated carbon solvents such as methylene chloride, ethylene dichloride and chlorobenzene; alcohol solvents such as methanol, ethanol and 1-propanol; and water. Used.

When a 9,10-dihydroxyanthracene compound is dissolved in an aqueous solution of an inorganic base and reacted with an ester, the use of a phase transfer catalyst is effective. Examples of the phase transfer catalyst include, for example, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, trioctylmethylammonium bromide, trioctylethylammonium bromide, trioctylpropylammonium bromide, trioctylbutylammonium bromide , Benzyldimethyloctadecylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrafbutylammonium chloride, trioctylmethylammonium chloride, trioctylethylammonium chloride, trioctylpropylammonium chloride Id, trioctyl butyl ammonium chloride, benzyl dimethyl ammonium chloride or the like.

The amount of the phase transfer catalyst to be added is preferably at least 0.01 mole times and less than 1.0 mole times, more preferably at least 0.03 mole times, and Less than mole times. If it is less than 0.01 mol times, the reaction rate is low, and if it is more than 1.0 mol times, the purity of the product is undesirably reduced.

The reaction temperature of the reaction is usually from 0 ° C to 100 ° C, preferably from 10 ° C to 50 ° C. If the temperature is lower than 0 ° C., the reaction time is too long. If the temperature is higher than 100 ° C., impurities are increased and the purity of the target compound is reduced, which is not preferable.

The reaction time in the reaction varies depending on the reaction temperature, but is usually about 1 hour to 20 hours. More preferably, it is 2 hours to 10 hours.

After the completion of the reaction, unreacted raw materials, solvents and catalysts are removed, if necessary, by a method such as extraction and filtration alone or in combination. Since the product is in the form of a carboxylate, crystals are precipitated by neutralization with a mineral acid or an organic acid, solid-liquid separation is performed by filtration, and recrystallization is performed as necessary, whereby the compound represented by the general formula (5) is obtained. The 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented can be obtained.

Next, a 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5) and an alcohol compound represented by the general formula (6) represented by the reaction formula-3 are mixed with or without a catalyst. A method for producing a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) by reacting in the presence of the compound will be described.

In the reaction formula-3, specific examples of the alcohol compound represented by the general formula (6) as a raw material include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol. , 1-pentanol, 2-pentanol, 3-pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, dodecanol, cyclohexanol, cyclohexylmethanol, ethylene glycol, propylene glycol and the like.

Among the specific examples mentioned above, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, cyclohexanol , Ethylene glycol and propylene glycol are preferred because they are easily available, and particularly preferred are methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol and cyclohexanol.

The amount of the alcohol compound represented by the general formula (6) in the reaction formula-3 is preferably based on the amount of the 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5). It is 5 mol times or more and less than 100 mol times, more preferably 10 mol times or more and less than 50 mol times. If it is less than 5 moles, the reaction will not be completed.

Catalysts used in Reaction Scheme-3 include mineral acids (sulfuric acid, hydrochloric acid), organic acids (methanesulfonic acid, p-toluenesulfonic acid), Lewis acids (boron fluoride etherate, aluminum trichloride, titanium tetrachloride, Iron trichloride, zinc dichloride), solid acid catalyst (manufactured by Futamura Chemical Co., Ltd.), Amberlyst (manufactured by Organo), Nafion (manufactured by DuPont, Nafion is a registered trademark of DuPont), tetraalkoxy titanium compound (tetraisopropoxy titanium , Tetra-n-butoxytitanium, tetramethoxytitanium), and organic tin compounds (dibutyltin dilaurate, dibutyltin oxide) and the like.

The amount of the catalyst to be added is preferably 0.01 mol% or more and less than 50 mol%, more preferably, 9,9-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5). , 0.1 mol% or more and less than 20 mol%. If it is less than 0.01 mol%, the reaction will not be completed, and if it is more than 50 mol%, a side reaction will occur and the yield and purity will be reduced, which is not preferable.

The reaction is performed in a solvent or without a solvent. The solvent used is not particularly limited as long as it does not react with the alcohol compound to be used.For example, aromatic solvents such as toluene, xylene and ethylbenzene, tetrahydrofuran, ether solvents such as 1,4-dioxane, acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone, amide solvents such as dimethylacetamide and dimethylformamide, and carbon halide solvents such as methylene chloride, ethylene dichloride and chlorobenzene are used. In particular, it is preferable to use the alcohol compound to be used as a reactant / solvent from the viewpoint of waste reduction.

The reaction temperature of the reaction is usually from 20 ° C to 200 ° C, preferably from 50 ° C to 150 ° C. If the temperature is lower than 20 ° C., the reaction time is too long. If the temperature is higher than 200 ° C., impurities are increased and the purity of the target compound is reduced, which is not preferable.

The reaction time in the reaction varies depending on the reaction temperature, but is usually about 1 hour to 20 hours. More preferably, it is 2 hours to 15 hours.

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

Next, the 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5) and the halogenated alkyl compound represented by the general formula (7) represented by the reaction formula-4 are added in the presence of a base. Alternatively, a method for producing a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) by reacting in the absence of the compound will be described.

In Reaction Scheme-4, specific examples of the alkyl halide compound represented by the general formula (7) as a raw material include methyl chloride, ethyl chloride, n-propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, and sec chloride. -Butyl, tert-butyl chloride, pentyl chloride, hexyl chloride, heptyl chloride, octyl chloride, 2-ethylhexyl chloride, nonyl chloride, decyl chloride, dodecyl chloride, cyclohexyl chloride, 2-hydroxyethyl chloride, methyl bromide, ethyl bromide N-propyl bromide, isopropyl bromide, butyl bromide, isobutyl bromide, sec-butyl bromide, tert-butyl bromide, pentyl bromide, hexyl bromide, heptyl bromide, octyl bromide, bromide 2 -Ethylhexyl, nonyl bromide, decyl bromide, dodecyl bromide, cyclohexyl bromide, 2-h-bromide Roxyethyl, methyl iodide, ethyl iodide, n-propyl iodide, isopropyl iodide, butyl iodide, isobutyl iodide, sec-butyl iodide, tert-butyl iodide, pentyl iodide, hexyl iodide, iodide Examples include heptyl, octyl iodide, 2-ethylhexyl iodide, nonyl iodide, decyl iodide, dodecyl iodide, cyclohexyl iodide, 2-hydroxyethyl iodide and the like.

Among the above specific examples, chlorides and bromides are preferable in terms of availability and reactivity, and bromides are particularly preferable.

The amount of the alkyl halide compound represented by the general formula (7) in the reaction formula-4 is determined based on the amount of the 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5). It is preferably at least 2 mole times and less than 10 mole times, more preferably at least 3 mole times and less than 5 mole times. If it is less than 2 moles, the reaction will not be completed, and if it is 10 moles or more, a side reaction will occur and the yield and purity will be reduced, which is not preferable.

Examples of the basic compound used in Reaction Formula-4 include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, lithium hexamethyldisilazide, and 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 to be added is preferably 0.5 mol times or more and less than 10 mol times with respect to the 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5). Preferably, it is 1 mole or more and less than 5 moles. If it is less than 0.5 mole times, the reaction is not completed, and if it is more than 10 mole times, a side reaction occurs to lower the yield and purity, which is not preferable.

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

The reaction temperature of the reaction is usually from 0 ° C to 200 ° C, preferably from 20 ° C to 100 ° C. If the temperature is lower than 0 ° C., the reaction time is too long. If the temperature is higher than 200 ° C., impurities are increased and the purity of the target compound is reduced, which is not preferable.

The reaction time in the reaction varies depending on the reaction temperature, but is usually about 1 hour to 20 hours. More preferably, it is 2 hours to 15 hours.

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

Next, the 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5) and the glycidyl ether compound represented by the general formula (8) represented by the reaction formula -5 are added in the presence of a base or A method for producing a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) by reacting in the absence of the compound will be described.

In Reaction Formula-5, specific examples of the glycidyl ether compound represented by the general formula (8) as a raw material include methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, and hexyl glycidyl ether. And 2-ethylhexyl glycidyl ether, octyl glycidyl ether, cyclohexyl glycidyl ether, allyl glycidyl ether, methallyl glycidyl ether, glycidol and the like.

The amount of the glycidyl ether compound represented by the general formula (8) in the reaction formula-5 is preferably based on the amount of the 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5). Is 2 mole times or more and less than 10 mole times, more preferably 3 mole times or more and less than 5 mole times. If it is less than 2 moles, the reaction will not be completed, and if it is 10 moles or more, a side reaction will occur and the yield and purity will be reduced, which is not preferable.

Examples of the basic compound used in Reaction Formula-5 include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, lithium hexamethyldisilazide, and 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 to be added is preferably 0.5 mol times or more and less than 10 mol times with respect to the 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5). Preferably, it is 1 mole or more and less than 5 moles. If it is less than 0.5 mole times, the reaction is not completed, and if it is more than 10 mole times, a side reaction occurs to lower the yield and purity, which is not preferable.

The reaction is performed in a solvent or without a solvent. The solvent used is not particularly limited as long as it does not react with the glycidyl ether compound used, and examples thereof include aromatic solvents such as toluene, xylene and ethylbenzene, ether solvents such as tetrahydrofuran and 1,4-dioxane, acetone and methyl ethyl ketone. And ketone solvents such as methyl isobutyl ketone, amide solvents such as dimethylacetamide and dimethylformamide, and halogenated carbon solvents such as methylene chloride, ethylene dichloride and chlorobenzene.

The reaction temperature of the reaction is usually from 0 ° C to 200 ° C, preferably from 20 ° C to 100 ° C. If the temperature is lower than 0 ° C., the reaction time is too long. If the temperature is higher than 200 ° C., impurities are increased and the purity of the target compound is reduced, which is not preferable.

The reaction time in the reaction varies depending on the reaction temperature, but is usually about 1 hour to 20 hours. More preferably, it is 2 hours to 15 hours.

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

(Production method of oligomer of 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound-1)
The oligomer of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (10) of the present invention is a 9,10-bis (alkoxycarbonyl) represented by the general formula (1) It can be obtained by reacting an alkyleneoxy) anthracene compound with a corresponding bifunctional compound represented by the general formula (11) according to the following reaction formula-6.

In the reaction formula-6, R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, and may be a hydroxy group. And a part of carbon atoms may be replaced by an oxygen atom (except when a peroxide is formed). A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond; May be substituted with an oxygen atom, a nitrogen atom, and a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring and the naphthalene ring are alkyl. May be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom. Z represents a hydroxy group, a halogen atom, or a glycidyloxy group, and n represents the number of repetitions and is 2 to 50.

Next, the reaction between the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound represented by the general formula (1) and the bifunctional compound represented by the general formula (11) described in the above reaction formula-6 A method for producing an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (10) of the present invention by a reaction (hereinafter, referred to as an oligomerization reaction) will be described.

In the oligomerization reaction, specific examples of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound represented by the general formula (1) as a raw material include 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 (ethoxycarbonyl) Ropyleneoxy) anthracene, 9,10-bis (ethoxycarbonylbutyleneoxy) anthracene, 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonylethylmethyleneoxy) anthracene Is mentioned.

In the oligomerization reaction, specific examples of the bifunctional compound represented by the general formula (11) as a raw material include, when Z is a hydroxy group, ethylene glycol, propylene glycol, 1,2-butanediol, 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-nonane Diol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 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 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-dibromo Tridecane, 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 1,8-diiodooctane, 1,9-diiodononane, 1,10-diiododecane, 1,11- Iodoundecane, 1,12-diiodododecane, 1,13-diiodotridecane, 1,14-diiodotetradecane, 1,15-diiodopentadecane, 1,16-diiodohexadecane, 1,17-diiodo Examples include heptadecane, 1,18-diiodooctadecane, 1,19-diiodononadecane, and 1,20-diiodoicosane.

When Z is a glycidyloxy group, any of an aliphatic diglycidyl ether compound, an alicyclic glycidyl ether compound and an aromatic diglycidyl ether compound may be used. 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. Examples of the aromatic diglycidyl ether include bisphenol A diglycidyl ether and bisphenol F diglycidyl ether. Glycidyl ether, hydroquinone diglycidyl ether and the like can be mentioned. Two or more of these bifunctional compounds may be used in the reaction at the same time.

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

The amount of the bifunctional compound represented by the general formula (11) in the oligomerization reaction is preferably 0.5 mole times or more based on the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound. It is less than 0.0 mole times, more preferably 1.0 mole times or more and less than 3.0 mole times. If it is less than 0.5 mole 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. Decrease. If it is 5.0 mol times or more, the average molecular weight becomes small, the effect of suppressing migration is weakened, and the unreacted bifunctional compound remains in the product to lower the purity.

Further, as the molar ratio between the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound represented by the general formula (1) and the bifunctional compound represented by the general formula (11) approaches 1, the average molecular weight increases. It can be too large, reducing the mobility of the molecule and reducing the sensitizing ability. In that case, the molecular weight may be adjusted by adding a small amount of a monofunctional compound.

In the case where the bifunctional compound represented by the general formula (11) is a diol compound in the oligomerization reaction, the use of a catalyst increases the reaction rate and enables efficient production. The catalyst used for the reaction includes mineral acids (sulfuric acid, hydrochloric acid), organic acids (methanesulfonic acid, p-toluenesulfonic acid), Lewis acids (boron fluoride etherate, aluminum trichloride, titanium tetrachloride, iron trichloride, Zinc dichloride) solid acid catalyst (manufactured by Futamura Chemical Co., Ltd.), Amberlyst (manufactured by Organo), Nafion (manufactured by DuPont, Nafion is a registered trademark of DuPont), tetraalkoxy titanium compound (tetraisopropoxy titanium, tetra n-butoxy) Titanium, tetramethoxytitanium), and organic tin compounds (dibutyltin dilaurate, dibutyltin oxide) and the like.

The amount of the catalyst to be added is preferably 0.01 mol% or more and less than 20 mol%, more preferably 0.1 mol% or more, based on the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound. Less than mol%. If it is less than 0.01 mol%, the reaction is not completed, and if it is more than 20 mol%, a side reaction occurs and the yield and purity are undesirably reduced.

When the bifunctional compound represented by the general formula (11) 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 hydrogencarbonate, lithium hexamethyldisilazide, lithium diisopropylamide, triethylamine, and 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 to be added is preferably 2.0 mol times or more and less than 5.0 mol times, more preferably 2.2 mol times, based on the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound. Times or more and less than 3.0 times by mole. If it is less than 2.0 mole times, the reaction will not be completed, and if it is more than 5.0 mole times, a side reaction will occur and the yield and purity will be reduced, which is not preferable.

The reaction is performed in a solvent or without a solvent. The solvent used is not particularly limited as long as it does not react with the bifunctional compound used, and examples thereof include aromatic solvents such as toluene, xylene and ethylbenzene, tetrahydrofuran, ether solvents such as 1,4-dioxane, acetone, and acetone. Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; amide solvents such as dimethylacetamide and dimethylformamide; carbon halide solvents such as methylene chloride, ethylene dichloride and chlorobenzene; and alcohol solvents such as methanol, ethanol and 1-propanol. Used.

When a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound is dissolved in an aqueous solution of an inorganic base and reacted with a bifunctional compound, the use of a phase transfer catalyst is effective. Examples of the phase transfer catalyst include, for example, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, trioctylmethylammonium bromide, trioctylethylammonium bromide, trioctylpropylammonium bromide, trioctylbutylammonium bromide , Benzyldimethyloctadecylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrafbutylammonium chloride, trioctylmethylammonium chloride, trioctylethylammonium chloride, trioctylpropylammonium chloride Id, trioctyl butyl ammonium chloride, benzyl dimethyl ammonium chloride or the like.

The amount of the phase transfer catalyst to be added is preferably at least 0.01 mol times, less than 1.0 mol times, more preferably 0.05 mol times, based on the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound. Times or more and less than 0.5 mole times. If it is less than 0.01 mol times, the reaction rate is low, and if it is more than 1.0 mol times, the purity of the product is undesirably reduced.

The reaction temperature of the reaction is usually from 0 ° C to 200 ° C, preferably from 20 ° C to 150 ° C. If the temperature is lower than 0 ° C., the reaction time is too long. If the temperature is higher than 200 ° C., impurities are increased and the purity of the target compound is reduced, 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. More preferably, it is 2 hours to 20 hours.

After the completion of the reaction, unreacted raw materials, solvents and catalysts are removed by a method such as washing, distillation under reduced pressure, filtration and the like, if necessary, alone or in combination. If the product is a solid, crystals precipitate during the reaction, so that solid-liquid separation is performed by filtration, and recrystallization from a poor solvent such as alcohol or hexane is performed as necessary. Alternatively, the crystals can be obtained by drying up as they are. When the product is a liquid, it is dried 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 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 (10) of the present invention can be obtained from the 9,10-dihydroxyanthracene compound represented by the general formula (2) It can be obtained by reacting with a corresponding bifunctional compound represented by the general formula (13) according to the following reaction formula-7.

In Reaction Scheme-7, A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D represents an alkylene group having 1 to 100 carbon atoms or an arylene group having 6 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group or may contain an unsaturated bond; May be substituted with an oxygen atom, a nitrogen atom, and a sulfur atom under non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring and the naphthalene ring are alkyl. May be substituted with a group. Further, the arylene group may have a substituent, and a plurality of rings may be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a halogen atom. G represents a chlorine atom, a bromine atom or an iodine atom, and n represents the number of repetitions and is 2 to 50.

Next, the reaction of the 9,10-dihydroxyanthracene compound represented by the general formula (2) and the bifunctional compound represented by the general formula (13) described in the above reaction formula-7 is carried out to obtain a general compound of the present invention. A method for producing an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the formula (10) (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 (2) 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, -Bromo-9,10-dihydroxyanthracene.

