WO2020213442A1

WO2020213442A1 - Photopolymerizable composition, coating film containing said photopolymerizable composition, and curing method therefor

Info

Publication number: WO2020213442A1
Application number: PCT/JP2020/015441
Authority: WO
Inventors: 井内啓太; 檜森俊一; 山田暁彦
Original assignee: 川崎化成工業株式会社
Priority date: 2019-04-15
Filing date: 2020-04-06
Publication date: 2020-10-22
Also published as: KR20210154963A; JP2020176254A

Abstract

[Problem] To provide a coating composition wherein a photoradical composition using a photoradical polymerization initiator that is markedly affected by oxygen inhibition can be cured without problems even in the presence of oxygen through a reduction in oxygen inhibition on the coating surface. [Solution] A photoradical polymerizable composition characterized by containing at least a radical polymerizable compound, a photoradical polymerization initiator, and a 9,10-bis(alkoxycarbonylalkyleneoxy)anthracene compound having an ester group and represented by general formula (1). (In general formula (1), A represents a C1-20 alkylene group that may be branched by an alkyl group, and R represents a C1-20 alkyl group.)

Description

Photopolymerizable composition, coating film containing the photopolymerizable composition, and curing method thereof

The present invention relates to a photopolymerizable composition, a coating film containing the photopolymerizable composition, and a curing method thereof, and particularly contains a photopolymerizable composition and the photopolymerizable composition which are cured by ultraviolet rays in a long wavelength range. The coating film to be polymerized and the curing method thereof.

Polymerizable compositions are used in various industrial fields, and among them, photopolymerizable compositions are excellent in terms of speed of curing, durability of chemical bonds formed, economic efficiency, etc., and are applicable. It is widely used in various applications such as coating materials, adhesives, sealing materials, adhesives, paints, inks, resists, dental materials, lenses, and molding materials.

In particular, in the manufacturing technique of a printed wiring board, a photopolymerizable composition is widely used as a resist material used for etching or plating. In this application, the photopolymerizable composition is laminated on a circuit-forming substrate such as a copper substrate, irradiated with energy rays such as ultraviolet rays to cure a predetermined portion of the photopolymerizable composition, and then the photopolymerizable composition. A resist pattern is formed on the substrate by removing the uncured portion of the substrate. In recent years, in display devices such as liquid crystals, organic EL displays, touch panels, and lighting devices, a process of forming a patterned cured coating film having an arbitrary shape at an arbitrary location by photolithography using a photopolymerizable composition has been performed. It is often used. And in such an application, it is required to form a fine pattern at high speed.

The photopolymerizable composition usually comprises a polymerizable compound and a photopolymerization initiator. When the photopolymerization initiator is irradiated with energy rays such as ultraviolet rays, the photopolymerization initiator absorbs energy and becomes an excited state, and the photopolymerization initiator in the excited state is decomposed to polymerize radicals and the like. A starting seed is generated, and the polymerizable compound starts polymerization by the starting seed and is cured.

On the other hand, as the energy ray used when forming the pattern, a high-pressure mercury lamp has been conventionally used, but due to problems such as high energy consumption, the running cost is low and the influence on the natural environment is small. A curing device using a light source has come to be used. However, unlike the high-pressure mercury lamp, this LED light source has a problem that the irradiation energy is weak because it irradiates light of a single wavelength. Therefore, a highly sensitive photopolymerizable composition is required. Further, when the photopolymerizable composition contains a pigment or the like, there is a problem that the transmittance of the irradiated light becomes low, the light reaching the photopolymerization initiator is reduced, and the light cannot be sufficiently cured, and the sensitivity is high. The photopolymerizable composition of the above is required.

Further, as the LED light source, an LED light source that irradiates light having a long wavelength such as 385 nm, 395 nm, or 405 nm is used, and the photopolymerization initiator currently used is such. There are few compounds that have sufficient absorption in the long wavelength region, and they are used to activate photopolymerization sensitizers such as dialkoxyanthracene and thioxanthone (Patent Documents 1 to 4). Furthermore, in recent years, in liquid crystal and organic EL applications, the photopolymerizable composition often contains a colorant such as a pigment, a filler, a light stabilizer, an ultraviolet absorber, etc., and a sufficient amount of light energy is used. In many cases, it is not possible to supply the photopolymerization initiator, and in that sense, a highly active photopolymerization sensitizer is required.

However, the currently used dialkoxyanthracene and thioxanthone have a problem that they are easily colored in the photopolymerization reaction and the cured coating film turns yellow. Further, during the curing of the coating film or during the storage of the cured product, the photopolymerization sensitizer migrates to the surface of the cured coating film or the like, causing problems such as powder blowing.

Further, when used as a resist or the like, it is required that the photopolymerizable composition has high activity and at the same time, the cured product obtained by polymerization and curing has excellent heat resistance. This is indispensable for preventing contamination of the curing device due to volatilization of VOCs (volatile organic compounds) such as residual monomers when heated as post-curing, or for ensuring long-term stability of the final cured product. .. As an index of the heat resistance, it is required that the temperature at which the cured product causes weight loss is high when the cured product is exposed to heat (for example, Patent Document 5).

Further, in order to prevent environmental pollution, there is a strong social demand for a final cured product in which the amount of VOC such as residual monomers of the final cured product is small and the VOC that volatilizes when heated is reduced.

Japanese Unexamined Patent Publication No. 06-059380 Japanese Unexamined Patent Publication No. 11-279212 Japanese Unexamined Patent Publication No. 11-140110 Japanese Unexamined Patent Publication No. 2001-106648 Japanese Patent No. 5672403

In view of the above-mentioned problems of the prior art, the present invention cures at a sufficient speed even in a situation where a light source having a low energy level such as an LED light source or irradiation energy is partially shielded, and migration It is an object of the present invention to provide a photopolymerizable composition which does not have the above-mentioned problems and has high heat resistance of the cured product.

In view of this situation, the present inventors have diligently studied to provide a technique that eliminates these drawbacks, and as a result, photopolymerized the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having the ester group of the present invention. The photopolymerizable composition contained as a sensitizer is cured at a sufficient speed even in a situation where a light source having a low energy level such as an LED light source or an irradiation energy is partially shielded, and VOC such as residual monomers is produced. We have found that a cured product having a small amount of light and good long-term stability can be obtained, and have completed the present invention.

First of all, the first invention is a photopolymerizable composition containing at least the following components (A) to (C), and the 5% weight loss temperature of the cured product is 200 ° C. or higher. It exists in a photopolymerizable composition characterized by.
(A) A 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the following general formula (1) (B) An ethylenically unsaturated group-containing polymerizable compound.
(C) Photopolymerization initiator.

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

The second invention is characterized in that, in (A), A is a 9,10-bis (alkoxycarbonylmethyleneoxy) anthracene compound having an ester group, wherein A in the general formula (1) is a methylene group. It exists in the photopolymerizable composition according to claim 1.

The third invention resides in a photopolymerizable composition, which further comprises (D) an alkali-soluble polymerizable compound in the photopolymerizable composition according to the first or second invention.

The fourth invention resides in the photopolymerizable composition according to the third invention, wherein the alkali-soluble polymerizable compound (D) is a compound having a hydroxyl group.

The fifth invention resides in the photopolymerizable composition according to the third or fourth invention, wherein the alkali-soluble polymerizable compound (D) is a compound having a carboxyl group.

The sixth invention resides in the photopolymerizable composition according to the third invention, wherein the alkali-soluble polymerizable compound (D) is an alkali-soluble resin.

The seventh invention resides in a photopolymerizable composition, which comprises further containing (E) a pigment in the photopolymerizable composition according to any one of the first to sixth inventions.

In the eighth invention, the (C) photopolymerization initiator is a biimidazole-based photopolymerization initiator, an alkylphenone-based photopolymerization initiator, a triazine-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, and an oxime-based light. The photopolymerizable composition according to any one of the first to seventh inventions, which comprises at least one photopolymerization initiator selected from the group consisting of polymerization initiators.

The ninth invention exists in the photopolymerizable composition according to any one of the first to seventh inventions, wherein the (C) photopolymerization initiator is a biimidazole-based photopolymerization initiator.

A tenth invention exists in the photopolymerizable composition according to any one of the first to seventh inventions, wherein the photopolymerization initiator (C) is an oxime ester-based photopolymerization initiator.

The eleventh invention is characterized by having a photopolymerizable coating film containing the photopolymerizable composition according to any one of the first to tenth inventions on a support. It resides in the membrane composition.

The twelfth invention is a cured product obtained by curing the photopolymerizable composition according to any one of the first to tenth inventions by light irradiation, and the 5% weight loss temperature thereof is 200 ° C. or higher. It exists in the cured product, which is characterized by the fact that.

The thirteenth invention is a photopolymerizable composition, which comprises irradiating the photopolymerizable composition according to any one of the first to tenth inventions with light in a wavelength range of 300 nm to 500 nm. It depends on the curing method of.

The fourteenth invention is a photopolymerizable composition in which the irradiation source of the light to be irradiated according to the thirteenth invention is an ultraviolet LED or a semiconductor laser having a center wavelength of 365 nm, 375 nm, 385 nm, 395 nm, and 405 nm. It depends on the curing method.

In the description of the present invention, the 5% thermal weight reduction temperature refers to a cured product obtained by polymerizing and curing a photopolymerizable composition by light irradiation, starting heating at 50 ° C. in a nitrogen atmosphere, and 20 at 1-minute intervals. This is the temperature at which the weight is reduced by 5% by weight of the initial weight when the heating temperature is increased by ° C. The weight of the cured product can be measured with a thermogravimetric measuring device.

By using the photopolymerizable composition of the present invention and the coating film containing the photopolymerizable composition, the speed is sufficient even in a light source having a low energy level such as an LED light source or in a situation where the irradiation energy is partially shielded. The cured product obtained is free from problems of powder blowing and migration, and the amount of VOC such as residual monomers is small, so that the 5% weight loss temperature of the cured product is 200 ° C. or higher.

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

The graph which showed the weight loss curve at the time of heating of the cured product in Example 1 (solid line) and Comparative Example 1 (dotted line) of this invention. The vertical axis shows the weight% of the cured product before heating, and the horizontal axis shows the heating temperature.

(9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group)
First, a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group used in the present invention will be described. The 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group used in the present invention is a compound of the following general formula (1).

In the general formula (1), examples of the alkylene group having 1 to 20 carbon atoms represented by A include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group and a nonylene group. Examples thereof include a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, an octadecylene group, a nonadesilene group, an icosilene group, and the alkylene group may be branched by an alkyl group. ..

In the general formula (1), the alkyl group having 1 to 8 carbon atoms represented by X or Y includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and an i-butyl group. , N-Pentyl group, i-Pentyl group, n-Hexyl group, n-Heptyl group, n-octyl group, 2-ethylhexyl group and the like, and examples of the halogen atom include fluorine atom, chlorine atom, bromine atom or iodine. Atomic can be mentioned.

