阅读说明：本技术 具有多环芳香族骨架的化合物及其内过氧化物化合物 (Compound having polycyclic aromatic skeleton and endoperoxide compound thereof ) 是由 桧森俊一 井内启太 山田晓彦 五东弘昭 榊原和久 于 2019-02-12 设计创作，主要内容包括：[课题]提供一种使用了具有多环芳香族骨架的化合物及具有多环芳香族骨架的内过氧化物化合物的新型自由基聚合方法。[解决手段]一种通式(1)所表示的具有多环芳香族骨架的内过氧化物化合物及作为其原料的具有多环芳香族骨架的化合物。通式(1)中,R表示碳原子数1～10的烷基、具有碳原子数1～5的烷氧基的烷氧基甲基、碳原子数6～10的芳基、具有碳原子数1～10的烷基的烷基羰基、具有碳原子数6～20的芳基的芳基羰基、具有碳原子数1～10的烷基的烷基氧基羰基、具有碳原子数6～10的芳基的芳基氧基羰基、具有碳原子数1～12的烷基的烷基氧基羰基甲基或具有碳原子数6～12的芳基的芳基氧基羰基甲基。([ problem ] to]Disclosed is a novel radical polymerization method using a compound having a polycyclic aromatic skeleton and an endoperoxide compound having a polycyclic aromatic skeleton. [ solution means ] to]An endoperoxide compound having a polycyclic aromatic skeleton represented by the general formula (1) and a compound having a polycyclic aromatic skeleton as a raw material thereof. In the general formula (1), R represents an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms, an alkyloxycarbonylmethyl group having an alkyl group having 1 to 12 carbon atoms or an aryloxycarbonylmethyl group having an aryl group having 6 to 12 carbon atoms.)

1. An endoperoxide compound having a polycyclic aromatic skeleton represented by the following general formula (1),

[ solution 1]

In the general formula (1), R represents any of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms, an alkyloxycarbonylmethyl group having an alkyl group having 1 to 12 carbon atoms, or an aryloxycarbonylmethyl group having an aryl group having 6 to 12 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

2. A process for producing an endoperoxide compound having a polycyclic aromatic skeleton represented by the following general formula (1), which comprises reacting a compound having a polycyclic aromatic skeleton represented by the following general formula (2) with molecular oxygen under irradiation with light having a peak wavelength in a wavelength range of 300nm to 410nm,

[ solution 2]

In the general formula (2), R represents any of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms, an alkyloxycarbonylmethyl group having an alkyl group having 1 to 12 carbon atoms, or an aryloxycarbonylmethyl group having an aryl group having 6 to 12 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom;

[ solution 3]

In the general formula (1), R represents any of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms, an alkyloxycarbonylmethyl group having an alkyl group having 1 to 12 carbon atoms, or an aryloxycarbonylmethyl group having an aryl group having 6 to 12 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

3. A process for producing an endoperoxide compound having a polycyclic aromatic skeleton represented by the following general formula (1), which comprises reacting a compound having a polycyclic aromatic skeleton represented by the general formula (2) with singlet oxygen generated from a singlet oxygen generator and molecular oxygen in the presence of a singlet oxygen generator other than the compound having a polycyclic aromatic skeleton represented by the following general formula (2),

[ solution 4]

In the general formula (2), R represents any of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms, an alkyloxycarbonylmethyl group having an alkyl group having 1 to 12 carbon atoms, or an aryloxycarbonylmethyl group having an aryl group having 6 to 12 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom;

[ solution 5]

In the general formula (1), R represents any of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms, an alkyloxycarbonylmethyl group having an alkyl group having 1 to 12 carbon atoms, or an aryloxycarbonylmethyl group having an aryl group having 6 to 12 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

4. An endoperoxide compound having a polycyclic aromatic skeleton represented by the following general formula (3),

[ solution 6]

In the general formula (3), R¹、R²Represents any one of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, or an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

5. A process for producing an endoperoxide compound having a polycyclic aromatic skeleton represented by the following general formula (3), which comprises reacting a compound having a polycyclic aromatic skeleton represented by the following general formula (4) with molecular oxygen under irradiation with light having a peak wavelength in a wavelength range of 300 to 410nm,

[ solution 7]

