JP2019073501A - Photopolymerization sensitizer having migration resistance - Google Patents

Abstract

To provide a photopolymerization sensitizer for giving a practically sufficient photo-curing rate without causing a problem of powdering or coloring of a cured product by bleeding of an additive such as a photopolymerization sensitizer to the surface due to blooming during photo-curing or during storage of a cured product.SOLUTION: There is provided a 9,10-bis(alkoxycarbonylalkylene)anthracene compound represented by the general formula (1). (A represents an alkylene group having 1 to 20 carbon atoms; R represents an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydroxy group in which part of the carbon atoms may be replaced by an oxygen atom; X and Y each independently represent H, an alkyl group having 1 to 8 carbon atoms or a halogen atom.)SELECTED DRAWING: None

Description

The present invention relates to a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group, a process for producing the same, and photopolymerization sensitization comprising the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group It relates to the agent.

A photocurable resin that is polymerized by active energy rays such as ultraviolet light and visible light cures quickly, and the amount of organic solvent used can be significantly reduced compared to a thermosetting resin, thus improving the working environment and environmental impact. It is excellent in that it can be reduced. Conventional photocurable resins themselves have a poor polymerization initiation function, and for curing, it is usually necessary to use a photopolymerization initiator. As a photoinitiator, alkylphenone type | system | group polymerization initiators, such as a hydroxy acetophenone and a benzophenone, an acyl phosphine oxide type | system | group photoinitiator, onium salt, etc. are used (patent document 1, 2, 3). When an onium salt initiator is used among these photopolymerization initiators, the light absorption of the onium salt is in the vicinity of 225 nm to 350 nm and there is no absorption at 350 nm or more, so a lamp with a long wavelength of 350 nm or more In such a case, there is a problem that the photocuring reaction does not progress easily, and it is general to add a photopolymerization sensitizer. Similarly, many photopolymerization initiators such as alkylphenone polymerization initiators do not have absorption at 350 nm or more. As photopolymerization sensitizers for these photopolymerization initiators, anthracene compounds and thioxanthone compounds are known, and in particular, anthracene compounds are often used due to the problem of color (Patent Document 4).

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

However, this 9,10-dialkoxyanthracene compound bleeds to the surface due to blooming during storage of the photopolymerizable composition before photocuring or the cured product after photocuring, and the surface of the cured product is cured. It is known to cause powdering and coloring problems.

For the photopolymerizable composition, for example, when these photopolymerization sensitizers are used as one component of a photoadhesive agent for bonding a film to a film, the photopolymerization sensitizer migrates to the film covered on the top ( Migration) and may cause problems with powder blowing and coloring of the photopolymerization sensitizer on the upper film.

In addition, although dry film resists used for processing of printed wiring boards, manufacturing of lead frames, manufacturing of metal masks, etc. are used, there is a need for resists compatible with 405 nm semiconductor lasers, and to cope with the wavelengths Thioxanthone and 9,10-dialkoxy anthracene compounds are used as photopolymerization sensitizers. However, dry film resists are stored and traded in a state in which a cover film is covered on a photosensitive resin composition, and a polyethylene film or a polypropylene film is used for the cover film etc. There is a problem that the agent migrates to reduce the sensitizing effect, or powder blowing occurs on the film (Patent Document 9).

A 9,10-bis (2-acyloxyalkoxy) anthracene compound in which an ester group which is a polar group is introduced into an alkoxy group of a 9,10-dialkoxyanthracene compound in order to suppress migration of such a photopolymerization sensitizer is It is reported (patent document 10). However, the 9,10-bis (2-acyloxyalkoxy) anthracene compound has a step of using an alkylene oxide compound at the time of production, which increases the number of steps, leading to an increase in cost, and the alkylene oxide compound, particularly ethylene oxide. The difficulty of obtaining and handling is a major problem in the production of the 9,10-bis (2-acyloxyalkoxy) anthracene compound.

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

Japanese Patent Application Publication No. 06-345614 Unexamined-Japanese-Patent No. 07-062010 Japanese Patent Application Publication No. 05-249606 JP 10-195117 A JP 2002-302507 A Japanese Patent Application Laid-Open No. 11-279212 JP 2000-344704 A WO 2007/126066 Patent 4605223 gazette JP, 2014-031346, A JP, 2014-101442, A

Therefore, it has migration resistance during photocuring or during storage of the cured product, and does not cause problems of powder blowing and coloring of the cured product, and it is a practical manufacturing method using readily available raw materials. There is a need to develop new photosensitizers that can be obtained by

As a result of intensive studies on the structure and physical properties of the anthracene compound, the present inventors showed that the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group shown in the present invention is increased in photopolymerization reaction in photopolymerization reaction. It has been found that the photopolymerization sensitizer is less likely to cause migration and blooming due to having an ester group that is a polar group while exhibiting an excellent effect as a photosensitizer, and that it is practical using easily available raw materials We found a manufacturing method and completed the present invention.

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

In the general formula (1), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group or may be substituted by a hydroxy group, and a part of carbon atoms is replaced by an oxygen atom, (Except when forming a peroxide). X and Y, which may be the same or different, each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

According to a second aspect of the present invention, a 9,10-dihydroxyanthracene compound represented by the following general formula (2) and an ester compound represented by the following general formula (3) are reacted: It exists in the manufacturing method of the 9, 10- bis (alkoxy carbonyl alkylene oxy) anthracene compound which has an ester group represented by Formula (1).

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

In the general formula (3), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group or may be substituted by a hydroxy group, and a part of carbon atoms is replaced by an oxygen atom, (Except when forming a peroxide). Z represents a chlorine atom, a bromine atom or an iodine atom.

In the general formula (1), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group or may be substituted by a hydroxy group, and a part of carbon atoms is replaced by an oxygen atom, (Except when forming a peroxide). X and Y, which may be the same or different, each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

According to a third aspect of the present invention, a 9,10-dihydroxyanthracene compound represented by the following general formula (2) is reacted with a carboxylic acid compound represented by the following general formula (4) to obtain a compound represented by the following general formula (5) 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound is synthesized, and the 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5) is 6) 9,10-bis (alkoxy) having an ester group represented by the following general formula (1) characterized by reacting an esterifying agent represented by the general formula (7) or the general formula (8) The present invention also relates to a method for producing a carbonylalkyleneoxy) anthracene compound.

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

In the general formula (4), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. 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, which may be the same or different, each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

In the general formula (6), R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group or may be substituted by a hydroxy group, and is a part of carbon atoms May be replaced by an oxygen atom (except when forming a peroxide).

In the general formula (7), R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group or may be substituted by a hydroxy group, and is a part of 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 the general formula (8), R ¹ represents a hydrogen atom or an alkyl group having 1 to 17 carbon atoms, and the alkyl group may be branched by an alkyl group or may be substituted by a hydroxy group, Some of the carbon atoms may be replaced by oxygen atoms (except when forming peroxides).

In the general formula (1), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group or may be substituted by a hydroxy group, and a part of carbon atoms is replaced by an oxygen atom, (Except when forming a peroxide). X and Y, which may be the same or different, each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

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

In the general formula (1), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group or may be substituted by a hydroxy group, and a part of carbon atoms is replaced by an oxygen atom, (Except when forming a peroxide). X and Y, which may be the same or different, each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

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

The sixth aspect of the present invention resides in a photopolymerizable composition comprising the photopolymerization initiator composition according to the fifth aspect and a cationic photopolymerizable compound.

The seventh aspect of the present invention resides in a photopolymerizable composition comprising the photopolymerization initiator composition according to the fifth aspect and a radical photopolymerizable compound.

An eighth aspect of the present invention relates to a polymerization method of polymerizing the photopolymerizable composition according to the sixth or seventh aspect by irradiating energy beam containing light in a wavelength range of 300 nm to 500 nm. It exists.

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

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 the photopolymerization reaction, but also increases the photopolymerization of the compound of the present invention. It is a useful compound that the degree of migration or blooming of the photopolymerization sensitizer is extremely low for the photopolymerizable composition contained as a photosensitizer. Also in the production method, it is not necessary to use an alkylene oxide compound which is difficult to obtain and difficult to handle, and the production process is easy and inexpensive.

(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 the general formula (1), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group or may be substituted by a hydroxy group, and a part of carbon atoms is replaced by an oxygen atom, (Except when forming a peroxide). X and Y, which may be the same or different, each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

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

In the general formula (1), examples of the alkyl group having 1 to 8 carbon atoms represented by X or Y include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and an i-butyl group And n-pentyl group, i-pentyl group, n-hexyl group, n-heptyl group, n-octyl group or 2-ethylhexyl group, etc., and examples of the halogen atom include fluorine atom, chlorine atom, bromine atom or iodine Atoms are mentioned.

In the general formula (1), examples of the alkyl group having 1 to 20 carbon atoms represented by R include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an 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, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl or n-icosyl and the like, As a group in which a group is substituted by a hydroxy group, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 3-hydro Cyclobutyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 7-hydroxyheptyl, 8-hydroxyoctyl, 6-hydroxy-2-ethylhexyl, 9-hydroxynonyl, 10- Hydroxydecyl, 11-hydroxyundecyl, 12-hydroxydodecyl, 2-hydroxy-3-methoxypropyl, 2-hydroxy-3-ethoxypropyl, 2-hydroxy-3-propoxypropyl, 2-hydroxy -3-butoxypropyl group, 2-hydroxy-3-pentyloxypropyl group, 2-hydroxy-3-hexyloxypropyl group, 2-hydroxy-3-octyloxypropyl group, 2-hydroxy-3- (2-ethylhexyl) Oxy) propyl group, 2,3-dihydroki Propyl, 2-hydroxy-3-allyloxy propyl, and 2-hydroxy-3-methallyl propyl group.

Specific examples of the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention include, for example, 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene, 9,10-bis (n-propoxycarbonylmethyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene, 9,10-bis (tert-) Butoxycarbonylmethyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene, 9,10-bis (methoxycarbonylpropyleneoxy) anthracene, 9,10-bis (ethoxycarbonyl carbonyl) X) anthracene, 9, 10-bis (isopropoxycarbonyl carbonyl oxy) anthracene, 9, 10 bis (tert- butoxycarbonyl carbonyl oxy) anthracene, 9, 10 bis (n- butoxycarbonyl carbonyl oxy) anthracene, 9, 10-Bis (methoxycarbonylmethylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonylmethylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonylethylmethyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylmethyl) Methyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylmethylmethyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylmethylmethyleneoxy) 9,10-bis (methoxycarbonylbutyleneoxy) anthracene, 9,10-bis (ethoxycarbonylbutyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylbutyleneoxy) anthracene, 9,10-bis (tert-) Examples include butoxycarbonylbutyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylbutyleneoxy) anthracene, 9,10-bis (2-hydroxyethoxycarbonylmethoxy) anthracene and the like.

