JP7129006B2 - Photopolymerization sensitizer with migration resistance - Google Patents

Description

The present invention provides a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group, a method for producing the same, and a photopolymerization sensitization containing a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group. Regarding agents.

Photo-curable resins, which are polymerized by active energy rays such as ultraviolet rays and visible rays, cure quickly and can significantly reduce the amount of organic solvents used compared to thermosetting resins, improving the working environment and reducing environmental impact. It is excellent in that it can be reduced. Conventional photocurable resins by themselves have poor polymerization initiation functions, and usually require the use of photopolymerization initiators for curing. As the photopolymerization initiator, an alkylphenone polymerization initiator such as hydroxyacetophenone or benzophenone, an acylphosphine oxide photopolymerization initiator, an onium salt, or the like is used (Patent Documents 1, 2, 3). Among these photopolymerization initiators, when an onium salt-based initiator is used, the onium salt absorbs light in the vicinity of 225 nm to 350 nm and does not absorb light at 350 nm or more, so a long wavelength lamp of 350 nm or more is used as a light source. In this case, there is a problem that the photo-curing reaction is difficult to proceed, and it is common to add a photopolymerization sensitizer. Similarly, many photopolymerization initiators such as alkylphenone-based polymerization initiators do not have absorption at 350 nm or more. Anthracene compounds and thioxanthone compounds are known as photopolymerization sensitizers for these photopolymerization initiators, and particularly anthracene compounds are often used due to the problem of color (Patent Document 4).

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

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

For photopolymerizable compositions, for example, when these photopolymerization sensitizers are used as one component of a photoadhesive that adheres film to film, the photopolymerization sensitizer migrates to the overlying film ( migration), which can cause dusting and staining problems of the photosensitizer on the top film.

In addition, dry film resists are used for processing such as the manufacture of printed wiring boards, the manufacture of lead frames, and the manufacture of metal masks. Thioxanthone and 9,10-dialkoxyanthracene compounds are used as photopolymerization sensitizers. However, dry film resists are stored and traded in a state in which a cover film is placed on the photosensitive resin composition. There is a problem that the agent migrates, the sensitizing effect is lowered, and dusting occurs on the film (Patent Document 9).

In order to suppress such migration of the photopolymerization sensitizer, a 9,10-bis(2-acyloxyalkoxy)anthracene compound in which an ester group, which is a polar group, is introduced into the alkoxy group of the 9,10-dialkoxyanthracene compound is used. It has been reported (Patent Document 10). However, the production of the 9,10-bis(2-acyloxyalkoxy)anthracene compound requires the use of an alkylene oxide compound in the production process, which increases the number of steps, leading to an increase in cost. Difficulty in obtaining and handling poses a serious problem in the production of the 9,10-bis(2-acyloxyalkoxy)anthracene compound.

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

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

Therefore, not only does it have migration resistance during photocuring or storage of the cured product and does not cause problems of powdering or coloring of the cured product, it is also a practical manufacturing method using easily available raw materials. There is a demand for the development of new photopolymerization sensitizers that can be obtained by

The present inventors have made further intensive studies on the structure and physical properties of anthracene compounds, and have found that the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group, which is shown in the present invention, exhibits an increase in photopolymerization in a photopolymerization reaction. At the same time as exhibiting excellent effects as a sensitizer, it was found that the presence of a polar ester group prevents the photopolymerization sensitizer from causing migration and blooming. A manufacturing method was discovered, and the present invention was completed.

That is, the 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 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 alkyl group may be branched by an alkyl group, may be substituted with a hydroxy group, and part of the carbon atoms may be replaced by oxygen atoms; may also be used (unless they form 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.

A second gist of the present invention is the following general formula 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): Disclosed is a method for producing a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group represented by formula (1).

In 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 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 alkyl group may be branched by an alkyl group, may be substituted with a hydroxy group, and part of the carbon atoms may be replaced by oxygen atoms; may also be used (unless they form peroxides). Z represents a chlorine atom, a bromine atom or an iodine atom.

In 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 alkyl group may be branched by an alkyl group, may be substituted with a hydroxy group, and part of the carbon atoms may be replaced by oxygen atoms; may also be used (unless they form 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.

The third 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) to obtain ) to synthesize a 9,10-bis(hydroxycarbonylalkyleneoxy)anthracene compound represented by the general formula (5) and the 9,10-bis(hydroxycarbonylalkyleneoxy)anthracene compound represented by the following general formula ( 6), a 9,10-bis(alkoxy The present invention relates to a method for producing a carbonyl alkyleneoxy) anthracene compound.

In 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 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. Z represents a chlorine atom, a bromine atom or an iodine atom.

In general formula (5), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. 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 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 substituted with a hydroxy group, and may be part of the carbon atoms. may be replaced by an oxygen atom (except when forming a peroxide).

In 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 substituted with a hydroxy group, and may be part of the carbon atoms. may be replaced by an oxygen atom (except when forming a peroxide). D represents a chlorine atom, a bromine atom or an iodine atom.

In 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 or may be substituted with a hydroxy group; A portion of the carbon atoms may be replaced by oxygen atoms (except when forming a peroxide).

In 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 alkyl group may be branched by an alkyl group, may be substituted with a hydroxy group, and part of the carbon atoms may be replaced by oxygen atoms; may also be used (unless they form 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.

A fourth gist 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 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 alkyl group may be branched by an alkyl group, may be substituted with a hydroxy group, and part of the carbon atoms may be replaced by oxygen atoms; may also be used (unless they form 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.

A fifth aspect of the present invention resides in a photopolymerization initiator composition containing the photopolymerization sensitizer described in the fourth aspect and a photopolymerization initiator.

A sixth aspect of the present invention resides in a photopolymerizable composition containing the photopolymerization initiator composition according to the fifth aspect and a photo-cationically polymerizable compound.

The seventh gist of the present invention resides in a photopolymerizable composition containing the photopolymerization initiator composition according to the fifth gist and a radically photopolymerizable compound.

The eighth aspect of the present invention is a polymerization method for polymerizing the photopolymerizable composition according to the sixth aspect or the seventh aspect by irradiating with energy rays containing light in the wavelength range of 300 nm to 500 nm. exist.

The ninth gist of the present invention is characterized in that the irradiation source of energy rays containing light in the wavelength range of 300 nm to 500 nm is an ultraviolet LED or semiconductor laser with a central wavelength of 365 nm, 375 nm, 385 nm, 395 nm, or 405 nm. It resides in the polymerization method according to the eighth summary.

The 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group of the present invention not only has a high effect as a photopolymerization sensitizer in a photopolymerization reaction, but also has a photopolymerization-enhancing effect. It is a useful compound in which the degree of migration or blooming of the photopolymerization sensitizer is extremely low in a photopolymerizable composition containing it as a sensitizer. Also, in the production method, there is no need to use an alkylene oxide compound that is difficult to obtain and handle, the production process is easy, and the product can be produced at a low cost.

(Compound)
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 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 alkyl group may be branched by an alkyl group, may be substituted with a hydroxy group, and part of the carbon atoms may be replaced by oxygen atoms; may also be used (unless they form 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 general formula (1), the alkylene group having 1 to 20 carbon atoms represented by A includes methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, nonadecylene group, icosylene group, etc., and the alkylene group may be branched by an alkyl group. .

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

In general formula (1), the alkyl group having 1 to 20 carbon atoms represented by R includes methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t -butyl group, n-pentyl group, i-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, 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, etc., the alkyl Groups substituted with hydroxy groups include 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxybutyl 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 group, 11-hydroxyundecyl group, 12-hydroxydodecyl group, 2-hydroxy-3-methoxypropyl group, 2-hydroxy-3-ethoxypropyl group, 2-hydroxy-3-propoxypropyl group, 2-hydroxy-3-butoxypropyl group, 2- hydroxy-3-pentyloxypropyl group, 2-hydroxy-3-hexyloxypropyl group, 2-hydroxy-3-octyloxypropyl group, 2-hydroxy-3-(2-ethylhexyloxy)propyl group, 2,3- dihydroxypropyl group, 2-hydroxy-3-allyloxypropyl group, 2-hydroxy-3-methallyloxypropyl group and the like.

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 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(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(methoxycarbonyl methylmethyleneoxy)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-hydroxyethoxycarbonylmethoxy)anthracene and the like.

Furthermore, 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-butoxycarbonylhexyleneoxy) ) anthracene, 9,10-bis(methoxycarbonylheptyleneoxy)anthracene, 9,10-bis(ethoxycarbonylheptyleneoxy)anthracene, 9,10-bis(isopropoxycarbonylheptyleneoxy)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, 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(methoxycarbonyldecyleneoxy)anthracene, 9,10 -bis(ethoxycarbonyldecyleneoxy)anthracene, 9,10-bis(isopropoxycarbonyldecyleneoxy)anthracene, 9,10-bis(tert-butoxycarbonyldecylene noxy)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-butoxycarbonylundecyleneoxy)anthracene, 9,10-bis(methoxycarbonyldode sileneoxy)anthracene, 9,10-bis(ethoxycarbonyldodecyleneoxy)anthracene, 9,10-bis(isopropoxycarbonyldodecyleneoxy)anthracene, 9,10-bis(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-butoxycarbonyltridecyleneoxy)anthracene, 9,10-bis (Methoxycarbonyltetradecyleneoxy)anthracene, 9,10-bis(ethoxycarbonyltetradecyleneoxy)anthracene, 9,10-bis(isopropoxycarbonyltetradecyleneoxy)anthracene, 9,10-bis(tert-butoxy) carbonyltetradecyleneoxy)anthracene, 9,10-bis(n-butoxycarbonyltetradecyleneoxy)anthracene, 9,10-bis(methoxycarbonylpentadecyleneoxy)anthracene, 9,10-bis(ethoxycarbonylpentade sileneoxy)anthracene, 9,10-bis(isopropoxycarbonylpentadecyleneoxy)anthracene, 9,10-bis(tert-butoxycarbonylpentadecyleneoxy)anthracene, 9,10-bis(n-butoxycarbonylpentadene) sileneoxy)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(methoxycarbonyloctadecyleneoxy) ) anthracene, 9,10-bis(ethoxycarbonyloctadecyleneoxy)anthracene, 9,10-bis(isopropoxycarbonyloctadecyleneoxy)anthracene, 9,10-bis(tert-butoxycarbonyloctadecyleneoxy)anthracene , 9,10-bis(n-butoxycarbonyloctadecyleneoxy)anthracene, 9,10-bis(methoxycarbonylnonadecyleneoxy)anthracene, 9,10-bis(ethoxycarbonylnonadecyleneoxy)anthracene, 9, 10-bis(isopropoxycarbonylnonadecyleneoxy)anthracene, 9,10-bis(tert-butoxycarbonylnonadecyleneoxy)anthracene, 9,10-bis(n-butoxycarbonylnonadecyleneoxy)anthracene, 9, 10-bis(methoxycarbonylicosyleneoxy)anthracene, 9,10-bis(ethoxycarbonylicosyleneoxy)anthracene, 9,10-bis(isopropoxycarbonylicosyleneoxy)anthracene, 9,10-bis(tert-butoxy carbonylicosyleneoxy)anthracene, 9,10-bis(n-butoxycarbonylicosyleneoxy)anthracene and the like.

Further, specific examples where X and/or Y are alkyl groups 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(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-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(isopropoxycarbonylmethylmethyleneoxy)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(methoxycarbonyloctyleneoxy)anthracene, 2-ethyl-9,10-bis(ethoxycarbonyl Octylene Oxygen c) 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-butoxycarbonylhexadecyleneoxy)anthracene, 2-ethyl-9,10- bis(n-butoxycarbonylhexadecyleneoxy)anthracene, 2-ethyl-9,10-bis(methoxycarbonylicosyleneoxy)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-hydroxyethoxycarbonylmethoxy)anthracene and the like.