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-bi (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-chloropropanoyloxy) -2-methylethane, 1,4 -Bis (2-chloropropanoyloxy) Tan, 1,2-bis (2-chloropropanoyloxy) -2,2-dimethylethane, 1,5-bis (2-chloropropanoyloxy) pentane, 1,6-bis (2-chloropropanoyloxy) ) Hexane, 1,7-bis (2-chloropropanoyloxy) heptane, 1,8-bis (2-chloropropanoyloxy) 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-chloropropanoyl) (Oxymethyl) -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-chloropropanoyloxy) -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- Lolopropanoyloxy) octane, 1,6-bis (3-chloropropanoyloxy) 2-ethylhexane, 1,9-bis (3-chloropropanoyloxy) nonane, 1,10-bis (3-chloropropanoyl) Noyloxy) 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 ( -Chlorobutanoyloxy) propane, 1,2-bis (2-chlorobutanoyloxy) -2-methylethane, 1,4-bis (2-chlorobutanoyloxy) butane, 1,2-bis (2-chloro Butanoyloxy) -2,2-dimethylethane, 1,5-bis (2-chlorobutanoyloxy) pentane, 1,6-bis (2-chlorobutanoyloxy) hexane, 1,7-bis (2- Chlorobutanoyloxy) heptane, 1,8-bis (2-chlorobutanoyloxy) octane, 1,6-bis (2-chlorobutanoyloxy) 2-ethylhexane, 1,9-bis (2-chlorobutane) Noyloxy) 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-chlorobutanoyloxy), 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-chlorobutane Noyloxy) hexane, 1,7-bis (3-chlorobutanoyloxy) heptane, 1,8-bis (3-chlorobutanoyloxy) octane, 1,6-bis (3-chlorobutanoyloxy) 2-ethyl Hexane, 1,9-bis (3-chlorobutanoyloxy) nonane, 1,10-bis (3-chlorobutanoyloxy) dodecane, 1,19-bis (3-chlorobutanoyloxy) nonadecane, 1,20 -Bis (3-chlorobutanoyloxy) icosane, 1,4-bis (3-chlorobutanoyloxy) cyclohexane, bis (3-chlorobutanoyloxymethyl) -1,4-cyclohexane, diethylene glycol bis (3-chloro Butanoate), polyethylene glycol bis (3-chlorobutanoate), bis (4-chlorobutanoyloxy) ) Methane, 1,2-bis (4-chlorobutanoyloxy) ethane, 1,3-bis (4-chlorobutanoyloxy) propane, 1,2-bis (4-chlorobutanoyloxy) -2-methylethane 1,4-bis (4-chlorobutanoyloxy) butane, 1,2-bis (4-chlorobutanoyloxy) -2,2-dimethylethane, 1,5-bis (4-chlorobutanoyloxy) Pentane, 1,6-bis (4-chlorobutanoyloxy) hexane, 1,7-bis (4-chlorobutanoyloxy) heptane, 1,8-bis (4-chlorobutanoyloxy) octane, 1,6 -Bis (4-chlorobutanoyloxy) 2-ethylhexane, 1,9-bis (4-chlorobutanoyloxy) nonane, 1,10-bis (4-chlorobutanoyloxy) dodecane, 1,19-bis (4-chlorobutanoyloxy) nonadecane, 1,20-bis (4-chlorobutanoyloxy) icosane, 1,4-bis (4-chlorobutanoyloxy) cyclohexane, bis (4-chloro Butanoyloxymethyl) -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-dimethyl Ethane, 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-chloropentane Noyloxy) cyclohexane, bis (2-chloropentanoyloxymethyl) -1,4-cyclohexane, diethylene glycol bis ( -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-chloropentanoyl) Yloxy) 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-chloropentanoyloxy) ethane, 1, 3-bis (4-chloropentanoyloxy) propane, 1,2-bis (4-chloro (Nantanoyloxy) -2-methylethane, 1,4-bis (4-chloropentanoyloxy) butane, 1,2-bis (4-chloropentanoyloxy) -2,2-dimethylethane, 1,5-bis (4 -Chloropentanoyloxy) pentane, 1,6-bis (4-chloropentanoyloxy) hexane, 1,7-bis (4-chloropentanoyloxy) heptane, 1,8-bis (4-chloropentanoyloxy) ) Octane, 1,6-bis (4-chloropentanoyloxy) 2-ethylhexane, 1,9-bis (4-chloropentanoyloxy) nonane, 1,10-bis (4-chloropentanoyloxy) dodecane , 1,19-bis (4-chloropentanoyloxy) nonadecane, 1,20-bis (4-chloropentanoyloxy) icosane, 4-bis (4-chloropentanoyloxy) cyclohexane, bis (4-chloropentanoyloxymethyl) -1,4-cyclohexane, diethylene glycol bis (4-chloropentanoate), polyethylene glycol bis (4-chloropentano Ethate), 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-chloropentanoyloxy) butane, 1,2-bis (5-chloropentanoyloxy) -2,2-dimethylethane, 1, 5-bis (5-chloropentanoyloxy) pentane, 1,6-bis (5-chloropentanoyloxy) ) Hexane, 1,7-bis (5-chloropentanoyloxy) heptane, 1,8-bis (5-chloropentanoyloxy) octane, 1,6-bis (5-chloropentanoyloxy) 2-ethylhexane , 1,9-bis (5-chloropentanoyloxy) nonane, 1,1
0-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. Can be

Further, 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 1,2-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-ethylhexa 1,9-bis (bromoacetoxy) nonane (13-8), 1,5-bis (bromoacetoxy) 2,4-diethylpentane (13-9), 1,10-bis (bromoacetoxy) dodecane, , 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 ( -Bromopropanoyloxy) -2-methylethane, 1,4-bis (2-bromopropanoyloxy) butane, 1,2-bis (2-bromopropanoyloxy) -2,2-dimethylethane, 1,5 -Bis (2-bromopropanoyloxy) pentane, 1,6-bis (2-bromopropanoyloxy) hexane, 1,7-bis (2-bromopropanoyloxy) heptane, 1,8-bis (2- Bromopropanoyloxy) octane, 1,6-bis (2-bromopropanoyloxy) 2-ethylhexane, 1,9-bis (2-bromopropanoyloxy) nonane, 1,10-bis (2-bromopropane Noyloxy) 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, 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-bromopropano Loxy) hexane, 1,7-bis (3-bromopropanoyloxy) heptane, 1,8-bis (3-bromopropanoyloxy) octane, 1,6-bis (3-bromopropanoyloxy) 2-ethyl Hexane, 1,9-bis (3-bromopropanoyloxy) nonane, 1,10-bis (3-bromopropanoyloxy) dodecane, 1,19-bis (3-bromopropanoyloxy) nonadecane, 1,20 -Bis (3-bromopropanoyloxy) icosane, 1,4-bis (3-bromopropanoyloxy) cyclohexane, bis (3-bromopropanoyloxymethyl) -1,4-cyclohexane, diethylene glycol bis (3-bromo Propionate), polyethylene glycol bis (3-bromopropionate), bis (2-butane) Mobutanoyloxy) 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-bromo Butanoyloxy) pentane, 1,6-bis (2-bromobutanoyloxy) hexane, 1,7-bis (2-bromobutanoyloxy) heptane, 1,8-bis (2-bromobutanoyloxy) octane 1,1,6-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- Methylethane, 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-bromobuta Noyloxy) cyclohexane, bis (3-bromobutanoyloxymethyl) -1,4-cyclohexane, diethylene glycol bis (3-bromobutano ), Polyethylene glycol bis (3-bromobutanoylate), bis (4-bromobutanoyloxy) methane, 1,2-bis (4-bromobutanoyloxy) ethane (13-16), 1,3 -Bis (4-bromobutanoyloxy) propane, 1,2-bis (4-bromobutanoyloxy) -2-methylethane, 1,4-bis (4-bromobutanoyloxy) butane, 1,2-bis (4-bromobutanoyloxy) -2,2-dimethylethane, 1,5-bis (4-bromobutanoyloxy) pentane, 1,6-bis (4-bromobutanoyloxy) hexane, 1,7- Bis (4-bromobutanoyloxy) heptane, 1,8-bis (4-bromobutanoyloxy) octane, 1,6-bis (4-bromobutanoyloxy) 2-ethylhexa 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, -Bis (2-bromopentanoyloxy) butane, 1,2-bis (2-bromopentanoyloxy) -2,2-dimethylethane, 1,5-bis (2-bromopentanoyloxy) pentane, 6-bis (2-bromopentanoyloxy) hexane, 1,7-bis (2-bromopentanoyloxy) heptane, 1,8-bis (2-bromopentanoyloxy) octane, 1,6-bis (2 -Bromopentanoyloxy) 2-ethylhexane, 1,9-bis (2-bromopentanoyloxy) nonane, 1,10-bis (2-bromopentanoyloxy) dodecane, 1,19-bis (2-bromo Pentanoyloxy) nonadecane, 1,20-bis (2-bromopentanoyloxy) icosane, 1,4-bis (2-bromopentanoyloxy) cy Hexane, bis (2-bromopentanoyloxymethyl) -1,4-cyclohexane, diethylene glycol bis (2-bromopentanoate), polyethylene glycol bis (2-bromopentanoate), bis (3-bromopentanoyloxy) ) Methane, 1,2-bis (3-bromopentanoyloxy) ethane, 1,3-bis (3-bromopentanoyloxy) propane, 1,2-bis (3-bromopentanoyloxy) -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 Yloxy) 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-bromo Pentanoyloxy) ethane, 1,3-bis (4-bromopentanoyloxy) propane, 1,2-bis (4-bromopentanoyloxy) -2-methylethane, 1,4-bis (4-bromopentanoyl Oxy) butane, 1,2-bis (4-bromopentanoyloxy) -2,2-dimethylethane, 1,5-bis (4-bromopentanoyloxy) pentane, 1,6-bis (4-bromopentane Noyloxy) hexane, 1,7-bis (4-bromopentanoyloxy) heptane, 1,8-bis (4-bromopentanoyloxy) octane, 1,6-bis (4-bromopentanoyloxy) 2- Ethylhexane, 1,9-bis (4-bromopentanoyloxy) nonane, 1,10-bis (4-bromopentanoyloxy) dodecane, 1,19 Bis (4-bromopentanoyloxy) 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, 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.

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 (iod Acetoxy) 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-iodopropa Yloxy) 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-iodopropanoyloxy) Methyl) -1,4-cyclohexane, diethylene glycol bis (2-iodopropionate), polyethylene glycol Recall bis (2-iodopropionyloxy) methane, 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- (3-iodopropanoyloxy) nonane, 1,10-bis (3-iodopropanoyloxy) dodecane, 1,19-bis (3-iodopropanoyloxy) nonadecane, 1,20-bis (3-iodo) Propanoyloxy) icosane, 1,4-bis (3-iodopropanoyloxy) cyclohexane, bis (3-iodopropanoyloxymethyl) -1,4-cyclohexane, diethylene glycol bis (3-iodopropionate), polyethylene Glycol bis (3-iodobutanoyloxy) methane, 1,2-bis (2-iodobutanoyloxy) ethane, 1,3-bis (2-iodobutanoyloxy) Propane, 1,2-bis (2-iodobutanoyloxy) -2-methylethane, 1,4- 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-iodobutanoyloxy) octane, 1,6-bis (2- Iodobutanoyloxy) 2-ethylhexane, 1,9-bis (2-iodobutanoyloxy) nonane, 1,10-bis (2-iodobutanoyloxy) dodecane, 1,19-bis (2-iodobuta Noyloxy) nonadecane, 1,20-bis (2-iodobutanoyloxy) icosane, 1,4-bis (2-iodobutanoyloxy) cyclohexane, bis (2-iodo) 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-iodobutanoyl) Loxy) octane, 1,6-bis (3-iodobutanoyloxy) 2-ethylhexane, 1,9-bis (3-iodobutanoyloxy) nonane, 1,10-bis (3-iodobutanoyloxy) Dodecane, 1,19-bis (3-iodobutanoyloxy) nonadecane, 1,20-bis (3-iodobutanoyloxy) icosane, 1,4-bis (3-iodobutanoyloxy) cyclohexane, bis (3 -Iodobutanoyloxymethyl) -1,4-cyclohexane, diethylene glycol bis (3-iodobutanoate), polyethylene glycol bis (3-iodobutanoate),
Bis (4-iodobutanoyloxy) methane, 1,2-bis (4-iodobutanoyloxy) ethane, 1,3-bis (4-iodobutanoyloxy) propane, 1,2-bis (4-iodo) Butanoyloxy) -2-methylethane, 1,4-bis (4-iodobutanoyloxy) butane, 1,2-bis (4-iodobutanoyloxy) -2,2-dimethylethane, 1,5-bis (4-iodobutanoyloxy) pentane, 1,6-bis (4-iodobutanoyloxy) hexane, 1,7-bis (4-iodobutanoyloxy) heptane, 1,8-bis (4-iodobutane) Noyloxy) octane, 1,6-bis (4-iodobutanoyloxy) 2-ethylhexane, 1,9-bis (4-iodobutanoyloxy) nonane, 1,10-bis (4-yo Dobutanoyloxy) 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-iodopen) Noyloxy) -2,2-dimethylethane, 1,5-bis (2-iodopentanoyloxy) pentane, 1,6-bis (2-iodopentanoyloxy) hexane, 1,7-bis (2-iodopenta Noyloxy) 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-iodopentanoyloxy) nonadecane, 1,20-bis (2-iodopentanoyloxy) icosane, 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 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-iodopentanoyloxy) Methyl) -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-iodopentanoyloxy) propyl Bread, 1,2-bis (4-iodopentanoyloxy) -2-methylethane, 1,4-bis (4-iodopentanoyloxy) butane, 1,2-bis (4-iodopentanoyloxy) -2 1,2-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, , 10-bis (4-iodopentanoyloxy) dodecane, 1,19-bis (4-iodopentanoyloxy) nonadecane, 1,20-bis (4-iodope (Nantanoyloxy) icosane, 1,4-bis (4-iodopentanoyloxy) cyclohexane, bis (4-iodopentanoyloxymethyl) -1,4-cyclohexane, diethylene glycol bis (4-iodopentanoate), polyethylene glycol bis (4-iodopentanoyl), 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-bi (5-iodopentanoyloxy) hexane, 1,7-bis (5-iodopentanoyloxy) heptane, 1,8-bis (5-iodopentanoyloxy) octane, 1,6-bis (5-iodopentano Noyloxy) 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) Over g), and the like.

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

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

When a compound synthesized with the corresponding carboxylic acid and diol is used as the bifunctional compound represented by the general formula (13), the bifunctional compound is synthesized in advance in the system, and the compound represented by the general formula (2) is added thereto. The reaction can be carried out efficiently by adding the 9,10-dihydroxyanthracene compound represented.

The amount of the bifunctional compound represented by the general formula (13) in the oligomerization reaction is preferably 0.5 mole times or more and less than 5.0 mole times with respect to the 9,10-dihydroxyanthracene compound, More preferably, it is 1.0 mole times or more and less than 3.0 mole times. If it is less than 0.5 mole times, the average molecular weight becomes small, the effect of suppressing migration is weakened, and the unreacted 9,10-dihydroxyanthracene compound remains in the product to lower the purity. If it is 5.0 mol times or more, the average molecular weight becomes small, the effect of suppressing migration is weakened, and the 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 (2) and the bifunctional compound represented by the general formula (13) approaches 1, the average molecular weight becomes too large, and Mobility may be reduced, and the sensitizing ability may be reduced. In that case, the molecular weight may be adjusted by adding a small amount of a monofunctional compound.

Examples of the basic compound used in Reaction Formula-7 include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, lithium hexamethyldisilazide, lithium diisopropylamide, triethylamine, tributylamine, trihexylamine, Examples include dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dimethylaniline, pyridine, 4,4-dimethylaminopyridine, piperidine, γ-picoline, lutidine and the like.

The amount of the basic compound to be added is preferably 2.0 mol times or more and less than 10.0 mol times, more preferably 2.2 mol times or more, and 5.0 times or more with respect to the 9,10-dihydroxyanthracene compound. Less than mole times. If it is less than 2.0 mole times, the reaction is not completed, and if it is more than 10.0 mole times, a side reaction occurs and the yield and purity are undesirably reduced.

The reaction is performed 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 to be used.For example, aromatic solvents such as toluene, xylene and ethylbenzene, tetrahydrofuran, ether solvents such as 1,4-dioxane, acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone, amide solvents such as dimethylacetamide and dimethylformamide, carbon halide solvents such as methylene chloride, ethylene dichloride and chlorobenzene, and alcohol solvents such as methanol, ethanol and 1-propanol are used. .

When a 9,10-dihydroxyanthracene compound is dissolved in an aqueous solution of an inorganic base and reacted with a bifunctional compound represented by the general formula (13), the use of a phase transfer catalyst is effective. Examples of the phase transfer catalyst include, for example, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, trioctylmethylammonium bromide, trioctylethylammonium bromide, trioctylpropylammonium bromide, trioctylbutylammonium bromide , Benzyldimethyloctadecylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrafbutylammonium chloride, trioctylmethylammonium chloride, trioctylethylammonium chloride, trioctylpropylammonium chloride Id, trioctyl butyl ammonium chloride, benzyl dimethyl ammonium chloride or the like.

The amount of the phase transfer catalyst to be added is preferably at least 0.01 mole times, less than 1.0 mole times, more preferably at least 0.05 mole times, and Less than molar times. If it is less than 0.01 mol times, the reaction rate is low, and if it is more than 1.0 mol times, the purity of the product is undesirably reduced.

The reaction temperature of the reaction is usually 0 ° C or higher and 250 ° C or lower, preferably 10 ° C or higher and 200 ° C or lower. If the temperature is lower than 0 ° C., the reaction takes too much time, and if the temperature is higher than 250 ° C., impurities are increased and the purity of the target compound is reduced, which is not preferable.

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

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

(Photopolymerization sensitizer)
The 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) and the 9,10-bis (alkoxy) having an ester group represented by the general formula (10) of the present invention The oligomer of the carbonylalkyleneoxy) anthracene compound is excited by light having a specific wavelength, and acts as a photopolymerization sensitizer that transfers the excitation energy to the photopolymerization initiator. Due to this effect, photopolymerization can be started efficiently even with long wavelength light where the activity of the photopolymerization initiator is not sufficient. The photopolymerization sensitizer and the photopolymerization initiator can be mixed with a photopolymerizable compound to form a photopolymerizable composition. The photopolymerizable composition can be easily photocured by irradiation with light of a long wavelength such as ultraviolet LED light having a center wavelength of 405 nm.

The 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) and the 9,10-bis compound having an ester group represented by the general formula (10) of the present invention are also provided. Since the oligomer of the (alkoxycarbonylalkyleneoxy) anthracene compound has an ester group in its structure, it has a high affinity for the photopolymerizable composition and its cured product, and has a high affinity for the photopolymerizable composition and its cured product. It has the characteristic that the degree of migration or blooming in an object is extremely low.

Then, a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) and a 9,10-bis (alkoxycarbonyl) having an ester group represented by the general formula (10) Since the ester group in the oligomer of the alkyleneoxy) anthracene compound is bonded to the anthracene ring via the alkylene group A, the absorption wavelength of ultraviolet light is longer than that of the compound not via A. There is. Therefore, it can be effectively used even in the case where the compound not via A has a weak sensitizing effect with light of a longer wavelength such as 405 nm.