In the general formula (4), R¹、R²Represents any one of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, or an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms; y is¹、Y²Represents a hydrogen atom,Any one of an alkyl group having 1 to 8 carbon atoms or a halogen atom;

[ solution 8]

In the general formula (3), R¹、R²Represents any one of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, or an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

6. A process for producing an endoperoxide compound having a polycyclic aromatic skeleton represented by the following general formula (3), which comprises reacting a compound having a polycyclic aromatic skeleton represented by the general formula (4) with singlet oxygen generated from the singlet oxygen generating agent and molecular oxygen in the presence of a singlet oxygen generating agent other than the compound having a polycyclic aromatic skeleton represented by the following general formula (4),

[ solution 9]

In the general formula (4), R¹、R²Represents any one of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, or an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms; y is¹、Y²Represents a hydrogen atom, an alkane having 1 to 8 carbon atomsAny one of a group or a halogen atom;

[ solution 10]

In the general formula (3), R¹、R²Represents any one of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, or an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

7. An endoperoxide compound having a polycyclic aromatic skeleton represented by the following general formula (5),

[ solution 11]

In the general formula (5), T represents an alkylene group having 1 to 20 carbon atoms, which may have an alkyl branch; r³、R⁴Represents an alkyl group having 1 to 20 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

8. A process for producing an endoperoxide compound having a polycyclic aromatic skeleton represented by the following general formula (5), which comprises reacting a compound having a polycyclic aromatic skeleton represented by the following general formula (6) with molecular oxygen under irradiation with light having a peak wavelength in a wavelength range of 300nm to 410nm,

[ solution 12]

In the general formula (6), T represents an alkylene group having 1 to 20 carbon atoms, which may have an alkyl branch; r³、R⁴Represents an alkyl group having 1 to 20 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom;

[ solution 13]

In the general formula (5), T represents an alkylene group having 1 to 20 carbon atoms, which may have an alkyl branch; r³、R⁴Represents an alkyl group having 1 to 20 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

9. A process for producing an endoperoxide compound having a polycyclic aromatic skeleton represented by the following general formula (5), which comprises reacting a compound having a polycyclic aromatic skeleton represented by the following general formula (6) with singlet oxygen generated from the singlet oxygen generating agent and molecular oxygen in the presence of a singlet oxygen generating agent other than the compound having a polycyclic aromatic skeleton represented by the following general formula (6),

[ solution 14]

In the general formula (6), T represents an alkylene group having 1 to 20 carbon atoms, which may have an alkyl branch; r³、R⁴Represents an alkyl group having 1 to 20 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom;

[ solution 15]

In the general formula (5), T represents an alkylene group having 1 to 20 carbon atoms, which may have an alkyl branch; r³、R⁴Represents an alkyl group having 1 to 20 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

10. A compound having a polycyclic aromatic skeleton represented by the following general formula (6),

[ solution 16]

In the general formula (6), T represents an alkylene group having 1 to 20 carbon atoms, which may have an alkyl branch; r³、R⁴Represents an alkyl group having 1 to 20 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

11. The compound having a polycyclic aromatic skeleton represented by the general formula (6) according to claim 10, wherein T in the general formula (6) is a methylene group.

12. A method for producing a compound having a polycyclic aromatic skeleton represented by the following general formula (6), characterized by reacting a 9, 10-dihydroxyanthracene compound represented by the following general formula (7) with a halogenated ester compound,

[ solution 17]

In the general formula (7), Y¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom;

[ solution 18]

In the general formula (6), T represents an alkylene group having 1 to 20 carbon atoms, which may have an alkyl branch; r³、R⁴Represents an alkyl group having 1 to 20 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

13. A photo radical polymerization initiator comprising the endoperoxide compound having a polycyclic aromatic skeleton according to claim 1, claim 4 or claim 7.

14. A thermal radical polymerization initiator comprising the endoperoxide compound having a polycyclic aromatic skeleton according to claim 1, claim 4 or claim 7.

15. A radically polymerizable composition comprising the photo radical polymerization initiator according to claim 13 and a radically polymerizable compound.

16. A radically polymerizable composition comprising the thermal radical polymerization initiator according to claim 14 and a radically polymerizable compound.

17. A radically polymerizable composition according to claim 15, further comprising a photo radical polymerization sensitizer.