Furthermore, 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(methoxycarbonylpropyleneoxy)anthracene, 2-amyl-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(ethoxycarbonylmethylmethyleneoxy)anthracene, 2-amyl-9,10-bis(ethoxy carbonylethylmethyleneoxy)anthracene, 2-amyl-9,10-bis(isopropoxycarbonylmethylmethyleneoxy)anthracene, 2-amyl-9,10-bis(tert-butoxycarbonylmethylmethyleneoxy)anthracene, 2-amyl- 9,10-bis(n-butoxycarbonylmethylmethyleneoxy)anthracene, 2-amyl-9,10-bis(methoxycarbonylbutyleneoxy)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-butoxy carbonylbutyleneoxy)anthracene, 2-amyl-9,10-bis(2-hydroxyethoxycarbonylmethoxy)anthracene and the like.

Specific examples of halogen atoms for X and/or Y include 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(ethoxycarbonylpropyleneoxy)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(methoxycarbonylmethylmethyleneoxy)anthracene, 2-chloro-9,10-bis(ethoxycarbonylmethylmethyleneoxy) ) anthracene, 2-chloro-9,10-bis(ethoxycarbonylethylmethyleneoxy)anthracene, 2-chloro-9,10-bis(isopropoxycarbonylmethylmethyleneoxy)anthracene, 2-chloro-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, 2-chloro-9,10-bis(tert-butoxycarbonylbutyleneoxy)anthracene , 2-chloro-9,10-bis(n-butoxycarbonylbutyleneoxy)anthracene, 2-chloro-9,10-bis(methoxycarbonyloctyleneoxy)anthracene, 2-chloro-9,10-bis(ethoxycarbonyl Octileo oxy)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-butoxycarbonylhexadecyleneoxy)anthracene, 2-chloro-9,10- bis(n-butoxycarbonylhexadecyleneoxy)anthracene, 2-chloro-9,10-bis(methoxycarbonylicosyleneoxy)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-hydroxyethoxycarbonylmethoxy)anthracene and the like.

Among the above-mentioned specific examples, 9,10-bis(methoxycarbonylmethyleneoxy)anthracene, 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene, 9,10-bis(n-propoxycarbonyl methyleneoxy)anthracene, 9,10-bis(isopropoxycarbonylmethyleneoxy)anthracene, 9,10-bis(tert-butoxycarbonylmethyleneoxy)anthracene, 9,10-bis(n-butoxycarbonylmethyleneoxy)anthracene, 9 , 10-bis(methoxycarbonylpropyleneoxy)anthracene, 9,10-bis(ethoxycarbonylpropyleneoxy)anthracene, 9,10-bis(isopropoxycarbonylpropyleneoxy)anthracene, 9,10-bis(tert-butoxycarbonylpropyleneoxy)anthracene oxy)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-hydroxyethoxycarbonylmethoxy)anthracene, 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(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-butoxycarbonylpropyleneoxy)anthracene, 2-ethyl-9,10-bis(methoxycarbonylmethylmethyleneoxy)anthracene, 2-ethyl-9,10-bis(ethoxycarbonylmethylmethylene) oxy)anthracene, 2-ethyl-9,10-bis(ethoxycarbonylethylmethyleneoxy)anthracene, 2-ethyl-9,10-bis(isopropoxycarbonylmethylmethyleneoxy)anthracene, 2-ethyl-9,10-bis (tert-butoxycarbonylmethylmethyleneoxy)anthracene, 2-ethyl-9,10-bis(n-butoxycarbonylmethylmethyleneoxy)anthracene, 2-ethyl-9,10-bis(2-hydroxyethoxycarbonylmethoxy)anthracene Preferably, 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(methoxycarbonylmethylmethyleneoxy)anthracene (1-6), 9,10-bis(ethoxycarbonyl Propyleneoxy)anthracene (1-7), 9,10-bis(ethoxycarbonylbutyleneoxy)anthracene (1-8), 2-ethyl-9,10-bis(isopropoxycarbonylmethyleneoxy)anthracene (1-9) , 9,10-bis(2-hydroxyeth) Xycarbonylmethoxy)anthracene (1-11) is particularly preferred.

(manufacturing method)
Next, the method for producing the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group of the present invention will be explained. The 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group represented by the general formula (1) of the present invention is made from a 9,10-dihydroxyanthracene compound represented by the following general formula (2). However, a method of synthesizing in a single step reaction using a 9,10-dihydroxyanthracene compound as a raw material (one-step production method) and a method of synthesizing in a two-step reaction via an intermediate (two-step production method) There is

In 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.

(One step manufacturing method)
First, the one-step production method of the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group of 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 a 9,10-dihydroxyanthracene compound represented by the general formula (2) as follows. It can be obtained by reacting with the corresponding ester compound represented by the general formula (3) in the presence or absence of a basic compound according to reaction formula-1.

In Reaction 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 alkyl group may be branched by an alkyl group, may be substituted with a hydroxy group, and part of the carbon atoms may be replaced by oxygen atoms; may also be used (unless they form 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. Z represents a chlorine atom, a bromine atom or an iodine atom.

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

Specific examples of the 9,10-dihydroxyanthracene compound as a starting material in the reaction include 9,10-dihydroxyanthracene, 2-methyl-9,10-dihydroxyanthracene, and 2-ethyl-9,10-dihydroxyanthracene. , 2-t-pentyl-9,10-dihydroxyanthracene, 2,6-dimethyl-9,10-dihydroxyanthracene, 2-chloro-9,10-dihydroxyanthracene, 2-bromo-9,10-dihydroxyanthracene, etc. mentioned.

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

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

In reaction formula-1, specific examples of the ester compound represented by the general formula (3) as a raw material include methyl chloroacetate, ethyl chloroacetate, n-propyl chloroacetate, isopropyl chloroacetate, n-butyl chloroacetate ( 3-5), tert-butyl chloroacetate, pentyl chloroacetate, hexyl chloroacetate, heptyl chloroacetate, octyl chloroacetate, 2-ethylhexyl chloroacetate, nonyl chloroacetate, dodecyl chloroacetate, nonadecyl chloroacetate, icosyl chloroacetate, 2 - methyl chloropropionate, methyl 3-chloropropionate, methyl 2-chloropropionate, methyl 3-chloropropionate, ethyl 2-chloropropionate, ethyl 3-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, heptyl 2-chloropropionate, heptyl 3-chloropropionate , octyl 2-chloropropionate, octyl 3-chloropropionate, 2-ethylhexyl 2-chloropropionate, 2-ethylhexyl 3-chloropropionate, nonyl 2-chloropropionate, nonyl 3-chloropropionate, 2-chloro dodecyl propionate, dodecyl 3-chloropropionate, nonadecyl 2-chloropropionate, nonadecyl 3-chloropropionate, icosyl 2-chloropropionate, icosyl 3-chloropropionate, methyl 2-chlorobutyrate, methyl 3-chlorobutyrate , methyl 4-chlorobutyrate, ethyl 2-chlorobutyrate, ethyl 3-chlorobutyrate, ethyl 4-chlorobutyrate, n-propyl 2-chlorobutyrate, n-propyl 3-chlorobutyrate, n-propyl 4-chlorobutyrate, 2 -isopropyl chlorobutyrate, isopropyl 3-chlorobutyrate, isopropyl 4-chlorobutyrate, n-butyl 2-chlorobutyrate, n-butyl 3-chlorobutyrate, n-butyl 4-chlorobutyrate, tert-butyl 2-chlorobutyrate, 3 - tert-butyl chlorobutyrate, tert-butyl 4-chlorobutyrate, pentyl 2-chlorobutyrate, pentachlorobutyrate 3-chlorobutyrate pentyl 4-chlorobutyrate, hexyl 2-chlorobutyrate, hexyl 3-chlorobutyrate, hexyl 4-chlorobutyrate, heptyl 2-chlorobutyrate, heptyl 3-chlorobutyrate, heptyl 4-chlorobutyrate, octyl 2-chlorobutyrate, octyl 3-chlorobutyrate, octyl 4-chlorobutyrate, 2-ethylhexyl 2-chlorobutyrate, 2-ethylhexyl 3-chlorobutyrate, 2-ethylhexyl 4-chlorobutyrate, nonyl 2-chlorobutyrate, nonyl 3-chlorobutyrate, 4- nonyl chlorobutyrate, dodecyl 2-chlorobutyrate, dodecyl 3-chlorobutyrate, dodecyl 4-chlorobutyrate, nonadecyl 2-chlorobutyrate, nonadecyl 3-chlorobutyrate, nonadecyl 4-chlorobutyrate, icosyl 2-chlorobutyrate, 3-chlorobutyric acid icosyl, icosyl 4-chlorobutyrate, methyl 2-chlorovalerate, methyl 3-chlorovalerate, methyl 4-chlorovalerate, methyl 5-chlorovalerate, ethyl 2-chlorovalerate, ethyl 3-chlorovalerate, 4-ethyl chlorovalerate, 5-ethyl chlorovalerate, n-propyl 2-chlorovalerate, n-propyl 3-chlorovalerate, n-propyl 4-chlorovalerate, n-propyl 5-chlorovalerate, Isopropyl 2-chlorovalerate, Isopropyl 3-chlorovalerate, Isopropyl 4-chlorovalerate, Isopropyl 5-chlorovalerate, n-butyl 2-chlorovalerate, n-butyl 3-chlorovalerate, 4-chlorovalerate n-butyl forate, n-butyl 5-chlorovalerate, tert-butyl 2-chlorovalerate, tert-butyl 3-chlorovalerate, tert-butyl 4-chlorovalerate, tert-butyl 5-chlorovalerate, 2-pentyl chlorovalerate, 3-pentyl chlorovalerate, 4-pentyl chlorovalerate, 5-pentyl chlorovalerate, 2-hexyl chlorovalerate, 3-hexyl chlorovalerate, 4-hexyl chlorovalerate, 5 -hexyl chlorovalerate, 2-heptyl chlorovalerate, 3-heptyl chlorovalerate, 4-heptyl chlorovalerate, 5-heptyl chlorovalerate, octyl 2-chlorovalerate, octyl 3-chlorovalerate, 4- octyl chlorovalerate, octyl 5-chlorovalerate, 2-ethylhexyl 2-chlorovalerate, 2-ethylhexyl 3-chlorovalerate, 2-ethylhexyl 4-chlorovalerate, 2-ethylhexyl 5-chlorovalerate, 2- nonyl chlorovalerate, 3-nonyl chlorovalerate, nonyl 4-chlorovalerate, nonyl 5-chlorovalerate, dodecyl 2-chlorovalerate, 3-dodecyl chlorovalerate, 4-dodecyl chlorovalerate, 5-dodecyl chlorovalerate, nonadecyl 2-chlorovalerate, nonadecyl 3-chlorovalerate, nonadecyl 4-chlorovalerate, nonadecyl 5-chlorovalerate, 2 -icosyl 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-bromoacetate Butyl (3-3), pentyl bromoacetate, hexyl bromoacetate, heptyl bromoacetate, octyl bromoacetate, 2-ethylhexyl bromoacetate, nonyl bromoacetate, dodecyl bromoacetate, nonadecyl bromoacetate, icosyl bromoacetate, 2-bromopropionic acid methyl (3-6), methyl 3-bromopropionate, methyl 2-bromopropionate, methyl 3-bromopropionate, ethyl 2-bromopropionate, ethyl 3-bromopropionate, n-propyl 2-bromopropionate , n-propyl 3-bromopropionate, isopropyl 2-bromopropionate, isopropyl 3-bromopropionate, n-butyl 2-bromopropionate, n-butyl 3-bromopropionate, tert-butyl 2-bromopropionate , tert-butyl 3-bromopropionate, pentyl 2-bromopropionate, pentyl 3-bromopropionate, hexyl 2-bromopropionate, hexyl 3-bromopropionate, heptyl 2-bromopropionate, 3-bromopropionic acid heptyl, octyl 2-bromopropionate, octyl 3-bromopropionate, 2-ethylhexyl 2-bromopropionate, 2-ethylhexyl 3-bromopropionate, nonyl 2-bromopropionate, nonyl 3-bromopropionate, 2- dodecyl bromopropionate, dodecyl 3-bromopropionate, nonadecyl 2-bromopropionate, nonadecyl 3-bromopropionate, icosyl 2-bromopropionate, icosyl 3-bromopropionate, methyl 2-bromobutyrate, 3-bromobutyric acid Methyl, methyl 4-bromobutyrate, ethyl 2-bromobutyrate, ethyl 3-bromobutyrate, ethyl 4-bromobutyrate (3-7), n-propyl 2-bromobutyrate, n-propyl 3-bromobutyrate, 4-bromo n-propyl butyrate, isopropyl 2-bromobutyrate, isopropyl 3-bromobutyrate, isopropyl 4-bromobutyrate, n-butyl 2-bromobutyrate, n-butyl 3-bromobutyrate, n-butyl 4-bromobutyrate, 2-bromo tert-butyl butyrate, tert-butyl 3-bromobutyrate, tert-butyl 4-bromobutyrate, 2-pentyl bromobutyrate, 3-pentyl bromobutyrate, 4-bromo Pentyl Butyrate, 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 4-bromobutyrate, 2 -dodecyl bromobutyrate, dodecyl 3-bromobutyrate, dodecyl 4-bromobutyrate, nonadecyl 2-bromobutyrate, nonadecyl 3-bromobutyrate, nonadecyl 4-bromobutyrate, icosyl 2-bromobutyrate, icosyl 3-bromobutyrate, 4-bromo Icosyl Butyrate, Methyl 2-Bromovalerate, Methyl 3-Bromovalerate, Methyl 4-Bromovalerate, Methyl 5-Bromovalerate, Ethyl 2-Bromovalerate, 3-Ethyl Bromovalerate, 4-Bromovalerate ethyl (3-8), ethyl 5-bromovalerate, n-propyl 2-bromovalerate, n-propyl 3-bromovalerate, n-propyl 4-bromovalerate, n-propyl 5-bromovalerate, Isopropyl 2-Bromovalerate, Isopropyl 3-Bromovalerate, Isopropyl 4-Bromovalerate, Isopropyl 5-Bromovalerate, n-Butyl 2-Bromovalerate, n-Butyl 3-Bromovalerate, 4-Bromovalerate n-Butyl Forate, n-Butyl 5-Bromovalerate, tert-Butyl 2-Bromovalerate, tert-Butyl 3-Bromovalerate, tert-Butyl 4-Bromovalerate, tert-Butyl 5-Bromovalerate, 2-Pentyl Bromovalerate, 3-Pentyl Bromovalerate, 4-Pentyl Bromovalerate, 5-Pentyl Bromovalerate, 2-Hexyl Bromovalerate, 3-Hexyl Bromovalerate, 4-Hexyl Bromovalerate, 5 -hexyl bromovalerate, 2-heptyl bromovalerate, 3-heptyl bromovalerate, 4-heptyl bromovalerate, 5-heptyl bromovalerate, octyl 2-bromovalerate, octyl 3-bromovalerate, 4- Octyl Bromovalerate, Octyl 5-Bromovalerate, 2-Ethylhexyl 2-Bromovalerate, 2-Ethylhexyl 3-Bromovalerate, 2-Ethylhexyl 4-Bromovalerate, 2-Ethylhexyl 5-Bromovalerate, 2- Nonyl Bromovalerate, 3-Bromovalerate Nonylic Acid, Nonyl 4-Bromovalerate, Nonyl 5-Bromovalerate, Dodecyl 2-Bromovalerate, 3-Bromovalerate Dodecyl Movalerate, 4-Bromovalerate, Dodecyl 5-Bromovalerate, Nonadecyl 2-Bromovalerate, Nonadecyl 3-Bromovalerate, Nonadecyl 4-Bromovalerate, Nonadecyl 5-Bromovalerate, 2-Bromo Icosyl Valerate, Icosyl 3-Bromovalerate, Icosyl 4-Bromovalerate, Icosyl 5-Bromovalerate, 2-Hydroxyethyl Bromoacetate (3-10), 2-Hydroxyethyl 2-Bromopropionate, 3 -2-hydroxyethyl-bromobutyrate, 2-hydroxyethyl-4-bromovalerate, and the like.