Further, for example, 9,10-bis (methoxycarbonylpentyleneoxy) anthracene, 9,10-bis (ethoxycarbonylpentyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylpentyleneoxy) anthracene, 9,10- Bis (tert-butoxycarbonylpentyloxy) anthracene, 9,10-bis (n-butoxycarbonylpentyleneoxy) anthracene, 9,10-bis (methoxycarbonylhexylenoxy) anthracene, 9,10-bis (ethoxycarbonyl) Hexyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylhexylenoxy) anthracene, 9,10-bis (tert-butoxycarbonylhexylenoxy) anthracene, 9,10-bis (n-buto) Cyclohexylhexylenoxy) anthracene, 9,10-bis (methoxycarbonylheptyleneoxy) anthracene, 9,10-bis (ethoxycarbonylheptyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylheptylene) Oxy) anthracene, 9,10-bis (tert-butoxycarbonylheptyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylheptyleneoxy) anthracene, 9,10-bis (methoxycarbonyloctylene oxy) Anthracene, 9,10-bis (ethoxycarbonyloctylenoxy) anthracene, 9,10-bis (isopropoxycarbonyloctylenoxy) anthracene, 9,10-bis (tert-butoxycarbonyloctylenoxy) ane 9,10-bis (n-butoxycarbonyloctylenoxy) anthracene, 9,10-bis (methoxycarbonylnonyleneoxy) anthracene, 9,10-bis (ethoxycarbonylnonyleneoxy) anthracene, 9,10- Bis (isopropoxycarbonylnonyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylnonyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylnonyleneoxy) anthracene, 9,10-bis (methoxy Carbonyl decylene oxy) anthracene, 9, 10-bis (ethoxycarbonyl decylene oxy) anthracene, 9, 10- bis (isopropoxycarbonyl decylene oxy) anthracene, 9, 10- bis (tert- butoxycarbonyl de sile) 9,10-bis (n-butoxycarbonyldecylene oxy) anthracene, 9,10-bis (methoxycarbonylundecylene oxy) anthracene, 9,10-bis (ethoxycarbonyl undecylenoxy) anthracene, 9,10- Bis (isopropoxycarbonylundecyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylundecyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylundecyleneoxy) anthracene, 9,10-bis (methoxycarbonyldode) Silene oxy) anthracene, 9,10-bis (ethoxycarbonyl dodecylene oxy) anthracene, 9,10-bis (isopropoxycarbonyl dodecylene oxy) anthracene, 9,10- (Tert-butoxycarbonyl dodecylene) anthracene, 9,10-bis (n-butoxycarbonyl dodecylene) anthracene, 9,10-bis (methoxycarbonyl tridecylene oxy) anthracene, 9,10-bis ( Ethoxycarbonyl tridecylene oxy) anthracene, 9, 10-bis (isopropoxycarbonyl tridecylene oxy) anthracene, 9, 10- bis (tert- butoxycarbonyl tridecylene oxy) anthracene, 9, 10- bis (n-butoxycarbonyl tride Silyleneoxy) anthracene, 9,10-bis (methoxycarbonyltetradecyleneoxy) anthracene, 9,10-bis (ethoxycarbonyltetradecyleneoxy) anthracene, 9,10-bis (isopropoxy) Rubenyltetradecylene oxy) anthracene, 9,10-bis (tert-butoxycarbonyltetradecylene oxy) anthracene, 9,10-bis (n-butoxycarbonyltetradecylene oxy) anthracene, 9,10-bis (methoxycarbonyl) Pentadecylene oxy) anthracene, 9,10-bis (ethoxycarbonyl pentadecylene oxy) anthracene, 9,10-bis (isopropoxycarbonyl pentadecylene oxy) anthracene, 9,10-bis (tert-butoxycarbonyl pentade) Silyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylpentadecyleneoxy) anthracene, 9,10-bis (methoxycarbonylhexadecyleneoxy) anthracene, 9,10-bis (ethoxycal) Bonyl hexadecylene oxy) anthracene, 9,10-bis (isopropoxycarbonylhexadecylene oxy) anthracene, 9,10-bis (tert-butoxycarbonyl hexadecylene oxy) anthracene, 9,10-bis (n-butoxy) Carbonyl hexadecylene oxy) anthracene, 9, 10-bis (methoxycarbonyl hepta decylene oxy) anthracene, 9, 10- bis (ethoxycarbonyl hepta decylene oxy) anthracene, 9, 10- bis (isopropoxycarbonyl heptadecylene) Oxy) anthracene, 9,10-bis (tert-butoxycarbonylheptadecylene oxy) anthracene, 9,10-bis (n-butoxycarbonylheptadecylene oxy) anthracene, 9,10-bis (methoxy) Rubonyl octadecylene oxy) anthracene, 9,10-bis (ethoxycarbonyl octadecylene oxy) anthracene, 9,10-bis (isopropoxycarbonyl octadecylene oxy) anthracene, 9,10-bis (tert-butoxycarbonyl octano) Decyleneoxy) anthracene, 9,10-bis (n-butoxycarbonyloctadecylene oxy) anthracene, 9,10-bis (methoxycarbonyl nonadecylene oxy) anthracene, 9,10-bis (ethoxycarbonyl nonadecylene oxy) ) Anthracene, 9,10-bis (isopropoxycarbonylnonadecylene oxy) anthracene, 9,10-bis (tert-butoxycarbonylnonadecylene oxy) anthracene, 9,10-bis (n-butoxycarb) Nilnonadecylenoxy) anthracene, 9,10-bis (methoxycarbonyloxycarbonyloxy) anthracene, 9,10-bis (ethoxycarbonyliconcyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylicosylene oxy) anthracene And 9,10-bis (tert-butoxycarbonyl isocylene oxy) anthracene, 9,10-bis (n-butoxycarbonyl isoscylene oxy) anthracene and the like.

Moreover, as X and / or Y are specific examples of the alkyl group, 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 (ethoxycarbonyl pro Pyreneoxy) anthracene, 2-ethyl-9,10-bis (isopropoxycarbonyl carbonyl oxy) 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-butoxycal Nylmethylmethyleneoxy) 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-butoxycarbonylbutylene oxy) anthracene, 2-ethyl-9,10-bis (methoxycarbonyl octylen oxy) anthracene, 2-ethyl-9,10-bis (ethoxycarbonyl octyrene alkylene ) Anthracene, 2-ethyl-9,10-bis (isopropoxycarbonyloctylene oxy) anthracene, 2-ethyl-9,10-bis (tert-butoxycarbonyloctylene oxy) anthracene, 2-ethyl-9,10- Bis (n-butoxycarbonyloctylenoxy) anthracene, 2-ethyl-9,10-bis (methoxycarbonylhexadecylene oxy) anthracene, 2-ethyl-9,10-bis (ethoxycarbonylhexadecylene oxy) anthracene, 2-ethyl-9,10-bis (isopropoxycarbonylhexadecylene oxy) anthracene, 2-ethyl-9,10-bis (tert-butoxycarbonylhexadecylene oxy) anthracene, 2-ethyl-9,10-bis (N-butoxycarbonyl Xadecylene oxy) anthracene, 2-ethyl-9, 10-bis (methoxycarbonyl isocyanyloxy) anthracene, 2-ethyl-9, 10-bis (ethoxycarbonyl isocyanyloxy) anthracene, 2-ethyl-9, 10 -Bis (isopropoxycarbonyl isocylene oxy) anthracene, 2-ethyl-9, 10-bis (tert-butoxycarbonyl iscosilene oxy) anthracene, 2-ethyl-9, 10-bis (n-butoxycarbonyl isocylene oxy) Anthracene, 2-ethyl-9,10-bis (2-hydroxyethoxycarbonylmethoxy) anthracene and the like can be mentioned.

Further, for example, 2-amyl-9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (ethoxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (n-) Propoxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene, 2-amyl-9, 10-Bis (n-butoxycarbonylmethyleneoxy) anthracene, 2-amyl-9, 10-bis (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 (ethoxycarbonylethyl methylene) Oxy) anthracene, 2-amyl-9,10-bis (isopropoxycarbonylmethylmethyleneoxy) anthracene, 2-amyl-9,10-bis (tert-butoxycarbonylmethylmethyleneoxy) anthracene, -Amyl-9,10-bis (n-butoxycarbonylmethylmethyleneoxy) anthracene, 2-amyl-9,10-bis (methoxycarbonylbutyleneoxy) anthracene, 2-amyl-9,10-bis (ethoxycarbonylbutylene oxy) ) Anthracene, 2-amyl-9,10-bis (isopropoxycarbonylbutyleneoxy) anthracene, 2-amyl-9,10-bis (tert-butoxycarbonylbutyleneoxy) anthracene, 2-amyl-9,10-bis ( Examples include n-butoxycarbonylbutyleneoxy) anthracene, 2-amyl-9,10-bis (2-hydroxyethoxycarbonylmethoxy) anthracene and the like.

Moreover, as X and / or Y is a specific example of a halogen atom, for example, 2-chloro-9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10-bis (ethoxycarbonylmethyleneoxy) Anthracene, 2-chloro-9,10-bis (n-propoxycarbonylcarbonyloxy) anthracene, 2-chloro-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10-bis (tert -Butoxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10-bis (methoxycarbonylpropyleneoxy) anthracene, 2-chloro-9, 10-bis (ethoxycarbonyl) Ropylene oxy) anthracene, 2-chloro-9,10-bis (isopropoxycarbonyl carbonyl oxy) 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-butoxyca) Bonylmethylmethyleneoxy) 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 (methoxycarbonyloctylenoxy) anthracene, 2-chloro-9,10-bis (ethoxycarbonyloctylene) C) anthracene, 2-chloro-9,10-bis (isopropoxycarbonyloctylene oxy) anthracene, 2-chloro-9,10-bis (tert-butoxycarbonyloctylene oxy) anthracene, 2-chloro-9,10 -Bis (n-butoxycarbonyloctylene oxy) anthracene, 2-chloro-9,10-bis (methoxycarbonylhexadecylene oxy) anthracene, 2-chloro-9,10-bis (ethoxycarbonylhexadecylene oxy) anthracene , 2-chloro-9,10-bis (isopropoxycarbonylhexadecylene oxy) anthracene, 2-chloro-9,10-bis (tert-butoxycarbonylhexadecylene oxy) anthracene, 2-chloro-9,10- Bis (n-butoxycarbonyl Hexadecylene oxy) anthracene, 2-chloro-9,10-bis (methoxycarbonyloxycarbonyloxy) anthracene, 2-chloro-9,10-bis (ethoxycarbonylicosylene oxy) anthracene, 2-chloro-9,10 -Bis (isopropoxycarbonyl isocylene oxy) anthracene, 2-chloro-9, 10-bis (tert- butoxycarbonyl iscosilene oxy) anthracene, 2-chloro-9, 10-bis (n-butoxycarbonyl isocylene oxy) Anthracene, 2-chloro-9,10-bis (2-hydroxyethoxycarbonylmethoxy) anthracene and the like can be mentioned.

Among the specific examples listed above, 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene, 9,10-bis (n-propoxycarbonyl) from the viewpoint of easiness of production. Methyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene, 9 9,10-bis (methoxycarbonylpropyleneoxy) anthracene, 9,10-bis (ethoxycarbonylpropyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylpropyleneoxy) anthracene, 9,10 Bis (tert-butoxycarbonylpropyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylpropyleneoxy) anthracene, 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonylmethylmethylene) Oxy) 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 (ethoxy) Rubonyl butylene oxy) anthracene, 9, 10-bis (isopropoxycarbonyl butylene oxy) anthracene, 9, 10-bis (tert-butoxycarbonyl butylene oxy) anthracene, 9, 10-bis (n-butoxycarbonyl butylene oxy) 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 (ethoxy) Rubenylmethylmethyleneoxy) 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) 9.) Anthracene is preferable, and 9,10-bis (methoxycarbonylmethyleneoxy) anthracene (1-1), 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene (1-2), 9,10 mentioned in the following structural formula -B (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 (ethoxy) Carbonylpropyleneoxy) anthracene (1-7), 9,10-bis (ethoxycarbonylcarbonyloxy) anthracene (1-8), 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene (1-9) ), 9, 10-bis (2-hydroxy ethyl) Particularly preferred is xyloxycarbonylmethoxy) anthracene (1-11).

(Manufacturing method)
Next, the process for producing 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 obtained by using a 9,10-dihydroxyanthracene compound represented by the following general formula (2) (A single-step preparation method) and a two-step preparation method via an intermediate (a two-step preparation method) using a 9,10-dihydroxyanthracene compound as a raw material There is.