18. A radically polymerizable composition according to claim 16, further comprising a decomposition accelerator for a thermal radical polymerization initiator.

19. A method for curing a radically polymerizable composition, comprising irradiating the radically polymerizable composition according to claim 15 or 17 with an energy ray containing light having a peak wavelength in a wavelength range of 230nm to 330nm to perform a polymerization reaction.

20. A method for curing a radically polymerizable composition, comprising irradiating the radically polymerizable composition according to claim 17 with an energy ray containing light having a peak wavelength in a wavelength range of 300nm to 410nm to perform a polymerization reaction.

21. A method for curing a radically polymerizable composition, comprising performing a polymerization reaction by heat-treating the radically polymerizable composition according to claim 16 or 18.

22. A method for curing a radical polymerizable composition, characterized in that a radical polymerizable composition comprising a compound having a polycyclic aromatic skeleton represented by the following general formula (2) and a radical polymerizable compound is irradiated with ultraviolet light in the presence of oxygen to produce a endoperoxide compound having a polycyclic aromatic skeleton represented by the following general formula (1), and the endoperoxide compound having a polycyclic aromatic skeleton is subjected to a polymerization reaction as a photo radical polymerization initiator and/or a thermal radical polymerization initiator;

[ solution 19]

In the general formula (2), R represents an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an arylcarbonyl group having 1 to 1 carbon atomAny one of an alkyloxycarbonyl group of an alkyl group of 10, an aryloxycarbonyl group of an aryl group having 6 to 10 carbon atoms, an alkyloxycarbonylmethyl group of an alkyl group having 1 to 12 carbon atoms, or an aryloxycarbonylmethyl group of an aryl group having 6 to 12 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom;

[ solution 20]

In the general formula (1), R represents any of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms, an alkyloxycarbonylmethyl group having an alkyl group having 1 to 12 carbon atoms, or an aryloxycarbonylmethyl group having an aryl group having 6 to 12 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

23. A method for curing a radical polymerizable composition, characterized in that a radical polymerizable composition comprising a compound having a polycyclic aromatic skeleton represented by the following general formula (4) and a radical polymerizable compound is irradiated with ultraviolet light in the presence of oxygen to produce a endoperoxide compound having a polycyclic aromatic skeleton represented by the following general formula (3), and the endoperoxide compound having a polycyclic aromatic skeleton is subjected to a polymerization reaction as a photo radical polymerization initiator and/or a thermal radical polymerization initiator;

[ solution 21]

In the general formula (4), R¹、R²Represents any one of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, or an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom;

[ solution 22]

In the general formula (3), R¹、R²Represents any one of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, or an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

24. A method for curing a radical polymerizable composition, characterized in that a radical polymerizable composition comprising a compound having a polycyclic aromatic skeleton represented by the following general formula (6) and a radical polymerizable compound is irradiated with ultraviolet light in the presence of oxygen to produce a endoperoxide compound having a polycyclic aromatic skeleton represented by the following general formula (5), and the endoperoxide compound having a polycyclic aromatic skeleton is subjected to a polymerization reaction as a photo radical polymerization initiator and/or a thermal radical polymerization initiator;

[ solution 23]

In the general formula (6), T represents an alkylene group having 1 to 20 carbon atoms, which may have an alkyl branch; r³、R⁴Represents an alkyl group having 1 to 20 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom;

[ solution 24]

In the general formula (5), T represents an alkylene group having 1 to 20 carbon atoms, which may have an alkyl branch; r³、R⁴Represents an alkyl group having 1 to 20 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

25. The method for curing a radically polymerizable composition according to any one of claims 22 to 24, wherein the ultraviolet ray to be irradiated is a light having a peak wavelength in a wavelength range of 300nm to 410 nm.

26. A photopolymerization sensitizer comprising a compound having a polycyclic aromatic skeleton represented by the following general formula (6),

[ solution 25]

In the general formula (6), T represents an alkylene group having 1 to 20 carbon atoms, which may have an alkyl branch; r³、R⁴Represents an alkyl group having 1 to 20 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

27. The photopolymerization sensitizer of claim 26, wherein T is a methylene group in the compound having a polycyclic aromatic skeleton represented by the general formula (6).