And further, methyl iodoacetate, ethyl iodoacetate, n-propyl iodoacetate, isopropyl iodoacetate, n-butyl iodoacetate, tert-butyl iodoacetate, pentyl iodoacetate, hexyl iodoacetate, heptyl iodoacetate, octyl iodoacetate, iodine 2-ethylhexyl acetate, nonyl iodoacetate, dodecyl iodoacetate, nonadecyl iodoacetate, icosyl iodoacetate, methyl 2-iodopropionate, 3-methyl iodopropionate, methyl 2-iodopropionate, methyl 3-iodopropionate, 2 -ethyl iodopropionate, ethyl 3-iodopropionate, n-propyl 2-iodopropionate, n-propyl 3-iodopropionate, isopropyl 2-iodopropionate, isopropyl 3-iodopropionate, 2-iodopropionate n-butyl, n-butyl 3-iodopropionate, tert-butyl 2-iodopropionate, tert-butyl 3-iodopropionate, pentyl 2-iodopropionate, pentyl 3-iodopropionate, 2-iodopropionic acid Hexyl, hexyl 3-iodopropionate, heptyl 2-iodopropionate, heptyl 3-iodopropionate, octyl 2-iodopropionate, octyl 3-iodopropionate, 2-ethylhexyl 2-iodopropionate, 3-iodopropionate acid 2-ethylhexyl, nonyl 2-iodopropionate, nonyl 3-iodopropionate, dodecyl 2-iodopropionate, dodecyl 3-iodopropionate, nonadecyl 2-iodopropionate, nonadecyl 3-iodopropionate, 2-iodo icosyl propionate, icosyl 3-iodopropionate, methyl 2-iodobutyrate, methyl 3-iodobutyrate, methyl 4-iodobutyrate, ethyl 2-iodobutyrate, ethyl 3-iodobutyrate, ethyl 4-iodobutyrate, 2-iodine n-propyl butyrate, n-propyl 3-iodobutyrate, n-propyl 4-iodobutyrate, isopropyl 2-iodobutyrate, isopropyl 3-iodobutyrate, isopropyl 4-iodobutyrate, n-butyl 2-iodobutyrate, 3-iodine n-butyl butyrate, n-butyl 4-iodobutyrate, tert-butyl 2-iodobutyrate, tert-butyl 3-iodobutyrate, tert-butyl 4-iodobutyrate, 2-pentyl iodobutyrate, 3-pentyl iodobutyrate, 4 - pentyl iodobutyrate, 2-hexyl iodobutyrate, 3-hexyl iodobutyrate, 4 -hexyl iodobutyrate, heptyl 2-iodobutyrate, heptyl 3-iodobutyrate, heptyl 4-iodobutyrate, octyl 2-iodobutyrate, octyl 3-iodobutyrate, octyl 4-iodobutyrate, 2-ethylhexyl 2-iodobutyrate, 3 - 2-ethylhexyl 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, nonadecyl 4-iodobutyrate, icosyl 2-iodobutyrate, icosyl 3-iodobutyrate, icosyl 4-iodobutyrate, 2-methyl iodovalerate, 3-methyl iodovalerate , 4-methyl iodovalerate, 5-methyl iodovalerate, 2-ethyl iodovalerate, 3-ethyl iodovalerate, 4-ethyl iodovalerate, 5-ethyl iodovalerate, 2-iodovalerate n- propyl, 3-iodovalerate n-propyl, 4-iodovalerate n-propyl, 5-iodovalerate n-propyl, 2-iodovalerate isopropyl, 3-iodovalerate isopropyl, 4-iodovalerate isopropyl, Isopropyl 5-iodovalerate, n-butyl 2-iodovalerate, n-butyl 3-iodovalerate, n-butyl 4-iodovalerate, n-butyl 5-iodovalerate, tert- 2-iodovalerate butyl, tert-butyl 3-iodovalerate, tert-butyl 4-iodovalerate, tert-butyl 5-iodovalerate, 2-pentyl iodovalerate, 3-pentyl iodovalerate, 4-pentyl iodovalerate, 5-Pentyl Iodovalerate, 2-Hexyl Iodovalerate, 3-Hexyl Iodovalerate, 4-Hexyl Iodovalerate, 5-Hexyl Iodovalerate, 2-Heptyl Iodovalerate, 3-Heptyl Iodovalerate, 4 - heptyl iodovalerate, 5-heptyl iodovalerate, 2-octyl iodovalerate, 3-octyl iodovalerate, 4-octyl iodovalerate, 5-octyl iodovalerate, 2-ethylhexyl iodovalerate, 2-Ethylhexyl Iodovalerate, 2-Ethylhexyl Iodovalerate, 2-Ethylhexyl Iodovalerate, 2-Ethylhexyl Iodovalerate, 3-Iodovalerate Nonyl Acid, 4-Iodovalerate Nonyl Acid, 5 - nonyl iodovalerate, 2-dodecyl iodovalerate, 3-dodecyl iodovalerate, 4-dodecyl iodovalerate, 5-dodecyl iodovalerate, 2- nonadecyl iodovalerate, 3-nonadecyl iodovalerate, 4-nonadecyl iodovalerate, nonadecyl 5-iodovalerate, 2-icosyl iodovalerate, 3-icosyl iodovalerate, 4-icosyl iodovalerate, 5-iodine icosyl valerate, and the like.

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

The amount of the ester compound represented by the general formula (3) in Reaction Formula-1 is preferably 2.0 times by mole or more, less than 10.0 times by mole, or more than 10.0 times by mole the 9,10-dihydroxyanthracene compound. Preferably, it is 2.2 mol times or more and less than 5.0 mol times. If it is less than 2.0 mol times, the reaction will not be completed, and if it is 10.0 mol times or more, side reactions will occur and the yield and purity will decrease.

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

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

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

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

The amount of the phase transfer catalyst to be added is preferably 0.01-fold or more and less than 1.0-fold, more preferably 0.05-fold or more and 0.5-fold with respect to the 9,10-dihydroxyanthracene compound. Less than mol times. If it is less than 0.01 mol times, the reaction rate will be slow, and if it is 1.0 mol times or more, the purity of the product will decrease, which is not preferable.

The reaction temperature of the reaction is usually 0°C or higher and 200°C or lower, preferably 10°C or higher and 100°C or lower. When the temperature is less than 0°C, the reaction time is too long, and when the temperature exceeds 100°C, impurities increase and the purity of the target compound decreases, both of which are undesirable.

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

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

(Two-step manufacturing method)
Next, the two-step production method of the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group of 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 a 9,10-dihydroxyanthracene compound represented by the general formula (2) as follows. According to reaction formula-2, first, 9 represented by general formula (5), which is an intermediate, is reacted with the corresponding carboxylic acid represented by general formula (4) in the presence or absence of a basic compound. , After synthesizing the 10-bis(hydroxycarbonylalkyleneoxy)anthracene compound, according to Reaction Scheme-3, the 9,10-bis(hydroxycarbonylalkyleneoxy)anthracene compound represented by general formula (5) and general formula (6 ), an alcohol compound represented by the general formula (7) according to the reaction formula-4, and a glycidyl ether compound represented by the general formula (8) according to the reaction formula-5. can obtain a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group represented by general formula (1).

In Reaction Formula-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. Z represents a chlorine atom, a bromine atom or an iodine atom.