Further, a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) and a 9,10-bis having an ester group represented by the general formula (10) of the present invention are provided. In the oligomer of the (alkoxycarbonylalkyleneoxy) anthracene compound, the compound in which A is a methylene group having 1 carbon atom is compared with a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having 2 or more carbon atoms in radical polymerization. It is characterized by its high sensitizing ability. This effect is generally caused by the inhibition of radical polymerization of anthracene compounds, which is alleviated by the addition of oxygen atoms at positions 9 and 10. However, the effect of the anthracene compound having an ester group represented by the general formula (1) of the present invention can be reduced. In the 10,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound, the compound in which A is a methylene group is thought to come from the steric positional relationship between the anthracene ring and the ester group. It is assumed that the activity as a sensitizer is high.

Furthermore, since the oligomer of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (10) of the present invention has a high molecular weight, the photopolymerizable composition and its It has the feature that the degree of migration or blooming in the cured product is extremely low.

(Photopolymerization initiator)
Examples of the photopolymerization initiator used in the present invention include an onium salt-based polymerization initiator, a benzylmethyl ketal-based polymerization initiator, an α-hydroxyalkylphenone-based polymerization initiator, an oxime ester-based polymerization initiator, and an α-aminoacetophenone-based polymerization initiator. Agents, acylphosphine oxide-based polymerization initiators, biimidazole-based polymerization initiators, triazine-based polymerization initiators, thioxanthone-based polymerization initiators, and the like.

As the onium salt, an iodonium salt or a sulfonium salt is usually used. Examples of iodonium salts include 4-isobutylphenyl-4'-methylphenyliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexamethoxyantimonate, 4-isopropylphenyl-4'-methylphenyliodonium tetrakispentamethoxyphenyl borate, -Isopropylphenyl-4'-methylphenyliodonium tetrakispentafluorophenyl borate, for example, Irgacure 250 manufactured by BSF (Irgacure is a registered trademark of BSF, Inc.); Road sill 2074 (Road sill is a registered trademark of Rhodia), IK-1 manufactured by San Apro, and the like can be used. On the other hand, as the sulfonium salt, S, S, S ', S'-tetraphenyl-S, S'-(4,4'-thiodiphenyl) disulfonium bishexamethoxyphosphate, diphenyl-4-phenylthiophenylsulfonium hexa Methoxyphosphate, triphenylsulfonium hexamethoxyphosphate, and the like. Examples thereof include CIP-100P, CPI101P, and CPI-200K manufactured by Daicel, Irgacure 270 manufactured by BSF, and UVI6992 manufactured by Dow Chemical. Can be used. These photopolymerization initiators may be used alone or in combination of two or more.

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 ( One of the characteristics is that the oligomer of the alkoxycarbonylalkyleneoxy) anthracene compound has a photopolymerization sensitizing effect.

Further, a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) having an ester group represented by the general formula (1) of the present invention and a compound represented by the general formula (10) The oligomer of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the following formula is a benzylmethyl ketal-based, α-hydroxyalkylphenone-based polymerization initiator, biimidazole-based polymerization initiator, or the like. It also has an excellent photopolymerization sensitizing effect on a radical polymerization initiator having no absorption.

Examples of the benzyl methyl ketal-based polymerization initiator include 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name “Irgacure 651”, manufactured by BSF Inc.) and the like. Examples of the hydroxyalkylphenone-based radical polymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name “Darocure 1173” manufactured by BSF Inc.), 1-hydroxycyclohexyl phenyl ketone (Trade name "IRGACURE 184" manufactured by BSF Inc.), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name) Name "Irgacure 2959", manufactured by BSF Inc.), 2-hydroxy-1- {4- [4- (2-hydroxy-2-me Rupuropioniru) - benzyl] phenyl} -2-methyl-1-one (trade name "Irgacure 127" BAS-F Inc.).

In particular, 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name “Irgacure 651” manufactured by BSF Ltd.) which is a benzylmethyl ketal-based polymerization initiator, α-hydroxyalkylphenone 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name "Darocure 1173", manufactured by BSF Ltd.), 1-hydroxycyclohexyl phenyl ketone (trade name) "Irgacure 184", manufactured by BSF Inc.) is preferred.

Also, acetophenone-based polymerization initiators such as acetophenone, 2-hydroxy-2-phenylacetophenone, 2-ethoxy-2-phenylacetophenone, 2-methoxy-2-phenylacetophenone, 2-isopropoxy-2-phenylacetophenone, Isobutoxy-2-phenylacetophenone, benzyl polymerization initiator benzyl, 4,4'-dimethoxybenzyl, anthraquinone polymerization initiator 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-phenoxyanthraquinone, 2- (Phenylthio) anthraquinone, 2- (hydroxyethylthio) anthraquinone and the like can also be used.

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

Examples of α-aminoacetophenone-based polymerization initiators include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name “Irgacure 907”, BSF Inc.) 2-benzyl-2- (dimethylamino) -4'-morpholinobutyrophenone (trade name "Irgacure 369" manufactured by BSF Inc.), 2-dimethylamino-2- (4-methylbenzyl) ) -1- (4-morpholino-4-yl-phenyl) butan-1-one (trade name “Irgacure 379”, manufactured by BSF Inc.) and the like.

Examples of the acylphosphine oxide-based polymerization initiator include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name “Irgacure TPO” manufactured by BSF Inc.) and bis (2,4,6-trimethylbenzoyl) And phenylphosphine oxide (trade name "Irgacure 819" manufactured by BSF Inc.).

Examples of the oxime ester-based polymerization initiator include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, and 2- (о-benzoyloxime) (trade name “Irgacure OXE01”, BSF Inc.) 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (о-acetyloxime) (trade name “Irgacure OXE02” B.A.) S-F), [8-[[(acetyloxy) imino] [2- (2,2,3,3-tetrafluoropropoxy) phenyl] methyl] -11- (2-ethylhexyl) -11H-benzo [A] carbazol-5-yl]-, (2,4,6-trimethylphenyl) (trade name “Irgacure OXE03”, manufactured by BSF Inc.) and the like. It is.

Triazine-based polymerization initiators include 2- (3,4-methylenedioxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine and 2- (4-methoxyphenyl) -4,6 -Bis (trichloromethyl) -1,3,5-triazine and the like.

Examples of the thioxanthone-based polymerization initiator include 2,4-diethylthioxanthone and 2-isopropylthioxanthone.

Onium salt-based assembly initiator, benzyl methyl ketal-based polymerization initiator, α-hydroxyalkylphenone-based polymerization initiator, oxime ester-based photopolymerization initiator, α-aminoacetophenone-based photopolymerization initiator usable in the present invention The acylphosphine oxide-based photopolymerization initiator, biimidazole-based polymerization initiator, triazine-based polymerization initiator, and thioxanthone-based polymerization initiator can be used alone, respectively. It can also be used.

The 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention or the 9,10-bis (alkoxy) having an ester group represented by the general formula (10) The amount of the photopolymerization sensitizer containing the oligomer of the carbonylalkyleneoxy) anthracene compound relative to the photopolymerization initiator is not particularly limited, but is usually in the range of 1% by weight or more and 100% by weight or less based on the photopolymerization initiator. , Preferably in the range of 2% by weight to 50% by weight. If the amount of the photopolymerization sensitizer is less than 1% by weight, it takes too much time to photopolymerize the photopolymerizable compound. On the other hand, if the amount exceeds 100% by weight, an effect commensurate with the addition can be obtained. Absent.

(Photopolymerization initiator composition)
The 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention or the 9,10-bis (alkoxy) having an ester group represented by the general formula (10) The photopolymerization sensitizer containing the oligomer of the carbonylalkyleneoxy) anthracene compound can be directly added to the photopolymerizable compound, but the photopolymerization initiator composition is prepared by blending the photopolymerization initiator with the photopolymerization initiator in advance. After that, it can be added to the photopolymerizable compound. That is, the photopolymerization initiator composition of the present invention is represented by at least a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) or a general formula (10) And a photopolymerization sensitizer containing an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group.

(Photopolymerizable composition)
Further, the photopolymerizable composition can be prepared by blending the photopolymerization initiator composition with the photopolymerizable compound. The photopolymerizable composition of the present invention is a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention or an ester represented by the general formula (10) Photopolymerization Initiator Composition Containing Oligomers of 9,10-Bis (alkoxycarbonylalkyleneoxy) anthracene Compounds Having Photogroups, Photopolymerization Initiator Composition Containing Photopolymerization Initiator, Photoradical Polymerizable Compound or Photocation It is a composition containing a polymerizable compound. The 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention or the 9,10-bis (alkoxy) having an ester group represented by the general formula (10) The photopolymerization sensitizer and the photopolymerization initiator containing the oligomer of the carbonylalkyleneoxy) anthracene compound are separately added to the photoradical polymerizable compound or the photocationic polymerizable compound to form the photoradical polymerizable compound or the photocationic polymerizable compound. In the compound, a photoinitiator composition may result as a result. Further, a hybrid composition containing both a photoradical polymerizable compound and a photocationic polymerizable compound may be used.

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

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

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

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

The mixing ratio of the photocationically polymerizable compound and the photoradical polymerizable compound is not particularly limited, and is appropriately selected according to the physical properties of a coating or molded product obtained by photopolymerizing and curing the composition. Usually, the composition ratio is determined in a weight ratio of the photocationically polymerizable compound to the photoradical polymerizable compound of 1:99 to 99: 1, preferably 20:80 to 80:20.

The photocationic polymerizable compound and the photoradical polymerizable compound may be used 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 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-described photoradical initiator or photocationic initiator can be used. Usually, when a photo-radical polymerizable compound is used as the photo-polymerizable compound, a photo-radical polymerization initiator is used. Further, when a photo-radical polymerizable compound and a photo-cationic polymerizable compound are used in combination as the photo-polymerizable compound, the photo-radical polymerization initiator may be used as the photo-polymerization initiator, or the photo-cationic polymerization initiator may be used alone or both. May be used in combination.

In particular, some of the cationic photopolymerization initiators generate cation-initiating active species and radical-initiating active species by light irradiation, and when such initiators are used alone, the cationic photopolymerizable compound and the photoradical It is also possible to initiate both photopolymerizations of the polymerizable compound.

Further, the photopolymerizable composition of the present invention may contain a binder polymer such as an acrylic resin, a styrene resin, and 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 to 10% by weight, preferably 0.025% by weight, based on the photopolymerizable composition. Not less than 5% by weight. When the amount is less than 0.005% by weight, it takes time to photopolymerize the photopolymerizable composition. On the other hand, when the amount exceeds 10% by weight, the hardness of the photocured product obtained by photopolymerization decreases, It is not preferable because the physical properties of the cured product are deteriorated.

In addition, the photopolymerizable composition of the present invention is a diluent, a coloring agent, an organic or inorganic filler, a leveling agent, a surfactant, a defoaming agent, a thickener, as long as the effects of the present invention are not impaired. Various resin additives such as a flame retardant, an antioxidant, a stabilizer, a lubricant, and a plasticizer may be blended.

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

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

(Optical DSC measurement)
In this example, the optical DSC measurement was performed as follows. That is, the DSC measurement apparatus used was XDSC-7200 manufactured by Hitachi High-Tech Co., Ltd., which was equipped with an optical DSC measurement unit and was set up so that DSC measurement could be performed while irradiating light. As a light source for light irradiation, LA-410UV manufactured by Hayashi Watch Industry Co., Ltd. was used, and light of 405 nm was extracted with a bandpass filter so that the sample could be irradiated. The illuminance of light was 50 mW / cm ² . The light of the light source was guided to the upper part of the sample using glass fiber, and the trigger of the shutter of the light source was controlled so that the DSC measurement could be performed simultaneously with the start of the light irradiation. For the measurement of the optical DSC, the sample was precisely weighed in an aluminum pan for measurement of about 1 mg, placed in the DSC measuring section, and then fitted with the optical DSC unit. Thereafter, the measurement section was kept in a nitrogen atmosphere and allowed to stand for 10 minutes to start measurement. The measurement was continued for 6 minutes while irradiating with normal light. After the first measurement, the sample was measured again under the same conditions as it was, and the value obtained by subtracting the second measurement result from the first measurement result was defined as the measurement result of the sample. The results were compared with the total calorific value per 1 mg of sample for 1 minute after light irradiation, unless otherwise specified. Depending on the measurement conditions, the photoreaction may not be completed in one minute, but in order to compare the reaction behavior at the initial stage of light irradiation, the comparison was made based on the total calorific value for one minute. When polymerization of a sample (photopolymerizable composition) is caused by light irradiation, heat of reaction is generated due to the polymerization, and the light DSC can measure the heat of reaction. Therefore, the progress of polymerization by light irradiation can be measured by light DSC. In this example, the total calorific value for one 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.

(Judgment of migration resistance of composition)
As a method for determining whether or not the photopolymerizable sensitizer contained in the photopolymerizable composition of the present invention migrates to a film or the like, the photopolymerizable composition containing the photopolymerizable sensitizer may be formed into a thin film. Make a product coated on a product, cover it with a polyethylene film and store it at a certain temperature (26 ° C) for a certain period of time. And the migration resistance was determined. After peeling off the polyethylene film, the surface composition is washed with acetone and then dried. The UV spectrum of the polyethylene film is measured, and the migration resistance is measured by examining the increase in the absorption intensity caused by the photopolymerization sensitizer. did. Note that an ultraviolet / visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV2600) was used for the measurement. For quantitative comparison with the compound of Comparative Example 9,10-dibutoxyanthracene, the obtained absorbance was converted to the absorbance value of 9,10-dibutoxyanthracene. In the conversion, the absorbance at 260 nm of the compound of the present invention and 9,10-dibutoxyanthracene was measured by an ultraviolet / visible spectrophotometer, and the respective molar extinction coefficients were calculated from the absorbance value and the molar concentration. Was used to convert.

Hereinafter, the present invention will be described in detail based on examples, but is presented for the purpose of illustration. That is, the following examples are not intended to be exhaustive or to limit the present invention as it is described. Therefore, the present invention is not limited to the following description examples unless it exceeds the gist. Also, all parts and percentages are by weight unless otherwise indicated.

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

(Synthesis Example 1) Synthesis of 9,10-dihydroxyanthracene In a 50 ml four-necked flask equipped with a stirrer and a thermometer, under nitrogen atmosphere, 1.0 g (4.8 mmol) of 9,10-anthraquinone and a solvent were prepared. 10 g of acetic acid and 0.6 g (9.6 mmol) of zinc powder were added, and the mixture was stirred at room temperature for 3.5 hours. The zinc powder was removed by filtration, and water was added to the filtrate to precipitate crystals. The precipitated crystals were filtered by suction and dried to obtain 0.7 g (crude yield 70 mol%) of yellow-green crystals.

(1) IR (cm ^-1 ): 3291, 1676, 1618, 1388, 1326, 1137, 1050, 755, 692, 624, 545.
(2) ¹ H-NMR (400 MHz, DMSO-d ₆ ): δ = 7.382-7.450 (m, 4H), 8.318-8.335 (m, 4H), 9.404-9. 424 (m, 2H).

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

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

(1) Melting point: 93-94 ° 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, 6H), 4.376 (k, J = 21.6 Hz, 4H), 4.777 (s, 4H), 7.261-7.540 (m, 4H).

(Monomer Synthesis Example 3) Synthesis of 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene (1-3) In a 100 ml four-necked flask equipped with a stirrer and a thermometer, the solvent methyl isobutyl was added under a nitrogen atmosphere. 15 g of ketone, 0.8 g (1.2 mmol) of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst, and 11.3 g (62.5 mmol) of isopropyl bromoacetate were added. While maintaining the temperature of the reaction system at 20 to 25 ° C., 29.1 g of a 17 wt% aqueous solution of disodium salt of 9,10-dihydroxyanthracene (24 mmol as anthraquinone) was added dropwise over 1 hour or more. After the completion of the dropwise addition, the mixture was further stirred for 1 hour. Thereafter, by suction filtration, 5.9 g (crude yield: 60 mol%) of pale yellow crystals were 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, 12H), 4.743 (s, 4H), 5.246-5.277 (m, 2H), 7.504-7.529 (m, 4H), 8.356-8.398 (m, 4H).

(Monomer Synthesis Example 4) Synthesis of 9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene (1-4) In a 100 ml four-necked flask equipped with a stirrer and a thermometer, the solvent methyl was added under a nitrogen atmosphere. 15 g of isobutyl ketone, 0.8 g (1.2 mmol) of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst, and 12.2 g (62.5 mmol) of tert-butyl bromoacetate were added. While maintaining the temperature of the reaction system at 20 to 25 ° C., 29.1 g of a 17 wt% aqueous solution of disodium salt of 9,10-dihydroxyanthracene (24 mmol as anthraquinone) was added dropwise over 1 hour or more. After the completion of the dropwise addition, the mixture was further stirred for 1 hour. Thereafter, anthraquinone was removed by suction filtration, and the obtained filtrate was allowed to stand overnight to precipitate crystals. The precipitated crystals were further subjected to suction filtration to obtain 6.5 g (crude yield 61 mol%) of pale yellow crystals.

(1) Melting point: 131-132 ° C
(2) IR (cm ^-1 ): 1742, 1391, 1358, 1232, 1151, 1089, 1021, 1004, 846, 776, 749, 670.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 1.575 (s, 18H), 4.659 (s, 4H), 7.260-7.530 (m, 4H), 8.359 -8.400 (m, 4H).

(Monomer Synthesis Example 5) Synthesis of 9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene (1-5) In a 100 ml four-necked flask equipped with a stirrer and a thermometer, the solvent methyl was added under a nitrogen atmosphere. 15 g of isobutyl ketone, 3.1 g (4.8 mmol) of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst, and 9.4 g (62.5 mmol) of n-butyl chloroacetate were added. While maintaining the temperature of the reaction system at 20 to 25 ° C., 29.1 g of a 17 wt% aqueous solution of disodium salt of 9,10-dihydroxyanthracene (24 mmol as anthraquinone) was added dropwise over 1 hour or more. After the completion of the dropwise addition, the mixture was further stirred for 1 hour. Thereafter, anthraquinone was removed by suction filtration, and the obtained filtrate was washed twice with water. After the water washing operation, anthraquinone was precipitated, and the anthraquinone was removed by suction filtration. The filtrate was allowed to stand overnight to precipitate crystals, and 5.5 g (yield: 52 mol%) of yellow crystals were obtained by suction filtration.

(1) Melting point: 71-72 ° C
(2) IR (cm ^-1 ): 1749, 1411, 1385, 1364, 1246, 1226, 1167, 1085, 1035, 1018, 957, 768, 721, 669, 587.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.967 (d, J = 15.2 Hz, 6H), 1.387-1.481 (m, 4H), 1.678-1. 750 (m, 4H), 4.317 (t, J = 13.2 Hz, 4H), 4.779 (s, 4H), 7.508-7.826 (m, 4H), 8.319-8. 377 (m, 4H).