In the general formula (2), X and Y, which may be the same or different, each represents 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): According to Reaction formula-1, it can obtain by making it react with the corresponding ester compound represented by General formula (3) in the presence or absence of a basic compound.

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, and the alkyl group may be branched by an alkyl group or may be substituted by a hydroxy group, and a part of carbon atoms is replaced by an oxygen atom, (Except when forming a peroxide). X and Y, which may be the same or different, each represents 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.

The 9,10-dihydroxyanthracene compound represented by General Formula (2) used as a raw material in Reaction formula-1 is obtained by reducing the corresponding 9,10-anthraquinone compound.

Specific examples of the 9,10-dihydroxyanthracene compound which is a raw material in the reaction include 9,10-dihydroxyanthracene, 2-methyl-9,10-dihydroxyanthracene, 2-ethyl-9,10-dihydroxyanthracene , 2-t-pentyl-9,10-dihydroxyanthracene, 2,6-dimethyl-9,10-dihydroxyanthracene, 2-chloro-9,10-dihydroxyanthracene, 2-bromo-9,10-dihydroxyanthracene, etc. It can be mentioned.

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

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

Specific examples of the ester compound represented by the general formula (3) which is a raw material in Reaction formula-1 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, ikosyl chloroacetate Methyl chloropropionate, methyl 3-chloropropionate, methyl 2-chloropropionate, methyl 3-chloropropionate, ethyl 2-chloropropionate, ethyl 3-chloropropionate, n-propyl 2-chloropropionate, 3-Chloropropionic acid n-propi , 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, dodecyl 2-chloropropionate, 3-chloro Dodecyl propionate, 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, isopropyl 2-chlorobutyrate, 3- Isopropyl chlorobutyrate, isopropyl 4-chlorobutyrate, n-butyl 2-chlorobutyrate, n-butyl 3-chlorobutyrate, n-butyl 4-chlorobutyrate, tert-butyl 2-chlorobutyrate, tert-butyl 3-chlorobutyrate, 4-Chlorobutyric acid tert-butyl, 2-chlorobutyric acid pentyl, 3-chlorobutyric acid salt Nthyl, 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-chlorobutyrate Nonyl chlorobutyrate, dodecyl 2-chlorobutyrate, dodecyl 3-chlorobutyrate, dodecyl 4-chlorobutyrate, nonadecyl 2-chlorobutyrate, nonadecyl 3-chlorobutyrate, nonadecyl 4-chlorobutyrate, icosyl 2-chlorobutyrate, 3-chlorobutyrate Ikosyl, icosyl 4-chlorobutyrate, methyl 2-chlorovalerate, 3- Methyl lorovalerate, methyl 4-chlorovalerate, methyl 5-chlorovalerate, ethyl 2-chlorovalerate, ethyl 3-chlorovalerate, ethyl 4-chlorovalerate, ethyl 5-chlorovalerate, 2-chloro N-propyl valerate, n-propyl 3-chlorovalerate, n-propyl 4-chlorovalerate, n-propyl 5-chlorovalerate, isopropyl 2-chlorovalerate, isopropyl 3-chlorovalerate, 4-chloro Isopropyl valerate, isopropyl 5-chlorovalerate, n-butyl 2-chlorovalerate, n-butyl 3-chlorovalerate, n-butyl 4-chlorovalerate, n-butyl 5-chlorovalerate, 2-chloro Tert-butyl valerate, tert-butyl 3-chlorovalerate, tert-butyl 4-chlorovalerate, tert-butyl 5-chlorovalerate, 2-chlorovalerate Pentyl, pentyl 3-chlorovalerate, pentyl 4-chlorovalerate, pentyl 5-chlorovalerate, hexyl 2-chlorovalerate, hexyl 3-chlorovalerate, hexyl 4-chlorovalerate, hexyl 5-chlorovalerate Heptyl 2-chlorovalerate, heptyl 3-chlorovalerate, heptyl 4-chlorovalerate, heptyl 5-chlorovalerate, octyl 2-chlorovalerate, octyl 3-chlorovalerate, octyl 4-chlorovalerate, Octyl 5-chlorovalerate, 2-ethylhexyl 2-chlorovalerate, 2-ethylhexyl 3-chlorovalerate, 2-ethylhexyl 4-chlorovalerate, 2-ethylhexyl 5-chlorovalerate, nonyl 2-chlorovalerate, 3-chlorovaleric nonyl acid, 4-chlorovalerate nonyl, 5-chlorovalerate nonyl, dodecyl 2-chlorovalerate, Dodecyl 3-chlorovalerate, dodecyl 4-chlorovalerate, dodecyl 5-chlorovalerate, nonadecyl 2-chlorovalerate, nonadecyl 3-chlorovalerate, nonadecyl 4-chlorovalerate, 5-chlorovalerate nonadecyl, 2 -Icosyl chlorovaleric acid, Icosyl 3-chlorovaleric acid, Icosyl 4-chlorovaleric acid, Icosyl 5-chlorovaleric acid and the like.

Further, 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, 2-bromopropionate Propyl, isopropyl 3-bromopropionate, n-butyl 2-bromopropionate, n-butyl 3-bromopropionate, tert-butyl 2-bromopropionate, tert-butyl 3-bromopropionate, 2-bromopropionate Pentyl, pentyl 3-bromopropionate, hexyl 2-bromopropionate, hexyl 3-bromopropionate, heptyl 2-bromopropionate, heptyl 3-bromopropionate, octyl 2-bromopropionate, octyl 3-bromopropionate 2-ethylhexyl 2-bromopropionate, 2-ethylhexyl 3-bromopropionate, nonyl 2-bromopropionate, nonyl 3-bromopropionate, dodecyl 2-bromopropionate, dodecyl 3-bromopropionate, 2-bu Nonadecyl mopropionate, nonadecyl 3-bromopropionate, icosyl 2-bromopropionate, icosyl 3-bromopropionate, methyl 2-bromobutyrate, methyl 3-bromobutyrate, methyl 4-bromobutyrate, ethyl 2-bromobutyrate, 3 -Ethyl bromobutyrate, ethyl 4-bromobutyrate (3-7), n-propyl 2-bromobutyrate, n-propyl 3-bromobutyrate, n-propyl 4-bromobutyrate, isopropyl 2-bromobutyrate, 3-bromobutyrate Isopropyl, isopropyl 4-bromobutyrate, n-butyl 2-bromobutyrate, n-butyl 3-bromobutyrate, n-butyl 4-bromobutyrate, tert-butyl 2-bromobutyrate, tert-butyl 3-bromobutyrate, 4- Bromobutyrate tert-butyl, pentyl 2-bromobutyrate, pentyl 3-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-bromobutyrate Icosyl butyrate, methyl 2-bromovalerate, methyl 3-bromovalerate Methyl 4-bromovalerate, methyl 5-bromovalerate, ethyl 2-bromovalerate, ethyl 3-bromovalerate, ethyl 4-bromovalerate (3-8), ethyl 5-bromovalerate, 2-bromo N-propyl valerate, n-propyl 3-bromovalerate, n-propyl 4-bromovalerate, n-propyl 5-bromovalerate, isopropyl 2-bromovalerate, isopropyl 3-bromovalerate, 4-bromo-valerate Isopropyl valerate, isopropyl 5-bromovalerate, n-butyl 2-bromovalerate, n-butyl 3-bromovalerate, n-butyl 4-bromovalerate, n-butyl 5-bromovalerate, 2-bromo Tert-butyl valerate, tert-butyl 3-bromovalerate, tert-butyl 4-bromovalerate, tert-butyl 5-bromovalerate, penched 2-bromovalerate Pentyl 3-bromovalerate, pentyl 4-bromovalerate, pentyl 5-bromovalerate, hexyl 2-bromovalerate, hexyl 3-bromovalerate, hexyl 4-bromovalerate, hexyl 5-bromovalerate, Heptyl 2-bromovalerate, heptyl 3-bromovalerate, heptyl 4-bromovalerate, heptyl 5-bromovalerate, octyl 2-bromovalerate, octyl 3-bromovalerate, octyl 4-bromovalerate, 5 -Octyl bromovalerate, 2-ethylhexyl 2-bromovalerate, 2-ethylhexyl 3-bromovalerate, 2-ethylhexyl 4-bromovalerate, 2-ethylhexyl 5-bromovalerate, nonyl 2-bromovalerate, 3 -Bromovaleric nonylic acid, Nonyl 4-bromovaleric acid, Nonyl 5-bromovaleric acid, Dodecyl 2-bromovaleric acid, 3-bromo Dodecyl movalerate, dodecyl 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 -Bromobutyric acid 2-hydroxyethyl, 4-bromovaleric acid 2-hydroxyethyl and the like.

Furthermore, methyl iodoacetate, ethyl iodoacetate, n-propyl iodoacetate, isopropyl iodoacetate, n-butyl iodoacetate, tert-butyl iodoacetate, pentyl iodoacetate, hexyl iodoacetate, heptyl iodoacetate, octyl iodoacetate, iodo 2-ethylhexyl acetate, nonyl iodoacetate, dodecyl iodoacetate, nonadecyl iodoacetate, icosyl iodoacetate, methyl 2-iodopropionate, methyl 3-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- N-butyl dopropionate, n-butyl 3-iodopropionate, tert-butyl 2-iodopropionate, tert-butyl 3-iodopropionate, pentyl 2-iodopropionate, pentyl 3-iodopropionate, 2- Hexyl iodopropionate, hexyl 3-iodopropionate, heptyl 2-iodopropionate, heptyl 3-iodopropionate, octyl 2-iodopropionate, octyl 3-iodopropionate, 2-ethylhexyl 2-iodopropionate, 3 2-ethylhexyl iodopropionate, nonyl 2-iodopropionate, nonyl 3-iodopropionate, dodecyl 2-iodopropionate, dodecyl 3-iodopropionate, nonadecyl 2-iodopropionate, nona 3-iodopropionate Syl, icosyl 2-iodopropionate, icosyl 3-iodopropionate, methyl 2-iodobutyrate, methyl 3-iodobutyrate, methyl 4-iodobutyrate, ethyl 2-iodobutyrate, ethyl 3-iodobutyrate, 4-iodobutyrate Ethyl, n-propyl 2-iodobutyrate, n-propyl 3-iodobutyrate, n-propyl 4-iodobutyrate, isopropyl 2-iodobutyrate, isopropyl 3-iodobutyrate, isopropyl 4-iodobutyrate, 2-iodobutyrate n- Butyl, n-butyl 3-iodobutyrate, n-butyl 4-iodobutyrate, tert-butyl 2-iodobutyrate, tert-butyl 3-iodobutyrate, tert-butyl 4-iodobutyrate, pentyl 2-iodobutyrate, 3- Pentyl iodobutyrate, pentyl 4-iodobutyrate, hexyl 2-iodobutyrate, hexyl 3-iodobutyrate, 4 -Iodobutyrate, heptyl 2-iodobutyrate, heptyl 3-iodobutyrate, heptyl 4-iodobutyrate, octyl 2-iodobutyrate, octyl 3-iodobutyrate, octyl 4-iodobutyrate, 2-ethylhexyl 2-iodobutyrate, 3 -Iodobutyrate 2-ethylhexyl, 4-iodobutyrate 2-ethylhexyl, 2-iodobutyrate nonyl 3-iodobutyrate nonyl 4-iodobutyrate nonyl 2-iodobutyrate dodecyl 3-iodobutyrate dodecyl 4-iodobutyrate dodecyl 2-iodobutyrate nonadecyl 3-iodobutyrate nonadecyl 4-iodobutyrate nonadecyl 2-iodobutyrate icosyl 3-iodobutyrate icosyl 4-iodobutyrate icosyl methyl 2-iodovaleric acid methyl 3-iodovaleric acid , 4-iodovalerate methyl, 5-iodovalerate methyl, 2-iodo valerate Ethyl, ethyl 3-iodovalerate, ethyl 4-iodovalerate, ethyl 5-iodovalerate, n-propyl 2-iodovalerate, n-propyl 3-iodovalerate, n-propyl 4-iodovalerate, 5-iodovalerate n-propyl, 2-iodovalerate isopropyl, 3-iodovalerate isopropyl, 4-iodovalerate isopropyl, 5-iodovalerate isopropyl, 2-iodovalerate n-butyl 3-iodoyoshi N-butyl chloroformate, n-butyl 4-iodovalerate, n-butyl 5-iodovalerate, tert-butyl 2-iodovalerate, tert-butyl 3-iodovalerate, tert-butyl 4-iodovalerate, Tert-Butyl 5-iodovalerate, pentyl 2-iodovalerate, pentyl 3-iodovalerate, pentyl 4-iodovalerate, 5-iodovalerate pe Chill, hexyl 2-iodovalerate, hexyl 3-iodovalerate, hexyl 4-iodovalerate, hexyl 5-iodovalerate, heptyl 2-iodovalerate, heptyl 3-iodovalerate, heptyl 4-iodovalerate , 5-iodovalerate heptyl, octyl 2-iodovalerate, octyl 3-iodovalerate, octyl 4-iodovalerate, octyl 5-iodovalerate, 2-ethylhexyl 2-iodovalerate, 3-iodovalerate 2-ethylhexyl, 2-ethylhexyl 4-iodovalerate, 2-ethylhexyl 5-iodovalerate, 2-iodovalerate nonyl, 3-iodovalerate nonylic acid, 4-iodovalerate nonyl, 5-iodovalerate nonyl , 2-iodovalerate dodecyl, 3-iodovalerate dodecyl, 4-iodovalerate dodecyl, 5-iodovalerate dodecyl, 2- Nonadecyl iodovalerate, nonadecyl 3-iodovalerate, nonadecyl 4-iodovalerate, nonadecyl 5-iodovalerate, icosyl 2-iodovalerate, icosyl 3-iodovalerate, icosyl 4-iodovalerate, 5-iodo Ikosyl valerate, etc. may be mentioned.