In Reaction Formula-3, A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. 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. Further, R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be substituted by a hydroxy group, and a part of carbon atoms may be replaced by oxygen atoms. (except when it forms a peroxide).

In Reaction Formula-4, A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. 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. Further, R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be substituted by a hydroxy group, and a part of carbon atoms may be replaced by oxygen atoms. (except when it forms a peroxide). D represents a chlorine atom, a bromine atom or an iodine atom.

In Reaction 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. R represents an alkyl group having 1 to 20 carbon atoms, the alkyl group may be branched by an alkyl group, may be substituted with a hydroxy group, and part of the carbon atoms may be replaced by oxygen atoms; may also be used (unless they form peroxides). R ¹ represents a hydrogen atom or an alkyl group having 1 to 17 carbon atoms, the alkyl group may be branched by an alkyl group, may be substituted with a hydroxy group, and some of the carbon atoms may be oxygen; It may be replaced by an atom (except when it forms a peroxide).

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

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

Next, in Reaction Scheme-2, specific examples of the carboxylic acid represented by the general formula (4), which is the other starting material, include chloroacetic acid, 2-chloropropionic acid, 3-chloropropionic acid, 2-chloro 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 specific examples given above, chloro compounds and bromo compounds are preferred in terms of availability and reactivity, and chloroacetic acid and bromoacetic acid are particularly preferred.

The amount of the carboxylic acid represented by the general formula (4) in Reaction Formula-2 is preferably 2.0 times by mole or more, less than 10.0 times by mole, or more than 10.0 times by mole the 9,10-dihydroxyanthracene compound. Preferably, it is 2.2 mol times or more and less than 5.0 mol times. If it is less than 2.0 mol times, the reaction will not be completed, and if it is 10.0 mol times or more, side reactions will occur and the yield and purity will decrease.

Basic compounds used in Reaction Formula-2 include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, lithium hexamethyldisilazide, lithium diisopropylamide, triethylamine, tributylamine, trihexylamine, Dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dimethylaniline, pyridine, 4,4-dimethylaminopyridine, piperidine, γ-picoline, lutidine and the like.

The amount of the basic compound to be added is preferably 2.0-fold or more and less than 10.0-fold by mol, more preferably 2.2-fold or more by mol, and 8.0-fold relative to the 9,10-dihydroxyanthracene compound. Less than mol times. If it is less than 2.0 mol times, the reaction will not be completed, and if it is 10.0 mol times or more, side reactions will occur and the yield and purity will decrease.

The reaction is carried out in a solvent or without solvent. Any type of solvent may be used as long as it does not react with the raw material used. Examples include aromatic solvents such as toluene, xylene, and ethylbenzene; ether solvents such as tetrahydrofuran and 1,4-dioxane; 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.

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

The amount of the phase transfer catalyst to be added is preferably 0.01-fold or more and less than 1.0-fold, more preferably 0.03-fold or more and 0.5-fold with respect to the 9,10-dihydroxyanthracene compound. Less than mol times. If it is less than 0.01 mol times, the reaction rate will be slow, and if it is 1.0 mol times or more, the purity of the product will decrease, which is not preferable.

The reaction temperature of the reaction is usually 0°C or higher and 100°C or lower, preferably 10°C or higher and 50°C or lower. When the temperature is less than 0°C, the reaction time is too long, and when the temperature exceeds 100°C, impurities increase and the purity of the target compound decreases, both of which are not preferable.

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

After completion of the reaction, unreacted raw materials, solvent and catalyst are removed by a single or a combination of operations such as extraction and filtration, if necessary. Since the product is in the form of a carboxylate, it is neutralized with a mineral acid or organic acid to precipitate crystals, followed by solid-liquid separation by filtration and, if necessary, recrystallization to obtain the product represented by the general formula (5). The represented 9,10-bis(hydroxycarbonylalkyleneoxy)anthracene compound can be obtained.

Next, a 9,10-bis(hydroxycarbonylalkyleneoxy)anthracene compound represented by general formula (5) and an alcohol compound represented by general formula (6) represented by reaction formula-3 are reacted in the presence or absence of a catalyst. A method for producing a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group represented by general formula (1) by reacting in the presence of the compound will be described.

Specific examples of the alcohol compound represented by the general formula (6) as a starting material in Reaction Formula-3 include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol. , pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, dodecanol, ethylene glycol, propylene glycol and the like.

Among the above-mentioned specific examples, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, ethylene glycol, and propylene glycol are preferable in terms of easy availability, and methanol is particularly preferred. , ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, ethylene glycol are preferred.

The amount of the alcohol compound represented by the general formula (6) in Reaction Formula-3 is preferably 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 times by mole, the reaction will not be completed, and if it is more than 100 times by mole, the reaction rate will be slow and the yield and purity will decrease.

Catalysts used in Reaction Formula-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 Corporation), Nafion (manufactured by DuPont, Nafion is a registered trademark of DuPont), tetraalkoxytitanium compound (tetraisopropoxytitanium , tetra-n-butoxytitanium, tetramethoxytitanium), organic tin compounds (dibutyltin dilaurate, dibutyltin oxide), and the like.

The amount of catalyst added is preferably 0.01 mol% or more and less than 50 mol%, more preferably , 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 50 mol % or more, side reactions will occur and the yield and purity will decrease.

The reaction is carried out in a solvent or without solvent. Any solvent can be used as long as it does not react with the alcohol compound used. Examples include aromatic solvents such as toluene, xylene and ethylbenzene; ether solvents such as tetrahydrofuran and 1,4-dioxane; 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 are used. In particular, it is preferable to use the alcohol compound to be used as both a reactant and a solvent in terms of waste reduction.

The reaction temperature of the reaction is usually 20°C or higher and 200°C or lower, preferably 50°C or higher and 150°C or lower. If it is less than 20°C, the reaction takes too long, and if it exceeds 200°C, impurities increase and the purity of the target compound decreases, both of which are undesirable.

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

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

Next, a 9,10-bis(hydroxycarbonylalkyleneoxy)anthracene compound represented by general formula (5) and a halogenated alkyl compound represented by general formula (7) represented by reaction formula-4 are combined 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 thereof will be described.

In Reaction formula-4, specific examples of the halogenated alkyl compound represented by general formula (7) as a starting 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, 2-hydroxyethyl chloride, methyl bromide, ethyl bromide, bromide n-propyl, isopropyl bromide, butyl bromide, isobutyl bromide, sec-butyl bromide, tert-butyl bromide, pentyl bromide, hexyl bromide, heptyl bromide, octyl bromide, 2-ethylhexyl bromide, nonyl bromide, decyl bromide, dodecyl bromide, 2-hydroxyethyl bromide, methyl iodide, ethyl iodide, n-propyl iodide, isopropyl iodide, butyl iodide, isobutyl iodide, sec-butyl iodide , tert-butyl iodide, pentyl iodide, hexyl iodide, heptyl iodide, octyl iodide, 2-ethylhexyl iodide, nonyl iodide, decyl iodide, dodecyl iodide, 2-hydroxyethyl iodide, etc. be done.

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

The amount of the halogenated alkyl compound represented by general formula (7) in Reaction Formula-4 is relative to the 9,10-bis(hydroxycarbonylalkyleneoxy)anthracene compound represented by general formula (5). , preferably 2 mol times or more and less than 10 mol times, more preferably 3 mol times or more and less than 5 mol times. If it is less than 2 mol times, the reaction will not be completed, and if it is 10 mol times or more, side reactions will occur and the yield and purity will decrease, which is not preferable.

Basic compounds used in Reaction Scheme-4 include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, 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 times by mole or more, less than 10 times by mole, or more than 9,10-bis(hydroxycarbonylalkyleneoxy)anthracene compound represented by the general formula (5). Preferably, it is 1 mol-fold or more and less than 5 mol-fold. If it is less than 0.5 mol times, the reaction will not be completed, and if it is 10 mol times or more, side reactions will occur and the yield and purity will decrease.

The reaction is carried out in a solvent or without solvent. Any solvent can be used as long as it does not react with the alcohol compound used. Examples include aromatic solvents such as toluene, xylene and ethylbenzene; ether solvents such as tetrahydrofuran and 1,4-dioxane; 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 are used.

The reaction temperature of the reaction is usually 0°C or higher and 200°C or lower, preferably 20°C or higher and 100°C or lower. If it is less than 0°C, the reaction takes too long, and if it exceeds 200°C, impurities increase and the purity of the target compound decreases, both of which are undesirable.

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

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

Next, a 9,10-bis(hydroxycarbonylalkyleneoxy)anthracene compound represented by general formula (5) and a glycidyl ether compound represented by general formula (8) represented by reaction formula-5 are combined in the presence of a base or A method for producing a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group represented by general formula (1) by reaction 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 (7) as a starting material include methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, and hexyl glycidyl ether. , 2-ethylhexyl glycidyl ether, octyl glycidyl ether, allyl glycidyl ether, methallyl glycidyl ether, glycidol and the like.

The amount of the glycidyl ether compound represented by the general formula (7) in Reaction Scheme-2 is, relative to the 9,10-bis(hydroxycarbonylalkyleneoxy)anthracene compound represented by the general formula (5), It is preferably 2 mol times or more and less than 10 mol times, more preferably 3 mol times or more and less than 5 mol times. If it is less than 2 mol times, the reaction will not be completed, and if it is 10 mol times or more, side reactions will occur and the yield and purity will decrease.

Basic compounds used in Reaction Formula-5 include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, 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 times by mole or more, less than 10 times by mole, or more than 9,10-bis(hydroxycarbonylalkyleneoxy)anthracene compound represented by the general formula (5). Preferably, it is 1 mol-fold or more and less than 5 mol-fold. If it is less than 0.5 mol times, the reaction will not be completed, and if it is 10 mol times or more, side reactions will occur and the yield and purity will decrease.

The reaction is carried out in a solvent or without solvent. Any solvent can be used as long as it does not react with the alcohol compound used. Examples include aromatic solvents such as toluene, xylene and ethylbenzene; ether solvents such as tetrahydrofuran and 1,4-dioxane; 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 are used.

The reaction temperature of the reaction is usually 0°C or higher and 200°C or lower, preferably 20°C or higher and 100°C or lower. When the temperature is less than 0°C, the reaction time is too long, and when the temperature exceeds 200°C, impurities increase and the purity of the target compound decreases, both of which are not preferable.

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

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

(Photopolymerization sensitizer)
The 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group represented by the general formula (1) of the present invention is excited by light of a specific wavelength, and the excitation energy is received by a photopolymerization initiator. Acts as a photopolymerization sensitizer. Due to this effect, it is possible to efficiently initiate photopolymerization even with long-wavelength light that does not sufficiently activate the photopolymerization initiator. The photopolymerization sensitizer and the photopolymerization initiator can be mixed with a photopolymerization compound to form a photopolymerizable composition. The photopolymerizable composition can be easily photocured by irradiation with long-wavelength light, such as ultraviolet LED light with a central wavelength of 405 nm.

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

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

As an onium salt, the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group of the present invention has a photopolymerization sensitization effect not only for iodonium salts but also for sulfonium salts. is one.

Further, the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group represented by the general formula (1) of the present invention includes benzyl methyl ketal-based, α-hydroxyalkylphenone-based polymerization initiators, and biimidazole. It has an excellent photopolymerization sensitization effect even for radical polymerization initiators that do not absorb light at long wavelengths, such as system polymerization initiators.

Benzyl methyl ketal-based radical polymerization initiators include 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name “Irgacure 651” manufactured by BASF) and the like. -Hydroxyalkylphenone-based radical polymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name "Darocure 1173" manufactured by BASF), 1-hydroxycyclohexylphenyl Ketone (trade name “Irgacure 184” manufactured by BSA), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one ( Trade name “Irgacure 2959” manufactured by BASF), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methyl-1 -On (trade name "Irgacure 127" manufactured by BASF).