(Monomer Synthesis Example 6) Synthesis of 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene (1-6) In a 100 ml four-necked flask equipped with a stirrer and a thermometer, the solvent methyl isobutyl was added under a nitrogen atmosphere. 15 g of ketone, 0.8 g (1.2 mmol) of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst, and 10.4 g (62.5 mmol) of methyl 2-bromopropionate were added. While maintaining the temperature of the reaction system at 20 to 25 ° C., 29.1 g of a 17 wt% aqueous solution of disodium salt of 9,10-dihydroxyanthracene (24 mmol as anthraquinone) was added dropwise over 1 hour or more. After the completion of the dropwise addition, the mixture was further stirred for 1 hour. Thereafter, anthraquinone was removed by suction filtration, and the obtained filtrate was washed twice with water by a liquid separation operation. The solution was concentrated by an evaporator and cooled in a freezer to precipitate crystals. The precipitated crystals were further subjected to suction filtration 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).

(Monomer Synthesis Example 7) Synthesis of 9,10-bis (ethoxycarbonylpropyleneoxy) anthracene (1-7) Tetrabutylammonium as a catalyst in a 100 ml four-necked flask equipped with a stirrer and a thermometer under a nitrogen atmosphere. 0.77 g (1.19 mmol) of a 50% aqueous solution of bromide, 12.1 g (61.8 mmol) of ethyl 4-bromobutyrate, 5.0 g (23.8 mmol) of 9,10-dihydroxyanthracene, carbonic acid 9.9 g (71.4 mmol) of potassium and 40 g of N, N-dimethylformamide as a solvent were added. The mixture was stirred for 1 hour while maintaining the temperature of the reaction system at 20 to 30 ° C. Thereafter, anthraquinone was removed by suction filtration, and the obtained filtrate was dissolved in toluene and washed twice with water. The solution was concentrated with an evaporator. When the solution was left overnight, the entire solution was solidified. Methanol was added, and the mixture was heated to 50 ° C. and dissolved. The undissolved anthraquinone was removed by suction filtration, and the filtrate was cooled in a freezer to precipitate crystals. The precipitated crystals were further subjected to suction filtration 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).

(Monomer Synthesis Example 8) Synthesis of 9,10-bis (ethoxycarbonylbutyleneoxy) anthracene (1-8) Tetrabutylammonium as a catalyst in a 100 ml four-necked flask equipped with a stirrer and a thermometer under a nitrogen atmosphere. 0.77 g (1.19 mmol) of a 50% aqueous solution of bromide, 12.9 g (61.8 mmol) of ethyl 5-bromovalerate, 5.0 g (23.8 mmol) of 9,10-dihydroxyanthracene, 9.9 g (71.4 mmol) of potassium carbonate and 40 g of N, N-dimethylformamide as a solvent were added. The mixture was stirred for 1 hour while maintaining the temperature of the reaction system at 20 to 30 ° C. Thereafter, anthraquinone was removed by suction filtration, and the obtained filtrate was dissolved in toluene, and washed twice with water by a liquid separation operation. The solution was concentrated with an evaporator. The mixture was left overnight, methanol was added, and undissolved anthraquinone was removed by suction filtration. The filtrate was cooled in a freezer to precipitate crystals. The precipitated crystals were further subjected to suction filtration 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).

(Monomer Synthesis Example 9) Synthesis of 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene (1-9) A 200-ml four-necked flask equipped with a stirrer and a thermometer was placed under a nitrogen atmosphere. 5.0 g (21,2 mmol) of 2-ethylanthraquinone, 9.1 g (86.4 mmol) of thiourea dioxide, 8.4 g (211.6 mmol) of sodium hydroxide, and 50 g of ion-exchanged water were added. Stirring was performed while gradually raising the temperature to 120 ° C. When the solution turned red-black, stirring was stopped, and the mixture was cooled at room temperature to prepare an aqueous solution of disodium salt of 2-ethyl-9,10-dihydroxyanthracene. Next, 15 g of methyl isobutyl ketone as a solvent and 2.7 g of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst were placed in another 200 ml four-necked flask equipped with a stirrer and a thermometer under a nitrogen atmosphere. Mmol) and 10.0 g (55.0 mmol) of isopropyl bromoacetate. While maintaining the temperature of the reaction system at 20 to 25 ° C., the aqueous solution of disodium salt of 2-ethyl-9,10-anthracenediol prepared above was added dropwise over 1 hour or more. After the completion of the dropwise addition, the mixture was further stirred for 1 hour. Thereafter, 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 = 7.6 Hz, 1H), 8.284-8.368 (m, 2H).

(Synthesis example of intermediate) Synthesis of 9,10-bis (hydroxycarbonylmethyleneoxy) anthracene (synthesis of general formula (5) as an intermediate)
Under a nitrogen atmosphere, 95 g of methyl isobutyl ketone (MIBK) as a solvent and 4.4 g of a 50% aqueous solution of tetrabutylammonium bromide (TBAB) as a catalyst were placed in a 300 ml four-necked flask equipped with a stirrer and a thermometer. 8 mmol) and 49.5 g (356 mmol) of bromoacetic acid. While maintaining the temperature of the reaction system at 20 to 30 ° C., 165.7 g (137 mmol) of an aqueous solution of 9,10-dihydroxyanthracene disodium salt (AHQ-Na) and sodium hydroxide and 11.4 g (285 mmol) of sodium hydroxide (Mmol) and 20 g of ion-exchanged water were added dropwise over 3 hours. After the addition was completed, the mixture was further stirred for 1.5 hours. Thereafter, unreacted raw materials and the like were separated by suction filtration, and 100 ml of toluene was added for extraction. The organic layer was separated, and 28.9 g (285 mmol) of 35% hydrochloric acid was added to the aqueous layer to perform acid precipitation. The precipitated crystals were filtered, washed with water and dried to obtain 33.3 g (yield 75 mol%) of yellow crystals.

(1) Melting point: 250 ° C. or higher (2) IR (cm ⁻¹ ): 1727, 1435, 1377, 1254, 1240, 1091, 934, 769, 592, 657.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 1.631 (br, 2H), 4.754 (br, 4H), 7.802-7.825 (m, 4H), 8.317 -8.340 (m, 4H)

(Monomer Synthesis Example 10) Synthesis of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene (1-2) (reaction with alcohol)
In a 1000 ml four-necked flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 78.7 g (241 mmol) of 9,10-bis (hydroxycarbonylmethyleneoxy) anthracene obtained in (Intermediate Synthesis Example) was added. 236.0 g (5119 mmol) and 3.9 g (39 mmol) of concentrated sulfuric acid were added. The temperature of the reaction system was maintained at 75 to 80 ° C., and the mixture was stirred for 10 hours while removing by-produced water with ethanol. The crystals precipitated by cooling were filtered off with suction, washed with methanol and dried to obtain 71.7 g (yield 78 mol%) of yellow crystals.

(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, 6H), 4.376 (k, J = 21.6 Hz, 4H), 4.777 (s, 4H), 7.261-7.540 (m, 4H).

(Monomer Synthesis Example 11) Synthesis of 9,10-bis (propoxycarbonylmethyleneoxy) anthracene (1-10) (reaction with alcohol)
0.4 g (1.2 mmol) of 9,10-bis (hydroxycarbonylmethyleneoxy) anthracene obtained in (Intermediate Synthesis Example) was placed in a 50 ml four-necked flask equipped with a stirrer and a thermometer under a nitrogen atmosphere. , 1.5 g (25 mmol) of 1-propanol and 0.01 g (0.1 mmol) of methanesulfonic acid. The mixture was stirred for 1.5 hours while maintaining the temperature of the reaction system at 50 to 60 ° C. Thereafter, insoluble components were separated by filtration, and methanol and ion-exchanged water were added to the filtrate to precipitate crystals. The precipitated crystals were collected by suction filtration, washed with methanol and dried to obtain 0.12 g (crude yield 25 mol) of yellow crystals.

(1) Melting point: 75-76 ° C
(2) IR (cm ^-1 ): 2950, 1747, 1400, 1380, 1359, 1206, 1162, 776.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.92 (t, J = 7.3 Hz, 6H), 1.744 (tq, J = 6.9 Hz, 7.3 Hz, 4H), 4.272 (t, J = 6.9 Hz, 4H), 4.785 (s, 4H), 7.496-7.534 (m, 4H), 8.349-8.411 (m, 4H).

(Monomer Synthesis Example 12) Synthesis of 9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene (1-5) (reaction with alcohol)
In a 300 ml four-necked flask equipped with a stirrer and a thermometer, 34.2 g (105 mmol) of 9,10-bis (hydroxycarbonylmethyleneoxy) anthracene obtained in (Intermediate Synthesis Example) was placed under a nitrogen atmosphere. -172.7 g (2330 mmol) of butanol and 1.7 g (17 mmol) of concentrated sulfuric acid were added. The temperature of the reaction system was maintained at 120 to 130 ° C., and the mixture was stirred for 14 hours while removing by-produced water. The crystals precipitated by cooling were filtered off with suction, washed with methanol and dried to obtain 26.5 g (yield 58 mol%) of yellow crystals.

(1) Melting point: 71-72 ° C
(2) IR (cm ^-1 ): 1749, 1411, 1385, 1364, 1246, 1226, 1167, 1085, 1035, 1018, 957, 768, 721, 669, 587.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.967 (d, J = 15.2 Hz, 6H), 1.387-1.481 (m, 4H), 1.678-1. 750 (m, 4H), 4.317 (t, J = 13.2 Hz, 4H), 4.779 (s, 4H), 7.508-7.826 (m, 4H), 8.319-8. 377 (m, 4H).

(Monomer Synthesis Example 13) Synthesis of 9,10-bis (2-hydroxyethoxycarbonylmethyleneoxy) anthracene (reaction with alcohol)
In a 50 ml four-necked flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 0.65 g (2.0 mmol) of 9,10-bis (hydroxycarbonylmethyleneoxy) anthracene obtained in (Intermediate Synthesis Example) Then, 3.0 g (48 mmol) of ethylene glycol and 0.2 g (2.1 mmol) of methanesulfonic acid were added. The mixture was stirred for 4 hours while maintaining the temperature of the reaction system at 50 to 60 ° C. After cooling, methanol and ion-exchanged water were added to precipitate crystals. The precipitated crystals were collected by suction filtration, washed with methanol and dried to obtain 0.47 g (yield 57 mol%) of yellow crystals.

(1) Melting point: 145-146 ° C
(2) IR (cm ^-1 ): 3505, 2950, 1733, 1674, 1578, 1077.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 3.804 (br., 4H), 4.340 (t, J = 5.0 Hz, 4H), 4.905 (s, 4H), 7.552-7.584 (m, 4H), 8.447-8.478 (m, 4H).

(Monomer Synthesis Example 14) Synthesis of 9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene (1-5) (reaction with alkyl halide)
In a 100 ml four-necked flask equipped with a stirrer and a thermometer, 2.0 g (6.2 mmol) of 9,10-bis (hydroxycarbonylmethyleneoxy) anthracene obtained in (Intermediate Synthesis Example) and N as a solvent were used. , N'-dimethylformamide (43.4 g) and potassium carbonate (0.87 g, 6.4 mmol) were added, followed by nitrogen substitution. Under a nitrogen atmosphere, 3.87 g (28.2 mmol) of n-butyl bromide was added, and the mixture was heated and stirred at 60 ° C. in a water bath. After the completion of the reaction, the mixture was cooled to room temperature, and the residue containing potassium carbonate was removed by suction filtration. The obtained filtrate was poured into water and extracted with 45.6 g of toluene, and the toluene layer was washed with water. The washed toluene layer was concentrated under reduced pressure by an evaporator to obtain 2.28 g (crude yield: 83.6 mol%) of orange crystals.

(1) Melting point: 71-72 ° C
(2) IR (cm ^-1 ): 1749, 1411, 1385, 1364, 1246, 1226, 1167, 1085, 1035, 1018, 957, 768, 721, 669, 587.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.967 (d, J = 15.2 Hz, 6H), 1.387-1.481 (m, 4H), 1.678-1. 750 (m, 4H), 4.317 (t, J = 13.2 Hz, 4H), 4.779 (s, 4H), 7.508-7.826 (m, 4H), 8.319-8. 377 (m, 4H).

(Monomer Synthesis Example 15) Synthesis of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene (1-2) A solvent, o-xylene, was placed in a 300 ml four-necked flask equipped with a stirrer and a thermometer under a nitrogen atmosphere. Was added, 29 g (45 mmol) of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst, and 33.1 g (270 mmol) of ethyl chloroacetate were added. While maintaining the temperature of the reaction system at 50 to 55 ° C., 100 g of a 18.8 wt% aqueous solution of disodium salt of 9,10-dihydroxyanthracene (90 mmol as anthraquinone) was added dropwise over 1 hour. After the completion of the dropwise addition, the mixture was further stirred for 1 hour. Thereafter, insolubles were removed by suction filtration, and the filtrate was cooled to 10 ° C. to precipitate crystals. The precipitated crystals were collected by suction filtration and dried to obtain 5.0 g (42 mol% of crude yield) of pale yellow crystals.

(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, 6H), 4.376 (k, J = 21.6 Hz, 4H), 4.777 (s, 4H), 7.261-7.540 (m, 4H).

(Monomer Synthesis Example 16) Synthesis of 9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene (1-5) In a 200 ml four-necked flask equipped with a stirrer and a thermometer, bromoacetic acid 20 To the mixture were added 2.0 g (144 mmol), 21.3 g (287 mmol) of n-butanol, 35.0 g of о-xylene as a solvent, and 1.0 g (10 mmol) of sulfuric acid as a catalyst. The temperature of the reaction system was maintained at 120 to 130 ° C., and the mixture was stirred for 1 hour while removing azeotropic water. After cooling to room temperature, the mixture was neutralized with an aqueous solution of sodium hydrogen carbonate, and the aqueous layer was removed. 1.8 g (2.8 mmol) of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst was added thereto, and 18.10-dihydroxyanthracene disodium salt 18. 61.5 g of a 7 wt% aqueous solution (55 mmol as anthraquinone) was added dropwise over 1 hour. After the completion of the dropwise addition, the mixture was further stirred for 1 hour. Thereafter, anthraquinone was removed by suction filtration, and the obtained filtrate was washed twice with water. Since anthraquinone was precipitated, the anthraquinone was removed by suction filtration, washed with water, and then concentrated. Methanol was added to the concentrated solution for crystallization, and the precipitated crystal was filtered by suction and dried to obtain 16.1 g (crude yield 66 mol%) of yellow crystals.

(1) Melting point: 71-72 ° C
(2) IR (cm ^-1 ): 1749, 1411, 1385, 1364, 1246, 1226, 1167, 1085, 1035, 1018, 957, 768, 721, 669, 587.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.967 (d, J = 15.2 Hz, 6H), 1.387-1.481 (m, 4H), 1.678-1. 750 (m, 4H), 4.317 (t, J = 13.2 Hz, 4H), 4.779 (s, 4H), 7.508-7.826 (m, 4H), 8.319-8. 377 (m, 4H).

(Monomer Synthesis Example 17) Synthesis of 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene (1-3) In a 300 ml four-necked flask equipped with a stirrer and a thermometer, bromoacetic acid was added under nitrogen atmosphere. 5 g (234 mmol), 28.1 g (467 mmol) of i-propanol, 75.0 g of о-xylene as a solvent, and 1.5 g (16 mmol) of sulfuric acid as a catalyst were added. While maintaining the temperature of the reaction system at 100 to 110 ° C., the mixture was stirred for 1 hour while removing the distillate (i-propanol containing by-product water). Further, 28.0 g (466 mmol) of i-propanol was added and the mixture was stirred for 2 hours. After cooling to room temperature, the mixture was neutralized with an aqueous solution of sodium hydrogen carbonate, and the aqueous layer was removed. 2.8 g (4.3 mmol) of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst was added thereto, and 18.10-dihydroxyanthracene disodium salt 18. 100 g of a 7 wt% aqueous solution (90 mmol as anthraquinone) was added dropwise over 1 hour. Thereafter, anthraquinone was removed by suction filtration, and the aqueous layer of the obtained filtrate was removed. After concentration, methanol was added to the concentrated solution for crystallization, and the precipitated crystals were collected by suction filtration and dried to obtain 17.6 g (crude yield: 45 mol%) of cream-colored crystals.

(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, 12H), 4.743 (s, 4H), 5.246-5.277 (m, 2H), 7.504-7.529 (m, 4H), 8.356-8.398 (m, 4H).

(Monomer Synthesis Example 18) Synthesis of 9,10-bis (n-pentyloxycarbonylmethyleneoxy) anthracene (1-11) In a 300 ml four-necked flask equipped with a stirrer and a thermometer, bromoacetic acid was placed under a nitrogen atmosphere. 32.5 g (234 mmol), n-pentanol 41.1 g (466 mmol), a solvent о-xylene 75.7 g, and a catalyst sulfuric acid 1.5 g (16 mmol) were added. The temperature of the reaction system was maintained at 140 to 150 ° C., and the mixture was stirred for 2 hours while removing azeotropic water. After cooling to room temperature, the mixture was neutralized with an aqueous solution of sodium hydrogen carbonate, and the aqueous layer was removed. 2.8 g (4.3 mmol) of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst was added thereto, and 18.10-dihydroxyanthracene disodium salt 18. 100 g of a 7 wt% aqueous solution (90 mmol as anthraquinone) was added dropwise over 1 hour. After the completion of the dropwise addition, the mixture was further stirred for 1 hour, heated from 55 to 60 ° C., and stirred for 1 hour. After cooling to room temperature, liquid separation and water washing were performed twice, anthraquinone was removed by suction filtration, and concentration was performed. Crystallization was performed by adding methanol to the concentrated solution, and the precipitated crystals were collected by suction filtration and dried to obtain 26.6 g (crude yield: 57 mol%) of pale yellow crystals.

(1) Melting point: 109-111 ° C
(2) IR (cm ^-1 ): 2693, 2922, 2855, 1750, 1470, 1436, 1381, 1368, 1356, 1274, 1200, 1164, 1052, 1006, 976, 951, 780, 711, 677, 608, 581,400.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 0.921 (t, J = 12.8 Hz, 6H), 1.363-1.396 (m, 8H), 1.696-1. 747 (m, 4H), 4.306 (t, J = 13.2 Hz, 4H), 4.780 (s, 4H), 7.505-7.536 (m, 4H), 8.356-8. 387 (m, 4H).