In the general formula (1), the alkyl groups having 1 to 20 carbon atoms represented by R include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group and t. -Butyl group, n-pentyl group, i-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n -Dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecil group, n-icosyl group and the like can be mentioned. Examples of those in which the group is substituted with a hydroxy group include 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 4-hydroxybutyl group. 5-Hydroxypentyl group, 6-hydroxyhexyl group, 7-hydroxyheptyl group, 8-hydroxyoctyl group, 6-hydroxy-2-ethylhexyl group, 9-hydroxynonyl group, 10-hydroxydecyl group, 11-hydroxyundecyl group. Group, 12-hydroxydodecyl group, 2-hydroxy-3-methoxypropyl group, 2-hydroxy-3-ethoxypropyl group, 2-hydroxy-3-propoxypropyl group, 2-hydroxy-3-butoxypropyl group, 2- Hydroxy-3-pentyloxypropyl group, 2-hydroxy-3-hexyloxypropyl group, 2-hydroxy-3-octyloxypropyl group, 2-hydroxy-3- (2-ethylhexyloxy) propyl group, 2,3- Examples thereof include a dihydroxypropyl group, a 2-hydroxy-3-allyloxypropyl group, and a 2-hydroxy-3-metharyloxypropyl group. Examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group, 4-n-dodecylcyclohexyl group, decahydronaphthyl group, hydroxycyclohexyl group and the like. Cycloalkylalkyl groups include cyclopropylmethyl group, cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, cycloheptylmethyl group, cyclooctylmethyl group, cyclononylmethyl group, cyclodecylmethyl group, 2 -Cyclobutylethyl group, 2-cyclopentylethyl group, 2-cyclohexylethyl group, 2-cycloheptylethyl group, 2-cyclooctylethyl group, 2-cyclononylethyl group, 2-cyclodecylethyl group, 3-cyclobutyl Propyl group, 3-cyclopentylpropyl group, 3-cyclohexylpropyl group, 3-cycloheptylpropyl group, 3-cyclooctylpropyl group, 3-cyclononylpropyl group, 3-cyclodecylpropyl group, 4-cyclobutylbutyl group, 4-Cyclopentylbutyl group, 4-cyclohexylbutyl group, 4-cycloheptylbutyl group, 4-cyclooctylbutyl group, 4-cyclononylbutyl group, 4-cyclodecylbutyl group, 3-3-adamantylpropyl group, decahydro Examples include a naphthylpropyl group.

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

Further, for example, 9,10-bis (methoxycarbonylpentyleneoxy) anthracene, 9,10-bis (ethoxycarbonylpentyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylpentyleneoxy) anthracene, 9,10- Bis (tert-butoxycarbonylpentyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylpentyleneoxy) anthracene, 9,10-bis (methoxycarbonylhexyleneoxy) anthracene, 9,10-bis (ethoxycarbonyl) Hexyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylhexyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylhexyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylhexyleneoxy) ) Anthracene, 9,10-bis (methoxycarbonylheptyleneoxy) anthracene, 9,10-bis (ethoxycarbonylheptyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylheptyleneoxy) anthracene, 9 , 10-bis (tert-butoxycarbonylheptyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylheptyleneoxy) anthracene, 9,10-bis (methoxycarbonyloctyleneoxy) anthracene, 9,10 -Bis (ethoxycarbonyloctyleneoxy) anthracene, 9,10-bis (isopropoxycarbonyloctyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonyloctyleneoxy) anthracene, 9,10-bis (n-) Butoxycarbonyloctyleneoxy) anthracene, 9,10-bis (methoxycarbonylnonyleneoxy) anthracene, 9,10-bis (ethoxycarbonylnonyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylnonyleneoxy) anthracene , 9,10-bis (tert-butoxycarbonylnonyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylnonyleneoxy) anthracene, 9,10-bis (methoxycarbonyldecyleneoxy) anthracene, 9,10 -Bis (ethoxycarbonyldecyleneoxy) anthracene, 9,10-bis (isopropoxycarbonyldecyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonyldecile) Noxy) anthracene, 9,10-bis (n-butoxycarbonyldecyleneoxy) anthracene, 9,10-bis (methoxycarbonylundesyleneoxy) anthracene, 9,10-bis (ethoxycarbonylundesyleneoxy) anthracene, 9,10- Bis (isopropoxycarbonylundesyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylundesyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylundesyleneoxy) anthracene, 9,10-bis (methoxycarbonyldodede) Silenoxy) anthracene, 9,10-bis (ethoxycarbonyldodecyleneoxy) anthracene, 9,10-bis (isopropoxycarbonyldodecyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonyldodecyleneoxy) ) Anthracene, 9,10-bis (n-butoxycarbonyldodecyleneoxy) anthracene, 9,10-bis (methoxycarbonyltridecyleneoxy) anthracene, 9,10-bis (ethoxycarbonyltridecyleneoxy) anthracene, 9, 10-bis (isopropoxycarbonyltridecyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonyltridecyleneoxy) anthracene, 9,10-bis (n-butoxycarbonyltridecyleneoxy) anthracene, 9,10-bis (Methoxycarbonyltetradecyleneoxy) anthracene, 9,10-bis (ethoxycarbonyltetradecyleneoxy) anthracene, 9,10-bis (isopropoxycarbonyltetradecyleneoxy) anthracene, 9,10-bis (tert-butoxy) Carbonyltetradecyleneoxy) anthracene, 9,10-bis (n-butoxycarbonyltetradecyleneoxy) anthracene, 9,10-bis (methoxycarbonylpentadecyleneoxy) anthracene, 9,10-bis (ethoxycarbonylpentade) Silenoxy) anthracene, 9,10-bis (isopropoxycarbonylpentadecyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylpentadesileneoxy) anthracene, 9,10-bis (n-butoxycarbonylpentade) Silenoxy) anthracene, 9,10-bis (methoxycarbonylhexadecyleneoxy) anthracene, 9,10-bis (ethoxycal) Bonylhexadecyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylhexadecileneoxy) anthracene, 9,10-bis (tert-butoxycarbonylhexadecyleneoxy) anthracene, 9,10-bis (n-butoxy) Carbonylhexadecyleneoxy) anthracene, 9,10-bis (methoxycarbonylheptadecyleneoxy) anthracene, 9,10-bis (ethoxycarbonylheptadecyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylheptadecylene) Oxy) anthracene, 9,10-bis (tert-butoxycarbonylheptadecyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylheptadecyleneoxy) anthracene, 9,10-bis (methoxycarbonyloctadecyleneoxy) ) Anthracene, 9,10-bis (ethoxycarbonyloctadecyleneoxy) anthracene, 9,10-bis (isopropoxycarbonyloctadecileneoxy) anthracene, 9,10-bis (tert-butoxycarbonyloctadecileneoxy) anthracene , 9,10-bis (n-butoxycarbonyloctadecileneoxy) anthracene, 9,10-bis (methoxycarbonylnonadecileneoxy) anthracene, 9,10-bis (ethoxycarbonylnonadecileneoxy) anthracene, 9, 10-bis (isopropoxycarbonylnonadecileneoxy) anthracene, 9,10-bis (tert-butoxycarbonylnonadecileneoxy) anthracene, 9,10-bis (n-butoxycarbonylnonadecileneoxy) anthracene, 9, 10-bis (methoxycarbonyl icosileneoxy) anthracene, 9,10-bis (ethoxycarbonyl icosileneoxy) anthracene, 9,10-bis (isopropoxycarbonyl icosileneoxy) anthracene, 9,10-bis (tert-butoxy) Examples thereof include carbonyl icosileneoxy) anthracene and 9,10-bis (n-butoxycarbonyl icosileneoxy) anthracene.

Specific examples of alkyl groups in which X and / or Y are alkyl groups include, for example, 2-ethyl-9,10-bis (methoxycarbonylmethyleneoxy) anthracene and 2-ethyl-9,10-bis (ethoxycarbonylmethyleneoxy). Anthracene, 2-ethyl-9,10-bis (n-propoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (tert) -Butoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (n-pentyloxycarbonylmethyleneoxy) anthracene, 2-ethyl -9,10-bis (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 (methoxycarbonylmethyl) Methyleneoxy) anthracene, 2-ethyl-9,10-bis (ethoxycarbonylmethylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (ethoxycarbonylethylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (Isopropoxycarbonylmethylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (tert-butoxycarbonylmethylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (n-butoxycarbonylmethylmethyleneoxy) anthracene, 2-Ethyl-9,10-bis (methoxycarbonylbutyleneoxy) anthracene, 2-ethyl-9,10-bis (ethoxycarbonylbutyleneoxy) anthracene, 2-ethyl-9,10-bis (isopropoxycarbonylbutyleneoxy) Anthracene, 2-ethyl-9,10-bis (tert-butoxycarbonylbutyleneoxy) anthracene, 2-ethyl-9,10-bis (n-butoxycarbonylbutyleneoxy) anthracene, 2-ethyl-9,10-bis ( Methoxycarbonyl octi Renoxy) anthracene, 2-ethyl-9,10-bis (ethoxycarbonyloctyleneoxy) anthracene, 2-ethyl-9,10-bis (isopropoxycarbonyloctyleneoxy) anthracene, 2-ethyl-9,10-bis (Tert-Butoxycarbonyloctyleneoxy) anthracene, 2-ethyl-9,10-bis (n-butoxycarbonyloctyleneoxy) anthracene, 2-ethyl-9,10-bis (methoxycarbonylhexadecyleneoxy) anthracene, 2-Ethyl-9,10-bis (ethoxycarbonylhexadecyleneoxy) anthracene, 2-ethyl-9,10-bis (isopropoxycarbonylhexadecyleneoxy) anthracene, 2-ethyl-9,10-bis (tert) -Butoxycarbonylhexadecyleneoxy) anthracene, 2-ethyl-9,10-bis (n-butoxycarbonylhexadecyleneoxy) anthracene, 2-ethyl-9,10-bis (methoxycarbonylicosileneoxy) anthracene, 2 -Ethyl-9,10-bis (ethoxycarbonyl icosileneoxy) anthracene, 2-ethyl-9,10-bis (isopropoxycarbonyl icosileneoxy) anthracene, 2-ethyl-9,10-bis (tert-butoxycarbonyl) Icosyleneoxy) anthracene, 2-ethyl-9,10-bis (n-butoxycarbonyl icosileneoxy) anthracene, 2-ethyl-9,10-bis (2-hydroxyethoxycarbonylmethyleneoxy) anthracene, 2-ethyl- 9,10-bis (cyclohexyloxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (cyclohexylmethyloxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (norbornyloxycarbonylmethyleneoxy) ) Anthracen and the like.