In particular, 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name “Irgacure 651” manufactured by BAS F Co., Ltd.), which is a benzyl methyl ketal radical polymerization initiator, α-hydroxyalkyl 2-Hydroxy-2-methyl-1-phenylpropan-1-one (trade name “Darocure 1173” manufactured by BAS F Co., Ltd.), 1-hydroxycyclohexylphenyl ketone (trade name), which is a phenone-based radical polymerization initiator The name "Irgacure 184" manufactured by BASF) is preferred.

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

Biimidazole-based polymerization initiators include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2 -(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5- 2,4,5-triarylimidazole dimers such as diphenylimidazole dimers, and the like.

The amount of the photopolymerization sensitizer containing the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group represented by the general formula (1) of the present invention, relative to the photopolymerization initiator, is not particularly limited. is usually in the range of 5% by weight or more and 100% by weight or less, preferably in the range of 10% by weight or more and 50% by weight or less, based on the photopolymerization initiator. If the amount of the photopolymerization sensitizer used is less than 5% by weight, it takes too much time to photopolymerize the photopolymerizable compound. do not have.

(Photoinitiator composition)
The photopolymerization sensitizer containing the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group represented by the general formula (1) of the present invention may be added directly to the photopolymerizable compound. However, it is also possible to prepare a photopolymerization initiator composition by blending it with a photopolymerization initiator in advance, and then add it to the photopolymerizable compound. That is, the photopolymerization initiator composition of the present invention comprises at least a photopolymerization sensitizer containing a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group represented by general formula (1). A composition containing a photopolymerization initiator.

(Photopolymerizable composition)
Furthermore, a photopolymerizable composition can be prepared by blending the photopolymerization initiator composition and a photopolymerizable compound. The photopolymerizable composition of the present invention comprises a photopolymerization sensitizer containing the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group of the present invention and a photopolymerization initiator containing a photopolymerization initiator. A composition containing a composition and a radically photopolymerizable compound or a cationic photopolymerizable compound. The photopolymerization sensitizer and the photopolymerization initiator containing the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group of the present invention are separately added to the radically photopolymerizable compound or the cationic photopolymerizable compound. may result in the formation of a photoinitiator composition in the radically photopolymerizable compound or the cationically photopolymerizable compound. Further, a hybrid composition containing both a radically photopolymerizable compound and a cationic photopolymerizable compound may be used.

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

Examples of photo-cationically polymerizable compounds include epoxy compounds, oxetane compounds, vinyl ethers, and the like. Typical epoxy compounds include alicyclic epoxy compounds, epoxy-modified silicones, aromatic glycidyl ethers, and the like. Examples of alicyclic epoxy compounds include 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (manufactured by Daicel Corporation, trade name: Celoxide 2021P, Celoxide is a registered trademark of Daicel Corporation), bis(3, 4-epoxycyclohexyl) adipate and the like. Examples of epoxy-modified silicone include UV-9300 manufactured by Toshiba GE Silicone. Examples of aromatic glycidyl compounds include 2,2'-bis(4-glycidyloxyphenyl)propane and the like. The oxetane compounds include 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol) (manufactured by Toagosei Co., Ltd., trade name: OXT-101), 2-ethylhexyloxetane (manufactured by Toagosei Co., Ltd., trade name: OXT-212), Xylylene bisoxetane (manufactured by Toagosei Co., Ltd., trade name: OXT-121), 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane (manufactured by Toagosei Co., Ltd., trade name: OXT -221) and the like. Vinyl ethers include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether and the like. These photo-cationically polymerizable compounds may be used singly or as a mixture of two or more.

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

The photopolymerization sensitizer of the present invention can act as a sensitizer in both radical photopolymerization and cationic photopolymerization. A photopolymerizable composition containing both polymerizable compounds can also be effectively polymerized.

The mixing ratio of the cationic photopolymerizable compound and the radical photopolymerizable compound is not particularly limited, and is appropriately selected according to the physical properties of the coating film or molded product obtained by photopolymerizing and curing the composition. Usually, the weight ratio of the cationic photopolymerizable compound to the radical photopolymerizable compound is determined within the range of 1:99 to 99:1, preferably 20:80 to 80:20.

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

As the photopolymerization initiator used in the photopolymerizable composition of the present invention, the photoradical initiator or photocationic initiator described above can be used. Usually, when a photoradical polymerizable compound is used as the photopolymerizable compound, a photoradical polymerization initiator is used. Furthermore, when a photoradical polymerizable compound and a photocationically polymerizable compound are used in combination as the photopolymerizable compound, the photoradical polymerization initiator or the photocationic polymerization initiator alone may be used as the photopolymerization initiator, or both may be used. may be mixed and used.

In particular, some photo-cationic polymerization initiators generate cationic-initiating active species and radical-initiating active species upon irradiation with light. It is also possible to initiate photopolymerization of both of the polymerizable compounds.

Furthermore, the photopolymerizable composition of the present invention may contain binder polymers such as acrylic resins, styrene resins and epoxy resins. Also, an alkali-soluble resin may be contained.

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

The photopolymerizable composition of the present invention may contain a diluent, a coloring agent, an organic or inorganic filler, a leveling agent, a surfactant, an antifoaming agent, a thickener, a diluent, a coloring agent, an organic or inorganic filler, a Various resin additives such as flame retardants, antioxidants, stabilizers, lubricants and plasticizers may be added.

(Photocured product)
A photocured product can be obtained by irradiating the photopolymerizable composition of the present invention with light for polymerization. When the photopolymerizable composition is irradiated with light to polymerize and photocured, the photopolymerizable composition can be formed into a film and photocured, or can be formed into a block and photocured. When the composition is formed into a film and then photocured, the liquid photopolymerizable composition is applied to a substrate such as a polyester film using a bar coater or the like so as to have a film thickness of 5 to 300 microns. On the other hand, it is also possible to apply a thin film or a thick film by a spin coating method or a screen printing method.

A photo-cured product is obtained by irradiating a coating film composed of the photopolymerizable composition thus prepared with ultraviolet light containing a wavelength range of 300 nm to 500 nm at an intensity of about 1 to 1000 mW/cm ² . can be done. Light sources used include high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, xenon lamps, gallium-doped lamps, black lights, 405 nm ultraviolet LEDs, 395 nm ultraviolet LEDs, 385 nm ultraviolet LEDs, 365 nm ultraviolet LEDs, blue LEDs, white LEDs, and fusion. company's D valve, V valve, etc. are mentioned. Natural light such as sunlight can also be used. In particular, it is characterized by having a sensitizing effect even with light including a wavelength range of long wavelengths such as 365 nm to 405 nm such as 405 nm ultraviolet LED, 395 nm ultraviolet LED, 385 nm ultraviolet LED, 375 nm ultraviolet LED, and 365 nm ultraviolet LED. and is preferred.

(Optical DSC measurement)
In the present invention, a photo-DSC measurement method can be used as a method for quantitatively evaluating the photopolymerization rate of the photopolymerizable composition under light irradiation. According to this method, the amount of heat generated during curing can be measured continuously and easily while the sample is directly irradiated with light. When a sample set in an optical DSC measurement device is irradiated with light, a curing reaction of light begins and heat generation is observed. The baseline of the DSC curve, which was horizontal before photocuring, shifted to the exothermic side, and returned to the original baseline after the reaction was completed. The calorific value can be obtained from the magnitude of the peak of this DSC curve. That is, the progress of polymerization can be evaluated by irradiating the photopolymerizable composition with light and measuring and comparing the amount of heat generated per 1 mg.

(Determination of migration resistance of composition)
As a method for determining whether the photopolymerization sensitizer contained in the photopolymerizable composition of the present invention migrates to a film or the like, the photopolymerization composition containing the photopolymerization sensitizer is formed into a thin film. Create a product that has been applied to an object, cover it with a polyethylene film, store it at a constant temperature (26°C) for a certain period of time, then peel off the polyethylene film and examine whether the photopolymerization sensitizer has migrated to the polyethylene film. , to determine the migration resistance. The peeled polyethylene film was dried after washing the composition on the surface with acetone, and the UV spectrum of the polyethylene film was measured to determine the migration resistance by examining the increase in absorption intensity caused by the photopolymerization sensitizer. did. For the measurement, an ultraviolet/visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV2600) was used. For quantitative comparison with 9,10-dibutoxyanthracene, which is a compound of Comparative Example, the obtained absorbance was converted to the absorbance value of 9,10-dibutoxyanthracene. For the conversion, the absorbance at 260 nm of the compound of the present invention and 9,10-dibutoxyanthracene is measured with an ultraviolet/visible spectrophotometer, and the molar extinction coefficient is calculated from the absorbance value and the molar concentration. converted using

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

Identification of the compounds of the present invention was carried out using the following instruments.
Infrared (IR) spectrophotometer: Model is50 FT-IR manufactured by Thermo
Nuclear magnetic resonance apparatus (NMR): manufactured by JEOL Ltd., model ECS-400
Melting point: Melting point measuring device manufactured by Gelencamp, model MFB-595 (according to JIS K0064)

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

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

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

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

(Synthesis Example 4) Synthesis of 9,10-bis(tert-butoxycarbonylmethyleneoxy)anthracene In a 100 ml four-necked flask equipped with a stirrer and a thermometer, 15 g of methyl isobutyl ketone as a solvent and a catalyst were placed in a nitrogen atmosphere. 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-anthracenediol (24 mmol as anthraquinone) was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was further stirred for 1 hour. Thereafter, anthraquinone was removed by suction filtration, and the resulting filtrate was allowed to stand overnight to precipitate crystals. The precipitated crystals were further filtered with suction to obtain 6.5 g of light yellow crystals (crude yield: 61 mol %).

(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).

(Synthesis Example 5) Synthesis of 9,10-bis(n-butoxycarbonylmethyleneoxy)anthracene In a 100 ml four-necked flask equipped with a stirrer and a thermometer, under nitrogen atmosphere, 15 g of methyl isobutyl ketone as a solvent and a catalyst were added. 3.1 g (4.8 mmol) of a 50% aqueous solution of tetrabutylammonium bromide and 9.4 g (62.5 mmol) of 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-anthracenediol (24 mmol as anthraquinone) was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was further stirred for 1 hour. Thereafter, anthraquinone was removed by suction filtration, and the resulting filtrate was washed twice with water. After washing with water, anthraquinone was precipitated and was removed by suction filtration. The filtrate was allowed to stand overnight to precipitate crystals, and suction filtration yielded 5.5 g (crude yield 52 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=13.2Hz, 4H), 4.779 (s, 4H), 7.508-7.826 (m, 4H), 8.319-8. 377 (m, 4H).

(Synthesis Example 6) Synthesis of 9,10-bis(methoxycarbonylmethylmethyleneoxy)anthracene In a 100 ml four-necked flask equipped with a stirrer and a thermometer, 15 g of methyl isobutyl ketone as a solvent and 15 g of methyl isobutyl ketone as a catalyst were placed in a nitrogen atmosphere. 0.8 g (1.2 mmol) of a 50% aqueous solution of tetrabutylammonium bromide and 10.4 g (62.5 mmol) of methyl 2-bromopropionate were added. While maintaining the temperature of the reaction system at 20 to 25° C., 29.1 g of a 17 wt % aqueous solution of disodium salt of 9,10-anthracenediol (24 mmol as anthraquinone) was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was further stirred for 1 hour. Thereafter, anthraquinone was removed by suction filtration, and the obtained filtrate was washed twice with water by a liquid separation operation. The solution was concentrated with an evaporator and cooled in a freezer to precipitate crystals. The precipitated crystals were filtered with suction to obtain 4.6 g of yellow crystals (crude yield: 50 mol %).

(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).