(Monomer Synthesis Example 19) Synthesis of 9,10-bis (cyclohexyloxycarbonylmethyleneoxy) anthracene (1-12) In a 300 ml four-necked flask equipped with a stirrer and a thermometer, bromoacetic acid was added under nitrogen atmosphere. 4 g (234 mmol), 46.8 g (467 mmol) of cyclohexanol, 75.0 g of o-xylene as a solvent, and 1.5 g (15 mmol) of sulfuric acid as a catalyst were added. The temperature of the reaction system was maintained at 140 to 150 ° C., and the mixture was stirred for 2 hours while removing azeotropic water. After cooling to room temperature, the mixture was neutralized with an aqueous solution of sodium hydrogen carbonate, and the aqueous layer was removed. 2.8 g (4.4 mmol) of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst was added thereto, and 18.10-dihydroxyanthracene disodium salt 18. 100 g of a 7 wt% aqueous solution (90 mmol as anthraquinone) was added dropwise over 1 hour. After the completion of the dropwise addition, the mixture was further stirred for 1 hour, heated from 55 to 60 ° C., and stirred for 1 hour. After cooling to room temperature, anthraquinone was removed by suction filtration, separated, washed twice with water, and concentrated. Methanol was added to the concentrated solution for crystallization, and the precipitated crystals were filtered by suction and dried to obtain 25.5 g (crude yield: 54 mol%) of pale yellow crystals.

(1) Melting point: 122-124 ° C
(2) IR (cm ^-1 ): 2930, 2857, 1745, 1677, 1621, 1453, 1438, 1399, 1369, 1360, 1206, 1168, 1086, 1035, 1006, 954, 922, 891, 813, 715. 693,672,659,608,585,455.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 1.239-1.596 (m, 12H), 1.754-1.786 (m, 4H), 1.939-1.961 ( m, 4H), 4.760 (s, 4H), 4.985-5.050 (m, 2H), 7.501-7.526 (m, 4H), 8.372-8.398 (m, 4H) 4H).

(Monomer Synthesis Example 20) Synthesis of 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene (1-3) 5.0 g of 9,10-anthraquinone under a nitrogen atmosphere in a 300 ml Erlenmeyer flask containing a stirrer. (24.0 mmol), 10.0 g of о-xylene, 10.4 g (59.7 mmol) of hydrosulfite, 4.8 g (120 mmol) of sodium hydroxide, and 57.3 g of ion-exchanged water were added. Stirred for hours. The thus-prepared aqueous solution of 9,10-dihydroxyanthracene disodium salt was transferred to a 100 ml dropping funnel.
In a 200 ml four-necked flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 10.0 g of о-xylene, 0.8 g (1.2 mmol) of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst, and isopropyl bromoacetate 13 Then, while maintaining the temperature of the reaction system at 20 to 30 ° C., the disodium salt aqueous solution of 9,10-dihydroxyanthracene previously transferred to the dropping funnel was added dropwise over 1 hour. Thereafter, anthraquinone and the like were removed by suction filtration, and the aqueous layer of the obtained filtrate was removed. The organic layer was washed once with ion-exchanged water, concentrated, and methanol was added to the concentrated solution for crystallization. The precipitated crystals were collected by suction filtration and dried to obtain 5.0 g (crude yield: 40 mol%) of cream-colored crystals.

(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, 12H), 4.743 (s, 4H), 5.246-5.277 (m, 2H), 7.504-7.529 (m, 4H), 8.356-8.398 (m, 4H).

(Oligomer Synthesis Example 1) Synthesis of oligomer obtained by reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 1,6-hexanediol (12-6)
1.7 g (4.5 mmol) of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Example 2 of monomer synthesis was placed in a 50 ml three-necked flask containing a stirrer. 0.80 g (6.8 mmol) of hexanediol was added, and the mixture was heated to 130 ° C. in an oil bath. Stirring was started after the raw materials were melted, and when the temperature reached 130 ° C., 0.064 g (0.225 mmol) of tetra-i-propoxytitanium (TPT) as a catalyst was added, and the pressure was reduced to 360 mmHg. 3.5 hours after the start of the pressure reduction, the pressure was reduced at 2 mmHg. Thereafter, the reaction was terminated 2.5 hours later, and a product was obtained as 1.47 g of a brown-black solid.

(1) Number average molecular weight: Mn = 3600
(2) IR (cm ^-1 ): 1750, 1731, 1401, 1382, 1350, 1272, 1167, 1082, 1020, 771, 699, 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 0.764 (s, 4H), 7.480-7.504 (m, 4H), 8.329-8.354 (m, 4H).

(Oligomer Synthesis Example 2) Synthesis of oligomer obtained by reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol (12-7)
1.7 g (4.5 mmol) of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Monomer Synthesis Example 2 was placed in a 50 ml three-necked flask containing a stirrer. 0.66 g (5.6 mmol) of methyl-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-propoxytitanium (TPT) as a catalyst was added, and the pressure was reduced to 360 mmHg. 4.5 hours after the start of the pressure reduction, the pressure was reduced at 2 mmHg. After one hour, the reaction was terminated, and 1.65 g of a brown-black syrup-like product was obtained.

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

(Oligomer Synthesis Example 3) Synthesis of oligomer obtained by reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 2,4-diethyl-1,5-pentanediol (12-9)
1.7 g (4.5 mmol) of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Monomer Synthesis Example 2 was placed in a 50 ml three-necked flask containing a stirrer. 0.90 g (5.6 mmol) of 4-diethyl-1,5-pentanediol was added, and the mixture was heated to 130 ° C. in an oil bath. Stirring was started after the raw materials were melted, and when the temperature reached 130 ° C., 0.064 g (0.225 mmol) of tetra-i-propoxytitanium (TPT) as a catalyst was added, and the pressure was reduced to 360 mmHg. Seven hours after the start of the pressure reduction, the pressure was reduced at 2 mmHg. Thereafter, the reaction was terminated 2.5 hours later, to obtain 1.55 g of a brown-black syrupy product.

(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 to 8.314 (m, 4H).

(Oligomer Synthesis Example 4) Synthesis of oligomer obtained by reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 1,9-nonanediol (12-11)
1.7 g (4.5 mmol) of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Monomer Synthesis Example 2 was placed in a 50 ml three-necked flask containing a stirrer. 0.90 g (5.6 mmol) of 9-nonanediol was added, and the mixture was heated to 130 ° C. in an oil bath. Stirring was started after the raw materials were melted, and when the temperature reached 130 ° C., 0.064 g (0.225 mmol) of tetra-i-propoxytitanium (TPT) as a catalyst was added, and the pressure was reduced to 360 mmHg. 3.5 hours after the start of the pressure reduction, the pressure was reduced at 2 mmHg. Then, after 3 hours, the reaction was terminated, and 1.78 g of a brownish syrupy product was obtained.

(1) Number average molecular weight: Mn = 3900
(2) IR (cm ^-1 ): 1753, 1732, 1382, 1350, 1272, 1167, 1029, 959, 771, 668, 607.
(3) 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).

(Oligomer Synthesis Example 5) Synthesis of oligomer obtained by reaction of 9,10-bis (hydroxycarbonylmethyleneoxy) anthracene with polyethylene glycol (molecular weight: 1000) (12-14)
1.5 g (4.5 mmol) of 9,10-bis (hydroxycarbonylmethyleneoxy) anthracene obtained by the same method as in the intermediate synthesis example was placed in a 50 ml three-necked flask containing a stirrer, and polyethylene glycol ( 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. 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. After 7 hours, the reaction was terminated, 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).

(Oligomer Synthesis Example 6) Synthesis of oligomer obtained by reaction of 9,10-bis (hydroxycarbonylmethyleneoxy) anthracene with 1,5-dibromopentane (12-5)
0.19 g (0.61 mmol) of 9,10-bis (hydroxycarbonylmethyleneoxy) anthracene obtained in the same manner as in the synthesis example of the intermediate was placed in a 50 ml branched flask containing a stirrer, and the solvent N, 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. And heated. Five hours after the start of heating, the mixture was cooled to room temperature, and the residue containing potassium carbonate was removed by suction filtration. The obtained filtrate was concentrated under reduced pressure by an evaporator to obtain a brown-black syrupy product in a yield of 0.45 g.

(1) Number average molecular weight: Mn = 830
(2) IR (cm ^-1 ): 2933, 2360, 1731, 1663, 1382, 1168, 1128, 772.
(3) 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).

(Oligomer Synthesis Example 7) Synthesis of oligomer obtained by reaction of 9,10-bis (hydroxycarbonylmethyleneoxy) anthracene with 1,9-dibromononane (12-11)
0.20 g (0.63 mmol) of 9,10-bis (hydroxycarbonylmethyleneoxy) anthracene obtained in the same manner as in the intermediate synthesis example was placed in a 50 ml branched flask containing a stirrer, and the solvent N, 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. And heated. Five hours after the start of heating, the mixture was cooled to room temperature, and the residue containing potassium carbonate was removed by suction filtration. The obtained filtrate was concentrated under reduced pressure by an evaporator to obtain a brown-black syrupy 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) ).

(Oligomer Synthesis Example 8) Synthesis of oligomer obtained by reaction of 9,10-dihydroxyanthracene with 1,2-bis (bromoacetoxy) ethane (12-1)
Under a nitrogen atmosphere, 1.6 g (5.3 mmol) of 1,2-bis (bromoacetoxy) ethane, 10 g of methyl isobutyl ketone as a solvent, and tetrabutyl ammonium 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 (4.8 mmol as anthraquinone) of a 18.8 wt% aqueous solution of disodium salt of 9,10-dihydroxyanthracene was added dropwise over 15 minutes. After the completion of the dropwise addition, the mixture was further stirred for 1 hour. Thereafter, suction filtration yielded 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).

(Oligomer Synthesis Example 9) Synthesis of oligomer obtained by reaction of 9,10-dihydroxyanthracene with 1,5-bis (bromoacetoxy) 3-methylpentane (12-7)
In a 200 ml four-necked flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 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. 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 disodium salt of 9,10-dihydroxyanthracene was added dropwise over 15 minutes. After the completion of the dropwise addition, the mixture was further stirred for 1 hour. Thereafter, 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)

(Oligomer Synthesis Example 10) Synthesis of oligomer obtained by reaction of 9,10-dihydroxyanthracene with 1,9-bis (bromoacetoxy) nonane (12-11)
In a 200 ml four-necked flask equipped with a stirrer and a thermometer, 9.7 g (24.0 mmol) of 1,9-bis (bromoacetoxy) nonane, 50 g of methyl isobutyl ketone as a solvent, and 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 a 18.8 wt% aqueous solution of disodium salt of 9,10-dihydroxyanthracene was added dropwise over 15 minutes. After completion of the dropwise addition, the mixture was further stirred for 2 hours. Thereafter, 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 8.9 g of a brown oil.

(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).

(Optical DSC measurement)
In this example, the optical DSC measurement was performed as follows. That is, the DSC measurement apparatus used was XDSC-7200 manufactured by Hitachi High-Tech Co., Ltd., which was equipped with an optical DSC measurement unit and was set up so that DSC measurement could be performed while irradiating light. As a light source for light irradiation, LA-410UV manufactured by Hayashi Watch Industry Co., Ltd. was used, and light of 405 nm was extracted with a bandpass filter so that the sample could be irradiated. The illuminance of light was 50 mW / cm ² . The light of the light source was guided to the upper part of the sample using glass fiber, and the trigger of the shutter of the light source was controlled so that the DSC measurement could be performed simultaneously with the start of the light irradiation. For the measurement of the optical DSC, the sample was precisely weighed in an aluminum pan for measurement of about 1 mg, placed in the DSC measuring section, and then fitted with the optical DSC unit. Thereafter, the measurement section was kept in a nitrogen atmosphere and allowed to stand for 10 minutes to start measurement. The measurement was continued for 6 minutes while irradiating with normal light. After the first measurement, the sample was measured again under the same conditions as it was, and the value obtained by subtracting the second measurement result from the first measurement result was defined as the measurement result of the sample. The results were compared with the total calorific value per 1 mg of sample for 1 minute after light irradiation, unless otherwise specified. Depending on the measurement conditions, the photoreaction may not be completed in one minute, but in order to compare the reaction behavior at the initial stage of light irradiation, the comparison was made based on the total calorific value for one minute. When polymerization of a sample (photopolymerizable composition) is caused by light irradiation, heat of reaction is generated due to the polymerization, and the light DSC can measure the heat of reaction. Therefore, the progress of polymerization by light irradiation can be measured by light DSC. In this example, the total calorific value for one 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.

(Hikari Rheometer)
In this example, the light Rheometer measurement was performed as follows. The transition of the complex viscosity of the photocurable composition was measured using a light Rheometer MCR102 manufactured by Anton Paar Co., Ltd., and the curing speed was measured from the viscosity increasing speed.
Measurement condition:
Measuring jig: Parallel plate (φ10mm)
Thickness: 100 μm
Swing angle: 5.0% constant frequency: 10 Hz constant temperature: 30 ° C. constant measurement atmosphere: nitrogen atmosphere UV irradiator: LLBK-UV manufactured by ITEC System (irradiation wavelength: 405 nm)
Irradiation intensity: 200 mW / cm ²
Irradiation start time: 30 seconds post-curing time: The time (second) at which the complex viscosity reached 40,000 Pa · s from the start of light irradiation was defined as the curing time.

First, a photopolymerization performance evaluation test of a photocationically polymerizable composition using the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group of the present invention as a photocationic polymerization sensitizer will be described below.

(Example 1 of light curing rate evaluation)
3 ', 4'-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, trade name: Celloxide 2021P, celloxide is a registered trademark of Daicel Corporation) as 100 parts by weight as the cationic photopolymerizable compound 4-isobutylphenyl-4'-methylphenyliodonium hexafluorophosphate, a photopolymerization initiator (manufactured by BS F, Inc., trade name Irgacure 250; "Irgacure" is B S F (Registered trademark) and 1 part by weight of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Monomer Synthesis Example 1 as a cationic photopolymerization sensitizer at room temperature. A polymerizable composition was prepared. When a photo-DSC measurement was performed on the photopolymerizable composition, a total calorific value for 5 minutes from the start of light irradiation was 256 mJ / mg.

(Evaluation example 2 of light curing speed)
Photocuring Rate Evaluation The light curing rate was changed except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene in Example 1 was changed to 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Example 2 for monomer synthesis. When the light DSC measurement was performed in the same manner as in the evaluation example 1 of the curing speed, the total calorific value for 5 minutes from the start of the light irradiation was 273 mJ / mg.

(Evaluation example 3 of light curing speed)
Photocuring rate evaluation Except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene in Example 1 was changed to 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Example 3 for monomer synthesis. When the optical DSC measurement was performed in the same manner as in the photo-curing speed evaluation example 1, the total calorific value for 5 minutes from the start of the light irradiation was 262 mJ / mg.

(Example 4 of light curing rate evaluation)
Photocuring rate evaluation Except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene in Example 1 was changed to 9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Monomer Synthesis Example 4. When the light DSC measurement was performed in the same manner as in the evaluation example 1 of the photocuring speed, the total calorific value for 5 minutes from the start of the light irradiation was 284 mJ / mg.

(Evaluation example 5 of light curing speed)
Photocuring rate evaluation Except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene in Example 1 was changed to 9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Example 5 for monomer synthesis. When the light DSC measurement was performed in the same manner as in Example 1 of the photocuring rate execution evaluation, the total calorific value for 5 minutes from the start of light irradiation was 248 mJ / mg.

(Example 6 of light curing rate evaluation)
Photocuring Rate Evaluation Except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene in Example 1 was changed to 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene obtained in the same manner as in Example 6 for monomer synthesis. When the optical DSC measurement was carried out in the same manner as in the photo-curing speed evaluation example 1, the total calorific value for 5 minutes from the start of the light irradiation was 226 mJ / mg.

(Evaluation example 7 of light curing speed)
Photocuring Rate Evaluation The light curing rate was changed except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene in Example 1 was changed to 9,10-bis (ethoxycarbonylpropyleneoxy) anthracene obtained in the same manner as in Example 7 for monomer synthesis. When the light DSC measurement was performed in the same manner as in the evaluation example 1 of the curing speed, the total calorific value for 5 minutes from the start of the light irradiation was 308 mJ / mg.

(Evaluation Example 8 of Photocuring Speed)
Photocuring Rate Evaluation The light curing rate was changed except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene in Example 1 was changed to 9,10-bis (ethoxycarbonylbutyleneoxy) anthracene obtained in the same manner as in Example 8 for monomer synthesis. When the light DSC measurement was performed in the same manner as in the evaluation example 1 of the curing speed, the total calorific value for 5 minutes from the start of the light irradiation was 285 mJ / mg.

(Evaluation Example 9 of Photocuring Speed)
Photocuring Rate Evaluation 9,10-Bis (methoxycarbonylmethyleneoxy) anthracene of Example 1 was added to 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Monomer Synthesis Example 9. The optical DSC measurement was performed in the same manner as in the photo-curing speed evaluation example 1 except that the change was changed, and the total calorific value for 5 minutes from the start of light irradiation was 260 mJ / mg.

(Evaluation example 17 of light curing speed)
Photocuring Rate Evaluation The light curing rate was changed except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene in Example 1 was changed to 9,10-bis (propoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Example 11 for monomer synthesis. When the optical DSC measurement was performed in the same manner as in the evaluation example 1 of the curing speed, the total calorific value for 5 minutes from the start of the light irradiation was 259 mJ / mg.

(Evaluation Example 18 of Photocuring Speed)
9,10-Bis (methoxycarbonylmethyleneoxy) anthracene in Example 1 was changed to 9,10-bis (2-hydroxyethoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Monomer Synthesis Example 13. Except for the above, the light DSC measurement was carried out in the same manner as in the photocuring speed evaluation example 1. As a result, the total calorific value for 5 minutes from the start of light irradiation was 237 mJ / mg.

(Evaluation Example 21 of Photocuring Speed)
9,10-Bis (methoxycarbonylmethyleneoxy) anthracene in Example 1 for photocuring rate evaluation was changed to 9,10-bis (n-pentyloxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Monomer Synthesis Example 18. Except for the above, when the light DSC measurement was performed in the same manner as in the evaluation example 1 of the photocuring speed, the total heat generation for 5 minutes from the start of the light irradiation was 268 mJ / mg.

(Evaluation Example 22 of Photocuring Speed)
Photocuring rate evaluation Except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene in Example 1 was changed to 9,10-bis (cyclohexyloxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Monomer Synthesis Example 19. When the optical DSC measurement was performed in the same manner as in the photo-curing speed evaluation example 1, the total calorific value for 5 minutes from the start of the light irradiation was 256 mJ / mg.

(Evaluation Example 23 of Photocuring Speed)
Photocuring Rate Evaluation The photopolymerization initiator of Example 1 was changed to diphenyl-4-phenylthiophenylsulfonium hexafluorophosphate (manufactured by Daicel, trade name: CPI-100P), and the photocationic polymerization sensitizer was subjected to monomer synthesis. Photo DSC measurement was carried out in the same manner as in Example 1 of the photocuring rate except that the 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Example 2 was used. The total calorific value was 200 mJ / mg.