Among the specific examples listed above, chloro compounds and bromo compounds are preferable in terms of reactivity, and in particular, compounds of the following structural formula and the like are preferable.

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

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

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

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

When a 9,10-dihydroxyanthracene compound is dissolved in an aqueous solution of an inorganic base and reacted with an ester, use of a phase transfer catalyst is effective. As a phase transfer catalyst, for example, tetramethyl ammonium bromide, tetraethyl ammonium bromide, tetrapropyl ammonium bromide, tetrabutyl ammonium bromide, trioctyl methyl ammonium bromide, trioctyl ethyl ammonium bromide, trioctyl propyl ammonium bromide, trioctyl butyl ammonium bromide , Benzyldimethyloctadecyl ammonium bromide, tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrapropyl ammonium chloride, tetrabutyl ammonium chloride, trioctyl methyl ammonium chloride, trioctyl ethyl ammonium chloride, trioctyl propyl ammonium chloride Id, trioctyl butyl ammonium chloride, benzyl dimethyl ammonium chloride or the like.

The amount of phase transfer catalyst added is preferably 0.01 mole times or more and less than 1.0 mole times, more preferably 0.05 mole times or more, with respect to the 9,10-dihydroxyanthracene compound. It is less than the molar ratio. If the amount is less than 0.01 mole, the reaction rate is slow, and if the amount is 1.0 mole or more, the purity of the product is unfavorably reduced.

The reaction temperature of the reaction is usually 0 ° C. or more and 200 ° C. or less, preferably 10 ° C. or more and 100 ° C. or less. If the temperature is lower than 0 ° C., the reaction time is too long, and if the temperature is higher than 100 ° C., impurities increase and the purity of the target compound decreases, which is not preferable.

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

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

(Two-step manufacturing method)
Next, a two-step process for producing a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group according to the present invention will be described. The 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention is a 9,10-dihydroxyanthracene compound represented by the general formula (2): In accordance with Reaction formula-2, first, it is reacted with a carboxylic acid represented by the corresponding general formula (4) in the presence or absence of a basic compound to obtain an intermediate represented by the general formula (5) 9 The 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5) and the general formula (6) are synthesized according to reaction formula-3 after the synthesis of the 1,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound. In accordance with the reaction formula-4 and the halogenated alkyl compound represented by the general formula (7) according to the reaction formula-5 To obtain a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by General Formula (1) by obtaining it by reacting with a glycidyl ether compound represented by General Formula (8) Can.

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, which may be the same or different, each represents 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, which may be the same or different, each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom. R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group or may be substituted by a hydroxy group, and a part of carbon atoms is replaced by an oxygen atom (Except when forming a peroxide).

In Reaction formula-4, A represents a C1-C20 alkylene group, This alkylene group may be branched by the alkyl group. X and Y, which may be the same or different, each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom. R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group or may be substituted by a hydroxy group, and a part of carbon atoms is replaced by an oxygen atom (Except when forming 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, which may be the same or different, each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom. R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group or may be substituted by a hydroxy group, and a part of carbon atoms is replaced by an oxygen atom, (Except when forming a peroxide). 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 by a hydroxy group, and a part of carbon atoms is oxygen It may be replaced by an atom (except when forming a peroxide).

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

As the 9,10-dihydroxyanthracene compound represented by General Formula (2) used as a raw material in Reaction formula-2, the same one as that described in Reaction formula-1 can be used, and the same method is applied. You can get it.

Next, specific examples of the carboxylic acid represented by the general formula (4), which is another raw material in Reaction formula-2, include chloroacetic acid, 2-chloropropionic acid, 3-chloropropionic acid and 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 listed above, chloro compounds and bromo compounds are preferable in terms of availability and reactivity, and in particular, chloroacetic acid and bromoacetic acid are preferable.

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

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

The addition amount of the basic compound is preferably 2.0 mol times or more and less than 10.0 mol times, more preferably 2.2 mol times or more, 8.0 mol-fold to the 9,10-dihydroxyanthracene compound. It is less than the molar ratio. If the amount is less than 2.0 molar times, the reaction will not be completed, and if it is 10.0 molar times or more, side reactions will occur to lower the yield and purity, which is not preferable.

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

When a 9,10-dihydroxyanthracene compound is dissolved in an aqueous solution of an inorganic base and reacted with an ester, use of a phase transfer catalyst is effective. As a phase transfer catalyst, for example, tetramethyl ammonium bromide, tetraethyl ammonium bromide, tetrapropyl ammonium bromide, tetrabutyl ammonium bromide, trioctyl methyl ammonium bromide, trioctyl ethyl ammonium bromide, trioctyl propyl ammonium bromide, trioctyl butyl ammonium bromide , Benzyldimethyloctadecyl ammonium bromide, tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrapropyl ammonium chloride, tetrabutyl ammonium chloride, trioctyl methyl ammonium chloride, trioctyl ethyl ammonium chloride, trioctyl propyl ammonium chloride Id, trioctyl butyl ammonium chloride, benzyl dimethyl ammonium chloride or the like.

The amount of phase transfer catalyst added is preferably 0.01 mole times or more and less than 1.0 mole times, more preferably 0.03 mole times or more, relative to the 9,10-dihydroxyanthracene compound. It is less than the molar ratio. If the amount is less than 0.01 mole, the reaction rate is slow, and if the amount is 1.0 mole or more, the purity of the product is unfavorably reduced.

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

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

After completion of the reaction, unreacted raw materials, solvent and catalyst are removed as necessary by operations such as extraction and filtration singly or in combination. Since the product is in the form of a carboxylate, crystals are precipitated by neutralization with a mineral acid or an organic acid, solid-liquid separation is performed by filtration, and recrystallization is carried out as necessary. The 9,10-bis (hydroxy carbonyl alkylene oxy) anthracene compound represented can be obtained.

Next, the 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5) and the alcohol compound represented by the general formula (6), which are represented by Reaction Formula-3, are not present 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 will be described.

Specific examples of the alcohol compound represented by the general formula (6) as the raw material in Reaction formula-3 include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol And 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 view of easy availability, particularly methanol Ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and ethylene glycol are preferred.

The use amount of the alcohol compound represented by the general formula (6) in the reaction formula-3 is preferably relative to the 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5) The molar ratio is 5 molar times or more and less than 100 molar times, more preferably 10 molar times or more and 50 molar times. If the amount is less than 5 moles, the reaction may not be completed, and if the amount is more than 100 moles, the reaction rate will be slow and the yield and purity will be reduced.

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

The amount of addition of the catalyst is preferably 0.01 mol% or more and less than 50 mol%, more preferably about 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by the general formula (5). 0.1 mol% or more and less than 20 mol%. If the amount is less than 0.01 mol%, the reaction will not be completed, and if it is 50 mol% or more, side reactions will occur to lower the yield and purity, which is not preferable.

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

The reaction temperature of the reaction is usually 20 ° C. or more and 200 ° C. or less, preferably 50 ° C. or more and 150 ° C. or less. If it is less than 20 ° C., the reaction time is too long, and if it is heated above 200 ° C., the amount of impurities increases and the purity of the target compound decreases, which is not preferable.

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

After completion of the reaction, unreacted raw material / solvent and catalyst are removed by a method combining one or more operations such as neutralization / washing / vacuum distillation / filtration, if necessary. When the product is solid, crystals are precipitated during the reaction, so solid-liquid separation is performed by filtration, and if necessary, recrystallization is performed from a poor solvent such as alcohol or hexane. Alternatively, it can be dried as it is to obtain crystals. When the product is a liquid, it is dried as it is, and if necessary, purification such as distillation can be performed to obtain a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group.

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

Specific examples of the halogenated alkyl compound represented by the general formula (7), which is a raw material in Reaction formula-4, include methyl chloride, ethyl chloride, n-propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, 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, octyl iodide 2 -Ethylhexyl, nonyl iodide, decyl iodide, dodecyl iodide, 2-hydroxyethyl iodide and the like can be mentioned.

Among the above-mentioned specific examples, chloride and bromide are preferable in view of easy availability and reactivity, and in particular, bromide is preferable.

As a usage-amount of the halogenated alkyl compound represented by General formula (7) in Reaction formula 4, with respect to the 9, 10- bis (hydroxy carbonyl alkylene oxy) anthracene compound represented by General formula (5) Preferably, it is 2 mol times or more and less than 10 mol times, more preferably 3 mol times or more and 5 mol times or less. If the amount is less than 2 moles, the reaction will not be completed, and if it is 10 moles or more, side reactions will occur to lower the yield and purity, which is not preferable.

As a basic compound used in Reaction formula 4, sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, lithium hexamethyldisilazide, lithium diisopropylamide And triethylamine, tributylamine, trihexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dimethylamine, pyridine, 4,4-dimethylaminopyridine, piperidine, γ-picoline, lutidine and the like.

The addition amount of the basic compound is preferably 0.5 mole times or more and less than 10 mole times with respect to the 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by General Formula (5) Preferably, it is 1 mole or more and less than 5 moles. If the amount is less than 0.5 molar times, the reaction is not completed, and if it is 10 molar times or more, side reactions occur and the yield and purity are unfavorably reduced.

The reaction is carried out in a solvent or without solvent. The solvent used is not particularly limited as long as it does not react with the alcohol compound to be used, for example, aromatic solvents such as toluene, xylene and ethylbenzene, ether solvents such as tetrahydrofuran and 1,4-dioxane, acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone, amide solvents such as dimethylacetamide and dimethylformamide, 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 more and 200 ° C. or less, preferably 20 ° C. or more and 100 ° C. or less. If the temperature is lower than 0 ° C., the reaction time is too long, and if the temperature is higher than 200 ° C., impurities increase and the purity of the target compound decreases, which is not preferable.