28. A photopolymerization initiator composition comprising the photopolymerization sensitizer as claimed in claim 26 or 27 and a photopolymerization initiator.

29. A photopolymerizable composition comprising the photopolymerization initiator composition as claimed in claim 28 and a photoradically polymerizable compound.

30. A polymerization method comprising irradiating the photopolymerizable composition according to claim 29 with an energy ray containing light having a wavelength in the range of 300nm to 500nm to polymerize the photopolymerizable composition.

31. The polymerization process of claim 30, wherein the irradiation source of energy rays containing light in the wavelength range of 300nm to 500nm is an ultraviolet LED or 405nm semiconductor laser having a central wavelength of 365nm, 375nm, 385nm, 395nm or 405 nm.

Technical Field

The present invention relates to a compound having a polycyclic aromatic skeleton and a endoperoxide compound thereof, particularly a compound having a polycyclic aromatic skeleton and a endoperoxide compound thereof, a process for producing the same, and a radically polymerizable composition containing the compound having a polycyclic aromatic skeleton and/or the endoperoxide compound thereof.

Background

In the reaction of producing a polymer compound by polymerization of a radically polymerizable compound, a radical polymerization initiator is generally used to initiate the polymerization reaction. In addition, when light irradiation is used as energy for initiating polymerization, a radical photopolymerization initiator is used to absorb and decompose light to generate radical species. As the photo radical polymerization initiator, there are known an alkyl-benzophenone-based photo radical polymerization initiator, an acylphosphine oxide-based photo radical polymerization initiator, an oxime ester-based photo radical polymerization initiator, and the like. By absorbing light of a specific wavelength, the bond at a specific site in these photo radical polymerization initiators is cleaved, and radicals are generated at the cleaved site, which become polymerization initiators to start polymerization of the polymerizable compound.

However, in the radical polymerization reaction using these radical polymerization initiators, it is known that inhibition by oxygen molecules (oxygen inhibition) becomes a problem. The oxygen inhibition means that a radical substance generated by a radical polymerization initiator reacts with, for example, oxygen molecules dissolved in a radical polymerizable composition to be deactivated, and a radical polymerization rate according to the added radical polymerization initiator cannot be obtained, and as a result, the oxygen molecules act as a radical polymerization inhibitor. In addition, it is generally known that such inhibition with oxygen not only significantly reduces the polymerization rate of radical polymerization, but also increases the time to the start of polymerization, i.e., the so-called Induction Period (IP) (non-patent document 1). Therefore, in the polymerization reaction of the radical polymerizable compound, for example, a nitrogen atmosphere is formed to remove oxygen present in the reaction system, or an oxygen impermeable film is coated to eliminate contact with oxygen, and the like, to perform polymerization. But these methods are labor and cost intensive. Here, in order to reduce this oxygen inhibition, it is known to use a compound which is less affected by oxygen inhibition as a radical polymerizable compound or the like (patent documents 1, 2, etc.). Further, in the case of coating an oxygen-impermeable film, there is also a problem that polymerization inhibition occurs at the initial stage of polymerization initiation and IP increases due to oxygen dissolved in a radical polymerization composition. In addition, in photo inkjet, photo 3D printer, and photo offset printing, which require high-speed scanning, not only the polymerization rate is reduced, but also the increase in IP becomes a big problem. Thus, a method for further reducing oxygen inhibition, a radical polymerization initiator and a radical polymerization method which are not inhibited by oxygen inhibition are desired.

The oxygen molecules responsible for oxygen inhibition of the radical polymerization are ground state oxygen molecules, i.e., triplet oxygen, having a diradical structure with 2 unpaired electrons in the orbitals of π y and π z. Therefore, triplet oxygen easily reacts with radical species, hindering radical polymerization. On the other hand, besides the ground-state triplet oxygen, the oxygen molecule may have a singlet oxygen structure in an excited state. The singlet oxygen is one of active oxygen, but does not have an unpaired electron on the orbit and is not a radical structure. Therefore, it is known that it does not inhibit radical polymerization and does not act as a polymerization inhibitor because it does not react with radical species. Thus, if the ground-state oxygen (triplet oxygen) can be excited to singlet oxygen, oxygen inhibition can be reduced.