(Evaluation Example 24 of Photocuring Speed)
Photocuring Rate Evaluation The cationic photopolymerizable compound of Example 1 was changed to (3,3 ′, 4,4′-diepoxy) bicyclohexyl (manufactured by Daicel, trade name: Celloxide 8010), and a cationic photopolymerization sensitizer was used. Photo-DSC was measured in the same manner as in Example 2 of the photocuring rate except that the monomer was changed to 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene, which was obtained in the same manner as in Example 2. The total heating value for 5 minutes was 416 mJ / mg.

(Comparative Example 1 for Evaluation of Photocuring Speed)
3 ′, 4′-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, trade name: Celloxide 2021P, celloxide is a registered trademark of Daicel Corporation) as 100 parts by weight as a photocationic polymerizable compound Photopolymerization initiator (4-methylphenyl) [4- (2-methylpropyl) phenyl] iodonium-hexafluorophosphate (trade name Irgacure 250, manufactured by BSF Inc .; 2 parts by weight of ASF Co., Ltd.) were mixed at room temperature to prepare a cationic photopolymerizable composition. When a photo-DSC measurement was performed on this photopolymerizable composition, the total calorific value for 5 minutes from the start of light irradiation was 3 mJ / mg.

(Comparative example 2 of evaluation of light curing speed)
Photocuring rate evaluation Evaluation of the photocuring rate except that 9,10-dibutoxyanthracene, a known photopolymerization sensitizer, was used instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene in Example 1. When the light DSC measurement was performed in the same manner as in Example 1, the total calorific value for 5 minutes from the start of light irradiation was 230 mJ / mg.

(Comparative example 3 of evaluation of light curing speed)
Photocuring Rate Evaluation Except for using 9,10-bis (octanoyloxy) anthracene, which is a known photopolymerization sensitizer, in place of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene in Example 1, When the light DSC measurement was performed in the same manner as in the evaluation example 1 of the curing speed, the total calorific value for 5 minutes from the start of the light irradiation was 234 mJ / mg.

(Comparative Example 7 for Evaluation of Photocuring Speed)
3 ′, 4′-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, trade name: Celloxide 2021P, celloxide is a registered trademark of Daicel Corporation) as 100 parts by weight as a photocationic polymerizable compound 2 parts by weight of diphenyl-4-phenylthiophenylsulfonium hexafluorophosphate (produced by Daicel, trade name: CPI-100P) as a photopolymerization initiator was mixed at room temperature to prepare a photocationically polymerizable composition. When a photo-DSC measurement was performed on this photopolymerizable composition, the total calorific value for 5 minutes from the start of light irradiation was 0 mJ / mg.

(Comparative Example 8 for Photocuring Speed Evaluation)
(4,3 ′, 4,4′-diepoxy) bicyclohexyl (manufactured by Daicel, trade name: celloxide 8010) as a photocationically polymerizable compound, and 100 parts by weight of photopolymerization initiator (4-methylphenyl) ) [4- (2-Methylpropyl) phenyl] iodonium-hexafluorophosphate (trade name Irgacure 250, manufactured by BSF Inc., "Irgacure" is a registered trademark of BSF Co.) Two parts by weight were mixed at room temperature to prepare a cationic photopolymerizable composition. When a photo-DSC measurement was performed on this photopolymerizable composition, the total calorific value for 5 minutes from the start of light irradiation was 2 mJ / mg.

Table 4 summarizes the results of Photocuring Speed Evaluation Examples 1 to 9, 17, 18, 21 to 24 and Photocuring Speed Evaluation Comparative Examples 1 to 3, 7, and 8.

Next, the photopolymerization performance evaluation test of the radical polymerizable composition using the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group of the present invention as a photoradical polymerization sensitizer will be described below.

(Evaluation Example 10 of Photocuring Speed)
As a photo-radical polymerizable compound, 2 parts by weight of 1-hydroxycyclohexyl phenyl ketone, which is a photo-polymerization initiator, based on 100 parts by weight of trimethylolpropane triacrylate, and a photo-radical polymerization sensitizer obtained in Monomer Synthesis Example 1. One part by weight of the obtained 9,10-bis (methoxycarbonylmethyleneoxy) anthracene was mixed at room temperature to prepare a photo-radical polymerizable composition. When a photo-DSC measurement was performed on this photopolymerizable composition, the total calorific value for 5 minutes from the start of light irradiation was 419 mJ / mg.

(Evaluation Example 11 of Light Curing Speed)
Photocuring rate evaluation The light curing rate was changed except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene in Example 10 was changed to 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Monomer Synthesis Example 2. When a light DSC measurement was performed in the same manner as in Example 10 of the curing rate evaluation, the total calorific value for 5 minutes from the start of light irradiation was 465 mJ / mg.

(Light Curing Speed Evaluation Example 12)
Photocuring rate evaluation Except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene in Example 10 was changed to 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Monomer Synthesis Example 3. When the light DSC measurement was performed in the same manner as in Example 10 of the photocuring rate evaluation, the total calorific value for 5 minutes from the start of light irradiation was 409 mJ / mg.

(Evaluation Example 13 of Light Curing Speed)
Photocuring rate evaluation Except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene in Example 10 was changed to 9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Monomer Synthesis Example 4. Was subjected to optical DSC measurement in the same manner as in Example 10 of the photocuring rate evaluation. The total calorific value for 5 minutes from the start of light irradiation was 443 mJ / mg.

(Evaluation Example 14 of Photocuring Speed)
Photocuring rate evaluation Except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene in Example 10 was changed to 9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Monomer Synthesis Example 5. Was subjected to optical DSC measurement in the same manner as in Example 10 of the photocuring rate evaluation. As a result, the total calorific value for 5 minutes from the start of light irradiation was 336 mJ / mg.

(Example 15 of light curing rate evaluation)
Photocuring rate evaluation Except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene in Example 10 was changed to 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene obtained in the same manner as in Monomer Synthesis Example 6. When the light DSC measurement was performed in the same manner as in Example 10 of the photocuring rate evaluation, the total calorific value for 5 minutes from the start of light irradiation was 552 mJ / mg.

(Light curing rate evaluation example 16)
Photocuring Rate Evaluation 9,10-bis (methoxycarbonylmethyleneoxy) anthracene of Example 10 was added to 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Monomer Synthesis Example 9. Optical DSC measurement was carried out in the same manner as in Example 10 of the photocuring rate evaluation except that the amount was changed. As a result, the total calorific value for 5 minutes from the start of light irradiation was 441 mJ / mg.

(Evaluation Example 19 of Photocuring Speed)
Photocuring rate evaluation The light curing rate was changed except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene in Example 10 was changed to 9,10-bis (propoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Monomer Synthesis Example 11. When a light DSC measurement was carried out in the same manner as in Example 10 of the curing rate evaluation, the total calorific value for 5 minutes from the start of light irradiation was 379 mJ / mg.

(Evaluation Example 20 of Photocuring Speed)
9,10-Bis (methoxycarbonylmethyleneoxy) anthracene of Example 10 for photocuring rate evaluation was changed to 9,10-bis (2-hydroxyethoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Monomer Synthesis Example 13. Except for the above, the light DSC measurement was carried out in the same manner as in Example 10 of the photocuring rate evaluation. The total calorific value for 5 minutes from the start of light irradiation was 420 mJ / mg.

(Evaluation Example 25 of Light Curing Speed)
9,10-Bis (methoxycarbonylmethyleneoxy) anthracene in Example 10 for photocuring rate evaluation was changed to 9,10-bis (n-pentyloxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Monomer Synthesis Example 18. Except for the above, the light DSC measurement was performed in the same manner as in Example 10 of the photocuring rate evaluation. The total calorific value for 5 minutes from the start of light irradiation was 376 mJ / mg.

(Light curing rate evaluation example 26)
Photocuring rate evaluation Except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene in Example 10 was changed to 9,10-bis (cyclohexyloxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Example 19 of monomer synthesis. When the light DSC measurement was performed in the same manner as in Example 10 of the photocuring rate evaluation, the total calorific value for 5 minutes from the start of light irradiation was 354 mJ / mg.

(Evaluation Example 27 of Photocuring Speed)
Photocuring Rate Evaluation The photopolymerization initiator of Example 10 was changed to 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name “Irgacure 651”, manufactured by BSF Inc.), and Except that the radical polymerization sensitizer was changed to 0.2 parts by weight of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Example 2 of the monomer synthesis, the photocuring rate was changed in the same manner as in Evaluation Example 10 of the present invention. Upon DSC measurement, the total calorific value for 5 minutes from the start of light irradiation was 487 mJ / mg.

(Evaluation Example 28 of Photocuring Speed)
Photocuring Rate Evaluation The photopolymerization initiator of Example 10 was 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name “Irgacure 907”, B.A.S. Photocuring rate except that the photoradical polymerization sensitizer was changed to 0.2 part by weight of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Example 2 of monomer synthesis. When optical DSC measurement was performed in the same manner as in Example 10 of evaluation, the total calorific value for 5 minutes from the start of light irradiation was 496 mJ / mg.

(Evaluation Example 29 of Photocuring Speed)
Photocuring Rate Evaluation The photopolymerization initiator of Example 10 was changed to 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name "Irgacure TPO" manufactured by BSF Inc.), and photoradical polymerization sensitization was performed. Photo DSC measurement was carried out in the same manner as in Evaluation Example 10 of the photocuring rate except that the agent was changed to 0.2 parts by weight of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Example 2 of monomer synthesis. As a result, the total calorific value for 5 minutes from the start of light irradiation was 635 mJ / mg.

(Evaluation Example 30 of Photocuring Speed)
Photo-radical polymerization started with 50 parts by weight of FA-310M (phenoxyethyl methacrylate, manufactured by Hitachi Chemical) and 50 parts by weight of FA-321M (EO-modified bisphenol A dimethacrylate, manufactured by Hitachi Chemical) as radical polymerizable compounds. [8-[[(acetyloxy) imino] [2- (2,2,3,3-tetrafluoropropoxy) phenyl] methyl] -11- (2-ethylhexyl) -11H-benzo [a] carbazole- 5-yl]-, (2,4,6-trimethylphenyl) (trade name “Irgacure OXE03” manufactured by BSF Inc.) was added in an amount of 0.5 part. Further, 0.2 part by weight of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene obtained in Monomer Synthesis Example 2 was added to prepare a photo-radical polymerizable composition. This was dropped onto quartz glass on a rheometer, sandwiched between parallel plates having a thickness of 100 μm and a diameter of 10 mm, and the photocurable composition unnecessary for viscosity measurement was wiped off. Thirty seconds after the start of the viscosity measurement of the photocurable composition, UV-LED light having a wavelength of 405 nm was irradiated. At this time, the time when the complex viscosity reached 40,000 Pa · s was 386 seconds.

(Evaluation Example 31 of Photocuring Speed)
Photo-radical polymerization started with 50 parts by weight of FA-310M (phenoxyethyl methacrylate, manufactured by Hitachi Chemical) and 50 parts by weight of FA-321M (EO-modified bisphenol A dimethacrylate, manufactured by Hitachi Chemical) as radical polymerizable compounds. 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer (2 parts) was added as an agent, and 0.17 part of leuco crystal violet (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a color former. Further, 0.6 part by weight of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene obtained in Monomer Synthesis Example 2 was added to prepare a photo-radical polymerizable composition. This was dropped onto quartz glass on a rheometer, sandwiched between parallel plates having a thickness of 100 μm and a diameter of 10 mm, and the photocurable composition unnecessary for viscosity measurement was wiped off. Thirty seconds after the start of the viscosity measurement of the photocurable composition, UV-LED light having a wavelength of 405 nm was irradiated. At this time, the time when the complex viscosity reached 40,000 Pa · s was 592 seconds.

(Light Curing Rate Evaluation Example 32)
Based on 100 parts by weight of biscoat # 230 (1,6-hexanediol diacrylate, manufactured by Osaka Organic Chemical Industry) as a radical polymerizable compound, 2- (4-methoxyphenyl) -4,6 is used as a photoradical polymerization initiator. 5 parts of bis (trichloromethyl) -1,3,5-triazine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. Further, 1 part by weight of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene obtained in Monomer Synthesis Example 2 was added to prepare a photo-radical polymerizable composition. This was dropped onto quartz glass on a rheometer, sandwiched between parallel plates having a thickness of 100 μm and a diameter of 10 mm, and the photocurable composition unnecessary for viscosity measurement was wiped off. Thirty seconds after the start of the viscosity measurement of the photocurable composition, UV-LED light having a wavelength of 405 nm was irradiated. At this time, the time when the complex viscosity reached 40,000 Pa · s was 85 seconds.

(Comparative Example 4 for Evaluation of Photocuring Speed)
As a photo-radical polymerizable compound, 2 parts by weight of 1-hydroxycyclohexyl phenyl ketone as a photo-polymerization initiator was mixed at room temperature with 100 parts by weight of trimethylolpropane triacrylate to prepare a photo-radical polymerizable composition. When a photo-DSC measurement was performed on this photopolymerizable composition, the total calorific value for 5 minutes from the start of light irradiation was 166 mJ / mg.

(Comparative Example 5 for Photocuring Speed Evaluation)
Photocuring rate evaluation Example 10 except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene of Example 10 was replaced with 9,10-dibutoxyanthracene which is a known photopolymerization sensitizer. When the light DSC measurement was performed in the same manner as in the above, the total heat generation for 5 minutes from the start of light irradiation was 212 mJ / mg.

(Comparative Example 6 for Photocuring Rate Evaluation)
Photocuring Rate Evaluation The photocuring rate was the same as in Example 10 except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene was replaced with 9,10-bis (octanoyloxy) anthracene, which is a known photopolymerization sensitizer. When optical DSC measurement was performed in the same manner as in Evaluation Example 10, the total calorific value for 5 minutes from the start of light irradiation was 298 mJ / mg.

(Comparative Example 9 for Photocuring Speed Evaluation)
As a photo-radical polymerizable compound, 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name "Irgacure 651" B.P.) is used as a photopolymerization initiator with respect to 100 parts by weight of trimethylolpropane triacrylate. 2 parts by weight (ASF) were mixed at room temperature to prepare a photo-radical polymerizable composition. When a photo-DSC measurement was performed on this photopolymerizable composition, the total calorific value for 5 minutes from the start of light irradiation was 346 mJ / mg.

(Comparative Example 10 for Evaluation of Photocuring Speed)
As the photo-radical polymerizable compound, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (photopolymerization initiator) is added to 100 parts by weight of trimethylolpropane triacrylate. 2 parts by weight (trade name "Irgacure 907", manufactured by BSF Inc.) were mixed at room temperature to prepare a photo-radical polymerizable composition. When a photo-DSC measurement was performed on the photopolymerizable composition, a total calorific value for 5 minutes from the start of light irradiation was 392 mJ / mg.

(Comparative Example 11 for Evaluation of Photocuring Speed)
As a photo-radical polymerizable compound, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name "Irgacure TPO", B.S. 2 parts by weight (manufactured by F Corporation) were mixed at room temperature to prepare a photo-radical polymerizable composition. When a photo-DSC measurement was performed on this photopolymerizable composition, the total calorific value for 5 minutes from the start of light irradiation was 566 mJ / mg.

(Light Curing Speed Evaluation Comparative Example 12)
The viscosity was measured in the same manner as in the photocuring rate evaluation example 30 except that 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene was not used in the photocuring rate evaluation example 30. At this time, the time when the complex viscosity reached 40,000 Pa · s was 1,822 seconds.

(Comparative Example 13 for Evaluation of Photocuring Speed)
The viscosity was measured in the same manner as in Photocuring Rate Evaluation Example 31 except that 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene was not added. At this time, the time when the complex viscosity reached 40,000 Pa · s was 1256 seconds.

(Comparative Example 14 for Photocuring Speed Evaluation)
The viscosity was measured in the same manner as in the photocuring rate evaluation example 32 except that the 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene was not added. At this time, the time when the complex viscosity reached 40,000 Pa · s was 335 seconds.

Table 5 summarizes the results of Photocuring Speed Evaluation Examples 10 to 16, 19, 20, 25 to 29 and Photocuring Speed Evaluation Comparative Examples 4 to 6, 9 to 11.

Table 6 summarizes the results of Photocuring Speed Evaluation Examples 30 to 32 and Photocuring Speed Evaluation Comparative Examples 12 to 14.

As is clear from comparison of the results of Photocuring Rate Evaluation Examples 1 to 9, 17, 18, 21 to 24 and Photocuring Rate Evaluation Comparative Examples 1, 7, and 8, the ester group of the present invention was used in photocationic polymerization. By adding a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having the following general formula (I) as a photopolymerization sensitizer, the total calorific value was increased, and it was found that the polymerization reaction was remarkably accelerated. In addition, as apparent from the comparison of the results of Photocuring Rate Evaluation Examples 10 to 16, 19, 20, 25 to 32 and Photocuring Rate Evaluation Comparative Examples 4, 9 to 14, the present invention is also applicable to photoradical polymerization. By adding the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group of the above, the total calorific value similarly increased, and it was found that the polymerization reaction was remarkably accelerated. That is, it can be seen that the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group of the present invention has a photopolymerization sensitizing effect in both photocation polymerization and photoradical polymerization.

Further, as apparent from the comparison of the results of Photocuring Rate Evaluation Examples 1 to 9, 17, 18, 21 to 24 and Photocuring Rate Evaluation Comparative Examples 2 and 3, the ester group of the present invention in photocationic polymerization was used. The 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having the formula (I) is equivalent to or more than 9,10-dibutoxyanthracene and 9,10-bis (octanoyloxy) anthracene, which are known photopolymerization sensitizers. It can be seen that the photopolymerization sensitizing effect of Further, as is clear from the comparison of the results of Photocuring Rate Evaluation Examples 10 to 16, 19, 20, 25 to 29 and Photocuring Rate Evaluation Comparative Examples 5 and 6, the ester of the present invention is also used in photoradical polymerization. The 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having a group is equivalent to 9,10-dibutoxyanthracene and 9,10-bis (octanoyloxy) anthracene which are also known photopolymerization sensitizers. It can be seen that the photopolymerization sensitization effect is higher than that. That is, the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group of the present invention is a known photopolymerization sensitizer in both photocationic polymerization and photoradical polymerization, which is 9,10-dibutoxy. It can be seen that the compound has a photopolymerization sensitizing effect equal to or higher than that of anthracene.

Further, as is apparent from comparison of the results of the photocuring rate evaluation examples 30 to 32 and the photocuring rate evaluation comparative examples 12 to 14, the 9,10-bis (alkoxycarbonylalkylene) having an ester group of the present invention is evident. It can be seen that by adding the oxy) anthracene compound, the time when the complex viscosity reached 40,000 Pa · s was remarkably shortened. This indicates that the addition of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group of the present invention significantly accelerates the polymerization rate. That is, the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group of the present invention is extremely effective also for an oxime ester-based polymerization initiator, a biimidazole-based polymerization initiator, and a triazine-based polymerization initiator. It can be seen that the photopolymerization sensitizing effect is excellent.