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

After completion of the reaction, unreacted raw material / solvent and catalyst are removed by a method combining one or more operations such as neutralization / washing / vacuum distillation / filtration, if necessary. When the product is solid, crystals are precipitated during the reaction, so solid-liquid separation is performed by filtration, and if necessary, recrystallization is performed from a poor solvent such as alcohol or hexane. Alternatively, it can be dried as it is to obtain crystals. When the product is a liquid, it is dried as it is, and if necessary, purification such as distillation can be performed to obtain a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group.

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

Specific examples of the glycidyl ether compound represented by the general formula (7), which is a raw material in Reaction formula-5, are methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether And 2-ethylhexyl glycidyl ether, octyl glycidyl ether, allyl glycidyl ether, methallyl glycidyl ether, glycidol and the like.

As the usage-amount of the glycidyl ether compound represented by General formula (7) in Reaction formula-2, with respect to the 9, 10- bis (hydroxy carbonyl alkylene oxy) anthracene compound represented by General formula (5), It is preferably at least 2 molar times and less than 10 molar times, more preferably at least 3 molar times and less than 5 molar times. If the amount is less than 2 moles, the reaction will not be completed, and if it is 10 moles or more, side reactions will occur to lower the yield and purity, which is not preferable.

As a basic compound used in Reaction formula-5, sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, lithium hexamethyldisilazide, lithium diisopropylamide And triethylamine, tributylamine, trihexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dimethylamine, pyridine, 4,4-dimethylaminopyridine, piperidine, γ-picoline, lutidine and the like.

The addition amount of the basic compound is preferably 0.5 mole times or more and less than 10 mole times with respect to the 9,10-bis (hydroxycarbonylalkyleneoxy) anthracene compound represented by General Formula (5) Preferably, it is 1 mole or more and less than 5 moles. If the amount is less than 0.5 molar times, the reaction is not completed, and if it is 10 molar times or more, side reactions occur and the yield and purity are unfavorably reduced.

The reaction is carried out in a solvent or without solvent. The solvent used is not particularly limited as long as it does not react with the alcohol compound to be used, for example, aromatic solvents such as toluene, xylene and ethylbenzene, ether solvents such as tetrahydrofuran and 1,4-dioxane, acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone, amide solvents such as dimethylacetamide and dimethylformamide, 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 more and 200 ° C. or less, preferably 20 ° C. or more and 100 ° C. or less. If the temperature is lower than 0 ° C., the reaction time is too long, and if the temperature is higher than 200 ° C., impurities increase and the purity of the target compound decreases, which is not preferable.

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

After completion of the reaction, unreacted raw material / solvent and catalyst are removed by a method combining one or more operations such as neutralization / washing / vacuum distillation / filtration, if necessary. When the product is solid, crystals are precipitated during the reaction, so solid-liquid separation is performed by filtration, and if necessary, recrystallization is performed from a poor solvent such as alcohol or hexane. Alternatively, it can be dried as it is to obtain crystals. When the product is a liquid, it is dried as it is, and if necessary, purification such as distillation can be performed 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 receives the excitation energy in the photopolymerization initiator. Acts as a photopolymerization sensitizer to deliver. As a result, photopolymerization can be efficiently initiated even by light of a long wavelength where the activity of the photopolymerization initiator is not sufficient. The photopolymerization sensitizer and the photopolymerization initiator can be mixed with the photopolymerization compound to form a photopolymerizable composition. The said photopolymerizable composition can be easily photocured also by irradiation of the light of a long wavelength, such as an ultraviolet LED light whose center wavelength is 405 nm, for example.

(Photopolymerization initiator)
As the photopolymerization initiators used in the present invention, onium salts, benzyl methyl ketals, α-hydroxyalkylphenone polymerization initiators, oxime ester photopolymerization initiators, α-aminoacetophenone photopolymerization initiators, acyl phosphine oxides A system photoinitiator, a biimidazole initiator, etc. can be used.

As the onium salt, an iodonium salt or a sulfonium salt is usually used. Examples of iodonium salts include 4-isobutylphenyl-4'-methylphenyliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexamethoxyantimonate, 4-isopropylphenyl-4'-methylphenyliodonium tetrakispentamethoxyphenylborate, 4 -Isopropylphenyl-4'-methylphenyliodonium tetrakispentafluorophenyl borate and the like, and examples thereof include IRGACURE 250 (IRGACURE is a registered trademark of BASF Co., Ltd.) manufactured by BASF Co., Ltd., Rhodia Lodesil 2074 (Lodesil is a registered trademark of Rhodia, Inc.), IK-1 manufactured by San-Apro, etc. can be used. On the other hand, as sulfonium salts, S, S, S ', S'-tetraphenyl-S, S'-(4, 4'-thiodiphenyl) disulfonium bishexamethoxyphosphate, diphenyl-4-phenylthiophenylsulfonium hexame ter Examples thereof include methoxyphosphate and triphenylsulfonium hexamethoxyphosphate. For example, CPI-100P, CPI101P, CPI-200K, manufactured by Daicel, IRGACURE 270, manufactured by BSF, UVI 6992, etc., manufactured by Dow Chemical Co. It 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 according to the present invention is also characterized by having a photopolymerization sensitizing effect not only to iodonium salts but also to sulfonium salts. It is one.

Further, the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention is a benzyl methyl ketal type, α-hydroxyalkyl phenone type polymerization initiator, biimidazole. It has an excellent photopolymerization sensitization effect even on radical polymerization initiators that do not have absorption at long wavelengths, such as a system polymerization initiator.

Examples of the benzyl methyl ketal radical polymerization initiator include 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name “IRGACURE 651”, manufactured by BFS Inc.) and the like, and α 2-Hydroxy-2-phenyl-1-phenylpropan-1-one (trade name "Darocure 1173" manufactured by BASF), 1-hydroxycyclohexylphenyl as a hydroxyalkyl phenone radical polymerization initiator Ketone (trade name “IRGACURE 184” by BSF Co., Ltd.), 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-methyl-propionyl) - benzyl] phenyl} -2-methyl-1-one (trade name "Irgacure 127" BAS-F Inc.).

In particular, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “IRGACURE 651” by BSF 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” by BSF Co., Ltd.) which is a phenone-based radical polymerization initiator, 1-hydroxycyclohexyl phenyl ketone (commodity The name “IRGACURE 184”, manufactured by BSA, Inc. is preferred.

Also, acetophenone which is an acetophenone type radical polymerization initiator, 2-hydroxy-2-phenylacetophenone, 2-ethoxy-2-phenylacetophenone, 2-methoxy-2-phenylacetophenone, 2-isopropoxy-2-phenylacetophenone, 2 -Isobutoxy-2-phenylacetophenone, benzyl as a benzyl radical polymerization initiator, 4,4'-dimethoxybenzyl, 2-ethyl anthraquinone as an anthraquinone radical polymerization initiator, 2-t-butyl anthraquinone, 2-phenoxy anthraquinone And 2- (phenylthio) anthraquinone, 2- (hydroxyethylthio) anthraquinone and the like can also be used.

As a biimidazole type polymerization initiator, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2 -(O-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5- The 2,4,5- triaryl imidazole dimers, such as a diphenyl imidazole dimer, etc. are mentioned.

The use amount of the photopolymerization sensitizer for the photopolymerization initiator containing the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention is not particularly limited. However, it is usually in the range of 5% by weight to 100% by weight, preferably in the range of 10% by weight to 50% by weight, based on the photopolymerization initiator. If the amount of the photopolymerization sensitizer used is less than 5% by weight, it takes too long to photopolymerize the photopolymerizable compound, while an effect corresponding to the addition is obtained even if it is used over 100% by weight Absent.

(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 directly added to the photopolymerizable compound. Although it can be, after preparing a photoinitiator composition by mix | blending with a photoinitiator beforehand, it can also be added to a 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 the general formula (1) It is a composition containing a photoinitiator.

(Photopolymerizable composition)
Furthermore, a photopolymerizable composition can also be prepared by blending the photopolymerization initiator composition with 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 the photopolymerization initiator It is a composition containing a composition and a radical 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 photoradically polymerizable compound or the photocationically polymerizable compound. The resulting photopolymerization initiator composition may be formed in a photoradically polymerizable compound or a photocationically polymerizable compound. Furthermore, it may be a hybrid composition containing both a photoradically polymerizable compound and a photocationically polymerizable compound.

As the photoradical polymerizable compound, for example, an organic compound having a double bond such as styrene, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, acrylic acid ester, methacrylic acid ester 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 preferable from the viewpoint of film forming ability and the like. As (meth) acrylic acid esters, methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, methyl methacrylate, butyl methacrylate, methacrylic acid Cyclohexyl, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tricyclo [5,2,1,2,6] decanedimethanol diacrylate, isobonyl methacrylate, epoxy acrylate, urethane acrylate, polyester acrylate, Polybutadiene acrylate, polyol acrylate, polyether acrylate, silicone resin acrylate, imido acrylate etc It is below. These radical photopolymerizable compounds may be used alone or in combination of two or more.

An epoxy compound, an oxetane compound, a vinyl ether etc. are mentioned as a photocationic-polymerizable compound. General epoxy compounds include alicyclic epoxy compounds, epoxy-modified silicones, and aromatic glycidyl ethers. Examples of alicyclic epoxy compounds include 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel, trade name: Celoxide 2021 P, Celoxide is a registered trademark of Daicel), bis (3, 4-epoxycyclohexyl) adipate and the like. As epoxy modified silicone, Toshiba GE silicone UV-9300 etc. are mentioned. As an aromatic glycidyl compound, 2,2'-bis (4-glycidyloxy phenyl) propane etc. are mentioned. As the oxetane compound, 3-ethyl-3-hydroxymethyl oxetane (oxetane alcohol) (manufactured by Toagosei Co., Ltd., trade name: OXT-101), 2-ethylhexyl oxetane (tradename: Toagosei, trade name: OXT-212), Xylylene bis oxetane (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. Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether and the like. These photocationic polymerizable compounds may be used alone or in combination of two or more.

Only a photo radically polymerizable compound may be used as a photopolymerizable compound, or both a photo radically polymerizable compound and a photo cationically polymerizable compound may be mixed and used.

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

There is no particular limitation on the mixing ratio of the cationic photopolymerizable compound and the photoradically polymerizable compound, and it is appropriately selected according to the physical properties of a coating film or a molded product obtained by photopolymerization and curing of the composition. Usually, the composition ratio of the cationic photopolymerizable compound and the photoradically polymerizable compound is determined in the range of 1:99 to 99: 1, preferably 20:80 to 80:20.

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

In particular, some of the cationic photopolymerization initiators generate cationically initiated active species and radically initiated active species by light irradiation, and when such an initiator is used, the cationically photopolymerizable compounds and photoradicals are used alone. It is also possible to initiate the photopolymerization of both of the polymerizable compounds.

Furthermore, the photopolymerizable composition of the present invention may contain a binder polymer such as an acrylic resin, a styrene resin, or an epoxy resin. Moreover, 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 to 10% by weight, preferably 0.025% by weight, based on the photopolymerizable composition. Above, it is 5 weight% or less. If it is less than 0.005% by weight, it takes time to photopolymerize the photopolymerizable composition, while if it is added in excess of 10% by weight, the hardness of the photocured product obtained by photopolymerization decreases. It is not preferable because the physical properties of the cured product are deteriorated.