Further, for example, 2-amyl-9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (ethoxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (n-). Propoxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene, 2-amyl-9, 10-bis (n-butoxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (n-pentyloxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (methoxycarbonylpropyleneoxy) anthracene, 2-Amil-9,10-bis (ethoxycarbonylpropyleneoxy) anthracene, 2-amyl-9,10-bis (isopropoxycarbonylpropyleneoxy) anthracene, 2-amyl-9,10-bis (tert-butoxycarbonylpropylene) Oxy) 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 (ethoxycarbonylethylmethyleneoxy) anthracene, 2-amyl-9,10-bis (isopropoxycarbonylmethylmethyleneoxy) anthracene, 2-amyl- 9,10-bis (tert-butoxycarbonylmethylmethyleneoxy) anthracene, 2-amyl-9,10-bis (n-butoxycarbonylmethylmethyleneoxy) anthracene, 2-amyl-9,10-bis (methoxycarbonylbutyleneoxy) ) Anthracene, 2-amyl-9,10-bis (ethoxycarbonylbutyleneoxy) anthracene, 2-amyl-9,10-bis (isopropoxycarbonylbutyleneoxy) anthracene, 2-amyl-9,10-bis (tert-) Butoxycarbonylbutyleneoxy) anthracene, 2-amyl-9,10-bis (n-butoxycarbonylbutyleneoxy) anthracene, 2-amyl-9,10-bis (2-hydroxyethoxycarbonylmethyleneoxy) anthracene, 2-a Mill-9,10-bis (cyclohexyloxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (cyclohexylmethyloxycarbonylmethyleneoxy) anthracene, 2-amyl-9,10-bis (norbornyloxycarbonyl) Methyleneoxy) anthracene and the like.

Specific examples of halogen atoms in which X and / or Y are halogen atoms include, for example, 2-chloro-9,10-bis (methoxycarbonylmethyleneoxy) anthracene and 2-chloro-9,10-bis (ethoxycarbonylmethyleneoxy). Anthracene, 2-chloro-9,10-bis (n-propoxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10-bis (tert) -Butoxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10-bis (methoxycarbonylpropyleneoxy) anthracene, 2-chloro-9, 10-Bis (ethoxycarbonylpropyleneoxy) anthracene, 2-chloro-9,10-bis (isopropoxycarbonylpropyleneoxy) anthracene, 2-chloro-9,10-bis (tert-butoxycarbonylpropyleneoxy) anthracene, 2- Chloro-9,10-bis (n-butoxycarbonylpropyleneoxy) anthracene, 2-chloro-9,10-bis (n-pentyloxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10-bis (methoxycarbonylmethyl) Methyleneoxy) anthracene, 2-chloro-9,10-bis (ethoxycarbonylmethylmethyleneoxy) anthracene, 2-chloro-9,10-bis (ethoxycarbonylethylmethyleneoxy) anthracene, 2-chloro-9,10-bis (Isopropoxycarbonylmethylmethyleneoxy) anthracene, 2-chloro-9,10-bis (tert-butoxycarbonylmethylmethyleneoxy) anthracene, 2-chloro-9,10-bis (n-butoxycarbonylmethylmethyleneoxy) anthracene, 2-Chloro-9,10-bis (methoxycarbonylbutyleneoxy) anthracene, 2-chloro-9,10-bis (ethoxycarbonylbutyleneoxy) anthracene, 2-chloro-9,10-bis (isopropoxycarbonylbutyleneoxy) Anthracene, 2-chloro-9,10-bis (tert-butoxycarbonylbutyleneoxy) anthracene, 2-chloro-9,10-bis (n-butoxycarbonylbutyleneoxy) anthracene, 2-chloro-9,10-bis ( Methylcarbonylok Tyreneoxy) anthracene, 2-chloro-9,10-bis (ethoxycarbonyloctyleneoxy) anthracene, 2-chloro-9,10-bis (isopropoxycarbonyloctyleneoxy) anthracene, 2-chloro-9,10-bis (Tert-Butyloxycarbonyloctyleneoxy) anthracene, 2-chloro-9,10-bis (n-butoxycarbonyloctyleneoxy) anthracene, 2-chloro-9,10-bis (methoxycarbonylhexadecyleneoxy) anthracene, 2-Chloro-9,10-bis (ethoxycarbonylhexadecyleneoxy) anthracene, 2-chloro-9,10-bis (isopropoxycarbonylhexadecyleneoxy) anthracene, 2-chloro-9,10-bis (tert) -Butoxycarbonylhexadecyleneoxy) anthracene, 2-chloro-9,10-bis (n-butoxycarbonylhexadecyleneoxy) anthracene, 2-chloro-9,10-bis (methoxycarbonylicocileneoxy) anthracene, 2 -Chloro-9,10-bis (ethoxycarbonyl icosileneoxy) anthracene, 2-chloro-9,10-bis (isopropoxycarbonyl icosileneoxy) anthracene, 2-chloro-9,10-bis (tert-butoxycarbonyl) Icosyleneoxy) anthracene, 2-chloro-9,10-bis (n-butoxycarbonyl icosileneoxy) anthracene, 2-chloro-9,10-bis (2-hydroxyethoxycarbonylmethyleneoxy) anthracene, 2-chloro- 9,10-bis (cyclohexyloxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10-bis (cyclohexylmethyloxycarbonylmethyleneoxy) anthracene, 2-chloro-9,10-bis (norbornyloxycarbonylmethyleneoxy) ) Anthracen and the like.

Among the specific examples given above, 9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene, and 9,10-bis (n-propoxycarbonyl) are considered to be easy to manufacture. Methyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylmethyleneoxy) anthracene, 9 , 10-bis (n-pentyloxycarbonylmethyleneoxy) anthracene, 9,10-bis (cyclohexyloxycarbonylmethyleneoxy) anthracene, 9,10-bis (methoxycarbonylpropyleneoxy) anthracene, 9,10-bis (ethoxycarbonyl) Propropyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylpropyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylpropyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylpropyleneoxy) anthracene, 9 , 10-bis (methoxycarbonylmethylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonylmethylmethyleneoxy) anthracene, 9,10-bis (ethoxycarbonylethylmethyleneoxy) anthracene, 9,10-bis (isopropoxycarbonyl) Methylmethyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylmethylmethyleneoxy) anthracene, 9,10-bis (n-butoxycarbonylmethylmethyleneoxy) anthracene, 9,10-bis (methoxycarbonylbutyleneoxy) anthracene , 9,10-bis (ethoxycarbonylbutyleneoxy) anthracene, 9,10-bis (isopropoxycarbonylbutyleneoxy) anthracene, 9,10-bis (tert-butoxycarbonylbutyleneoxy) anthracene, 9,10-bis (n) -Butoxycarbonylbutyleneoxy) anthracene, 9,10-bis (2-hydroxyethoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (methoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (Ethoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (n-pro) Poxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9, 10-Bis (n-butoxycarbonylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (methoxycarbonylpropyleneoxy) anthracene, 2-ethyl-9,10-bis (ethoxycarbonylpropyleneoxy) anthracene, 2-ethyl -9,10-bis (isopropoxycarbonylpropyleneoxy) anthracene, 2-ethyl-9,10-bis (tert-butoxycarbonylpropyleneoxy) anthracene, 2-ethyl-9,10-bis (n-butoxycarbonylpropyleneoxy) ) Anthracene, 2-ethyl-9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (ethoxycarbonylmethylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (ethoxy) Carbonylethylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (isopropoxycarbonylmethylmethyleneoxy) anthracene, 2-ethyl-9,10-bis (tert-butoxycarbonylmethylmethyleneoxy) anthracene, 2-ethyl- 9,10-bis (n-butoxycarbonylmethylmethyleneoxy) anthracene and 2-ethyl-9,10-bis (2-hydroxyethoxycarbonylmethyleneoxy) anthracene are preferable, and 9,10-bis (2-hydroxyethoxycarbonylmethyleneoxy) anthracene listed in the following structural formula is preferable. Methoxycarbonylmethyleneoxy) anthracene (1-1), 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene (1-2), 9,10-bis (n-propoxycarbonylmethyleneoxy) anthracene (1-10), 9,10-Bis (isopropoxycarbonylmethyleneoxy) anthracene (1-3), 9,10-bis (tert-butoxycarbonylmethyleneoxy) anthracene (1-4), 9,10-bis (n-butoxycarbonylmethylene) Oxy) anthracene (1-5), 9,10-bis (n-pentyloxycarbonylmethyleneoxy) anthracene (1-11), 9,10-bis (methoxycarbonylmethylmethyleneoxy) anthracene (1-6), 9 , 10-bis (ethoxycal Bonylpropyleneoxy) anthracene (1-7), 9,10-bis (ethoxycarbonylbutyleneoxy) anthracene (1-8), 2-ethyl-9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene (1-9) ), 9,10-Bis (cyclohexyloxycarbonylmethyleneoxy) anthracene (1-12) is particularly preferred.

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

(Method for producing an antoceran compound represented by the general formula (1))
The 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound can be obtained, for example, by reacting the 9,10-dihydroxyanthracene compound with an ester compound such as a bromoacetic acid ester in the presence of a basic compound.

The 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention is the 9,10-dihydroxyanthracene compound represented by the general formula (2) as follows. It can be obtained by reacting with the corresponding ester compound represented by the general formula (3) in the presence or absence of the basic compound according to the reaction formula-1.