On the other hand, it is known that this singlet oxygen has an electron-withdrawing property and reacts with an olefin or the like. For example, it is known that an olefin having an allylic hydrogen reacts with singlet oxygen to produce an allylic hydroperoxide, and that singlet oxygen performs a Diels-Alder addition reaction to a 1, 3-conjugated diene to produce a 1, 4-endoperoxide (non-patent document 2).

Due to spin-forbidden, direct excitation from the ground state triplet oxygen to the singlet oxygen does not occur. Therefore, the dye is generally generated by using a dye (photosensitizer) such as rose bengal or methylene blue under irradiation of a specific light. That is, it is known that a dye as a photosensitizer is first photoexcited, the excited substance is converted into a triplet excited state by intersystem crossing, triplet-triplet energy transfer occurs from the triplet excited state of the dye to triplet oxygen in a ground state, and oxygen is excited into singlet oxygen molecules while the dye returns to the ground state (patent document 3). At this time, the dye acts as a singlet oxygen generator. In the present specification, the compound that excites the ground-state oxygen to singlet oxygen is referred to as a singlet oxygen generator.

Patent document 4 discloses that a photosensitive dye such as a xanthene dye, a thiazine dye, or an acridine dye is exposed to light having a wavelength of 300nm to 1400nm to excite oxygen in a ground state to singlet oxygen, and the singlet oxygen is reacted with an olefin and a 1, 3-conjugated diene to generate a hydroperoxide and a peroxide; it is disclosed that the hydroperoxide group functions as a graft site of styrene to produce high impact polystyrene having a core-shell morphology.

Further, it is known that the central ring of an anthracene compound functions as a diene and reacts with singlet oxygen to generate an endoperoxide. For example, it is known that a 9, 10-diphenylanthracene derivative reacts with singlet oxygen to produce an endoperoxide (non-patent document 3). In this case, 9, 10-diphenylanthracene functions as a singlet oxygen scavenger. In the present specification, the compound which reacts with singlet oxygen to generate endoperoxide is referred to as singlet oxygen scavenger.

On the other hand, in photo radical polymerization, it is known that an anthracene compound such as a 9, 10-dialkoxyanthracene compound or a 9, 10-bis (alkoxycarbonyloxy) anthracene compound acts as a photo radical polymerization sensitizer. For example, it is known that 9, 10-dibutoxyanthracene, 9, 10-dioctanoyloxyanthracene, and the like are used as a photopolymerization sensitizer which can be radical-polymerized even under a long-wavelength light of 385nm to activate a photo-radical polymerization initiator in a radical polymerization reaction using a photo-radical polymerization initiator (patent documents 5, 6, 7, and the like).

Further, patent document 8 shows that a 9, 10-bis (substituted carbonyloxy) anthracene compound itself is decomposed to generate a radical species, which becomes an initiator of radical polymerization.

Further, examples of 1, 4-dialkoxynaphthalene compounds used as photo radical polymerization sensitizers, and examples of 1, 4-dialkoxynaphthalene compounds used together with 9, 10-dialkoxyanthracene compounds used as photo radical polymerization sensitizers are known (patent documents 9,10, and 11).

Further, patent document 12 discloses a method for producing an anthracene endoperoxide by reacting a polysubstituted anthracene derivative with oxygen under ultraviolet irradiation.

As the thermal radical polymerization initiator, in addition to the azo polymerization initiator, a ketone peroxide polymerization initiator, a hydroperoxide polymerization initiator, a dialkyl peroxide polymerization initiator, a peroxyketal polymerization initiator, a peroxide polymerization initiator, a peroxydicarbonate polymerization initiator, a diacylperoxide polymerization initiator, and the like are known (patent document 13).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2003-206319

Patent document 2: japanese patent laid-open publication No. 2004-277660

Patent document 3: japanese patent laid-open No. 2008-221159

Patent document 4: japanese Kohyo publication No. 2012-514079

Patent document 5: japanese patent laid-open publication No. 2015-183139

Patent document 6: japanese patent laid-open publication No. 2017-57249

Patent document 7: japanese patent laid-open publication No. 2016-84447

Patent document 8: japanese patent laid-open publication No. 2011-

Patent document 9: japanese patent laid-open publication No. 2015-105292

Patent document 10: japanese patent laid-open publication No. 2011-246606

Patent document 11: japanese laid-open patent publication No. 2007 and 118396

Patent document 12: japanese patent laid-open publication No. 2003-261572

Patent document 13: japanese patent laid-open publication No. 2011-236297

Non-patent document

Non-patent document 1: GEORGE ODIAN, PRINCIPLES OF POLYMERIZATION fountain Edition (2004), p255-256