(Synthesis Example 7) Synthesis of 9,10-bis(ethoxycarbonylpropyleneoxy)anthracene In a 100 ml four-necked flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, a 50% aqueous solution of tetrabutylammonium bromide as a catalyst was added. 0.77 g (1.19 mmol), 12.1 g (61.8 mmol) of ethyl 4-bromobutyrate, 5.0 g (23.8 mmol) of 9,10-anthracenediol, 9.9 g of potassium carbonate ( 71.4 mmol) and 40 g of N,N-dimethylformamide as a solvent were added. The temperature of the reaction system was kept at 20-30° C. and stirred for 1 hour. Thereafter, anthraquinone was removed by suction filtration, and the resulting filtrate was dissolved in toluene and washed twice with water. The solution was concentrated with an evaporator. When left overnight, the entire solution solidified, so methanol was added and heated to 50° C. to dissolve. Undissolved anthraquinone was removed by suction filtration, and the filtrate was cooled in a freezer to precipitate crystals. The precipitated crystals were filtered with suction to obtain 5.4 g of yellow crystals (crude yield: 51 mol %).

(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).

(Synthesis Example 8) Synthesis of 9,10-bis(ethoxycarbonylbutyleneoxy)anthracene In a 100 ml four-necked flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, a 50% aqueous solution of tetrabutylammonium bromide as a catalyst was added. 0.77 g (1.19 mmol), 12.9 g (61.8 mmol) of ethyl 5-bromovalerate, 5.0 g (23.8 mmol) of 9,10-anthracenediol, 9.9 g of potassium carbonate (71.4 mmol) and 40 g of N,N-dimethylformamide as a solvent were added. The temperature of the reaction system was kept at 20-30° C. and stirred for 1 hour. Thereafter, anthraquinone was removed by suction filtration, and the resulting filtrate was dissolved in toluene and washed twice with water by liquid separation. The solution was concentrated with an evaporator. After standing overnight, methanol was added and undissolved anthraquinone was removed by suction filtration. The filtrate was cooled in a freezer to precipitate crystals. The precipitated crystals were filtered with suction to obtain 6.2 g of orange crystals (crude yield: 55 mol %).

(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).

(Synthetic Example 9) Synthesis of 2-ethyl-9,10-bis(isopropoxycarbonylmethyleneoxy)anthracene Into a 200 ml four-necked flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 2-ethylanthraquinone was added at 5 times. 0 g (21.2 mmol), 9.1 g (86.4 mmol) of thiourea dioxide, 8.4 g (211.6 mmol) of sodium hydroxide, and 50 g of deionized water were added, and the temperature was gradually raised to 120°C. Stirring was performed while warming. When the solution turned reddish black, stirring was stopped and the solution was cooled to room temperature to prepare an aqueous solution of disodium salt of 2-ethyl-9,10-anthracenediol. Next, 15 g of methyl isobutyl ketone as a solvent and 2.7 g (4.23 g) of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst were 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 were added. While maintaining the temperature of the reaction system at 20 to 25° C., the disodium salt aqueous solution of 2-ethyl-9,10-anthracenediol prepared above was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was further stirred for 1 hour. Thereafter, the aqueous layer was removed, and the organic layer was concentrated by an evaporator to obtain 4.5 g of orange oil (crude yield 48 mol %).

( ¹ ) melting point: liquid at room temperature;
(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 = 9.2Hz, 1H), 7.461-7.512 ( m, 2H), 7.766-7.790 (m, 1H), 8.119 (d, J=7.6Hz, 1H), 8.284-8.368 (m, 2H).

(Intermediate Synthesis Example) Synthesis of 9,10-bis(hydroxycarbonylmethoxy)anthracene (synthesis of intermediate of general formula (5))
In a 300 ml four-necked flask equipped with a stirrer and a thermometer, 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 (6. 8 mmol) and 49.5 g (356 mmol) of bromoacetic acid were added. 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-anthracenediol disodium salt (AHQ-Na) and sodium hydroxide and 11.4 g (285 mmol) of sodium hydroxide were added. millimoles) and 20 g of ion-exchanged water were added dropwise over 3 hours. After the dropwise addition was completed, the mixture was further stirred for 1.5 hours. After that, unreacted raw materials and the like were filtered off 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 for acid precipitation. 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)

(Synthesis Example 10) Synthesis of 9,10-bis(ethoxycarbonylmethoxy)anthracene (reaction with alcohol))
78.7 g (241 mmol) of 9,10-bis(hydroxycarbonylmethoxy)anthracene obtained in (Synthesis Example 1) and 236.5 mmol of ethanol were placed in a 1000 ml four-necked flask equipped with a stirrer and a thermometer under a nitrogen atmosphere. 0 g (5119 mmol) and 3.9 g (39 mmol) of concentrated sulfuric acid were added. The temperature of the reaction system was kept at 75 to 80° C., and the mixture was stirred for 10 hours while removing by-product water together with ethanol. Crystals precipitated upon cooling were collected by suction filtration, washed with methanol and then 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).

(Synthesis Example 11) Synthesis of 9,10-bis(propoxycarbonylmethoxy)anthracene (reaction with alcohol))
0.4 g (1.2 mmol) of 9,10-bis(hydroxycarbonylmethoxy)anthracene obtained in (Synthesis Example 1), 1 - 1.5 g (25 mmol) of propanol and 0.01 g (0.1 mmol) of methanesulfonic acid were added. The mixture was stirred for 1.5 hours while maintaining the temperature of the reaction system at 50-60°C. Thereafter, insoluble matter was filtered off, and methanol and ion-exchanged water were added to the filtrate to precipitate crystals. The precipitated crystals were filtered by suction, washed with methanol and then 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 = 0.992 (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).

(Synthesis Example 12) Synthesis of 9,10-bis(n-butoxycarbonylmethoxy)anthracene (reaction with alcohol))
34.2 g (105 mmol) of 9,10-bis(hydroxycarbonylmethoxy)anthracene obtained in (Synthesis Example 1) and 1-butanol were placed in a 300 ml four-necked flask equipped with a stirrer and a thermometer under a nitrogen atmosphere. 172.7 g (2330 mmol) 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-product water. Crystals precipitated upon cooling were collected by suction filtration, washed with methanol and then 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=13.2Hz, 4H), 4.779 (s, 4H), 7.508-7.826 (m, 4H), 8.319-8. 377 (m, 4H).

(Synthesis Example 13) Synthesis of 9,10-bis(2-hydroxyethoxycarbonylmethoxy)anthracene (reaction with alkyl halide)
0.65 g (2.0 mmol) of 9,10-bis(hydroxycarbonylmethoxy)anthracene obtained in (Synthesis Example 1), ethylene 3.0 g (48 mmol) of 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 50-60°C. After cooling, methanol and deionized water were added to precipitate crystals. Precipitated crystals were collected by suction filtration, washed with methanol and then 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).

(Synthetic Example 14) Synthesis of 9,10-bis(butoxycarbonylmethoxy)anthracene 2.0 g (6 .2 mmol), 43.4 g of N,N'-dimethylformamide as a solvent, and 0.87 g (6.4 mmol) of potassium carbonate were added, and nitrogen substitution was performed. 3.87 g (28.2 mmol) of butyl bromide was added under a nitrogen atmosphere, and the mixture was heated to 60° C. in a water bath and stirred. After completion of the reaction, the mixture was cooled to room temperature, and the residue containing potassium carbonate was removed by suction filtration. The resulting 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 using 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=13.2Hz, 4H), 4.779 (s, 4H), 7.508-7.826 (m, 4H), 8.319-8. 377 (m, 4H).

(Optical DSC measurement)
Optical DSC measurement in this example was performed as follows. Specifically, XDSC-7200 manufactured by Hitachi High-Tech Co., Ltd. was used as the DSC measurement apparatus, and an optical DSC measurement unit was attached to the apparatus so that DSC measurement could be performed while irradiating light. LA-410UV manufactured by Hayashi Tokei Kogyo Co., Ltd. was used as a light source for light irradiation, and 405 nm light was extracted by a band-pass filter so that the sample could be irradiated with the light. The illuminance of light was 50 mW/cm ² . A glass fiber was used to guide the light from the light source to the top of the sample, and the shutter of the light source was trigger-controlled so that DSC measurement could be performed simultaneously with the start of light irradiation. For the optical DSC measurement, about 1 mg of a sample was precisely weighed in an aluminum pan for measurement, placed in the DSC measurement section, and then attached to the optical DSC unit. After that, the inside of the measuring section was kept in a nitrogen atmosphere and allowed to stand still for 10 minutes, and the measurement was started. The measurement continued for 6 minutes under normal light irradiation. After the first measurement, the sample was left as it was and another measurement was performed under the same conditions. The results were compared in terms of the total calorific value per 1 mg of sample 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 photoirradiation, the total calorific value for one minute was compared. When the sample (photopolymerizable composition) is polymerized with light irradiation, reaction heat is generated accompanying the polymerization, and the photo-DSC can measure the reaction heat. Therefore, the progress of polymerization due to light irradiation can be measured by optical DSC. In this example, the total calorific value for 1 minute after light irradiation is measured. As long as the same polymerizable compound is used, when the values are compared, the larger the value, the more efficiently the polymerization progresses. can be considered to exist.

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

(Photocuring speed evaluation example 1)
3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (manufactured by Daicel Corporation, trade name: Celoxide 2021P, Celoxide is a registered trademark of Daicel Corporation) as a photo-cationically polymerizable compound per 100 parts by weight , a photopolymerization initiator 4-isobutylphenyl-4'-methylphenyliodonium hexafluorophosphate (manufactured by BASF, trade name Irgacure 250, "Irgacure" is BASF (registered trademark)) and 1 part by weight of 9,10-bis(methoxycarbonylmethyleneoxy)anthracene obtained in Synthesis Example 1 as a photocationic polymerization sensitizer were mixed at room temperature to obtain a photocationically polymerizable composition. prepared the product. Photo-DSC measurement of this photopolymerizable composition revealed that the total calorific value for 5 minutes from the start of photoirradiation was 256 mJ/mg.

(Photocuring speed evaluation example 2)
Evaluation of Photocuring Speed Photocuring 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 Synthesis Example 2. Optical DSC measurement was performed in the same manner as in Speed Evaluation Example 1, and the total calorific value for 5 minutes from the start of light irradiation was 273 mJ/mg.

(Photocuring speed evaluation example 3)
Photocuring speed evaluation Example 1 except that 9,10-bis(methoxycarbonylmethyleneoxy)anthracene was changed to 9,10-bis(isopropoxycarbonylmethyleneoxy)anthracene obtained in the same manner as in Synthesis Example 3 When optical DSC measurement was performed in the same manner as in Cure Speed Evaluation Example 1, the total calorific value for 5 minutes from the start of photoirradiation was 262 mJ/mg.

(Photocuring speed evaluation example 4)
Evaluation of Photocuring Speed 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 Synthesis Example 4. When photo-DSC measurement was performed in the same manner as in Photo-curing Speed Evaluation Example 1, the total calorific value for 5 minutes from the start of photo-irradiation was 284 mJ/mg.

(Photocuring speed evaluation example 5)
Evaluation of Photocuring Speed 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 Synthesis Example 5. When photo-DSC measurement was performed in the same manner as in Photo-curing Speed Evaluation Example 1, the total amount of heat generated for 5 minutes from the start of photo-irradiation was 248 mJ/mg.

(Photocuring speed evaluation example 6)
Photocuring speed evaluation Example 1 was replaced with 9,10-bis(methoxycarbonylmethylmethyleneoxy)anthracene obtained in the same manner as in Synthesis Example 6. When optical DSC measurement was performed in the same manner as in Evaluation Example 1 for curing speed implementation, the total calorific value for 5 minutes from the start of photoirradiation was 226 mJ/mg.