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

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

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

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

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

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

Specific examples of the ester compound represented by the general formula (3) as a raw material in Reaction Formula-1 include methyl chloroacetate, ethyl chloroacetate (3-12), n-propyl chloroacetate, isopropyl chloroacetate, and chloro N-butyl acetate (3-5), tert-butyl chloroacetate, pentyl chloroacetate, hexyl chloroacetate, heptyl chloroacetate, octyl chloroacetate, 2-ethylhexyl chloroacetate, nonyl chloroacetate, dodecyl chloroacetate, nonadesyl chloroacetate, Icosyl chloroacetate, cyclohexyl chloroacetate, cyclohexylmethylchloroacetic acid, methyl 2-chloropropionate, methyl 3-chloropropionate, methyl 2-chloropropionate, methyl 3-chloropropionate, ethyl 2-chloropropionate, 3- Ethyl chloropropionate, n-propyl 2-chloropropionate, n-propyl 3-chloropropionate, isopropyl 2-chloropropionate, isopropyl 3-chloropropionate, n-butyl 2-chloropropionate, 3-chloropropion N-butyl acid, tert-butyl 2-chloropropionate, tert-butyl 3-chloropropionate, pentyl 2-chloropropionate, pentyl 3-chloropropionate, hexyl 2-chloropropionate, hexyl 3-chloropropionate , 2-Chloropropionate heptyl, 3-chloropropionate heptyl, 2-chloropropionate octyl, 3-chloropropionate octyl, 2-chloropropionate 2-ethylhexyl, 3-chloropropionate 2-ethylhexyl, 2-chloro Nonyl propionate, Nonyl 3-chloropropionate, Dodecyl 2-chloropropionate, Dodecyl 3-chloropropionate, Nonadesyl 2-chloropropionate, Nonadesyl 3-chloropropionate, Icosyl 2-chloropropionate, 3-Chloropropion Icosyl acid, methyl 2-chlorobutyrate, methyl 3-chlorobutyrate, methyl 4-chlorobutyrate, ethyl 2-chlorobutyrate, ethyl 3-chlorobutyrate, ethyl 4-chlorobutyrate, n-propyl 2-chlorobutyrate, 3-chloro N-propyl butyrate, n-propyl 4-chlorobutyrate, isopropyl 2-chlorobutyrate, isopropyl 3-chlorobutyrate, isopropyl 4-chlorobutyrate, n-butyl 2-chlorobutyrate, n-butyl 3-chlorobutyrate, 4-chloro N-Butyl butyrate, tert-butyl 2-chlorobutyrate, tert-butyl 3-chlorobutyrate, 4 -Tert-Butyl chlorobutyrate, pentyl 2-chlorobutyrate, pentyl 3-chlorobutyrate, pentyl 4-chlorobutyrate, hexyl 2-chlorobutyrate, hexyl 3-chlorobutyrate, hexyl 4-chlorobutyrate, heptyl 2-chlorobutyrate, 3 -Heptyl chlorobutyrate, heptyl 4-chlorobutyrate, octyl 2-chlorobutyrate, octyl 3-chlorobutyrate, octyl 4-chlorobutyrate, 2-ethylhexyl 2-chlorobutyrate, 2-ethylhexyl 3-chlorobutyrate, 2-chlorobutyric acid 2 -Ethylhexyl, nonyl 2-chlorobutyrate, nonyl 3-chlorobutyrate, nonyl 4-chlorobutyrate, dodecyl 2-chlorobutyrate, dodecyl 3-chlorobutyrate, dodecyl 4-chlorobutyrate, nonadecil 2-chlorobutyrate, nonadecil 3-chlorobutyrate , 4-Chlorobutyrate nonadesyl, 2-chlorobutyrate icosyl, 3-chlorobutyrate icosyl, 4-chlorobutyrate icosyl, 2-chlorovalerate methyl, 3-chlorovalerate methyl, 4-chlorovalerate methyl, 5-chlorovalerate Methyl herate, ethyl 2-chlorovalerate, ethyl 3-chlorovalerate, ethyl 4-chlorovalerate, ethyl 5-chlorovalerate, n-propyl 2-chlorovalerate, n-propyl 3-chlorovalerate, 4 -N-propyl chlorovalerate, n-propyl 5-chlorovalerate, isopropyl 2-chlorovalerate, isopropyl 3-chlorovalerate, isopropyl 4-chlorovalerate, isopropyl 5-chlorovalerate, 2-chlorovaleric acid n-Butyl, n-butyl 3-chlorovalerate, n-butyl 4-chlorovalerate, n-butyl 5-chlorovalerate, tert-butyl 2-chlorovalerate, tert-butyl 3-chlorovalerate, 4 -Tert-butyl chlorovalerate, tert-butyl 5-chlorovalerate, pentyl 2-chlorovalerate, pentyl 3-chlorovalerate, pentyl 4-chlorovalerate, pentyl 5-chlorovalerate, 2-chlorovaleric acid Hexil, 3-chlorovalerate hexyl, 4-chlorovalerate hexyl, 5-chlorovalerate hexyl, 2-chlorovalerate heptyl, 3-chlorovalerate heptyl, 4-chlorovalerate heptyl, 5-chlorovalerate heptyl , 2-chlorovalerate octyl, 3-chlorovalerate octyl, 4-chlorovalerate octyl, 5-chlorovalerate octyl, 2-chlorovalerate 2-ethylhexyl, 3-chlorovalerate 2-ethylhexyl, 4-chloro 2-Ethylhexyl valerate, 2-ethylhexyl 5-chlorovalerate, nonyl 2-chlorovalerate, 3-chlorovaleric acid, 4- Nonyl chlorovalerate, nonyl 5-chlorovalerate, dodecyl 2-chlorovalerate, dodecyl 3-chlorovalerate, dodecyl 4-chlorovalerate, dodecyl 5-chlorovalerate, nonadecil 2-chlorovalerate, 3-chloro Examples thereof include nonadesyl valerate, nonadesyl 4-chlorovalerate, nonadesyl 5-chlorovalerate, icosyl 2-chlorovalerate, icosyl 3-chlorovalerate, icosyl 4-chlorovalerate, and icosyl 5-chlorovalerate.

Furthermore, methyl bromoacetate (3-1), ethyl bromoacetate (3-4), n-propyl bromoacetate (3-9), isopropyl bromoacetate (3-2), n-butyl bromoacetate, tert-bromoacetate. Butyl (3-3), pentyl bromoacetate (3-10), hexyl bromoacetate, heptyl bromoacetate, octyl bromoacetate, 2-ethylhexyl bromoacetate, nonyl bromoacetate, dodecyl bromoacetate, nonadesyl bromoacetate, icosyl bromoacetate, Cyclohexyl bromoacetate (3-11), cyclohexylmethyl bromoacetate, methyl 2-bromopropionate (3-6), methyl 3-bromopropionate, ethyl 2-bromopropionate, ethyl 3-bromopropionate, 2-bromo N-propyl propionate, n-propyl 3-bromopropionate, isopropyl 2-bromopropionate, isopropyl 3-bromopropionate, n-butyl 2-bromopropionate, n-butyl 3-bromopropionate, 2-bromo Tert-butyl propionate, tert-butyl 3-bromopropionate, pentyl 2-bromopropionate, 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, 3-bromopropion Nonyl acid acid, dodecyl 2-bromopropionate, dodecyl 3-bromopropionate, nonadecil 2-bromopropionate, nonadecil 3-bromopropionate, icosyl 2-bromopropionate, icosyl 3-bromopropionate, methyl 2-bromobutyrate , Methyl 3-bromobutyrate, methyl 4-bromobutyrate, ethyl 2-bromobutyrate, ethyl 3-bromobutyrate, ethyl 4-bromobutyrate (3-7), n-propyl 2-bromobutyrate, n-bromobutyrate Propyl, n-propyl 4-bromobutyrate, isopropyl 2-bromobutyrate, isopropyl 3-bromobutyrate, isopropyl 4-bromobutyrate, n-butyl 2-bromobutyrate, n-butyl 3-bromobutyrate, n-bromobutyrate Butyl, tert-butyl 2-bromobutyrate, tert-butyl 3-bromobutyrate, tert-butyl 4-bromobutyrate, pentyl 2-bromobutyrate, 3-bromodairy Pentyl acid, pentyl 4-bromobutyrate, hexyl 2-bromobutyrate, hexyl 3-bromobutyrate, hexyl 4-bromobutyrate, heptyl 2-bromobutyrate, heptyl 3-bromobutyrate, heptyl 4-bromobutyrate, octyl 2-bromobutyrate , 3-bromobutyrate octyl, 4-bromobutyrate octyl, 2-bromobutyrate 2-ethylhexyl, 3-bromobutyrate 2-ethylhexyl, 4-bromobutyrate 2-ethylhexyl, 2-bromobutyrate nonyl, 3-bromobutyrate nonyl, 4 -Nonyl bromobutyrate, dodecyl 2-bromobutyrate, dodecyl 3-bromobutyrate, dodecyl 4-bromobutyrate, nonadesyl 2-bromobutyrate, nonadesyl 3-bromobutyrate, nonadesyl 4-bromobutyrate, icosyl 2-bromobutyrate, 3-bromo Icosyl butyrate, Icosyl 4-bromobutyrate, methyl 2-bromovalerate, methyl 3-bromovalerate, methyl 4-bromovalerate, methyl 5-bromovalerate, ethyl 2-bromovalerate, ethyl 3-bromovalerate , 4-Bromovalerate ethyl (3-8), 5-bromovalerate ethyl, 2-bromovalerate n-propyl, 3-bromovalerate n-propyl, 4-bromovalerate n-propyl, 5-bromo N-propyl valerate, isopropyl 2-bromovalerate, isopropyl 3-bromovalerate, isopropyl 4-bromovalerate, isopropyl 5-bromovalerate, n-butyl 2-bromovalerate, n-bromovalerate 3-bromovalerate Butyl, n-butyl 4-bromovalerate, n-butyl 5-bromovalerate, tert-butyl 2-bromovalerate, tert-butyl 3-bromovalerate, tert-butyl 4-bromovalerate, 5-bromo Tert-butyl valerate, pentyl 2-bromovalerate, pentyl 3-bromovalerate, pentyl 4-bromovalerate, pentyl 5-bromovalerate, hexyl 2-bromovalerate, hexyl 3-bromovalerate, 4- Hexyl bromovalerate, hexyl 5-bromovalerate, heptyl 2-bromovalerate, heptyl 3-bromovalerate, heptyl 4-bromovalerate, heptyl 5-bromovalerate, octyl 2-bromovalerate, 3-bromo Octyl valerate, octyl 4-bromovalerate, octyl 5-bromovalerate, 2-ethylhexyl 2-bromovaleric acid, 2-ethylhexyl 3-bromovaleric acid, 2-ethylhexyl 4-bromovalerate, 5-bromovaleric acid 2-Ethylhexyl, 2-bromovalerate nonyl, 3-bromovaleric acid, 4-bromovalerate nonyl, 5-bromovalerate nonyl, 2-bromovaleric Dodecyl herbate, dodecyl 3-bromovalerate, dodecyl 4-bromovalerate, dodecyl 5-bromovalerate, nonadecil 2-bromovalerate, nonadecil 3-bromovalerate, nonadecil 4-bromovalerate, 5-bromovaleric acid Nonadesyl, 2-bromovalerate icosyl, 3-bromovalerate icosyl, 4-bromovalerate icosyl, 5-bromovalerate icosyl, bromoacetate-2-hydroxyethyl, 2-bromopropionate-2-hydroxyethyl, 3 -2-Hydroxyethyl-bromobutyric acid, -2-hydroxyethyl 4-bromovaleric acid and the like can be mentioned.