Non-patent document 2: songben Zhengsheng, Toyota saint, journal of the society for organic Synthesis and chemistry, Vol.35, No. 3 (1977), p.188-200

Non-patent document 3: demet Karaca Balta et al, Macromolecules 2012, 45, p.119-125

Non-patent document 4: tung mountain meaning, "optimization of UV technology" p95 ~ 106 (science & technology, 2008)

Disclosure of Invention

Technical problem to be solved by the invention

The present invention addresses the problem of providing a novel radical polymerization method for producing an endoperoxide compound having a polycyclic aromatic skeleton from a compound having a polycyclic aromatic skeleton by positively utilizing oxygen that initiates oxygen inhibition in the polymerization reaction of a radical polymerizable compound, wherein the endoperoxide compound having a polycyclic aromatic skeleton is used as a radical polymerization initiator; also provided are a novel radical polymerizable composition using the compound having a polycyclic aromatic skeleton of the present invention and a polymerization method thereof.

Means for solving the problems

The present inventors have conducted intensive studies on the reactivity of a compound having a polycyclic aromatic skeleton with oxygen, and as a result, have found that, in radical polymerization of a radical polymerizable compound in the presence of oxygen, when a compound having a specific polycyclic aromatic skeleton is present and irradiated with a specific wavelength, the ground state oxygen is excited to singlet oxygen, and the singlet oxygen reacts with the compound having a polycyclic aromatic skeleton to produce an endoperoxide compound having a polycyclic aromatic skeleton. Further, it has been found that the endoperoxide compound having a polycyclic aromatic skeleton has an ability to initiate radical polymerization of a radically polymerizable compound.

That is, the first invention of the present invention is directed to an endoperoxide compound having a polycyclic aromatic skeleton represented by the following general formula (1).

[ solution 1]

In the general formula (1), R represents any of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms, an alkyloxycarbonylmethyl group having an alkyl group having 1 to 12 carbon atoms, or an aryloxycarbonylmethyl group having an aryl group having 6 to 12 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

A second invention resides in a method for producing a polycyclic aromatic skeleton-containing endoperoxide compound represented by the following general formula (1), characterized by reacting a polycyclic aromatic skeleton-containing compound represented by the following general formula (2) with molecular oxygen under irradiation with light having a peak wavelength in a wavelength range of 300nm to 410 nm.

[ solution 2]

In the general formula (2), R represents any of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms, an alkyloxycarbonylmethyl group having an alkyl group having 1 to 12 carbon atoms, or an aryloxycarbonylmethyl group having an aryl group having 6 to 12 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

[ solution 3]

In the general formula (1), R represents any of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms, an alkyloxycarbonylmethyl group having an alkyl group having 1 to 12 carbon atoms, or an aryloxycarbonylmethyl group having an aryl group having 6 to 12 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

A third invention is a method for producing a polycyclic aromatic skeleton-containing endoperoxide compound represented by the following general formula (1), characterized by reacting a polycyclic aromatic skeleton-containing compound represented by the general formula (2) with singlet oxygen generated from molecular oxygen and the singlet oxygen generating agent in the presence of the singlet oxygen generating agent other than the polycyclic aromatic skeleton-containing compound represented by the following general formula (2).

[ solution 4]

In the general formula (2), R represents any of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms, an alkyloxycarbonylmethyl group having an alkyl group having 1 to 12 carbon atoms, or an aryloxycarbonylmethyl group having an aryl group having 6 to 12 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

[ solution 5]

In the general formula (1), R represents any of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms, an alkyloxycarbonylmethyl group having an alkyl group having 1 to 12 carbon atoms, or an aryloxycarbonylmethyl group having an aryl group having 6 to 12 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

The fourth invention is directed to an endoperoxide compound having a polycyclic aromatic skeleton represented by the following general formula (3).