Next, the photopolymerization performance evaluation test of the photocationic polymerizable composition using the oligomer of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group of the present invention as the photocationic polymerization sensitizer is described below. I do.

"Light Curing Rate Evaluation Example 33"
3 ′, 4′-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, trade name: Celloxide 2021P, celloxide is a registered trademark of Daicel Corporation) as 100 parts by weight as a photocationic polymerizable compound 2 parts by weight of photopolymerization initiator (4-methylphenyl) [4- (2-methylpropyl) phenyl] iodonium-hexafluorophosphate (trade name Irgacure 250, manufactured by BSF Inc.) As a cationic photopolymerization sensitizer, oligomer is obtained by reacting 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene obtained in the same manner as in Synthesis Example 2 with 3-methyl-1,5-pentanediol. One part by weight of the oligomer was mixed at room temperature to prepare a cationic photopolymerizable composition. When a photo-DSC measurement was performed on this photopolymerizable composition, the total calorific value for one minute from the start of light irradiation was 132 mJ / mg.

"Photocuring rate evaluation example 34"
An oligomer obtained by reacting 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol in “Evaluation Example 33 of Photocuring Rate” was obtained in the same manner as in Example 3 of oligomer synthesis. Same as “Example 33 of photocuring rate evaluation” except that the obtained oligomer was obtained by reacting 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 2,4-diethyl-1,5-pentanediol. When the optical DSC measurement was performed, the total calorific value for one minute from the start of the light irradiation was 114 mJ / mg.

"Example 35 of light curing rate evaluation"
An oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 3-methyl-1,5-pentanediol in “Evaluation Example 33 of Photocuring Rate” was obtained in the same manner as in Example 4 of oligomer synthesis. An optical DSC measurement was performed in the same manner as in “Example 33 of photocuring rate evaluation” except that the oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 1,9-nonanediol was used. As a result, the total heat generation for one minute from the start of light irradiation was 128 mJ / mg.

"Example 39 of light curing rate evaluation"
An oligomer obtained by reacting 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol in “Photocuring Rate Evaluation Example 33” was obtained in the same manner as in Oligomer Synthesis Example 9. Optical DSC measurement was performed in the same manner as in “Example 33 of photocuring rate evaluation” except that the oligomer obtained by reacting 9,10-dihydroxyanthracene with 1,5-bis (bromoacetoxy) 3-methylpentane was used. As a result, the total heat generation for one minute from the start of light irradiation was 89 mJ / mg.

"Light Curing Rate Evaluation Example 40"
An oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol in “Photocuring Rate Evaluation Example 33” was obtained in the same manner as in oligomer synthesis Example 10. Optical DSC measurement was carried out in the same manner as in “Example 33 of photocuring rate evaluation” except that the obtained oligomer was obtained by reacting 9,10-dihydroxyanthracene with 1,9-bis (bromoacetoxy) nonane. The total calorific value for one minute from the start of light irradiation was 146 mJ / mg.

"Comparative Example 15 for Light Curing Speed Evaluation"
3 ′, 4′-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, trade name: Celloxide 2021P, celloxide is a registered trademark of Daicel Corporation) as 100 parts by weight as a photocationic polymerizable compound 2 parts by weight of a photopolymerization initiator (4-methylphenyl) [4- (2-methylpropyl) phenyl] iodonium-hexafluorophosphate (trade name Irgacure 250, manufactured by BSF Inc.) The mixture was mixed at room temperature to prepare a cationic photopolymerizable composition. When a photo-DSC measurement was performed on this photopolymerizable composition, the total calorific value for one minute from the start of light irradiation was 0.4 mJ / mg.

"Photocuring speed evaluation comparative example 16"
A known photopolymerization sensitizer is used instead of the oligomer obtained by reacting 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol in "Evaluation Example of Photocuring Rate Example 33" Optical DSC measurement was conducted in the same manner as in “Evaluation Example 33 of photocuring rate” except that 9,10-dibutoxyanthracene was used. The total heat generation for one minute from the start of light irradiation was 99 mJ / mg. there were.

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

"Evaluation Example 36 of Photocuring Speed"
To 100 parts by weight of trimethylolpropane triacrylate as a photoradical polymerizable compound, 2 parts by weight of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator, and oligomer synthesis Example 2 as a photoradical polymerization sensitizer 0.05 parts by weight of an oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 3-methyl-1,5-pentanediol obtained by the same method are mixed at room temperature, and the photo-radical is mixed. A polymerizable composition was prepared. When a photo-DSC measurement was performed on this photopolymerizable composition, the total calorific value for one minute from the start of light irradiation was 186 mJ / mg.

"Evaluation Example 37 of Photocuring Speed"
An oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol in “Photocuring Rate Evaluation Example 36” was obtained in the same manner as in oligomer synthesis Example 3. The same as “Example 36 of photocuring rate evaluation” except that the obtained oligomer was obtained by reacting 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 2,4-diethyl-1,5-pentanediol. When the light DSC measurement was performed, the total calorific value for one minute from the start of light irradiation was 213 mJ / mg.

"Example 38 of evaluation of light curing speed"
An oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 3-methyl-1,5-pentanediol in “Photocuring Rate Evaluation Example 36” was obtained in the same manner as in the oligomer synthesis Example 4. An optical DSC measurement was carried out in the same manner as in “Evaluation Example 36 of photocuring rate” except that the oligomer obtained by reacting 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 1,9-nonanediol was used. As a result, the total heat generation for one minute from the start of light irradiation was 196 mJ / mg.

"Light Curing Rate Evaluation Example 41"
An oligomer obtained by reacting 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol in “Evaluation Example 36 of Photocuring Rate” was obtained in the same manner as in Example 9 of oligomer synthesis. The optical DSC measurement was carried out in the same manner as in “Example 36 of photocuring rate evaluation” except that the oligomer obtained by reacting 9,10-dihydroxyanthracene with 1,5-bis (bromoacetoxy) 3-methylpentane was used. As a result, the total heat generation for one minute from the start of light irradiation was 226 mJ / mg.

"Light Curing Rate Evaluation Example 42"
An oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol in “Photocuring Rate Evaluation Example 36” was obtained in the same manner as in Oligomer Synthesis Example 10. An optical DSC measurement was conducted in the same manner as in “Example 36 of photocuring rate evaluation” except that the obtained oligomer was obtained by reacting 9,10-dihydroxyanthracene with 1,9-bis (bromoacetoxy) nonane. The total calorific value for one minute from the start of light irradiation was 199 mJ / mg.

"Photocuring speed evaluation comparative example 17"
2 parts by weight of 1-hydroxycyclohexylphenyl ketone as a photoinitiator were mixed at room temperature with 100 parts by weight of trimethylolpropane triacrylate as a photoradical polymerizable compound to prepare a photoradical polymerizable composition. When a photo-DSC measurement was performed on this photopolymerizable composition, the total calorific value for one minute from the start of light irradiation was 76 mJ / mg.

"Photocuring speed evaluation comparative example 18"
The oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol in "Evaluation Example of Photocuring Rate 36" is a known photopolymerization sensitizer. Optical DSC measurement was carried out in the same manner as in “Evaluation example 36 of photocuring rate” except for using 9,10-dibutoxyanthracene. The total calorific value for one minute from the start of light irradiation was 125 mJ / mg. .

Table 7 summarizes the results of Photocuring Speed Evaluation Examples 33 to 42 and Photocuring Speed Evaluation Comparative Examples 15 to 18.

As is clear from comparison of the results of the photocuring rate evaluation examples 33, 34, 35, 39, and 40 with the photocuring rate evaluation comparative example 15, the 9,10-bis (alkoxycarbonyl) of the present invention was used in photocationic polymerization. By adding the oligomer of the alkyleneoxy) anthracene compound, the total calorific value was increased, indicating that the polymerization reaction was remarkably accelerated. Further, as is clear from comparison of the results of Photocuring Rate Evaluation Examples 36, 37, 38, 41, and 42 with Photocuring Rate Comparative Example 17, the 9,10-bis (alkoxy) of the present invention is also applicable to photoradical polymerization. By adding the oligomer of the carbonylalkyleneoxy) anthracene compound, the total calorific value was increased, indicating that the polymerization reaction was remarkably accelerated. 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.

Furthermore, as apparent from comparison of the results of the photocuring rate evaluation examples 33, 34, 35, 39, and 40 with the photocuring rate evaluation comparative example 16, the 9,10-bis ( It can be seen that the oligomer of the alkoxycarbonylalkyleneoxy) anthracene compound has a photopolymerization sensitizing effect equal to or higher than that of 9,10-dibutoxyanthracene which is a known photopolymerization sensitizer. In addition, as is clear from comparison of the results of the photo-curing rate evaluation examples 36, 37, 38, 41, and 42 with the photo-curing rate comparative example 18, the 9,10-bis (alkoxy) of the present invention is also applicable to the photo-radical polymerization. It can be seen that the oligomer of the carbonylalkyleneoxy) anthracene compound has a photopolymerization sensitizing effect equal to or higher than that of 9,10-dibutoxyanthracene which is a known photopolymerization sensitizer.

Next, the evaluation results of the migration resistance will be described.

(Evaluation example of migration resistance of composition containing 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound in cationic photopolymerization)
(Example 1 of migration resistance evaluation)
Monomer Synthesis Example 1 was used as a photopolymerization sensitizer for 100 parts of 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Ceroxide 2021P manufactured by Daicel) as an epoxy photocationically polymerizable compound. One part of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene synthesized in the same manner was mixed, and the prepared composition was applied on a polyester film using a bar coater so that the film thickness became 12 μm. Next, a low-density polyethylene film (thickness: 30 μm) was put on the obtained coated product, and the product was stored for one day in a dark place and stored for seven days. After washing with acetone and drying, the UV spectrum of the film was measured, and the absorbance at 260 nm was measured. The absorbance attributable to the obtained 9,10-bis (methoxycarbonylmethyleneoxy) anthracene was converted to 9,10-dibutoxyanthracene. The absorbance was 0.015 after storage for one day and 0.003 after storage for seven days.

(Evaluation example 2 of migration resistance)
Instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene synthesized in the same manner as in Monomer Synthesis Example 2 is used. The test was conducted in the same manner as in Example 1 except for the migration resistance evaluation. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the value obtained by converting the absorbance attributable to 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene into 9,10-dibutoxyanthracene was 0.007 after storage for one day. 0.007 after storage for 7 days.

(Evaluation example 3 of migration resistance)
Instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene synthesized in the same manner as in Monomer Synthesis Example 3 is used as the photopolymerization sensitizer. Except for this, the test was conducted in the same manner as in Example 1 for evaluating the migration resistance. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the value obtained by converting the absorbance attributable to 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene into 9,10-dibutoxyanthracene was 0.1% after one day of storage. 007, 0.007 after storage for 7 days.

(Example 4 of migration resistance evaluation)
Instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene synthesized by the same method as in Example 4 was used. The test was conducted in the same manner as in Example 1 except for performing the migration resistance evaluation. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance attributable to 9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene was converted to 9,10-dibutoxyanthracene, which was 0% after storage for one day. 0.010 and 0.014 after storage for 7 days.

(Evaluation example 5 of migration resistance)
Instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene synthesized in the same manner as in Monomer Synthesis Example 5 was used. The test was conducted in the same manner as in Example 1 except for performing the migration resistance evaluation. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the value of the absorbance attributable to 9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene converted to 9,10-dibutoxyanthracene was 0 after storage for one day. It was 0.0011 and 0.007 after storage for 7 days.

(Example 6 of migration resistance evaluation)
Instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene synthesized in the same manner as in Monomer Synthesis Example 6 is used as the photopolymerization sensitizer. Except for this, the test was conducted in the same manner as in Example 1 for evaluating the migration resistance. As a result of measuring the absorbance at 260 nm of the acetone-washed polyethylene film, the value obtained by converting the absorbance due to 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene into 9,10-dibutoxyanthracene was 0.1% after storage for one day. 007, 0.003 after storage for 7 days.

(Evaluation example 7 of migration resistance)
Instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonylpropyleneoxy) anthracene synthesized in the same manner as in Monomer Synthesis Example 7 is used. The test was conducted in the same manner as in Example 1 except for the migration resistance evaluation. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the value of the absorbance attributable to 9,10-bis (ethoxycarbonylpropyleneoxy) anthracene converted to 9,10-dibutoxyanthracene was 0.015 after storage for one day. After storage for 7 days was 0.013.

(Example 8 of migration resistance evaluation)
Instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonylbutyleneoxy) anthracene synthesized in the same manner as in Monomer Synthesis Example 8 is used. The test was conducted in the same manner as in Example 1 except for the migration resistance evaluation. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the value obtained by converting the absorbance attributable to 9,10-bis (ethoxycarbonylbutyleneoxy) anthracene into 9,10-dibutoxyanthracene was 0.012 after storage for one day. 0.010 after storage for 7 days.

(Evaluation example 9 of migration resistance)
Instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) was synthesized in the same manner as in Monomer Synthesis Example 9 as a photopolymerization sensitizer. Except for using anthracene, the test was conducted in the same manner as in Example 1 for evaluating the migration resistance. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the value obtained by converting the absorbance due to 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene into 9,10-dibutoxyanthracene was one day. It was 0.015 after storage and 0.015 after seven days storage.

(Evaluation Example 19 of Migration Resistance)
As a photopolymerization sensitizer, instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 9,10-bis (n-pentyloxycarbonylmethyleneoxy) anthracene synthesized by the same method as in Monomer Synthesis Example 18 was used. The test was conducted in the same manner as in Example 1 for evaluating the migration resistance, except that it was used. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the value obtained by converting the absorbance attributable to 9,10-bis (n-pentyloxycarbonylmethyleneoxy) anthracene into 9,10-dibutoxyanthracene is one day after storage. It was 0.014 after storage for 7 days and 0.011.

(Evaluation example 20 of migration resistance)
Instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 9,10-bis (cyclohexyloxycarbonylmethyleneoxy) anthracene synthesized in the same manner as in Monomer Synthesis Example 19 is used as the photopolymerization sensitizer. Except for this, the test was conducted in the same manner as in Example 1 for evaluating the migration resistance. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the value obtained by converting the absorbance attributable to 9,10-bis (cyclohexyloxycarbonylmethyleneoxy) anthracene into 9,10-dibutoxyanthracene was 0.1% after storage for one day. 013 and 0.010 after storage for 7 days.

(Comparative Example 1 for Evaluation of Migration Resistance)
Example of migration resistance evaluation Example except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene was replaced by 9,10-dibutoxyanthracene, a known photopolymerization sensitizer, instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene Prepared as in 1. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance of 9,10-dibutoxyanthracene was 0.737 after storage for one day and 0.843 after storage for seven days.

Table 8 summarizes the results of the migration resistance evaluation examples 1 to 9, 19, and 20 and the migration resistance evaluation comparative example 1.

(Evaluation example of migration resistance of composition containing 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound in photoradical polymerization)
(Evaluation example 10 of migration resistance)
100 parts of trimethylolpropane triacrylate as a photoradical polymerizable compound and 1 part of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene synthesized by the same method as in Monomer Synthesis Example 1 as a photoradical polymerization sensitizer. The mixed and prepared composition was applied on a polyester film using a bar coater so as to have a thickness of 12 μm. Next, a low-density polyethylene film (thickness: 30 μm) was put on the obtained coated product, and one that was stored in a dark place for one day and one that was stored for seven days were prepared. 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 260 nm was measured. The absorption due to 9,10-bis (methoxycarbonylmethyleneoxy) anthracene was one It was 0.015 after 7 days storage and 0.016 after 7 days storage.

(Evaluation example 11 of migration resistance)
Evaluation of migration resistance except that 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene synthesized in the same manner as in Example 2 was used instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene. Prepared and tested as in Example 10. The absorbance at 260 nm of the polyethylene film washed with acetone was measured. The absorption due to 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene was 0.014 after storage for one day and 0.015 after storage for seven days. .

(Evaluation example 12 of migration resistance)
Migration resistance evaluation except that 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene was used instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene to synthesize 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene. Prepared and tested as in Example 10. The absorbance at 260 nm of the polyethylene film washed with acetone was measured. The absorption due to 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene was 0.024 after storage for one day and 0.022 after storage for seven days. Was.

(Evaluation example 13 of migration resistance)
Migration resistance except for using 9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene synthesized in the same manner as in Example 4 in place of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene It was prepared and tested as in Evaluation Example 10. The absorbance at 260 nm of the polyethylene film washed with acetone was measured. The absorption due to 9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene was 0.037 after storage for one day and 0.033 after storage for seven days. there were.

(Evaluation example 14 of migration resistance)
Migration resistance except that 9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene was synthesized in the same manner as in Example 5 instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene. It was prepared and tested as in Evaluation Example 10. The absorbance at 260 nm of the polyethylene film washed with acetone was measured. The absorption attributed to 9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene was 0.022 after storage for one day and 0.015 after storage for seven days. there were.

(Evaluation example 15 of migration resistance)
Migration resistance evaluation except that 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene was used instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene to synthesize 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene. Prepared and tested as in Example 10. The absorbance at 260 nm of the polyethylene film washed with acetone was measured. The absorption due to 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene was 0.007 after one day storage and 0.004 after seven days storage. Was.

(Evaluation example 16 of migration resistance)
Evaluation of migration resistance except that 9,10-bis (ethoxycarbonylpropyleneoxy) anthracene synthesized in the same manner as in Example 7 was used instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene. Prepared and tested as in Example 10. The absorbance at 260 nm of the polyethylene film washed with acetone was measured. The absorption due to 9,10-bis (ethoxycarbonylpropyleneoxy) anthracene was 0.032 after storage for one day and 0.030 after storage for seven days. .

(Evaluation example 17 of migration resistance)
Migration resistance evaluation was performed except that 9,10-bis (ethoxycarbonylbutyleneoxy) anthracene synthesized in the same manner as in Example 8 was used instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene. Prepared and tested as in Example 10. The absorbance at 260 nm of the polyethylene film washed with acetone was measured. The absorption due to 9,10-bis (ethoxycarbonylbutyleneoxy) anthracene was 0.022 after one day storage and 0.021 after seven days storage. .

(Evaluation example 18 of migration resistance)
Synthesis of Monomer Instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene synthesized in the same manner as in Example 9 was used. Evaluation of migration resistance A sample was prepared and tested in the same manner as in Example 10. The absorbance at 260 nm of the polyethylene film washed with acetone was measured. The absorption due to 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene was 0.031 after storage for one day and 0 after storage for seven days. 0.032.