(Photocuring speed evaluation example 7)
Evaluation of Photocuring Speed Photocuring 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 Synthesis Example 7. Optical DSC measurement was performed in the same manner as in Speed Evaluation Example 1, and the total calorific value for 5 minutes from the start of light irradiation was 308 mJ/mg.

(Photocuring speed evaluation example 8)
Evaluation of Photocuring Speed Photocuring 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 Synthesis Example 8. Optical DSC measurement was performed in the same manner as in Speed Evaluation Example 1, and the total calorific value for 5 minutes from the start of light irradiation was 285 mJ/mg.

(Photocuring speed evaluation example 9)
Evaluation of Photocuring Speed 9,10-bis(methoxycarbonylmethyleneoxy)anthracene in Example 1 was replaced with 2-ethyl-9,10-bis(isopropoxycarbonylmethyleneoxy)anthracene obtained in the same manner as in Synthesis Example 9. Optical DSC measurement was carried out in the same manner as in Photocuring Speed Evaluation Example 1, except that the total amount of heat generated for 5 minutes from the start of photoirradiation was 260 mJ/mg.

(Photocuring speed evaluation example 17)
Photocuring speed evaluation Photocuring speed except that 9,10-bis(methoxycarbonylmethyleneoxy)anthracene in Example 1 was changed to 9,10-bis(propoxycarbonylmethoxy)anthracene obtained in the same manner as in Synthesis Example 11 Optical DSC measurement was carried out in the same manner as in Practical Evaluation Example 1, and the total calorific value for 5 minutes from the start of light irradiation was 259 mJ/mg.

(Photocuring speed evaluation example 18)
Evaluation of Photocuring Speed Except that 9,10-bis(methoxycarbonylmethyleneoxy)anthracene in Example 1 was changed to 9,10-bis(2-hydroxyethoxycarbonylmethoxy)anthracene obtained in the same manner as in Synthesis Example 13. When photo-DSC measurement was performed in the same manner as in Photo-curing Speed Evaluation Example 1, the total amount of heat generated for 5 minutes from the start of photo-irradiation was 237 mJ/mg.

(Photocuring speed evaluation comparative example 1)
3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (manufactured by Daicel Corporation, trade name: Celoxide 2021P, Celoxide is a registered trademark of Daicel Corporation) as a photo-cationically polymerizable compound per 100 parts by weight, Photopolymerization initiator (4-methylphenyl)[4-(2-methylpropyl)phenyl]iodonium-hexafluorophosphate (manufactured by BASF, trade name Irgacure 250, “Irgacure” is Bee (registered trademark of ASF Co., Ltd.) was mixed at room temperature to prepare a cationic photopolymerizable composition. Photo-DSC measurement was performed on this photopolymerizable composition, and the total calorific value for 5 minutes from the start of photoirradiation was 3 mJ/mg.

(Photocuring speed evaluation comparative example 2)
Evaluation of photocuring speed Evaluation of photocuring speed except that 9,10-dibutoxyanthracene, a known photopolymerization sensitizer, was used instead of 9,10-bis(methoxycarbonylmethyleneoxy)anthracene in Example 1. When optical 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 for photocuring speed evaluation)
Photocuring speed evaluation Example 1, except for using 9,10-bis(octanoyloxy)anthracene, a known photopolymerization sensitizer, instead of 9,10-bis(methoxycarbonylmethyleneoxy)anthracene. When optical DSC measurement was performed in the same manner as in Evaluation Example 1 for curing speed implementation, the total amount of heat generated for 5 minutes from the start of photoirradiation was 234 mJ/mg.

Table 1 summarizes the results of Photocuring Speed Evaluation Examples 1 to 9, 17 and 18 and Photocuring Speed Evaluation Comparative Examples 1 to 3.

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

(Photocuring speed evaluation example 10)
As the photoradical polymerizable compound, 2 parts by weight of 1-hydroxycyclohexylphenyl ketone, which is a photopolymerization initiator, with respect to 100 parts by weight of trimethylolpropane triacrylate, and the photoradical polymerization sensitizer obtained in Synthesis Example 1. 1 part by weight of 9,10-bis(methoxycarbonylmethyleneoxy)anthracene was mixed at room temperature to prepare a radically photopolymerizable composition. Photo-DSC measurement was performed on this photopolymerizable composition, and the total calorific value for 5 minutes from the start of light irradiation was 419 mJ/mg.

(Photocuring speed evaluation example 11)
Evaluation of Photocuring Speed Photocuring 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 Synthesis Example 2. Optical DSC measurement was carried out in the same manner as in Example 10 for speed evaluation, and the total calorific value for 5 minutes from the start of light irradiation was 465 mJ/mg.

(Photocuring speed evaluation example 12)
Evaluation of Photocuring Speed Photocuring 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 Example 3. Optical DSC measurement was performed in the same manner as in Example 10 for speed evaluation, and the total calorific value for 5 minutes from the start of light irradiation was 409 mJ/mg.

(Photocuring speed evaluation example 13)
Photocuring speed evaluation Example 10 9,10-bis(methoxycarbonylmethyleneoxy)anthracene was changed to 9,10-bis(tert-butoxycarbonylmethyleneoxy)anthracene obtained in the same manner as in Example 4. Photo-DSC measurement was carried out in the same manner as in Example 10 for curing speed evaluation, and the total amount of heat generated for 5 minutes from the start of photo-irradiation was 443 mJ/mg.

(Photocuring speed evaluation example 14)
Photocuring speed evaluation Example 10 9,10-bis(methoxycarbonylmethyleneoxy)anthracene was changed to 9,10-bis(n-butoxycarbonylmethyleneoxy)anthracene obtained in the same manner as in Example 5. Photo DSC measurement was carried out in the same manner as in Example 10 for curing speed evaluation, and the total amount of heat generated for 5 minutes from the start of photoirradiation was 336 mJ/mg.

(Photocuring speed evaluation example 15)
Evaluation of Photocuring Speed Photocuring except that 9,10-bis(methoxycarbonylmethylmethyleneoxy)anthracene in Example 10 was changed to 9,10-bis(methoxycarbonylmethylmethyleneoxy)anthracene obtained in the same manner as in Example 6. Optical DSC measurement was performed in the same manner as in Example 10 for speed evaluation, and the total calorific value for 5 minutes from the start of light irradiation was 552 mJ/mg.

(Photocuring speed evaluation example 16)
Evaluation of Photocuring Speed 9,10-bis(methoxycarbonylmethyleneoxy)anthracene in Example 10 was replaced with 2-ethyl-9,10-bis(isopropoxycarbonylmethyleneoxy)anthracene obtained in the same manner as in Example 9. Photo DSC measurement was performed in the same manner as in Photocuring Speed Evaluation Example 10, except that the total amount of heat generated for 5 minutes from the start of photoirradiation was 441 mJ/mg.

(Photocuring speed evaluation example 19)
Photocuring speed evaluation Photocuring speed evaluation except that 9,10-bis(methoxycarbonylmethyleneoxy)anthracene in Example 10 was changed to 9,10-bis(propoxycarbonylmethoxy)anthracene obtained in the same manner as in Example 11 Optical DSC measurement was performed in the same manner as in Example 10, and the total calorific value for 5 minutes from the start of light irradiation was 379 mJ/mg.

(Photocuring speed evaluation example 20)
Photocuring speed evaluation Example 10 9,10-bis(methoxycarbonylmethyleneoxy)anthracene was changed to 9,10-bis(2-hydroxyethoxycarbonylmethoxy)anthracene obtained in the same manner as in Example 13. Photo-DSC measurement was carried out in the same manner as in Example 10 for evaluation of curing speed, and the total calorific value for 5 minutes from the start of photo-irradiation was 420 mJ/mg.

(Photocuring speed evaluation comparative example 4)
As a radical photopolymerizable compound, 100 parts by weight of trimethylolpropane triacrylate was mixed with 2 parts by weight of 1-hydroxycyclohexylphenyl ketone as a photopolymerization initiator at room temperature to prepare a radically photopolymerizable composition. Photo-DSC measurement of this photopolymerizable composition revealed that the total calorific value for 5 minutes from the start of photoirradiation was 166 mJ/mg.

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

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

Table 2 summarizes the results of Photocuring Speed Evaluation Examples 10 to 16, 19 and 20 and Photocuring Speed Evaluation Comparative Examples 4 to 6.

As is clear from a comparison of the results of Photocuring Speed Evaluation Examples 1 to 9, 17, and 18 and Photocuring Speed Evaluation Comparative Example 1, the 9,10-bis( It can be seen that the addition of the alkoxycarbonylalkyleneoxy)anthracene compound as a photopolymerization sensitizer increases the total calorific value and significantly accelerates the polymerization reaction. Further, as is clear from a comparison of the results of Photocuring Speed Evaluation Examples 10 to 16, 19, and 20 and Photocuring Speed Evaluation Comparative Example 4, 9 and 10 having an ester group of the present invention are also used in photoradical polymerization. It can be seen that the addition of the -bis(alkoxycarbonylalkyleneoxy)anthracene compound similarly increases the total calorific value, significantly accelerating the polymerization reaction. 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 cationic photopolymerization and radical photopolymerization.

Furthermore, as is clear from a comparison of the results of Photocuring Speed Evaluation Examples 1 to 9, 17, and 18 and Photocuring Speed Evaluation Comparative Examples 2 and 3, 9 having an ester group of the present invention in photocationic polymerization, The 10-bis(alkoxycarbonylalkyleneoxy)anthracene compound has a photopolymerization increase equal to or greater than that of 9,10-dibutoxyanthracene and 9,10-bis(octanoyloxy)anthracene, which are known photopolymerization sensitizers. It can be seen that it has an emotional effect. Further, as is clear from a comparison of the results of Photocuring Speed Evaluation Examples 10 to 16, 19 and 20 and Photocuring Speed Evaluation Comparative Examples 5 and 6, 9 having an ester group of the present invention is also used in photoradical polymerization. ,10-bis(alkoxycarbonylalkyleneoxy)anthracene compounds are equivalent to or greater than 9,10-dibutoxyanthracene and 9,10-bis(octanoyloxy)anthracene, which are also known photopolymerization sensitizers. It can be seen that it has a photopolymerization sensitization effect. That is, the 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group of the present invention is 9,10-dibutoxy, which is a known photopolymerization sensitizer in both cationic photopolymerization and radical photopolymerization. It can be seen that it has a photopolymerization sensitization effect equal to or greater than that of anthracene.

(Evaluation example of migration resistance in photocationic polymerization)
(Migration resistance evaluation example 1)
100 parts of 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (Celoxide 2021P manufactured by Daicel Corporation) as an epoxy photo-cationically polymerizable compound, and the same as in Synthesis Example 1 as a photopolymerization sensitizer 1 part of 9,10-bis(methoxycarbonylmethyleneoxy)anthracene synthesized by the above method was mixed, and the prepared composition was applied on a polyester film using a bar coater to a thickness of 12 microns. Next, a low-density polyethylene film (thickness: 30 microns) was covered on the obtained coated material, and the polyethylene film was peeled off after storage in a dark place for one day and seven days. was washed with acetone and dried, the UV spectrum of the film was measured and the absorbance at 260 nm was measured. The absorbance due to the obtained 9,10-bis(methoxycarbonylmethyleneoxy)anthracene was converted to 9,10-dibutoxyanthracene. The absorbance was 0.015 after one day storage and 0.003 after seven days storage.

(Migration resistance evaluation example 2)
Except for using 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene synthesized in the same manner as in Synthesis Example 2 instead of 9,10-bis(methoxycarbonylmethyleneoxy)anthracene as a photopolymerization sensitizer. was tested in the same manner as in Migration Resistance Evaluation Example 1. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance attributed to 9,10-bis(ethoxycarbonylmethyleneoxy)anthracene converted to 9,10-dibutoxyanthracene was 0.007 after storage for one day. , was 0.007 after seven days of storage.