[ solution 6]

In the general formula (3), R¹、R²Represents any one of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, or an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

A fifth aspect of the present invention is a method for producing a endoperoxide compound having a polycyclic aromatic skeleton represented by the following general formula (3), wherein the compound having a polycyclic aromatic skeleton represented by the following general formula (4) is reacted with molecular oxygen under irradiation with light having a peak wavelength in a wavelength range of 300nm to 410 nm.

[ solution 7]

In the general formula (4), R¹、R²Represents any one of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, or an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

[ solution 8]

In the general formula (3), R¹、R²Represents any one of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, or an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

A sixth aspect of the present invention is a method for producing a polycyclic aromatic skeleton-containing endoperoxide compound represented by the following general formula (3), characterized by reacting a polycyclic aromatic skeleton-containing compound represented by the general formula (4) with singlet oxygen generated from molecular oxygen and the singlet oxygen generating agent in the presence of the singlet oxygen generating agent other than the polycyclic aromatic skeleton-containing compound represented by the following general formula (4).

[ solution 9]

In the general formula (4), R¹、R²Represents any one of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, or an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

[ solution 10]

In the general formula (3), R¹、R²Represents any one of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, or an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

A seventh invention is directed to an endoperoxide compound having a polycyclic aromatic skeleton represented by the following general formula (5).

[ solution 11]

In the general formula (5), T represents an alkylene group having 1 to 20 carbon atoms, which may have an alkyl branch; r³、R⁴Represents an alkyl group having 1 to 20 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

An eighth aspect of the present invention is a method for producing a endoperoxide compound having a polycyclic aromatic skeleton represented by the following general formula (5), wherein the method comprises reacting a compound having a polycyclic aromatic skeleton represented by the following general formula (6) with molecular oxygen under irradiation with light having a peak wavelength in a wavelength range of 300nm to 410 nm.

[ solution 12]

In the general formula (6), T represents an alkylene group having 1 to 20 carbon atoms, which may have an alkyl branch; r³、R⁴Represents an alkyl group having 1 to 20 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

[ solution 13]

In the general formula (5), T represents an alkylene group having 1 to 20 carbon atoms, which may have an alkyl branch; r³、R⁴Represents an alkyl group having 1 to 20 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

A ninth aspect of the present invention is a method for producing a polycyclic aromatic skeleton-containing endoperoxide compound represented by the following general formula (5), wherein the compound having a polycyclic aromatic skeleton represented by the general formula (6) and singlet oxygen generated from molecular oxygen by the singlet oxygen generator are reacted in the presence of a singlet oxygen generator other than the polycyclic aromatic skeleton-containing compound represented by the following general formula (6).

[ solution 14]

In the general formula (6), T represents an alkylene group having 1 to 20 carbon atoms, which may have an alkyl branch; r³、R⁴Represents an alkyl group having 1 to 20 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

[ solution 15]

In the general formula (5), T represents an alkylene group having 1 to 20 carbon atoms, which may have an alkyl branch; r³、R⁴Represents an alkyl group having 1 to 20 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

A tenth invention is directed to a compound having a polycyclic aromatic skeleton represented by the following general formula (6).

[ solution 16]

In the general formula (6), T represents an alkylene group having 1 to 20 carbon atoms, which may have an alkyl branch; r³、R⁴Represents an alkyl group having 1 to 20 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

An eleventh invention is directed to the compound having a polycyclic aromatic skeleton represented by the general formula (6) in the tenth invention, wherein T in the general formula (6) is a methylene group.

A twelfth aspect of the present invention is a method for producing a compound having a polycyclic aromatic skeleton represented by general formula (6), wherein a 9, 10-dihydroxyanthracene compound represented by general formula (7) is reacted with a halogenated ester compound.

[ solution 17]

In the general formula (7), Y¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

[ solution 18]

In the general formula (6), T represents an alkylene group having 1 to 20 carbon atoms, which may have an alkyl branch; r³、R⁴Represents an alkyl group having 1 to 20 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

A thirteenth aspect of the present invention is directed to a photo radical polymerization initiator containing the endoperoxide compound having a polycyclic aromatic skeleton according to any one of the first, fourth, or seventh aspects.

A fourteenth aspect of the present invention is directed to a thermal radical polymerization initiator containing the endoperoxide compound having a polycyclic aromatic skeleton according to any one of the first, fourth, or seventh aspects.