Furthermore, methyl iodoacetate, ethyl iodoacetate, n-propyl iodoacetate, isopropyl iodoacetate, n-butyl iodoacetate, tert-butyl iodoacetate, pentyl iodoacetate, hexyl iodoacetate, heptyl iodoacetate, octyl iodoacetate, iodine 2-Ethylhexyl acetate, nonyl iodoacetate, dodecyl iodoacetate, nonadesyl iodoacetate, icosyl iodoacetate, methyl 2-iodopropionate, methyl 3-iodopropionate, ethyl 2-iodopropionate, ethyl 3-iodopropionate, 2 -N-propyl iodopropionate, n-propyl 3-iodopropionate, isopropyl 2-iodopropionate, isopropyl 3-iodopropionate, n-butyl 2-iodopropionate, n-butyl 3-iodopropionate, 2 -Tert-butyl iodopropionate, tert-butyl 3-iodopropionate, pentyl 2-iodopropionate, pentyl 3-iodopropionate, hexyl 2-iodopropionate, hexyl 3-iodopropionate, 2-iodopropionic acid Heptyl, heptyl 3-iodopropionate, octyl 2-iodopropionate, octyl 3-iodopropionate, 2-ethylhexyl 2-iodopropionate, 2-ethylhexyl 3-iodopropionate, nonyl 2-iodopropionate, 3- Nonyl iodopropionate, dodecyl 2-iodopropionate, dodecyl 3-iodopropionate, nonadecil 2-iodopropionate, nonadecil 3-iodopropionate, icosyl 2-iodopropionate, icosyl 3-iodopropionate, 2-iodo Methyl butyrate, 3-iodobutyrate, 4-iodobutyrate, 2-iodobutyrate, 3-iodobutyrate, 4-iodobutyrate, 2-iodobutyrate n-propyl, 3-iodobutyrate n-propyl, 4 -N-propyl iodobutate, isopropyl 2-iodobutyrate, isopropyl 3-iodobutyrate, isopropyl 4-iodobutyrate, n-butyl 2-iodobutyrate, n-butyl 3-iodobutyrate, n-butyl 4-iodobutyrate, 2 -Iodobutyrate tert-butyl, 3-iodobutyrate tert-butyl, 4-iodobutyrate tert-butyl, 2-iodobutyrate pentyl, 3-iodobutyrate pentyl, 4-iodobutyrate pentyl, 2-iodobutyrate hexyl, 3-iodo Hexyl butyrate, 4-iodobutyrate hexyl, 2-iodobutyrate heptyl, 3-iodobutyric acid Heptyl, 4-iodobutyrate heptyl, 2-iodobutyrate octyl, 3-iodobutyrate octyl, 4-iodobutyrate octyl, 2-iodobutyrate 2-ethylhexyl, 3-iodobutyrate 2-ethylhexyl, 4-iodobutyrate 2-ethylhexyl, 2-Idobutyrate nonyl, 3-iodobutyrate nonyl, 4-iodobutyrate nonyl, 2-iodobutyrate dodecyl, 3-iodobutyrate dodecyl, 4-iodobutyrate dodecyl, 2-iodobutyrate nonadecil, 3-iodobutyrate nonadecil, 4- Nonadesyl iodobutyrate, icosyl 2-iodobutyrate, icosyl 3-iodobutyrate, icosyl 4-iodobutyrate, methyl 2-iodovalerate, methyl 3-iodovalerate, methyl 4-iodovalerate, 5-methyliodovalerate, 2-Idovalerate ethyl, 3-iodovalerate ethyl, 4-iodovalerate ethyl, 5-iodovalerate ethyl, 2-iodovalerate n-propyl, 3-iodovalerate n-propyl, 4-iodovalerate N-propyl valerate, n-propyl 5-iodovalerate, isopropyl 2-iodovalerate, isopropyl 3-iodovalerate, isopropyl 4-iodovalerate, isopropyl 5-iodovalerate, n-butyl 2-iodovalerate , 3-iodovalerate n-butyl, 4-iodovalerate n-butyl, 5-iodovalerate n-butyl, 2-iodovalerate tert-butyl, 3-iodovalerate tert-butyl, 4-iodovalerate Tert-butyl herate, tert-butyl 5-iodovalerate, pentyl 2-iodovalerate, 3-iodovalerate pentyl, 4-iodovalerate pentyl, 5-iodovalerate pentyl, 2-iodovalerate hexyl, 3 -Hexyl iodovalerate, 4-hexyl iodovalerate, 5-hexyl iodovalerate, 2-heptyl valerate, 3-heptyl valerate, 4-heptyl valerate, 5-heptyl valerate, 2- Octyl iodovalerate, octyl 3-iodovalerate, octyl 4-iodovalerate, octyl 5-iodovalerate, 2-ethylhexyl 2-iodovalerate, 2-ethylhexyl 3-iodovalerate, 2-iodovalerate 2 -Ethylhexyl, 5-iodovalerate 2-ethylhexyl, 2-iodovalerate nonyl, 3-iodovalerate, 4-iodovalerate nonyl, 5-iodovalerate nonyl, 2-iodovalerate dodecyl, 3- Dodecyl iodovalerate, 4-dodecyl iodovalerate, 5-dodecyl iodovalerate, 2-nonadecil iodovalerate, 3-nonadecil iodovalerate, 4-yo Examples thereof include do-valerate nonadesyl, 5-iodovalerate nonadesyl, 2-iodovalerate icosyl, 3-iodovalerate icosyl, 4-iodovalerate icosyl, 5-iodovalerate icosyl and the like.

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

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

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

In the reaction formula-1, when a compound synthesized with the corresponding carboxylic acid and alcohol is used as the ester compound represented by the general formula (3), the ester compound is synthesized in advance in the system, and the general formula (2) is used therein. By adding the 9,10-dihydroxyanthracene compound represented by)), the reaction can be carried out efficiently.

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, and trihexylamine. Examples thereof include dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dimethylaniline, pyridine, 4,4-dimethylaminopyridine, piperidine, γ-picolin, rutidin and the like.

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

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

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

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

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

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

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

(Photopolymerizable composition)
The photopolymerizable composition of the present invention is a photopolymerizable composition containing at least the following components (A) to (C), and the 5% weight loss temperature of the cured product is 200 ° C. or higher. It is a photopolymerizable composition characterized by.
(A) A 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) (B) An ethylenically unsaturated group-containing polymerizable compound.
(C) Photopolymerization initiator.

((A) 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group)
The 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention is excited by light of a specific wavelength, and the excitation energy is received by the photopolymerization initiator. Acts as a photopolymerization sensitizer to pass. Due to this effect, photopolymerization can be efficiently initiated even with long-wavelength light in which 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 photopolymerizable composition can be easily photocured by irradiation with light having a long wavelength such as ultraviolet LED light having a center wavelength of 405 nm.

The 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention has an ester group via an alkylene group in its structure. It has a high affinity with the photopolymerizable composition and its cured product, and has a feature that the degree of migration or blooming in the photopolymerizable composition and its cured product is extremely low. Further, in the general formula (1), when R is a cycloalkyl group or a cycloalkylalkyl group, the solubility in various monomers is improved, so that it can be dissolved in various monomers at a high concentration, and the range of application is widened. have. In particular, the case of a cyclohexyl group has high solubility.

Further, the ester group in the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention is bonded to the anthracene ring via the alkylene group A. Therefore, there is a feature that the absorption wavelength of ultraviolet rays is on the longer wavelength side as compared with the compound which does not mediate A. Therefore, it can be effectively used even when the sensitizing effect is weak in the compound not mediated by A.

Further, in the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention, A is a methylene group having 1 carbon atom, and A is 2 carbon atoms. Compared with the above 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound, it is characterized in its high sensitizing ability in radical polymerization. This effect is generally alleviated by the addition of an oxygen atom at the 9th and 10th positions of the anthracene compound, which inhibits radical polymerization, but has an ester group represented by the general formula (1) of the present invention9. , 10-Bis (alkoxycarbonylalkyleneoxy) anthracene compounds in which A is a methylene group are thought to come from the steric positional relationship between the anthracene ring and the ester group, but in particular, the inhibition is weakened and radical polymerization is increased. It seems to have high activity as a sensitizer.

By using a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention as a photopolymerization sensitizer, the photopolymerization rate of the photopolymerizable composition can be increased. It is considered that it is significantly promoted, and as a result, the thermally decomposable substance in the cured product is reduced, and the 5% weight loss temperature of the cured product is increased as compared with the photopolymerization composition containing no photopolymerization sensitizer of the present invention. Be done. Then, it is considered that the effect reduces the volatile components and improves the heat resistance of the cured product.

In particular, when an alkali-soluble polymerizable compound described later is contained in the photopolymerizable composition, it is important that the 5% weight loss temperature of the cured product is 200 ° C. or higher. A resist material used for etching or the like is assumed to be used as an alkali-soluble polymerizable compound. In that case, a cured portion and an uncured portion are formed by patterned light irradiation, and the uncured alkali is used. It is envisioned that soluble polymerizable compounds will be removed. In that case, in the cured product having a low 5% weight loss temperature of the cured product, unreacted monomers remain in the cured portion and the cured portion is partially removed by alkaline cleaning. May become unclear and the pattern of the expected shape may not be formed. Therefore, it is important that the 5% weight loss temperature of the cured product is 200 ° C. or higher. In particular, when curing is performed using light of a single wavelength having low irradiation energy such as LED light, a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group of the present invention is used as a photopolymerization sensitizer. By using it, a cured coating film that can withstand patterning can be formed.

Further, when the pigment is contained in the photopolymerizable composition, a part of the light irradiated by the pigment is absorbed, so that the photopolymerization of the photopolymerizable composition often does not proceed sufficiently. In particular, when a black pigment is added, the effect is remarkable. Even in such a state where the irradiation light is weakened, a sufficient curing rate can be maintained by using the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group of the present invention as a photopolymerization sensitizer. , A cured film can be formed.

((C) Photopolymerization Initiator)
Examples of the photopolymerization initiator used in the present invention include a benzylmethyl ketal-based polymerization initiator, an α-hydroxyalkylphenone-based polymerization initiator, an oxime ester-based polymerization initiator, an α-aminoacetophenone-based polymerization initiator, and an acylphosphine oxide-based polymerization initiator. An initiator, a biimidazole-based polymerization initiator, a triazine-based polymerization initiator, a thioxanthone-based polymerization initiator, and the like can be used.

The 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention is a benzylmethyl ketal-based polymerization initiator, an α-hydroxyalkylphenone-based polymerization initiator, or bi. It has an excellent photopolymerization sensitizing effect on radical polymerization initiators such as imidazole-based polymerization initiators that do not absorb at long wavelengths. Further, even in a polymerization reaction using a polymerization initiator such as an acylphosphine oxide having absorption in a long wavelength region, it has an effect of increasing the polymerization rate or an effect of improving the physical properties of the obtained polymer. ..

Examples of the benzylmethyl ketal polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name "Irgacure 651" manufactured by BASF) and the like, and α- As a hydroxyalkylphenone-based radical polymerization initiator, 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name "Darocure 1173" manufactured by BASF), 1-hydroxycyclohexylphenyl ketone (Product name "Irgacure 184" manufactured by BASF), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one (product) Name "Irgacure 2959" manufactured by BASF), 2-Hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methyl-1- On (trade name "Irgacure 127" manufactured by BASF) can be mentioned.

In particular, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name "Irgacure 651" manufactured by BASF), which is a benzylmethyl ketal polymerization initiator, α-hydroxyalkylphenone. 2-Hydroxy-2-methyl-1-phenylpropan-1-one (trade name "DaroCure 1173" manufactured by BAS), 1-hydroxycyclohexylphenylketone (trade name), which is a system radical polymerization initiator. "Irgacure 184" manufactured by BASF) is preferable.

In addition, acetophenone, 2-hydroxy-2-phenylacetophenone, 2-ethoxy-2-phenylacetophenone, 2-methoxy-2-phenylacetophenone, 2-isopropoxy-2-phenylacetophenone, 2-isopropoxy-2-phenylacetophenone, which are acetophenone-based polymerization initiators, Isobutoxy-2-phenylacetophenone, benzyl-based polymerization initiator benzyl, 4,4'-dimethoxybenzyl, anthraquinone-based polymerization initiator 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-phenoxyantraquinone, 2- (Phenylthio) anthraquinone, 2- (hydroxyethylthio) anthraquinone and the like can also be used.

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

As an α-aminoacetophenone-based polymerization initiator, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (trade name "Irgacure 907", BASF, Inc.) , 2-Benzyl-2- (dimethylamino) -4'-morpholinobtyrophenone (trade name "Irgacure 369" manufactured by B.S.F.), 2-dimethylamino-2- (4-methylbenzyl) ) -1- (4-morpholino-4-yl-phenyl) butane-1-one (trade name "Irgacure 379" manufactured by BASF Co., Ltd.) and the like.