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

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

A photocured product is obtained by irradiating the coating film comprising the photopolymerizable composition prepared in this manner with ultraviolet light containing a wavelength range of 300 nm to 500 nm at a strength of about 1 to 1000 mW / cm ^2. Can. As a light source to be used, high pressure mercury lamp, super high pressure mercury lamp, metal halide lamp, xenon lamp, gallium doped lamp, black light, 405 nm ultraviolet LED, 395 nm ultraviolet LED, 385 nm ultraviolet LED, 365 nm ultraviolet LED, blue LED, white LED, fusion Company-made D valve, V valve, etc. are mentioned. Also, natural light such as sunlight can be used. In particular, it is characterized that light having a wavelength range of 365 nm to 405 nm such as 405 nm UV LED, 395 nm UV LED, 385 nm UV LED, 375 nm UV LED, 365 nm UV LED has a sensitizing effect even in a wavelength range of 365 nm to 405 nm. And is preferred.

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

(Determination of migration resistance of composition)
As a method of determining whether the photopolymerization sensitizer contained in the photopolymerizable composition of the present invention migrates (migrates) to a film or the like, the photopolymerizable composition containing the photopolymerization sensitizer is formed into a thin film The product is coated with a polyethylene film, covered with a polyethylene film, stored at a constant temperature (26 ° C) for a fixed period, and then peeled off the polyethylene film to check whether the photopolymerization sensitizer has migrated to the polyethylene film , Migration resistance was determined. The peeled polyethylene film is washed after washing the surface composition with acetone, and the UV spectrum of the polyethylene film is measured, and the migration resistance is measured by examining the increase in absorption intensity caused by the photopolymerization sensitizer. did. In addition, the ultraviolet and visible spectrophotometer (made by Shimadzu, type | model: UV2600) was used for the said measurement. For quantitative comparison with the compound of the comparative example, 9,10-dibutoxyanthracene, the obtained absorbance was converted to the value of the absorbance of 9,10-dibutoxyanthracene. For 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 absorption coefficient is calculated from the absorbance value and the molar concentration, and the ratio It converted using.

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

Identification of the compound of the present invention was performed using the following equipment.
Infrared (IR) spectrophotometer: manufactured by Thermo, model is50 FT-IR
Nuclear Magnetic Resonance Device (NMR): Nippon Electronics Co., 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, under a nitrogen atmosphere, 15 g of a solvent methyl isobutyl ketone and a catalyst tetra 0.8 g (1.2 mmol) of a 50% aqueous solution of butyl ammonium 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 (24 mmol as anthraquinone) of a 17 wt% aqueous solution of 9,10-anthracenediol disodium salt was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was further stirred for 1 hour. Thereafter, suction filtration was performed to obtain 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, 6 H), 4.792 (s, 4 H), 7. 261-7.545 (m, 4 H), 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, under a nitrogen atmosphere, 15 g of a solvent methyl isobutyl ketone and a catalyst tetra 0.8 g (1.2 mmol) of a 50% aqueous solution of butyl ammonium 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 (24 mmol as anthraquinone) of a 17 wt% aqueous solution of 9,10-anthracenediol disodium salt was added dropwise over 1 hour. After completion of the dropwise addition, 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, 6 H), 4.376 (k, J = 21.6 Hz, 4 H), 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, under a nitrogen atmosphere, 15 g of methyl isobutyl ketone as a solvent and a catalyst 0.8 g (1.2 mmol) of a 50% aqueous solution of tetrabutylammonium bromide and 11.3 g (62.5 mmol) of isopropyl bromoacetate were added. While maintaining the temperature of the reaction system at 20 to 25 ° C., 29.1 g (24 mmol as anthraquinone) of a 17 wt% aqueous solution of 9,10-anthracenediol disodium salt was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was further stirred for 1 hour. Thereafter, suction filtration was performed to obtain 5.9 g (crude yield 60 mol%) of light 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, 12 H), 4.743 (s, 4 H), 5.246-5.277 (m, 2H), 7.504-7.529 (m, 4H), 8.356-8.398 (m, 4H).

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, under a nitrogen atmosphere, 15 g of a methyl isobutyl ketone solvent and a catalyst 0.8 g (1.2 mmol) of a 50% aqueous solution of tetrabutylammonium bromide 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 (24 mmol as anthraquinone) of a 17 wt% aqueous solution of 9,10-anthracenediol disodium salt was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was further stirred for 1 hour. Thereafter, the anthraquinone was removed by suction filtration, and the obtained filtrate was allowed to stand overnight to precipitate crystals. The precipitated crystals were further subjected to suction filtration to obtain 6.5 g (crude yield: 61 mol%) of light yellow crystals.

(1) Melting point: 131-132 ° C
(2) IR (cm < ^-1 >): 1742, 1391, 1358, 1232, 1151, 1089, 1021, 1004, 846, 776, 749, 670.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 1.575 (s, 18 H), 4.659 (s, 4 H), 7. 260-7.530 (m, 4 H), 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 a nitrogen atmosphere, 15 g of a solvent methyl isobutyl ketone, a catalyst Of a 50% aqueous solution of tetrabutylammonium bromide in the above were added and 9.4 g (62.5 mmol) of butyl chloroacetate. While maintaining the temperature of the reaction system at 20 to 25 ° C., 29.1 g (24 mmol as anthraquinone) of a 17 wt% aqueous solution of 9,10-anthracenediol disodium salt was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was further stirred for 1 hour. Thereafter, the anthraquinone was removed by suction filtration, and the obtained filtrate was washed twice with water. After the water washing operation, anthraquinone was precipitated, so the anthraquinone 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, 6 H), 1.387-1.481 (m, 4 H), 1.678-1. 750 (m, 4H), 4.317 (t, J = 13.2 Hz, 4H), 4.779 (s, 4H), 7.508-7.826 (m, 4H), 8.319-8. 377 (m, 4H).

Synthesis Example 6 Synthesis of 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene In a 100 ml four-necked flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 15 g of methyl isobutyl ketone as a solvent and a catalyst 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 (24 mmol as anthraquinone) of a 17 wt% aqueous solution of 9,10-anthracenediol disodium salt was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was further stirred for 1 hour. Thereafter, the anthraquinone was removed by suction filtration, and the obtained filtrate was washed twice with water by separation operation. The solution was concentrated by an evaporator and cooled by a freezer to precipitate crystals. The precipitated crystals were further subjected to suction filtration to obtain 4.6 g (crude yield: 50 mol%) of yellow crystals.

(1) Melting point: 130-131 ° C
(2) IR (cm < ^-1 >): 1737, 1366, 1207, 1134, 1078, 1061, 1020, 970, 748, 681.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 1.644 (d, J = 6.4 Hz, 6 H), 3.770 (s, 6 H), 4.904 (k, J = 20. 4 Hz, 2 H), 7.464-7.489 (m, 4 H), 8. 229-8.332 (m, 4 H).

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 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), 40 g of N, N-dimethylformamide as solvent were added. The mixture was stirred for 1 hour while maintaining the temperature of the reaction system at 20 to 30 ° C. Thereafter, the anthraquinone was removed by suction filtration, and the obtained filtrate was dissolved in toluene and washed twice with water. The solution was concentrated with an evaporator. After standing overnight, the whole solution solidified, methanol was added, and the mixture was heated to 50 ° C. for dissolution. Undissolved anthraquinone was removed by suction filtration, and the filtrate was cooled in a freezer to precipitate crystals. The precipitated crystals were further subjected to suction filtration to obtain 5.4 g (crude yield: 51 mol%) of yellow crystals.

(1) Melting point: 95-96 ° C
(2) IR (cm < ^-1 >): 1721, 1351, 1312, 1239, 1183, 1164, 1081, 1024, 1015, 913, 767, 742, 669.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 1.307 (t, J = 14.0 Hz, 6 H), 2.340-2.408 (m, 4 H), 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 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), 40 g of N, N-dimethylformamide as solvent were added. The mixture was stirred for 1 hour while maintaining the temperature of the reaction system at 20 to 30 ° C. After that, the anthraquinone was removed by suction filtration, and the obtained filtrate was dissolved in toluene, and washed twice with water by liquid separation operation. The solution was concentrated with an evaporator. It was left to stand overnight, methanol was added and undissolved anthraquinone was removed by suction filtration. The filtrate was cooled in a freezer to precipitate crystals. The precipitated crystals were further subjected to suction filtration to obtain 6.2 g (crude yield 55 mol%) of orange crystals.

(1) Melting point: 57-58 ° C
(2) IR (cm- ¹ ): 1722, 1403, 1337, 1284, 1269, 1229, 1178, 1167, 1068, 1021, 934, 763, 675.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 1.286 (t, J = 14.4 Hz, 6 H), 2.018-2.103 (m, 8 H), 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).

Synthesis Example 9 Synthesis of 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene In a 200 ml four-necked flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 2-ethylanthraquinone 5 .0 g (21,2 millimoles), 9.1 g (86.4 millimoles) of thiourea dioxide, 8.4 g (211.6 millimoles) of sodium hydroxide, 50 g of ion exchanged water, gradually rising to 120 ° C. Stirring was performed while warming. Stirring was stopped when the solution turned red-black, and cooled at room temperature to prepare an aqueous disodium salt solution of 2-ethyl-9,10-anthracenediol. Next, in another 200 ml four-necked flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 15 g of methyl isobutyl ketone as a solvent and 2.7 g of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst 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 aqueous solution of disodium salt of 2-ethyl-9,10-anthracenediol prepared above was added dropwise over 1 hour or more. After completion of the dropwise addition, the mixture was further stirred for 1 hour. Thereafter, the aqueous layer was removed, and the organic layer was concentrated by an evaporator to obtain an orange oil with a yield of 4.5 g (crude yield: 48 mol%).

(1) Melting point: liquid at room temperature (2) IR (cm- ¹ ): 1728, 1673, 1454, 1385, 1373, 1324, 1286, 1206, 962, 931, 901, 825, 772, 750, 712.
(3) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 1.237-1.371 (m, 15 H), 2.816-2.899 (m, 2 H), 4.731 (s, 4 H) , 5.014-5.123 (m, 1 H), 5.225-5. 301 (m, 1 H), 7.391 (d, J = 9.2 Hz, 1 H), 7.461-7.512 (m. m, 2H), 7.766-7.790 (m, 1 H), 8. 119 (d, J = 7.6 Hz, 1 H), 8.284-8.368 (m, 2 H).

Intermediate Synthesis Example Synthesis of 9,10-bis (hydroxycarbonylmethoxy) anthracene (Synthesis of Intermediate Formula (5))
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 in a 300 ml four-necked flask equipped with a stirrer and a thermometer. 8 mmol) and 49.5 g (356 mmol) of bromoacetic acid were added. 165.7 g (137 mmol) of an aqueous solution of disodium salt of 9,10-anthracenediol (AHQ-Na) and sodium hydroxide while maintaining the temperature of the reaction system at 20 to 30 ° C. and 11.4 g of sodium hydroxide (285 An aqueous solution obtained by mixing millimoles) and 20 g of deionized water was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was further stirred for 1.5 hours. Thereafter, unreacted raw materials and the like were separated by suction filtration, and extracted by adding 100 ml of toluene. The organic layer was separated, and 28.9 g (285 millimoles) of 35% hydrochloric acid was added to the aqueous layer for acid precipitation. The precipitated crystals were filtered, washed with water and then 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)
In a 1000 ml four-necked flask equipped with a stirrer and a thermometer, under nitrogen atmosphere, 78.7 g (241 mmol) of 9,10-bis (hydroxycarbonylmethoxy) anthracene obtained in (Synthesis example 1), ethanol 236. 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 stirring was carried out for 10 hours while removing by-produced water with ethanol. The crystals precipitated by cooling were separated by suction filtration, washed with methanol and dried to obtain 71.7 g (yield: 78 mol%) of yellow crystals.