(Evaluation Example 21 for Migration Resistance)
Migration resistance except that 9,10-bis (n-pentyloxycarbonylmethyleneoxy) anthracene was synthesized in the same manner as in Example 18 in place of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene. It was prepared and tested in the same manner as in Example 10. The absorbance at 260 nm of the polyethylene film washed with acetone was measured. The absorption due to 9,10-bis (n-pentyloxycarbonylmethyleneoxy) anthracene was 0.051 after one day storage and 0.032 after seven days storage. Met.

(Evaluation example 22 of migration resistance)
Migration resistance evaluation except that 9,10-bis (cyclohexyloxycarbonylmethyleneoxy) anthracene was used instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene to synthesize 9,10-bis (cyclohexyloxycarbonylmethyleneoxy) anthracene. Prepared and tested as in Example 10. The absorbance at 260 nm of the polyethylene film washed with acetone was measured. The absorption due to 9,10-bis (cyclohexyloxycarbonylmethyleneoxy) anthracene was 0.051 after storage for one day and 0.035 after storage for seven days. Was.

(Migration resistance evaluation comparative example 2)
Migration resistance was evaluated in the same manner as in Example 10 except that 9,10-dibutoxyanthracene, a known photoradical sensitizer, was used instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene. . As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance of the obtained 9,10-dibutoxyanthracene was 1.661 after storage for one day and 1.741 after seven days.

Table 9 summarizes the results of the migration resistance evaluation examples 10 to 18, 21, and 22 and the migration resistance evaluation comparative example 2.

As is apparent from a comparison between the migration resistance evaluation examples 1 to 9, 19 and 20 and the migration resistance evaluation comparative example 1, the photocationic polymerizable composition is a known photocationic polymerization sensitizer. 9,10-Dibutoxyanthracene has migrated to a considerable extent to the film overlying the photocationically polymerizable composition, whereas the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound of the present application In each case, the degree of migration is extremely low, and it can be said that the migration resistance is excellent.

On the other hand, as is apparent from a comparison between the migration resistance evaluation examples 10 to 18, 21, and 22 and the migration resistance evaluation comparative example 2, the known photoradical polymerization sensitization was also found in the photoradical polymerizable composition. The agent 9,10-dibutoxyanthracene migrates to a considerable extent in the film overlying the photoradical polymerizable composition, whereas the 9,10-bis (alkoxycarbonylalkyleneoxy) In any case, the anthracene compound has a very low migration degree and can be said to be excellent in migration resistance.

(Evaluation example of migration resistance of composition containing oligomer of 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound in cationic photopolymerization)
(Evaluation example 23 of migration resistance)
To 100 parts of 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Ceroxide 2021P manufactured by Daicel) as an epoxy photocationically polymerizable compound, oligomers were used as photopolymerization sensitizers as in Example 2 A composition prepared by mixing one part of an oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol, which was synthesized by the method described in 1), was coated on a polyester film. It was applied using a bar coater so that the thickness became 12 microns. Next, a low-density polyethylene film (thickness: 30 μm) was put on the obtained coated product, and the product stored for 4 days in a dark place and the product stored for 7 days were respectively stored, and then the polyethylene film was peeled off. After washing with acetone and drying, the UV spectrum of the film was measured, and the absorbance at 230 nm was measured. The absorption due to the oligomer obtained by the reaction of the obtained 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol is 0.004 after storage for 4 days, and storage for 7 days. Later it was 0.005.

(Evaluation example 24 of migration resistance)
Oligomer Synthesis As a photopolymerization sensitizer, oligomer is synthesized by the same method as in Example 3 instead of oligomer obtained by reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol. The migration resistance was evaluated in the same manner as in Example 23 except that the oligomer 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 acetone-washed polyethylene film, the absorption due to the oligomer obtained by the reaction between 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.

(Evaluation example 25 of migration resistance)
Oligomer Synthesis As a photopolymerization sensitizer, oligomers were synthesized in the same manner as in Example 4 instead of oligomers obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol. The migration resistance was evaluated in the same manner as in Example 23 except that the oligomer 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 caused by the oligomer obtained by the reaction between 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 1,9-nonanediol was measured after storage for four days. 0.004, and 0.005 after storage for 7 days.

(Evaluation example 29 of migration resistance)
Oligomer as the photopolymerization sensitizer Instead of the oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol, oligomer was synthesized in the same manner as in Example 9. The migration resistance was evaluated in the same manner as in Example 23 except that the oligomer of 9,10-dihydroxyanthracene and 1,5-bis (bromoacetoxy) 3-methylpentane was used. As a result of measuring the absorbance at 230 nm of the polyethylene film washed with acetone, the absorption resulting from the oligomer obtained by the reaction between 10,10-dihydroxyanthracene and 1,5-bis (bromoacetoxy) 3-methylpentane was measured after storage for four days. 0.005 and 0.007 after storage for 7 days.

(Evaluation example 30 of migration resistance)
Oligomer synthesized by the same method as in Example 10 instead of the oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol as a photopolymerization sensitizer The migration resistance was evaluated in the same manner as in Example 23 except that the oligomer of 9,10-dihydroxyanthracene and 1,9-bis (bromoacetoxy) nonane was used. As a result of measuring the absorbance at 230 nm of the polyethylene film washed with acetone, the absorption resulting from the oligomer obtained by the reaction between 9,10-dihydroxyanthracene and 1,9-bis (bromoacetoxy) nonane was 0.1% after storage for four days. 006, 0.007 after storage for 7 days.

(Migration resistance evaluation comparative example 3)
As a photopolymerization sensitizer, a known photopolymerization sensitizer is used instead of the oligomer obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol. Except for using 10-dibutoxyanthracene, it was prepared in the same manner as in Example 23 for evaluating migration resistance. 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.

(Evaluation example of migration resistance of composition containing oligomer of 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound in photoradical polymerization)
(Evaluation example 26 of migration resistance)
Trimethylolpropane triacrylate (100 parts) as a photoradical polymerizable compound, and oligomers (9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 3-methyl) synthesized as a photoradical polymerization sensitizer in the same manner as in Example 2. A composition prepared by mixing 0.05 parts of the oligomer obtained by the reaction with 1,5-pentanediol was applied on a polyester film using a bar coater so that the film thickness became 12 μm. Next, a low-density polyethylene film (thickness: 30 μm) was put on the obtained coated product, and those stored for 4 days and those stored for 7 days in a dark place were prepared. After peeling off, washing the polyethylene film with acetone and drying, the UV spectrum of the polyethylene film was measured, and the absorbance at 230 nm was measured. As a result, it was confirmed that 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 3-methyl-1, The absorption due to the oligomer obtained by the reaction with 5-pentanediol was 0.004 after storage for 4 days, and 0.005 after storage for 7 days.

(Evaluation example 27 of migration resistance)
Oligomers obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol are replaced by oligomers synthesized by the same method as in Example 3. Migration resistance was evaluated in the same manner as in Example 26 except that an oligomer obtained by reacting (ethoxycarbonylmethyleneoxy) anthracene with 2,4-diethyl-1,5-pentanediol was used. The absorbance at 230 nm of the polyethylene film washed with acetone was measured. The absorption due to the oligomer obtained by the reaction between 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.

(Evaluation example 28 of migration resistance)
Oligomers obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol are replaced by oligomers synthesized in the same manner as in Example 4 to obtain 9,10-bis. Migration resistance was evaluated in the same manner as in Example 26 except that an oligomer obtained by reacting (ethoxycarbonylmethyleneoxy) anthracene with 1,9-nonanediol was used. The absorbance at 230 nm of the polyethylene film washed with acetone was measured. The absorption due to the oligomer obtained by the reaction between 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene and 1,9-nonanediol was measured after storage for four days. 0.005, and 0.005 after storage for 7 days.

(Evaluation example 31 of migration resistance)
Oligomers obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol are replaced by oligomers 9,10-dihydroxy synthesized in the same manner as in Example 9. Migration resistance was evaluated in the same manner as in Example 26 except that an oligomer obtained by reacting anthracene 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 due to the oligomer obtained by the reaction between 9,10-dihydroxyanthracene and 1,5-bis (bromoacetoxy) 3-methylpentane was stored for four days. 0.003 after storage for 7 days and 0.007 after storage for 7 days.

(Evaluation example 32 of migration resistance)
Oligomers obtained by the reaction of 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene with 3-methyl-1,5-pentanediol are replaced by oligomers synthesized in the same manner as in Example 10 to obtain 9,10-dihydroxy. Except for using an oligomer obtained by the reaction of anthracene with 1,9-bis (bromoacetoxy) nonane, the migration resistance was evaluated and prepared in the same manner as in Example 26. The absorbance at 230 nm of the polyethylene film washed with acetone was measured. The absorption caused by the oligomer obtained by the reaction between 9,10-dihydroxyanthracene and 1,9-bis (bromoacetoxy) nonane was 0.1% after storage for 4 days. 003, 0.007 after storage for 7 days.

(Comparative Example 4 for Evaluation 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, a known photoradical sensitizer, is used. The test was conducted in the same manner as in Example 26 of the migration resistance evaluation 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 storage for four days and 0.060 after seven days.

Table 10 summarizes the results of the migration resistance evaluation examples 23 to 32 and the migration resistance evaluation comparative examples 3 and 4.

As is apparent from a comparison between the migration resistance evaluation examples 23, 24, 25, 29, and 30 and the migration resistance comparison example 3, the photocationic polymerizable composition is a known photocationic polymerization sensitizer. 9,10-Dibutoxyanthracene has migrated to a considerable extent to the film overlying the cationic photopolymerizable composition, whereas the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound of the present invention has In any case, the degree of migration is extremely low, and it can be said that the oligomer is excellent in migration resistance. Furthermore, as apparent from a comparison between the migration resistance evaluation examples 26, 27, 28, 31, and 32 and the migration resistance comparative example 4, the known photoradical polymerization was also included in the photoradical polymerizable composition. The sensitizer 9,10-dibutoxyanthracene migrates to a considerable extent in the film coated on the photoradical polymerizable composition, whereas the 9,10-bis (alkoxycarbonyl) of the invention In any case, the degree of migration of the oligomer of the alkyleneoxy) anthracene compound is extremely low, and it can be said that the oligomer has excellent migration resistance.

From the above results, the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group and the oligomer thereof according to the present invention are known photopolymerization sensitizers in photocation polymerization and photoradical polymerization. Compared with the 10-dibutoxyanthracene compound, the compound has not only the same photopolymerization sensitizing ability but also a high migration resistance due to its structure having a polar ester group. It is understood that this is a very useful compound.

The 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group and the oligomer thereof according to the present invention exhibit an excellent effect as a photopolymerization sensitizer in a photopolymerization reaction and, at the same time, have a polar ester group. Is a very industrially useful compound in which the photopolymerization sensitizer hardly causes migration and blooming.

Claims (17)

1. A 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the following general formula (1).
   

   

   (In the general formula (1), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms; The group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, provided that the alkyl group does not contain an oxygen atom, and X and Y may be the same or different; Represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.)
2. 2. The 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound according to claim 1, wherein A in the general formula (1) is a methylene group.
3. An oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having a repeating unit having an ester group represented by the following general formula (10).
   

   

   (In the general formula (10), n represents the number of repetitions and is 2 to 50, A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D is a carbon atom. Represents an alkylene group having the number of 1 to 100 or an arylene group having a carbon number of 6 to 20, wherein the alkylene group may be branched by an alkyl group or may contain an unsaturated bond; May be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom under non-adjacent conditions, or may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring and the naphthalene ring are substituted with an alkyl group. The arylene group may have a substituent, and a plurality of rings may be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. There .X, Y may be the same or different, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.)
4. 4. The oligomer of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound according to claim 3, wherein A in the general formula (10) is a methylene group.
5. An ester represented by the following general formula (1) characterized by reacting a 9,10-dihydroxyanthracene compound represented by the following general formula (2) with an ester compound represented by the following general formula (3) A process for producing a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having a group.
   

   

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

   

   (In the general formula (3), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms; The group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, may be substituted by a hydroxy group, and may have a part of carbon atoms replaced by an oxygen atom (provided that G is a chlorine atom, a bromine atom or an iodine atom.)
   

   

   (In the general formula (1), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms; The group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, may be substituted by a hydroxy group, and may have a part of carbon atoms replaced by an oxygen atom (provided that X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.)
6. A 9,10-dihydroxyanthracene compound represented by the following general formula (2) is reacted with a carboxylic acid compound represented by the following general formula (4) to give a 9,10-dihydroxyanthracene compound represented by the following general formula (5). A bis (hydroxycarbonylalkyleneoxy) anthracene compound is synthesized, and a 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5) is synthesized with the following general formula (6), general formula (7) or A method for producing a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the following general formula (1), characterized by reacting an esterifying agent represented by the general formula (8): .
   

   

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

   

   (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. G represents a chlorine atom, a bromine atom or an iodine atom.)
   

   

   (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. X and Y may be the same or different; Atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.)
   

   

   (In the general formula (6), R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, and may be a hydroxy group. May be substituted, and some of the carbon atoms may be replaced by oxygen atoms (except when peroxides are formed).)
   

   

   (In the general formula (7), R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, and may be a hydroxy group. It may be substituted, and a part of carbon atoms may be replaced by an oxygen atom (however, excluding cases where a peroxide is formed. G represents a chlorine atom, a bromine atom, or an iodine atom.)
   

   

   (In the general formula (8), R ¹ represents a hydrogen atom or an alkyl group having 1 to 17 carbon atoms, and the alkyl group may be branched by an alkyl group, and may be a cycloalkyl group or a cycloalkylalkyl group. And may be substituted by a hydroxy group, and a part of carbon atoms may be replaced by an oxygen atom (except when a peroxide is formed), provided that R ¹ has 1 to 17 carbon atoms. In the case of the alkyl group of the formula (1), the number of carbon atoms of R ¹ is 3 less than the number of carbon atoms of R, except when the number of carbon atoms of R in formula (1) is 1 to 3.)
   

   

   (In the general formula (1), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms; The group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, may be substituted by a hydroxy group, and may have a part of carbon atoms replaced by an oxygen atom (provided that X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.)
7. A repeating unit characterized by reacting a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound represented by the following general formula (1) with a bifunctional compound represented by the following general formula (11): A method for producing an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the following general formula (10).
   

   

   (In the general formula (1), 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 20 carbon atoms. The alkyl group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, may be substituted with a hydroxy group, or may have a part of carbon atoms replaced by an oxygen atom. Good (however, excluding the case of forming a peroxide), X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom.
   

   

   (In the general formula (11), 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 non-adjacent conditions, and may contain an alicyclic compound, a benzene ring or a naphthalene ring, The benzene ring and naphthalene ring may be substituted with an alkyl group, and the arylene group may have a substituent, and a plurality of rings are bonded by an alkylene group, an oxygen atom, a nitrogen atom, and a sulfur atom. Z represents a hydroxy group, a halogen atom, or a glycidyloxy group.)
   

   

   (In the general formula (10), n represents the number of repetitions and is 2 to 50, A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D is a carbon atom. Represents an alkylene group having the number of 1 to 100 or an arylene group having a carbon number of 6 to 20, wherein the alkylene group may be branched by an alkyl group or may contain an unsaturated bond; May be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom under non-adjacent conditions, or may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring and the naphthalene ring are substituted with an alkyl group. The arylene group may have a substituent, and a plurality of rings may be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. There .X, Y may be the same or different, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.)
8. A repeating unit characterized by reacting a 9,10-dihydroxyanthracene compound represented by the following general formula (2) with a bifunctional compound represented by the following general formula (13) is represented by the following general formula (10) A method for producing an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the following formula:
   

   

   (In the general formula (2), X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, 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, wherein the alkylene group may be branched by an alkyl group or may contain an unsaturated bond, and the carbon atoms of the alkylene structure are oxygen atom, nitrogen atom, sulfur May be substituted with an atom, or may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring and the naphthalene ring may be substituted with an alkyl group. And a plurality of rings may be bonded by an alkylene group, an oxygen atom, a nitrogen atom, a sulfur atom, and G is a chlorine atom, a bromine atom or C represents an atom.)
   

   

   (In the general formula (10), n represents the number of repetitions and is 2 to 50, A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D is a carbon atom. Represents an alkylene group having the number of 1 to 100 or an arylene group having a carbon number of 6 to 20, wherein the alkylene group may be branched by an alkyl group or may contain an unsaturated bond; May be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom under non-adjacent conditions, or may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring and the naphthalene ring are substituted with an alkyl group. The arylene group may have a substituent, and a plurality of rings may be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. There .X, Y may be the same or different, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.)
9. A photopolymerization sensitizer containing a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the following general formula (1).
   

   

   (In the general formula (1), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms; The group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, may be substituted by a hydroxy group, and may have a part of carbon atoms replaced by an oxygen atom (provided that X and Y may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.)
10. In a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1), A is a methylene group, R is not substituted with a hydroxy group, and a part of carbon atoms is not substituted. Is an alkyl group having 1 to 20 carbon atoms, which is not replaced by an oxygen atom.
11. A photopolymerization sensitizer containing an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having a repeating unit having an ester group represented by the following general formula (10).
    

    

    (In the general formula (10), n represents the number of repetitions and is 2 to 50, A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. D is a carbon atom. Represents an alkylene group having the number of 1 to 100 or an arylene group having a carbon number of 6 to 20, wherein the alkylene group may be branched by an alkyl group or may contain an unsaturated bond; May be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom under non-adjacent conditions, or may contain an alicyclic compound, a benzene ring or a naphthalene ring, and the benzene ring and the naphthalene ring are substituted with an alkyl group. The arylene group may have a substituent, and a plurality of rings may be bonded by an alkylene group, an oxygen atom, a nitrogen atom, or a sulfur atom. There .X, Y may be the same or different, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group or a halogen atom.)
12. The photopolymerization sensitizer containing an oligomer of a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound according to claim 11, wherein A in the general formula (10) is a methylene group.
13. A photopolymerization initiator composition comprising the photopolymerization sensitizer according to any one of claims 9 to 12 and a photopolymerization initiator.
14. A photopolymerizable composition comprising the photopolymerization initiator composition according to claim 13 and a photocationically polymerizable compound.
15. A photopolymerizable composition comprising the photopolymerization initiator composition according to claim 13 and a photoradical polymerizable compound.
16. A polymerization method for 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 a wavelength range of 300 nm to 500 nm is an ultraviolet LED or a 405 nm semiconductor laser having a center wavelength of 365 nm, 375 nm, 385 nm, 395 nm or 405 nm, according to claim 16, characterized in that: Polymerization method.