Acylphosphine oxide-based polymerization initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name "Irgacure TPO" manufactured by BASF), bis (2,4,6-trimethylbenzoyl). Examples thereof include phenylphosphine oxide (trade name "Irgacure 819" manufactured by BASF Co., Ltd.).

As an oxime ester-based polymerization initiator, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (о-benzoyloxime) (trade name "Irgacure OXE01" BASF) , Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (о-acetyloxime) (trade name "Irgacure OXE02" B.A. S.F.), [8-[[(Acetyloxy) imino] [2- (2,2,3,3-tetrafluoropropoxy) phenyl] methyl] -11- (2-ethylhexyl) -11H-benzo [A] Carbazole-5-yl]-, (2,4,6-trimethylphenyl) (trade name "Irgacure OXE03" manufactured by BASF) and the like can be mentioned.

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

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

Onium salt-based aggregation initiator, benzylmethyl ketal-based polymerization initiator, α-hydroxyalkylphenone-based polymerization initiator, oxime ester-based photopolymerization initiator, α-aminoacetophenone-based photopolymerization initiator that can be used in the present invention. , Acylphosphine oxide-based photopolymerization initiator, biimidazole-based polymerization initiator, triazine-based polymerization initiator, and thioxanthone-based polymerization initiator can be used alone, but a plurality of types can be combined according to the intended use. It can also be used.

Among the above-mentioned photopolymerization initiators, biimidazole-based photopolymerization initiators, alkylphenone-based photopolymerization initiators, triazine-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, and oxime-based photopolymerization initiators are preferable. ..

The biimidazole-based photopolymerization initiator and the oxime ester-based photopolymerization initiator are particularly preferable in terms of the high effect and activity of the photopolymerization sensitizer of the present invention.

The amount of the photopolymerization sensitizer containing the 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) of the present invention for the photopolymerization initiator is not particularly limited. However, it is usually in the range of 5% by weight or more and 100% by weight or less, preferably 10% by weight or more and 50% by weight or less with respect to the photopolymerization initiator. If the amount of the photopolymerization sensitizer used is less than 5% by weight, it takes too much time to photopolymerize the polymerizable compound, while if it is used in excess of 100% by weight, the effect commensurate with the addition cannot be obtained. ..

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

((B) Ethylene unsaturated group-containing polymerizable compound)
As the ethylenically unsaturated group-containing polymerizable compound, for example, an organic compound having a double bond such as styrene, vinyl acetate, acrylonitrile, methacrylonitrile, acrylamide, acrylic acid ester, and methacrylic acid ester can be used. Among these radically polymerizable compounds, acrylic acid ester and methacrylic acid ester (hereinafter, both are collectively referred to as (meth) acrylic acid ester) are preferable from the viewpoint of film forming ability and the like. Examples of the (meth) acrylate ester include methyl acrylate, butyl acrylate, cyclohexyl acrylate, -2-ethylhexyl acrylate, -2-hydroxyethyl acrylate, isobornyl acrylate, methyl methacrylate, butyl methacrylate, and methacrylic acid. Cyclohexyl, phenoxyethyl methacrylate, nonylphenoxy-polypropylene glycol acrylate, 1,2,2,6,6-pentamethylpiperidyl methacrylate, tetraethylene glycol diacrylate, trimethylpropantriacrylate, pentaerythritol triacrylate, tricyclo [5,2] , 1,02,6] Decanedimethanol diacrylate, polypropylene glycol dimethacrylate, ethylene oxide (EO) modified bisphenol A diacrylate, EO modified bisphenol A dimethacrylate, propylene oxy degree (PO) modified bisphenol A diacrylate, PO modified bisphenol A dimethacrylate, EO-modified neopentyl glycol diacrylate, EO-modified neopentyl glycol dimethacrylate, EO-modified glycerol triacrylate, epichlorohydrin (ECH) -modified diacrylate, ECH-modified dimethacrylate, ECH-modified ethylene glycol diacrylate, ECH-modified ethylene glycol Dimethacrylate, ECH-modified propylene glycol diacrylate, ECH-modified propylene glycol dimethacrylate, ECH-modified phthalic acid diacrylate, ECH-modified phthalic acid dimethacrylate PO-modified glycerol triacrylate, ECH-modified glycerol triacrylate, EO-modified glycerol trimethacrylate, PO-modified Gglycerol trimethacrylate, ECH-modified glycerol trimethacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropanetriacrylate, isobonyl methacrylate, epoxy acrylate, urethane acrylate, polyester acrylate, polybutadiene acrylate, polyol acrylate, polyether acrylate, silicone. Examples thereof include resin acrylates and imide acrylates. These polymerizable compounds may be one kind or a mixture of two or more kinds.

((D) Alkali-soluble polymerizable compound)
The photopolymerizable composition of the present invention can contain an alkali-soluble polymerizable compound. As the alkali-soluble polymerizable compound, a compound having a hydroxyl group and / or a carboxyl group and an ethylenically unsaturated bond group can be preferably used. A compound having a group that generates a hydroxyl group during the reaction and a thyrene unsaturated bond group, such as an epoxy compound, may also be used.

Examples of the compound having a hydroxyl group and an ethylenically unsaturated bond group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth). ) Acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, glycerol mono (meth) ) Acrylate, dihydroxy acrylate, glycerol (meth) acrylate, pentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate and the like can be mentioned. Further, 2-hydroxy3-acryloyloxypropyl methacrylate, pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, pentaerythritol diacrylate, isocyanuric acid EO-modified diacrylate, pentaerythritol tri (meth) acrylate, Examples thereof include dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate. Examples thereof include, but are not limited to, glycidyl (meth) acrylate that produces a hydroxyl group by the reaction.

Examples of the compound having a carboxyl group and an ethylenically unsaturated bond group include acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinate, crotonic acid, isocrotonic acid, tiglic acid, 3-methylcrotonic acid and 2-methyl. Examples thereof include -2-pentenoic acid, α-hydroxyacrylic acid, α-chloroacrylic acid and cinnamic acid. Further, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and the like can be mentioned. In addition, monosuccinate (2-acryloyloxyethyl), monosuccinate (2-methacryloyloxyethyl), mono-phthalate (2-acryloyloxyethyl), mono-phthalate (2-methacryloyloxyethyl) and the like can be mentioned. Further, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate and the like can be mentioned.

The alkali-soluble polymerizable compound may be not only a monomer but also an oligomerized compound or an alkali-soluble resin. As the alkali-soluble resin, those generally used for negative resists can be used, as long as they are soluble in an aqueous alkali solution, and are not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, benzyl ( One or more selected from meta) acrylate, styrene, γ-methylstyrene, N-vinyl-2-pyrrolidone, glycidyl (meth) acrylate, etc., and (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, Examples thereof include a copolymer composed of fumaric acid, vinyl acetic acid, and one or more selected from these anhydrides, such as a polymer obtained by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the above copolymer. Can also be exemplified. Further, for example, a carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene. , Alious diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates and other diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate-based polyols, polyether-based polyols, Carboxylic group-containing urethane resin by double addition reaction of diol compounds such as polyester-based polyol, polyolefin-based polyol, acrylic-based polyol, bisphenol A-based alkylene oxide adduct diol, compound having phenolic hydroxyl group and alcoholic hydroxyl group, aliphatic Diisocyanate compounds such as diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, polycarbonate-based polyol, polyether-based polyol, polyester-based polyol, polyolefin-based polyol, acrylic polyol, bisphenol A-based alkylene oxide adduct diol , A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride at the end of a urethane resin by a double addition reaction of a diol compound such as a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group, diisocyanate, and a bisphenol A type epoxy resin. , (Meta) acrylate of bifunctional epoxy resin such as hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin or its partial acid anhydride modified product , A compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as a carboxyl group-containing urethane resin or a hydroxyalkyl (meth) acrylate by a double addition reaction of a carboxyl group-containing dialcohol compound and a diol compound is added. , End (meth) acrylicized carboxyl group-containing urethane resin and the like. Commercially available alkali-soluble resins include Dianal NR series (manufactured by Mitsubishi Rayon), Viscort R-264, KS resist 106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Ebeclyl3800 (manufactured by Daicel UCB), and Acrycure RD- Examples thereof include F8 (manufactured by Nippon Catalyst Co., Ltd.) and Foret ZAH-110 (manufactured by Soken Kagaku Co., Ltd.).

((E) Pigment)
As the pigment, either an inorganic pigment or an organic pigment can be used. As the inorganic pigment, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide can be used. Examples of organic pigments include azo pigments such as insoluble azo pigments, condensed azo pigments, azolakes and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments and quinophthalone pigments. Polycyclic pigments, dye chelate (for example, basic dye type chelate, acidic dye type chelate, etc.), dyeing lake (basic dye type lake, acidic dye type lake), nitro pigment, nitroso pigment, aniline black, daylight Fluorescent pigments can be mentioned. These pigments may be used alone or in combination of two or more.

The dye is not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used. One type of dye may be used alone, or two or more types may be used in combination. Moreover, you may use a pigment and a dye together.

The dispersant for dispersing the pigment is not particularly limited, and examples thereof include a pigment dispersion such as a polymer dispersant. Specific examples thereof include polyoxyalkylene polyalkylene polyamines, vinyl polymers and copolymers, acrylic polymers and copolymers, polyesters, polyamides, polyimides, polyurethanes, amino polymers, silicon-containing polymers, sulfur-containing polymers, fluorine-containing polymers, and epoxies. Examples thereof include resins containing one or more of the main components.

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

In the photopolymerizable composition of the present invention, the amount of the photopolymerization initiator composition used is in the range of 0.005% by weight or more and 10% by weight or less, preferably 0.025% by weight, based on the photopolymerizable composition. The above is 5% by 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 cured product obtained by photopolymerization decreases and it is cured. It is not preferable because it deteriorates the physical properties of the object.

In addition to the above, the photopolymerizable composition of the present invention contains a diluent, an organic or inorganic filler, a leveling agent, a surfactant, a defoaming agent, and a thickener, as long as the effects of the present invention are not impaired. , Flame retardants, surface modifiers, penetration promoters, moisturizers, fixers, fungicides, preservatives, antioxidants, UV absorbers, chelating agents, pH adjusters, stabilizers, lubricants, plasticizers, etc. Various resin additives may be blended.

(Polymerization method)
A cured product can be obtained by irradiating the photopolymerizable composition of the present invention with light and polymerizing the composition. When the photopolymerizable composition is irradiated with light to be polymerized and photocured, the photopolymerizable composition can be molded into a film and photocured, or can be molded into a lump and photocured. When it is molded into a film and photocured, the liquid photopolymerizable composition is applied to a substrate such as a polyester film using a bar coater or the like so as to have a film thickness of 5 to 300 microns. On the other hand, it is also possible to apply a thinner film thickness or a thicker film thickness by a spin coating method or a screen printing method.