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

Synthesis Example 11 Synthesis of 9,10-bis (propoxycarbonylmethoxy) anthracene (Reaction with Alcohol)
In a 50 ml four-necked flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 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 to 60 ° C. Thereafter, insolubles were separated by filtration, 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 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, 6 H), 1.744 (tq, J = 6.9 Hz, 7.3 Hz, 4 H), 4.272 (t, J = 6.9 Hz, 4 H), 4.785 (s, 4 H), 7.496-7.534 (m, 4 H), 8.349-8.411 (m, 4 H).

Synthesis Example 12 Synthesis of 9,10-bis (n-butoxycarbonylmethoxy) anthracene (Reaction with alcohol)
In a 300 ml four-necked flask equipped with a stirrer and a thermometer, under nitrogen atmosphere, 34.2 g (105 mmol) of 9,10-bis (hydroxycarbonylmethoxy) anthracene obtained in (Synthesis example 1), 1-butanol 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 stirring was performed for 14 hours while removing by-produced water. The crystals precipitated by cooling were separated 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, 6 H), 1.387-1.481 (m, 4 H), 1.678-1. 750 (m, 4H), 4.317 (t, J = 13.2 Hz, 4H), 4.779 (s, 4H), 7.508-7.826 (m, 4H), 8.319-8. 377 (m, 4H).

Synthesis Example 13 Synthesis of 9,10-bis (2-hydroxyethoxycarbonylmethoxy) anthracene (Reaction with alkyl halide)
In a 50 ml four-necked flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 0.65 g (2.0 mmol) of 9,10-bis (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 to 60 ° C. After cooling, methanol and ion exchanged water were added to precipitate crystals. The precipitated crystals were filtered by suction, washed with methanol and dried to give 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).

Synthesis Example 14 Synthesis of 9,10-bis (butoxycarbonylmethoxy) anthracene In a 100 ml four-necked flask equipped with a stirrer and a thermometer, 2.0 g (6 parts of 9,10-bis (hydroxycarbonylmethoxy) anthracene .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 purged with nitrogen. Under a nitrogen atmosphere, 3.87 g (28.2 mmol) of butyl bromide was added, and the mixture was heated to 60 ° C. with a water bath and stirred. After completion of the reaction, the reaction solution was cooled to room temperature, and the residue containing potassium carbonate was removed by suction filtration. The obtained filtrate was poured into water and extracted with 45.6 g of toluene, and the toluene layer was washed with water. The washed toluene layer was concentrated under reduced pressure 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, 6 H), 1.387-1.481 (m, 4 H), 1.678-1. 750 (m, 4H), 4.317 (t, J = 13.2 Hz, 4H), 4.779 (s, 4H), 7.508-7.826 (m, 4H), 8.319-8. 377 (m, 4H).

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

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

(Photo-curing speed evaluation example 1)
As a photocationic polymerizable compound, 100 parts by weight of 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, trade name: Celoxide 2021 P, Celoxide is a registered trademark of Daicel Corporation) Photopolymerization initiator 4-isobutylphenyl-4'-methylphenyliodonium hexafluorophosphate (manufactured by BAS S F., trade name IRGACURE 250, "IRGACURE" is BAS F, Inc. 2 parts by weight, and 1 part by weight of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene obtained in Synthesis Example 1 as a photocationic polymerization sensitizer, mixed at room temperature to form a photocationically polymerizable composition Prepared. When the light DSC measurement was performed about this photopolymerizable composition, the total calorific value for 5 minutes from the light irradiation start was 256 mJ / mg.

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

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

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

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

(Photo-curing speed evaluation example 6)
Photo-curing rate evaluation 9,10-bis (methoxycarbonylmethyleneoxy) anthracene of Example 1 was changed to 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene obtained in the same manner as in Example 6. Curing speed: When the DSC measurement was conducted in the same manner as in the evaluation example 1, the total calorific value for 5 minutes from the start of light irradiation was 226 mJ / mg.

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

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

(Photo-curing speed evaluation example 9)
Photocuring rate evaluation 9,10-Bis (methoxycarbonylmethyleneoxy) anthracene of Example 1 was replaced with 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene obtained as in Synthesis Example 9 When the light DSC measurement was performed in the same manner as in the photocuring speed evaluation example 1 except for the above, the total calorific value for 5 minutes from the start of light irradiation was 260 mJ / mg.

(Photo-curing speed evaluation example 17)
Evaluation of photo-curing speed Photo-curing speed except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene of Example 1 was changed to 9,10-bis (propoxycarbonylmethoxy) anthracene obtained as in Synthesis Example 11. When the light DSC measurement was performed like implementation evaluation example 1, the total calorific value for 5 minutes from light irradiation start was 259 mJ / mg.

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

(Photo-curing speed evaluation comparative example 1)
100 parts by weight of 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate as a cationic photopolymerizable compound (manufactured by Daicel, trade name: Celoxide 2021 P, Celoxide is a registered trademark of Daicel) Photopolymerization initiator (4-methylphenyl) [4- (2-methylpropyl) phenyl] iodonium-hexafluorophosphate (manufactured by BAS S F., trade name Irgacure 250, "Irgacure" is a -Two parts by weight of A.S.F. (registered trademark) were mixed at room temperature to prepare a photocationic polymerizable composition. When the light DSC measurement was performed about this photopolymerizable composition, the total calorific value for 5 minutes from the light irradiation start was 3 mJ / mg.

(Photo-curing speed evaluation comparative example 2)
Evaluation of photocuring speed Evaluation of photocuring speed except using 9,10-dibutoxyanthracene which is a known photopolymerization sensitizer instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene of Example 1 The optical DSC measurement was performed in the same manner as in Example 1. As a result, the total calorific value for 5 minutes from the start of light irradiation was 230 mJ / mg.

(Photo-curing speed evaluation comparative example 3)
Evaluation of Photo-Curing Speed Light was used except that 9,10-bis (octanoyloxy) anthracene, which is a known photopolymerization sensitizer, was used in place of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene of Example 1. Curing Speed When DSC measurement was conducted in the same manner as in the evaluation example 1, the total calorific value for 5 minutes from the start of light irradiation was 234 mJ / mg.

The results of the photocuring speed evaluation examples 1 to 9, 17, and 18 and the photocuring speed evaluation comparative examples 1 to 3 are summarized in Table 1.

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

(Photo-curing speed evaluation example 10)
2 parts by weight of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator as photoradically polymerizable compound per 100 parts by weight of trimethylolpropane triacrylate, obtained in Synthesis Example 1 as a photoradical polymerization sensitizer One part by weight of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene was mixed at room temperature to prepare a photoradically polymerizable composition. When the light DSC measurement was performed about this photopolymerizable composition, the total calorific value for 5 minutes from the light irradiation start was 419 mJ / mg.

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

(Photo-curing speed evaluation example 12)
Photo-curing rate evaluation Photo-curing except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene of Example 10 was changed to 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene obtained in the same manner as Example 3. Evaluation of light When DSC measurement was performed in the same manner as in Example 10, the total calorific value for 5 minutes from the start of light irradiation was 409 mJ / mg.

(Photo-curing speed evaluation example 13)
Evaluation of Photo-Curing Rate The light was obtained except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene of Example 10 was changed to 9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene obtained in the same manner as Example 4. Evaluation of Curing Rate When photo DSC measurement was performed in the same manner as in Example 10, the total calorific value for 5 minutes from the start of light irradiation was 443 mJ / mg.

(Photo-curing speed evaluation example 14)
Evaluation of Photo-Curing Rate The light was obtained except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene of Example 10 was changed to 9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene obtained in the same manner as Example 5. Evaluation of Curing Rate When photo DSC measurement was performed in the same manner as in Example 10, the total calorific value for 5 minutes from the start of light irradiation was 336 mJ / mg.

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

(Photo-curing speed evaluation example 16)
Photo-Curing Rate Evaluation The 9,10-bis (methoxycarbonylmethyleneoxy) anthracene of Example 10 was changed to 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene obtained in the same manner as Example 9. When the light DSC measurement was performed in the same manner as in Example 10 of the light curing rate evaluation except for the above, the total calorific value for 5 minutes from the start of the light irradiation was 441 mJ / mg.

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

(Photo-curing speed evaluation example 20)
Evaluation of Photo-Curing Rate The light was changed except that 9,10-bis (methoxycarbonylmethyleneoxy) anthracene of Example 10 was changed to 9,10-bis (2-hydroxyethoxycarbonylmethoxy) anthracene obtained in the same manner as Example 13. Evaluation of Curing Rate When DSC measurement was performed in the same manner as in Example 10, the total calorific value for 5 minutes from the start of light irradiation was 420 mJ / mg.

(Photo Curing Speed Evaluation Comparative Example 4)
A photoradically polymerizable composition was prepared by mixing 2 parts by weight of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator at room temperature with 100 parts by weight of trimethylolpropane triacrylate as the photoradically polymerizable compound. When the light DSC measurement was performed about this photopolymerizable composition, the total calorific value for 5 minutes from the light irradiation start was 166 mJ / mg.

(Photo-curing speed evaluation comparative example 5)
Evaluation of photo-curing rate Example 10 of photo-curing rate evaluation except using 9,10-bis (methoxycarbonylmethyleneoxy) anthracene of Example 10 as 9,10-dibutoxyanthracene which is a known photopolymerization sensitizer The light DSC measurement was carried out in the same manner as above, and the total calorific value for 5 minutes from the start of light irradiation was 212 mJ / mg.

(Photo-curing speed evaluation comparative example 6)
Photocuring Rate Evaluation Photocuring rate except using 9,10-bis (methoxycarbonylmethyleneoxy) anthracene of Example 10 as 9,10-bis (octanoyloxy) anthracene which is a known photopolymerization sensitizer When the light DSC measurement was performed similarly to evaluation example 10, the total calorific value for 5 minutes from the light irradiation start was 298 mJ / mg.

The results of the photocuring speed evaluation examples 10 to 16, 19 and 20 and the photocuring speed evaluation comparative examples 4 to 6 are summarized in Table 2.

9,10-Bis having the ester group of the present invention in photocationic polymerization, as is apparent by comparing the results of the photocuring speed evaluation examples 1 to 9, 17, 18 and the photocuring speed evaluation comparative example 1. By adding the alkoxycarbonyl alkyleneoxy) anthracene compound as a photopolymerization sensitizer, it is understood that the total calorific value is increased and the polymerization reaction is remarkably promoted. Moreover, as it becomes clear by comparing the results of the photo-curing speed evaluation examples 10 to 16, 19, 20 and the photo-curing speed evaluation comparative example 4, 9, 10 having the ester group of the present invention also in photo radical polymerization. It can be seen that the addition of a bis (alkoxycarbonylalkyleneoxy) anthracene compound likewise increases the total calorific value and significantly promotes the polymerization reaction. That is, it is understood that the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group of the present invention has a photopolymerization sensitizing effect in both of the photocationic polymerization and the photoradical polymerization.

Furthermore, as it is apparent by comparing the results of the photo-curing speed evaluation examples 1 to 9, 17, 18 and the photo-curing speed evaluation comparative examples 2 and 3, it has the ester group of the present invention in photo cationic polymerization9, The 10-bis (alkoxycarbonylalkyleneoxy) anthracene compound is a photopolymerization sensitizer equivalent to or more than the 9,10-dibutoxyanthracene and 9,10-bis (octanoyloxy) anthracene which are known photopolymerization sensitizers. It turns out that it has an affective effect. Moreover, as it becomes clear by comparing the results of the photo-curing speed evaluation examples 10 to 16, 19, 20 and the photo-curing speed evaluation comparative examples 5 and 6, the photo radical polymerization also has the ester group of the present invention 9 , 10-Bis (alkoxycarbonylalkyleneoxy) anthracene compounds are in turn equal to or greater than the 9,10-dibutoxyanthracenes and 9,10-bis (octanoyloxy) anthracenes, which are likewise known photopolymerization sensitizers. It turns out 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 of cationic photopolymerization and photoradical polymerization. It turns out that it has the photopolymerization sensitization effect equal to or more than anthracene.