(Migration resistance evaluation example 3)
Using 9,10-bis(isopropoxycarbonylmethyleneoxy)anthracene synthesized in the same manner as in Synthesis Example 3 instead of 9,10-bis(methoxycarbonylmethyleneoxy)anthracene as a photopolymerization sensitizer. Except for this, the test was carried out in the same manner as in Migration Resistance Evaluation Example 1. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance due to 9,10-bis(isopropoxycarbonylmethyleneoxy)anthracene converted to 9,10-dibutoxyanthracene was 0.00 after storage for one day. 007, and 0.007 after seven days of storage.

(Migration resistance evaluation example 4)
9,10-bis(tert-butoxycarbonylmethyleneoxy)anthracene synthesized in the same manner as in Synthesis Example 4 is used instead of 9,10-bis(methoxycarbonylmethyleneoxy)anthracene as a photosensitizer. The test was carried out in the same manner as in Migration Resistance Evaluation Example 1 except for the above. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance attributed to 9,10-bis(tert-butoxycarbonylmethyleneoxy)anthracene converted to 9,10-dibutoxyanthracene was 0 after storage for one day. 0.010 and 0.014 after 7 days storage.

(Migration resistance evaluation example 5)
9,10-bis(n-butoxycarbonylmethyleneoxy)anthracene synthesized in the same manner as in Synthesis Example 5 is used instead of 9,10-bis(methoxycarbonylmethyleneoxy)anthracene as a photosensitizer. The test was carried out in the same manner as in Migration Resistance Evaluation Example 1 except for the above. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance attributed to 9,10-bis(n-butoxycarbonylmethyleneoxy)anthracene converted to 9,10-dibutoxyanthracene was 0 after storage for one day. 0.011 and 0.007 after 7 days storage.

(Migration resistance evaluation example 6)
Using 9,10-bis(methoxycarbonylmethylmethyleneoxy)anthracene synthesized in the same manner as in Synthesis Example 6 instead of 9,10-bis(methoxycarbonylmethylmethyleneoxy)anthracene as a photopolymerization sensitizer. Except for this, the test was carried out in the same manner as in Migration Resistance Evaluation Example 1. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance attributed to 9,10-bis(methoxycarbonylmethylmethyleneoxy)anthracene converted to 9,10-dibutoxyanthracene was 0.00 after storage for one day. 007, and 0.003 after seven days of storage.

(Migration resistance evaluation example 7)
Except for using 9,10-bis(ethoxycarbonylpropyleneoxy)anthracene synthesized in the same manner as in Synthesis Example 7 instead of 9,10-bis(methoxycarbonylmethyleneoxy)anthracene as a photopolymerization sensitizer. was tested in the same manner as in Migration Resistance Evaluation Example 1. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance due to 9,10-bis(ethoxycarbonylpropyleneoxy)anthracene converted to 9,10-dibutoxyanthracene was 0.015 after storage for one day. , was 0.013 after seven days of storage.

(Migration resistance evaluation example 8)
Except for using 9,10-bis(ethoxycarbonylbutyleneoxy)anthracene synthesized in the same manner as in Synthesis Example 8 instead of 9,10-bis(methoxycarbonylmethyleneoxy)anthracene as a photopolymerization sensitizer. was tested in the same manner as in Migration Resistance Evaluation Example 1. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance attributed to 9,10-bis(ethoxycarbonylbutyleneoxy)anthracene converted to 9,10-dibutoxyanthracene was 0.012 after storage for one day. , was 0.010 after seven days of storage.

(Migration resistance evaluation example 9)
2-ethyl-9,10-bis(isopropoxycarbonylmethyleneoxy)anthracene synthesized in the same manner as in Synthesis Example 9 instead of 9,10-bis(methoxycarbonylmethyleneoxy)anthracene as a photosensitizer The test was carried out in the same manner as in Migration Resistance Evaluation Example 1 except for using . As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance attributed to 2-ethyl-9,10-bis(isopropoxycarbonylmethyleneoxy)anthracene was converted to 9,10-dibutoxyanthracene. It was 0.015 after storage and 0.015 after storage for 7 days.

(Migration resistance evaluation comparative example 1)
Migration resistance evaluation example except that 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer, is used instead of 9,10-bis(methoxycarbonylmethyleneoxy)anthracene as the photopolymerization sensitizer. 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 one day storage and 0.843 after seven days storage.

Table 3 summarizes the results of migration resistance evaluation examples 1 to 9 and migration resistance evaluation comparative example 1.

(Evaluation example of migration resistance of composition in photoradical polymerization)
(Migration resistance evaluation example 10)
100 parts of trimethylolpropane triacrylate as a photoradical polymerizable compound and 1 part of 9,10-bis(methoxycarbonylmethyleneoxy)anthracene synthesized in the same manner as in Synthesis Example 1 as a photoradical polymerization sensitizer are mixed. Then, the prepared composition was applied on a polyester film using a bar coater so that the film thickness was 12 microns. Next, a low-density polyethylene film (thickness: 30 microns) was covered on the obtained coated material, 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, 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. It was 0.015 after 1-day storage and 0.016 after 7-day storage.

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

(Migration resistance evaluation example 12)
Evaluation of migration resistance except for using 9,10-bis(isopropoxycarbonylmethyleneoxy)anthracene synthesized in the same manner as in Synthesis Example 3 instead of 9,10-bis(methoxycarbonylmethyleneoxy)anthracene. Prepared and tested as in Example 10. The absorbance at 260 nm of the acetone-washed polyethylene film was measured, and the absorption attributed to 9,10-bis(isopropoxycarbonylmethyleneoxy)anthracene was 0.024 after one day storage and 0.022 after seven days storage. rice field.

(Migration resistance evaluation example 13)
Evaluation of migration resistance except for using 9,10-bis(tert-butoxycarbonylmethyleneoxy)anthracene synthesized in the same manner as in Synthesis Example 4 instead of 9,10-bis(methoxycarbonylmethyleneoxy)anthracene Prepared and tested as in Example 10. The absorbance at 260 nm of the acetone-washed polyethylene film was measured. there were.

(Migration resistance evaluation example 14)
Evaluation of migration resistance except for using 9,10-bis(n-butoxycarbonylmethyleneoxy)anthracene synthesized in the same manner as in Synthesis Example 5 instead of 9,10-bis(methoxycarbonylmethyleneoxy)anthracene Prepared and tested as in Example 10. The absorbance at 260 nm of the acetone-washed polyethylene film was measured. there were.

(Migration resistance evaluation example 15)
Evaluation of migration resistance except for using 9,10-bis(methoxycarbonylmethylmethyleneoxy)anthracene synthesized in the same manner as in Synthesis Example 6 instead of 9,10-bis(methoxycarbonylmethylmethyleneoxy)anthracene. Prepared and tested as in Example 10. The absorbance at 260 nm of the acetone-washed polyethylene film was measured, and the absorption attributed to 9,10-bis(methoxycarbonylmethylmethyleneoxy)anthracene was 0.007 after one day storage and 0.004 after seven days storage. rice field.

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

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

(Migration resistance evaluation example 18)
Except that 2-ethyl-9,10-bis(isopropoxycarbonylmethyleneoxy)anthracene synthesized in the same manner as in Synthesis Example 9 was used instead of 9,10-bis(methoxycarbonylmethyleneoxy)anthracene. It was prepared and tested in the same manner as in Migration Evaluation Example 10. The absorbance at 260 nm of the acetone-washed polyethylene film was measured. 0.032.

(Migration Comparative Example 2)
A test was performed in the same manner as in Migration Resistance Evaluation 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 one day storage and 1.741 after seven days.

Table 4 summarizes the results of migration resistance evaluation Examples 10 to 18 and migration resistance evaluation comparative example 2.

As is clear from a comparison of Migration Resistance Evaluation Examples 1 to 9 and Migration Resistance Evaluation Comparative Example 1, in the photocationic polymerizable composition, 9,10-, which is a known photocationic polymerization sensitizer, Dibutoxyanthracene migrates to a large extent to the overlying film of the photocationically polymerizable composition, whereas the 9,10-bis(methoxycarbonylmethyleneoxy)anthracene compounds of the present application Also, the degree of migration is extremely low, and it can be said that the migration resistance is excellent.

On the other hand, as is clear from a comparison of Migration Resistance Evaluation Examples 10 to 18 and Migration Resistance Evaluation Comparative Example 2, 9, which is a known radical photopolymerization sensitizer, is also included in the radical photopolymerizable composition. The 9,10-bis(methoxycarbonylmethyleneoxy)anthracene compounds of the present application are In either case, the degree of migration is extremely low, and it can be said that the migration resistance is excellent.

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

Claims (10)

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

(In 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 The group may be branched by an alkyl group, and 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.) 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 method for producing a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having a group.

(In 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 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 The groups may be branched by alkyl groups, may be substituted by hydroxy groups, and some of the carbon atoms may be replaced by oxygen atoms (except when forming peroxides). (Z represents a chlorine atom, a bromine atom or an iodine atom.)

(In 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 The groups may be branched by alkyl groups, may be substituted by hydroxy groups, and 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.) A 9,10-dihydroxyanthracene compound represented by the following general formula (2) and a carboxylic acid compound represented by the following general formula (4) are reacted to form a 9,10-dihydroxyanthracene compound represented by the following general formula (5). A bis(hydroxycarbonylalkyleneoxy)anthracene compound is synthesized, and the 9,10-bis(hydroxycarbonylalkyleneoxy)anthracene compound represented by the general formula (5) and the following general formula (6) or general formula (7) 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:

(In 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 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. Z 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, hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.)

(In 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 substituted with a hydroxy group, and may moieties may be replaced by oxygen atoms (except when forming a peroxide).

(In 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 substituted with a hydroxy group, and may part may be replaced by an oxygen atom (except when forming a peroxide. D represents a chlorine atom, a bromine atom, or an iodine atom.)

(In 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 The group may be branched by alkyl groups , may be substituted by hydroxy groups, and 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.) A 9,10-dihydroxyanthracene compound represented by the following general formula (2) and a carboxylic acid compound represented by the following general formula (4) are reacted to form 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) and an esterifying agent represented by the general formula (8) are combined. 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:

(In 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 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. Z 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, hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.)

(In general formula (8), R ¹ represents a hydrogen atom or an alkyl group having 1 to 17 carbon atoms, the alkyl group may be branched by an alkyl group, may be substituted by a hydroxy group, and some of the carbon atoms are It may be substituted (except when it forms a peroxide). )

(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 is -CH ₂ CH(OH)CH ₂ OR ¹ and R ¹ represents a hydrogen atom or an alkyl group having 1 to 17 carbon atoms, the alkyl group may be branched by an alkyl group, may be substituted by a hydroxy group, and some of the carbon atoms are It may be substituted (except when it forms 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. ) A photopolymerization sensitizer containing a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group represented by the following general formula (1).

(In 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 The groups may be branched by alkyl groups, may be substituted by hydroxy groups, and 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.) A photopolymerization initiator composition comprising the photopolymerization sensitizer according to claim 5 and a photopolymerization initiator. A photopolymerizable composition comprising the photopolymerization initiator composition according to claim 6 and a photocationically polymerizable compound. A photopolymerizable composition comprising the photopolymerization initiator composition according to claim 6 and a radically photopolymerizable compound. 9. A polymerization method for polymerizing the photopolymerizable composition according to claim 7 or 8 by irradiating it with energy rays containing light in the wavelength range of 300 nm to 500 nm. Polymerization according to claim 9 , characterized in that the irradiation source of energy rays containing light in the wavelength range of 300 nm to 500 nm is an ultraviolet LED or semiconductor laser with a center wavelength of 365 nm, 375 nm, 385 nm, 395 nm, 405 nm. Method.