The cured product is obtained by irradiating the coating film composed of the photopolymerizable composition thus prepared with energy rays (ultraviolet rays) containing a wavelength range of 300 nm to 500 nm at an intensity of about 1 to 1000 mW / cm ² . Can be obtained. The light sources used are high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, xenon lamps, gallium-doped lamps, black lights, 405 nm ultraviolet LEDs, 395 nm ultraviolet LEDs, 385 nm ultraviolet LEDs, 365 nm ultraviolet LEDs, semiconductor lasers, blue LEDs, and white. Examples include LEDs, D-valves manufactured by Fusion, and V-valves. It is also possible to use natural light such as sunlight. In particular, it is characterized by having a sensitizing effect even with light having a wavelength range of a long wavelength range such as 365 nm to 405 nm, such as a 405 nm ultraviolet LED, a 395 nm ultraviolet LED, a 385 nm ultraviolet LED, a 375 nm ultraviolet LED, and a 365 nm ultraviolet LED. An ultraviolet LED or a semiconductor laser having a central wavelength of 365 nm, 375 nm, 385 nm, 395 nm, and 405 nm is preferable as the irradiation source.

(5% weight loss temperature)
A cured product can be obtained by irradiating the photopolymerizable composition of the present invention with light to polymerize it, but since it is rapidly cured by light irradiation, a coating agent can be obtained from the viewpoint of quick curing and low VOC. It can be applied to paints, printing inks, photosensitive printing plates, adhesives, various photoresists, and the like. Further, the cured product of the present invention can suppress the weight loss of the cured product even when so-called post-baking is performed for the purpose of enhancing the adhesion to the substrate. When the cured product of the present invention is heat-treated, the temperature when the weight of the cured product before heating is reduced by 5% (5% weight reduction temperature) is 200 ° C. or higher, preferably 230 ° C. or higher, more preferably. Is 250 ° C. or higher.

The following abbreviations in the table mean as described.
FA-310M: Phenoxyethyl methacrylate
FA-321M: EO-modified bisphenol A dimethacrylate

(5% weight loss temperature measuring device)
A TG / DTA7200 manufactured by Hitachi, Ltd. was used for measuring the weight loss temperature. An aluminum open sample pan having a diameter of 5 mm was used as the sample container.

(5% weight loss temperature measurement)
Place the cured product on a sample pan of known weight and weigh the cured product. Then, the sample pan was set in TG / DTA, and the weight change was measured while raising the temperature from 50 ° C. to 500 ° C. at a rate of 20 ° C./min.

(Photo-curing measuring device)
As a method for determining photocuring, a Photo-Rheometer MCR102 manufactured by Anton Pearl Co., Ltd. was used to measure the complex viscosity. It can be confirmed that the complex viscosity increases as the photocuring reaction proceeds.

(Photo-curing measurement method)
The transition of the complex viscosity of the photopolymerizable composition was measured with a Photo-Rheometer, and the curing rate was measured from the viscosity increase rate.
Measurement condition:
Measuring jig: Parallel plate (φ10 mm)
Thickness: 100 μm
Swing angle: 5.0% Constant frequency: 10 Hz Constant temperature: 30 ° C Constant Measurement atmosphere: Air atmosphere UV irradiator: LLBK-UV manufactured by Aitec System (irradiation wavelength: 405 nm)
Irradiation intensity: 200 mW / cm ²
Irradiation start time: 30 seconds later Curing time: The time (seconds) when the complex viscosity reached 30,000 Pa · s from the start of light irradiation was defined as the curing time.

Hereinafter, the present invention will be described in detail based on examples, but the present invention has been presented for the purpose of illustration. That is, the following examples are not intended to be exhaustive or to limit the invention as it is described. Therefore, the present invention is not limited to the following description examples as long as the gist is not exceeded. Unless otherwise noted, all parts and percentages are weight-based.

The compound of the present invention was identified using the following equipment.
Infrared (IR) spectrophotometer: manufactured by Thermo, model is50 FT-IR
Nuclear Magnetic Resonance Device (NMR): JEOL Ltd., Model ECS-400

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

(1) Melting point: 93-94 ° C
(2) IR (cm ^-1 ): 174,1742,1382,1367,1241,1212,1168,1087,1034,1004,936,809,768,720,691,669,585.
(3) ^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ = 1.370 (t, J = 14 Hz, 6H), 4.376 (k, J = 21.6 Hz, 4H), 4.777 (s, 4H), 7.261-7.540 (m, 4H).

(Ingredient Synthesis Example 2) Synthesis of 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene (1-3) In a 100 ml four-necked flask equipped with a stirrer and a thermometer, methyl isobutyl solvent is used in a nitrogen atmosphere. 15 g of ketone, 0.8 g (1.2 mmol) of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst, and 11.3 g (62.5 mmol) of isopropyl bromoacetate were added. While maintaining the temperature of the reaction system at 20 to 25 ° C., 29.1 g (24 mmol as anthraquinone) of a 17 wt% aqueous solution of the disodium salt of 9,10-dihydroxyanthracene was added dropwise over 1 hour. After completion of the dropping, the mixture was further stirred for 1 hour. Then, by suction filtration, pale yellow crystals with a yield of 5.9 g (crude yield 60 mol%) were obtained.

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

(Example 1)
50 parts by weight of FA-310M (manufactured by Hitachi Chemical Co., Ltd.) and 50 parts by weight of FA-321M as an ethylenically unsaturated group-containing polymerizable compound, and 10 parts by weight of hydroxyethyl methacrylate (HEMA) as an alkali-soluble photopolymerizable compound are mixed. Then, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole (HABI) (manufactured by Tokyo Kasei Co., Ltd.) was used as a photopolymerization initiator. 0.17 parts by weight of Leuco Crystal Violet (LCV) (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a hydrogen donor. Further, as a 9,10-bis (alkoxycarbonylmethyleneoxy) anthracene compound having an ester group, 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene (ECP-A) synthesized in the same manner as in Example 2 of raw material synthesis was added. A photopolymerizable composition was obtained by adding 0.0 parts by weight. Using a UV-LED (model number: LLBK1-BA-15 × 20UV405, center wavelength: 405 nm) manufactured by Aitec System Co., Ltd., light irradiation for 5 minutes was performed twice at an illuminance of 100 mW / cm ² to prepare a cured product. Obtained. As a result of measuring the 5% weight loss temperature of the obtained cured product, it was 267 ° C. The results are shown in Table 1. Moreover, the graph of TG is shown in FIG. 1 (solid line).

(Comparative Example 1)
In Example 1, 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene (ECP-A) was not added, and the procedure was the same as in Example 1. As a result, the 5% weight loss temperature of the obtained cured product was measured and found to be 118 ° C. The results are shown in Table 1. The TG graph is shown in FIG. 1 (dotted line).

(Example 2)
50 parts by weight of FA-310M (manufactured by Hitachi Chemical Co., Ltd.) and 50 parts by weight of FA-321M as an ethylenically unsaturated group-containing polymerizable compound, and 10 parts by weight of hydroxyethyl methacrylate (HEMA) as an alkali-soluble photopolymerizable compound are mixed. Then, 0.5 part by weight of Irgacure OXE03 (manufactured by BASF) was added as a photopolymerization initiator. Further, 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene (ECM-A) synthesized in the same manner as in Example 1 of Raw Material Synthesis as a 9,10-bis (alkoxycarbonylmethyleneoxy) anthracene compound having an ester group was used. 0 parts by weight was added to obtain a photopolymerizable composition. Using a UV-LED (model number: LLBK1-BA-15 × 20UV405, center wavelength: 405 nm) manufactured by Aitec System Co., Ltd., light irradiation for 5 minutes was performed twice at an illuminance of 100 mW / cm ² to prepare a cured product. Obtained. As a result of measuring the 5% weight loss temperature of the obtained cured product, it was 202 ° C. The results are shown in Table 2.

(Comparative Example 2)
In Example 2, 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene (ECM-A) was not added, and the procedure was the same as in Example 2. As a result, the 5% weight loss temperature of the obtained cured product was measured and found to be 143 ° C. The results are shown in Table 2.

(Example 3)
50 parts by weight of FA-310M (manufactured by Hitachi Chemical Co., Ltd.) and 50 parts by weight of FA-321M as an ethylenically unsaturated group-containing polymerizable compound, and follet ZAH-110 (manufactured by Soken Kagaku Co., Ltd., acid value:) which is an alkali-soluble resin. 100 mgKOH / g, weight average molecular weight: about 15,000, components: methacrylic ester copolymer, solvent 1-methoxy-2-propyl acetate) 10 parts by weight were mixed and 2,2'-bis as a photopolymerization initiator. (2-Chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole (HABI) (manufactured by Tokyo Kasei Co., Ltd.) in 2 parts by weight and leucocrystal violet (LCV) as a hydrogen donor (Manufactured by Wako Pure Chemical Industries, Ltd.) was added in an amount of 0.17 parts by weight. Further, 9,10-bis (propoxycarbonylmethyleneoxy) anthracene (ECP-A) synthesized in the same manner as in Example 2 of Raw Material Synthesis as a 9,10-bis (alkoxycarbonylmethyleneoxy) anthracene compound having an ester group was prepared as 1. 0 parts by weight was added to obtain a photopolymerizable composition. Using a UV-LED (model number: LLBK1-BA-15 × 20UV405, center wavelength: 405 nm) manufactured by Aitec System Co., Ltd., light irradiation for 5 minutes was performed twice at an illuminance of 100 mW / cm ² to prepare a cured product. Obtained. As a result of measuring the 5% weight loss temperature of the obtained cured product, it was 236 ° C. The results are shown in Table 3.

(Comparative Example 3)
In Example 3, 9,10-bis (propoxycarbonylmethyleneoxy) anthracene (ECP-A) was not added, and the procedure was the same as in Example 1. As a result, the 5% weight loss temperature of the obtained cured product was measured and found to be 178 ° C. The results are shown in Table 3.

(Example 4)
A propylene glycol monomethyl ether acetate solution containing 50 parts by weight of FA-310M (manufactured by Hitachi Chemical Co., Ltd.) and 50 parts by weight of FA-321M as an ethylenically unsaturated group-containing polymerizable compound and 20% by weight of carbon black as a pigment was prepared. 1.2 parts were added. To this, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole (HABI) (manufactured by Tokyo Kasei Co., Ltd.) was added as a photopolymerization initiator. 0.17 parts by weight of Leuco Crystal Violet (LCV) (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a hydrogen donor. Further, 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene (ECM-A) synthesized in the same manner as in Example 1 of Raw Material Synthesis as a 9,10-bis (alkoxycarbonylmethyleneoxy) anthracene compound having an ester group is 0. A photopolymerizable composition was obtained by adding 6 parts by weight. This was dropped onto quartz glass on a rheometer, sandwiched between parallel plates having a thickness of 100 μm and a diameter of 10 mm, and the photopolymerizable composition unnecessary for viscosity measurement was wiped off. Thirty seconds after the start of the viscosity measurement of the photopolymerizable composition, the UV-LED was irradiated with light having a wavelength of 405 nm. At this time, the time when the complex viscosity reached 30,000 Pa · s was 980 seconds. The results are shown in Table 4.