(Example of evaluation of migration resistance in photo cationic polymerization)
Migration Resistance Evaluation Example 1
As an epoxy photocationic polymerizable compound, 100 parts of 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021P manufactured by Daicel Corporation) as a photopolymerization sensitizer as in Synthesis Example 1 One part of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene synthesized by the method of 1) was mixed, and the prepared composition was coated on a polyester film using a bar coater so as to have a film thickness of 12 microns. Next, a low density polyethylene film (film thickness of 30 microns) is covered on the obtained coated material, stored for 1 day in the dark, and stored for 7 days, after each storage, the polyethylene film is peeled off, and the polyethylene film The film was washed with acetone and dried, and then the UV spectrum of the film was measured to measure the absorbance at 260 nm. The absorbance attributable 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 that 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene synthesized in the same manner as in Synthesis Example 2 is used as a photopolymerization sensitizer instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene Were tested in the same manner as in the migration resistance evaluation example 1. As a result of measuring the absorbance at 260 nm of the acetone-washed polyethylene film, the value obtained by converting the absorbance attributable to 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene into 9,10-dibutoxyanthracene is 0.007 after one day storage 7 days after storage was 0.007.

Migration Resistance Evaluation Example 3
Using 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene synthesized by the same method as in Synthesis Example 3 as a photopolymerization sensitizer instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene The test was conducted in the same manner as in the migration resistance evaluation example 1 except for the following. As a result of measuring the absorbance at 260 nm of the acetone-washed polyethylene film, a value obtained by converting the absorbance attributable to 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene into 9,10-dibutoxyanthracene is 0. 0 after storage for one day. 007, it was 0.007 after 7 days storage.

Migration Resistance Evaluation Example 4
As a photopolymerization sensitizer, 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 The test was conducted in the same manner as in the migration resistance evaluation example 1 except for the following. As a result of measuring the absorbance at 260 nm of the acetone-washed polyethylene film, the value obtained by converting the absorbance attributable to 9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene into 9,10-dibutoxyanthracene is 0 after storage for one day .010 and after 7 days storage was 0.014.

Migration Resistance Evaluation Example 5
As a photopolymerization sensitizer, 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 The test was conducted in the same manner as in the migration resistance evaluation example 1 except for the following. As a result of measuring the absorbance at 260 nm of the acetone-washed polyethylene film, the value obtained by converting the absorbance attributable to 9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene into 9,10-dibutoxyanthracene is 0 after storage for one day .011, 7 days after storage was 0.007.

Migration Resistance Evaluation Example 6
Using 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene synthesized in the same manner as in Synthesis Example 6 as a photopolymerization sensitizer instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene The test was conducted in the same manner as in the migration resistance evaluation example 1 except for the following. As a result of measuring the absorbance at 260 nm of the acetone-washed polyethylene film, a value obtained by converting the absorbance attributable to 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene into 9,10-dibutoxyanthracene is 0. 0 after storage for one day. 007, it was 0.003 after 7 days storage.

Migration Resistance Evaluation Example 7
Except that 9,10-bis (ethoxycarbonylpropyleneoxy) anthracene synthesized by the same method as in Synthesis Example 7 is used as a photopolymerization sensitizer instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene Were tested in the same manner as in the migration resistance evaluation example 1. As a result of measuring the absorbance at 260 nm of the acetone-washed polyethylene film, the value obtained by converting the absorbance attributable to 9,10-bis (ethoxycarbonylpropyleneoxy) anthracene into 9,10-dibutoxyanthracene is 0.015 after one day storage After storage for seven days, it was 0.013.

Migration Resistance Evaluation Example 8
Except that 9,10-bis (ethoxycarbonylbutyleneoxy) anthracene synthesized by the same method as Synthesis Example 8 is used as a photopolymerization sensitizer instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene Were tested in the same manner as in the migration resistance evaluation example 1. As a result of measuring the absorbance at 260 nm of the acetone-washed polyethylene film, the value obtained by converting the absorbance attributable to 9,10-bis (ethoxycarbonylbutyleneoxy) anthracene into 9,10-dibutoxyanthracene is 0.012 after one day storage , After storage for seven days was 0.010.

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 photopolymerization sensitizer Migration resistance evaluation was carried out in the same manner as Example 1 except using. As a result of measuring the absorbance at 260 nm of the acetone-washed polyethylene film, the value obtained by converting the absorbance attributable to 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene into 9,10-dibutoxyanthracene is one day It was 0.015 after storage and 0.015 after 7 days storage.

(Migration resistance evaluation comparative example 1)
Migration resistance evaluation example except that 9,10-dibutoxyanthracene which is a known photopolymerization sensitizer is used as a photopolymerization sensitizer instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene Prepared similarly to 1. As a result of measuring the absorbance at 260 nm of the acetone-washed polyethylene film, the absorbance of 9,10-dibutoxyanthracene was 0.737 after one day storage and 0.843 after seven days storage.

The results of the migration resistance evaluation examples 1 to 9 and the migration resistance evaluation comparative example 1 are summarized in Table 3.

(Example of evaluation of migration resistance of composition in photo radical 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 as a photoradical polymerization sensitizer in the same manner as in Synthesis Example 1 The prepared composition was coated on a polyester film using a bar coater so that the film thickness became 12 microns. Next, a low density polyethylene film (film thickness of 30 microns) is covered on the obtained coated material to prepare one stored for one day and one stored for seven days in the dark, and after each storage, the covered polyethylene film is After peeling off and washing the polyethylene film with acetone and drying, the UV spectrum of the polyethylene film was measured and the absorbance at 260 nm was measured, but the absorption attributable to 9,10-bis (methoxycarbonylmethyleneoxy) anthracene is one It was 0.015 after day storage and 0.016 after 7 days storage.

Migration Resistance Evaluation Example 11
Evaluation of migration resistance except using 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene synthesized in the same manner as in Synthesis Example 2 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, but the absorption attributable 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 using 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene synthesized by the same method as 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, but the absorption attributable to 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene was 0.024 after one day storage and 0.022 after seven days storage The

Migration Resistance Evaluation Example 13
Evaluation of migration resistance except 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, but the absorption attributable to 9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene was 0.037 after one day storage and 0.033 after seven days storage. there were.

Migration Resistance Evaluation Example 14
Evaluation of migration resistance except using 9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene synthesized by the same method as Synthesis Example 5 in place 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, but the absorption attributable to 9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene was 0.022 after one day storage and 0.015 after seven days storage. there were.

Migration Resistance Evaluation Example 15
Evaluation of migration resistance except using 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene synthesized in the same manner as in Synthesis Example 6 in place 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, but the absorption attributable to 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene was 0.007 after one day storage and 0.004 after seven days storage. The

Migration Resistance Evaluation Example 16
Migration resistance evaluation example except using 9,10-bis (ethoxycarbonylpropyleneoxy) anthracene synthesized by the same method as Synthesis Example 7 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, but the absorption attributable 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
Evaluation of migration resistance except using 9,10-bis (ethoxycarbonylbutyleneoxy) anthracene synthesized in the same manner as in Synthesis Example 8 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, but the absorption attributable 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
Resistant to 9,10-bis (methoxycarbonylmethyleneoxy) anthracene instead of using 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene synthesized in the same manner as in Synthesis Example 9 instead of 9,10-bis (methoxycarbonylmethyleneoxy) anthracene Evaluation of Migration The same preparation and test as in Example 10 were conducted. The absorbance at 260 nm of the acetone-washed polyethylene film was measured, but the absorption due to 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene was 0.031 after one day storage and 0 after seven days storage It was .032.

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

Migration Resistance Evaluation Examples 10 to 18 and Migration resistance evaluation Comparative Example 2 are summarized in Table 4.

Migration Resistance Evaluation As is clear by comparing Examples 1 to 9 with Migration Resistance Evaluation Comparative Example 1, 9, 10- which are known photo cationic polymerization sensitizers in the photo cationic polymerizable composition. In contrast to the 9,10-bis (methoxycarbonylmethyleneoxy) anthracene compound of the present application, dibutoxyanthracene has migrated to a considerable extent to the film coated on the photocationically polymerizable composition. The degree of migration is very low, and it can be said that the migration resistance is excellent.

On the other hand, as is apparent from comparison of migration resistance evaluation examples 10 to 18 with migration resistance evaluation comparative example 2, even in the photo radical polymerizable composition, it is a known photo radical polymerization sensitizer 9 The 9,10-bis (methoxycarbonylmethyleneoxy) anthracene compound of the present application is, while 10, 10-dibutoxyanthracene is transferred to a film to which the radically photopolymerizable composition is covered to a considerable extent, In any 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 9,10-di that is a known photopolymerization sensitizer in photocationic polymerization and photoradical polymerization. It is an excellent compound with high migration resistance due to its structure having a polar ester group as well as having equivalent photopolymerization sensitization ability as compared with the butoxyanthracene compound, and is extremely useful as a photopolymerization sensitizer It is found that the compound is

Claims (9)

The 9,10- bis (alkoxy carbonyl alkylene oxy) anthracene compound which has an ester group represented by following General formula (1).
(In the general formula (1), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms, the alkyl The 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 an oxygen atom (except when forming a peroxide) And X and Y may be the same or different and each represents 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) Process for producing a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having a group.

(In the general formula (2), X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.)
(In the general formula (3), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms, the alkyl The 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 an oxygen atom (except when forming a peroxide) Z represents a chlorine atom, a bromine atom or an iodine atom.)
(In the general formula (1), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms, the alkyl The 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 an oxygen atom (except when forming a peroxide) And X and Y may be the same or different and each represents 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) is reacted with a carboxylic acid compound represented by the following general formula (4) to obtain 9,10- 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), the general formula (7) or A process for producing a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the following general formula (1) characterized by reacting an esterifying agent represented by the general formula (8) .

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

(In the general formula (4), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. 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, and hydrogen Represents an atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.)
(In the general formula (6), R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group or may be substituted by a hydroxy group; A part may be replaced by an oxygen atom (except when forming a peroxide).
(In the general formula (7), R represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be branched by an alkyl group, may be substituted by a hydroxy group, and one of carbon atoms 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 the general formula (8), R ¹ represents a hydrogen atom or an alkyl group having 1 to 17 carbon atoms, and the alkyl group may be branched by an alkyl group or may be substituted by a hydroxy group And some of the carbon atoms may be replaced by oxygen atoms (except when forming peroxides).

(In the general formula (1), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms, the alkyl The 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 an oxygen atom (except when forming a peroxide) And X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom). The photopolymerization sensitizer which contains the 9,10- bis (alkoxy carbonyl alkylene oxy) anthracene compound which has an ester group represented by following General formula (1).
(In the general formula (1), A represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be branched by an alkyl group. R represents an alkyl group having 1 to 20 carbon atoms, the alkyl The 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 an oxygen atom (except when forming a peroxide) And X and Y may be the same or different and each represents 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 4 and a photopolymerization initiator. A photopolymerizable composition comprising the photopolymerization initiator composition according to claim 5 and a photocationic polymerizable compound. A photopolymerizable composition comprising the photopolymerization initiator composition according to claim 5 and a photoradically polymerizable compound. A polymerization method of polymerizing the photopolymerizable composition according to claim 6 or 7 by irradiating an energy ray containing light in a wavelength range of 300 nm to 500 nm. The polymerization according to claim 8, wherein 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 having a central wavelength of 365 nm, 375 nm, 385 nm, 395 nm, 405 nm. Method.