(Comparative Example 4)
It was carried out as in Example 4 except that 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene (ECM-A) was not added in Example 4. As a result, the time when the complex viscosity reached 30,000 Pa · s was 1810 seconds. The results are shown in Table 4.

(Comparative Example 5)
The procedure was carried out as in Example 4 except that no pigment was added and 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene (ECM-A) was not added in Example 4. As a result, the time when the complex viscosity reached 30,000 Pa · s was 1170 seconds. The results are shown in Table 4.

Comparing Example 1 and Comparative Example 1, curing obtained by polymerizing and curing a photopolymerizable composition containing a methacrylate having a hydroxy group as an alkali-soluble photopolymerizable compound and a biimidazole-based photopolymerization initiator by light irradiation. When the 9,10-bis (alkoxycarbonylmethyleneoxy) anthracene compound having an ester group of the present invention was not added, the 5% polymerization reduction temperature was 118 ° C., which was extremely low, and there were many VOC components. It is suggested that it is the remaining cured product. On the other hand, when the 9,10-bis (alkoxycarbonylmethyleneoxy) anthracene compound having an ester group of the present invention was added, the 5% polymerization reduction temperature was 267 ° C., suggesting that the cured product had a small VOC component. ing. The weight loss curves of the cured products of Example 1 and Comparative Example 1 during heating are shown in FIG. 1, and the 9,10-bis (alkoxycarbonylmethyleneoxy) anthracene compound having the ester group of the present invention is also shown in this figure. It can be seen that the temperature at which weight loss occurs when added is extremely high.

Further, by comparing Example 2 and Comparative Example 2, a photopolymerizable composition containing a methacrylate having a hydroxy group as an alkali-soluble photopolymerizable compound and an oxime ester-based photopolymerization initiator was polymerized and cured by light irradiation. Even in the obtained cured product, when the 9,10-bis (alkoxycarbonylmethyleneoxy) anthracene compound having an ester group of the present invention was not added, the 5% polymerization reduction temperature was 143 ° C. It is suggested that the product is a cured product in which a large amount of the VOC component remains. On the other hand, when the 9,10-bis (alkoxycarbonylmethyleneoxy) anthracene compound having an ester group of the present invention is added, the 5% polymerization reduction temperature is 202 ° C. and 200 ° C. or higher, and the cured product has a small VOC component. It is suggested that.

Further, by comparing Example 3 and Comparative Example 3, when an alkali-soluble resin is used as the alkali-soluble photopolymerizable compound, a photopolymerizable composition containing a biimidazole-based photopolymerization initiator is irradiated with light. Even in the cured product obtained by polymerization curing, when the 9,10-bis (alkoxycarbonylmethyleneoxy) anthracene compound having an ester group of the present invention is not added, the 5% polymerization reduction temperature is 178 ° C., which is extremely high. It is suggested that it is a cured product that is low and has a large amount of VOC components remaining. On the other hand, when the 9,10-bis (alkoxycarbonylmethyleneoxy) anthracene compound having an ester group of the present invention was added, the 5% polymerization reduction temperature was 236 ° C., suggesting that the cured product had a small VOC component. Has been done.

Furthermore, when Comparative Example 4 and Comparative Example 5 are compared, when carbon black, which is a black pigment, is added, when light is irradiated, a part of the light irradiated in the photopolymerizable composition is due to the black pigment. It can be seen that the time for the complex viscosity of the polymerizable composition to reach 30,000 Pa · S is increasing because the amount of light absorbed and reaching the photopolymerization initiator is reduced, that is, the polymerization rate is slowed down. Even under such conditions, by adding 9,10-bis (ethoxycarbonylmethyleneoxy) anthracene (ECM-A) as the 9,10-bis (alkoxycarbonylmethyleneoxy) anthracene compound having an ester group of the present invention. This is thought to be because energy can be efficiently propagated to the initiator even with a reduced amount of light, but the time it takes for the complex viscosity of the polymerizable composition to reach 30,000 Pa · S is extremely fast, and the pigment It is faster than when it does not contain, and a significant improvement in the polymerization rate can be seen.

Next, the evaluation result of migration resistance will be described.
(Judgment of migration resistance of composition)
As a method for determining whether or not the photopolymerizable sensitizer contained in the photopolymerizable composition of the present invention migrates to a film or the like, the photopolymerizable composition containing the photopolymerizable sensitizer is formed into a thin film. Create a product coated on an object, cover it with a polyethylene film, store it at a constant temperature (26 ° C) for a certain period of time, then peel off the polyethylene film and check whether the photopolymerization sensitizer has transferred to the polyethylene film. , The migration resistance was judged. The peeled polyethylene film is dried after washing the surface composition with acetone, the UV spectrum of the polyethylene film is measured, and the migration resistance is measured by examining the increase in absorption intensity due to the photopolymerization sensitizer. did. An ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV2600) was used for the measurement. For quantitative comparison with the compound of the comparative example, 9,10-dibutoxyanthracene, the obtained absorbance was converted into the absorbance value of 9,10-dibutoxyanthracene. For conversion, the absorbance of the compound of the present invention and 9,10-dibutoxyanthracene at 260 nm was measured with an ultraviolet / visible spectrophotometer, the molar extinction coefficient of each was calculated from the absorbance value and the molar concentration, and the ratio was calculated. Was converted using.

(Example of evaluation of migration resistance of a composition containing a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound)
(Migration resistance evaluation Example 1)
As a photoradical polymerizable compound, 100 parts of trimethylolpropane triacrylate and as a photoradical polymerization sensitizer, 1 part of 9,10-bis (ethoxycarbonylmethoxy) anthracene synthesized by the same method as in Example 1 of raw material synthesis are mixed. Then, the prepared composition was applied on a polyester film using a bar coater so as to have a film thickness of 12 microns. Next, a low-density polyethylene film (thickness: 30 microns) was covered on the obtained coating material to prepare one that was stored in a dark place for one day and one that was stored for seven days, and after each storage, the covered polyethylene film was applied. After peeling, 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 due to 9,10-bis (ethoxycarbonylmethoxy) anthracene was one day. It was 0.014 after storage and 0.015 after storage for 7 days.

(Migration resistance evaluation Example 2)
Migration resistance evaluation was carried out except that 9,10-bis (isopropoxycarbonylmethyleneoxy) anthracene synthesized by the same method as in Example 2 of raw material synthesis was used instead of 9,10-bis (ethoxycarbonylmethoxy) anthracene. It was prepared and tested in the same manner as in Example 1. The absorbance at 260 nm of the polyethylene film washed with acetone was measured, and the absorption due to 9,10-bis (ethoxycarbonylbutyleneoxy) anthracene was 0.024 after storage for one day and 0.022 after storage for seven days. ..

(Migration resistance evaluation comparative example 1)
The test was carried out in the same manner as in Example 1 for evaluation of migration resistance except that 9,10-dibutoxyanthracene, which is a known photoradical sensitizer, was used instead of 9,10-bis (ethoxycarbonylmethoxy) anthracene. As a result of measuring the absorbance at 260 nm of the polyethylene film washed with acetone, the absorbance of the obtained 9,10-dibutoxyanthracene was 1.661 after storage for one day and 1.741 after seven days.

Table 5 summarizes the results of migration resistance evaluation Examples 1 and 2 and migration resistance evaluation Comparative Example 1.

As is clear from comparing Migration Resistance Evaluation Examples 1 and 2 with Migration Resistance Evaluation Comparative Example 1, 9,10-di, which is a known photopolymerization sensitizer in a photoradical polymerizable composition. Butoxyanthracene is transferred to a film overlaid on the photoradical polymerizable composition to a considerable extent, whereas the photopolymerization sensitizer of the present application, 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene. In each case, the degree of migration of the compound is extremely low, and it can be said that the compound has excellent migration resistance.

The photoradical polymerizable composition containing a 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the general formula (1) is a photoradical polymerization initiator having a remarkable effect of oxygen inhibition. Even when used, it is an industrially very useful photoradical polymerizable composition that reduces oxygen inhibition on the surface of the coating film and can be cured without problems even in the presence of oxygen.

Claims

A photopolymerizable composition containing at least the following components (A) to (C), wherein the cured product has a 5% weight loss temperature of 200 ° C. or higher. ..
(A) A 9,10-bis (alkoxycarbonylalkyleneoxy) anthracene compound having an ester group represented by the following general formula (1) (B) An ethylenically unsaturated group-containing polymerizable compound.
(C) Photopolymerization initiator.

(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 The group may be branched by an alkyl group, may be a cycloalkyl group or a cycloalkylalkyl group, may be substituted with a hydroxy group, and a part of carbon atoms may be replaced by an oxygen atom (provided that the group is replaced by an oxygen atom). (Except when forming a peroxide). X and Y may be the same or different, and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom).
The light according to claim 1, wherein in (A), A in the general formula (1) is a 9,10-bis (alkoxycarbonylmethyleneoxy) anthracene compound having an ester group, which is a methylene group. Polymerizable composition.
A photopolymerizable composition according to claim 1 or 2, wherein the photopolymerizable composition further contains (D) an alkali-soluble polymerizable compound.
(D) The photopolymerizable composition according to claim 3, wherein the alkali-soluble polymerizable compound is a compound having a hydroxyl group.
(D) The photopolymerizable composition according to claim 3 or 4, wherein the alkali-soluble polymerizable compound is a compound having a carboxyl group.
(D) The photopolymerizable composition according to claim 3, wherein the alkali-soluble polymerizable compound is an alkali-soluble resin.
A photopolymerizable composition according to any one of claims 1 to 6, further comprising a pigment (E) in the photopolymerizable composition.
(C) A group in which the photopolymerization initiator comprises a biimidazole-based photopolymerization initiator, an alkylphenone-based photopolymerization initiator, a triazine-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, and an oxime-based photopolymerization initiator. The photopolymerizable composition according to any one of claims 1 to 7, characterized in that it contains at least one photopolymerization initiator selected from the above.
(C) The photopolymerizable composition according to any one of claims 1 to 7, wherein the photopolymerization initiator is a biimidazole-based photopolymerization initiator.
(C) The photopolymerizable composition according to any one of claims 1 to 7, wherein the photopolymerization initiator is an oxime ester-based photopolymerization initiator.
A photopolymerizable coating film composition comprising a photopolymerizable coating film containing the photopolymerizable composition according to any one of claims 1 to 10 on a support.
A cured product obtained by curing the photopolymerizable composition according to any one of claims 1 to 10 by light irradiation, wherein the 5% weight loss temperature is 200 ° C. or higher. Hardened product.
A method for curing a photopolymerizable composition, which comprises irradiating the photopolymerizable composition according to any one of claims 1 to 10 with light in a wavelength range of 300 nm to 500 nm.
The method for curing a photopolymerizable composition according to claim 13, wherein the irradiation source of the light to be irradiated is an ultraviolet LED or a semiconductor laser having a center wavelength of 365 nm, 375 nm, 385 nm, 395 nm, and 405 nm.