A fifteenth aspect of the present invention is a radical polymerizable composition comprising the photo-radical polymerization initiator according to the thirteenth aspect and a radical polymerizable compound.

A sixteenth aspect of the present invention is a radical polymerizable composition comprising the thermal radical polymerization initiator according to the fourteenth aspect of the present invention and a radical polymerizable compound.

A seventeenth aspect of the present invention is a radical polymerizable composition according to the fifteenth aspect of the present invention, further comprising a photo radical polymerization sensitizer.

An eighteenth aspect of the present invention is a radical polymerizable composition, wherein the radical polymerizable composition according to the sixteenth aspect further contains a decomposition accelerator for a thermal radical polymerization initiator.

A nineteenth aspect of the present invention is a method for curing a radical polymerizable composition, wherein a polymerization reaction is performed by irradiating the radical polymerizable composition according to the fifteenth or seventeenth aspect of the present invention with an energy ray containing light having a peak wavelength in a wavelength range of 230nm to 330 nm.

A twentieth aspect of the present invention is a method for curing a radical polymerizable composition, wherein a polymerization reaction is performed by irradiating the radical polymerizable composition according to the seventeenth aspect of the present invention with an energy ray containing light having a peak wavelength in a wavelength range of 300nm to 410 nm.

A twenty-first aspect of the present invention is a method for curing a radically polymerizable composition, wherein the radically polymerizable composition according to the sixteenth or eighteenth aspect of the present invention is subjected to a heat treatment to thereby perform a polymerization reaction.

A twenty-second aspect of the present invention is a method for curing a radical polymerizable composition, comprising irradiating a radical polymerizable composition containing a compound having a polycyclic aromatic skeleton represented by the following general formula (2) with ultraviolet light in the presence of oxygen to produce a endoperoxide compound having a polycyclic aromatic skeleton represented by the following general formula (1), and polymerizing the endoperoxide compound having a polycyclic aromatic skeleton as a photo-radical polymerization initiator and/or a thermal radical polymerization initiator.

[ solution 19]

In the general formula (2), R represents any of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms, an alkyloxycarbonylmethyl group having an alkyl group having 1 to 12 carbon atoms, or an aryloxycarbonylmethyl group having an aryl group having 6 to 12 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

[ solution 20]

In the general formula (1), R represents an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms, an alkyloxy group having an alkyl group having 1 to 12 carbon atomsAny one of a carbonylmethyl group or an aryloxycarbonylmethyl group having an aryl group having 6 to 12 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

A twenty-third aspect of the present invention is a method for curing a radically polymerizable composition, comprising irradiating a radically polymerizable composition containing a compound having a polycyclic aromatic skeleton represented by the following general formula (4) with ultraviolet light in the presence of oxygen to produce a endoperoxide compound having a polycyclic aromatic skeleton represented by the following general formula (3), and polymerizing the endoperoxide compound having a polycyclic aromatic skeleton as a photo radical polymerization initiator and/or a thermal radical polymerization initiator.

[ solution 21]

In the general formula (4), R¹、R²Represents any one of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, and an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

[ solution 22]

In the general formula (3), R¹、R²Represents an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atomsAny one of an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms or an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

A twenty-fourth aspect of the present invention is a method for curing a radical polymerizable composition, comprising irradiating a radical polymerizable compound with ultraviolet rays in the presence of oxygen to produce a endoperoxide compound having a polycyclic aromatic skeleton represented by the following general formula (5) in a radical polymerizable composition containing a compound having a polycyclic aromatic skeleton represented by the following general formula (6), and polymerizing the endoperoxide compound having a polycyclic aromatic skeleton as a photo radical polymerization initiator and/or a thermal radical polymerization initiator.

[ solution 23]

In the general formula (6), T represents an alkylene group having 1 to 20 carbon atoms, which may have an alkyl branch; r³、R⁴Represents an alkyl group having 1 to 20 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

[ solution 24]

In the general formula (5), T represents an alkylene group having 1 to 20 carbon atoms, which may have an alkyl branch; r³、R⁴Represents an alkyl group having 1 to 20 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

A twenty-fifth aspect of the present invention is the method for curing a radical polymerizable composition according to any one of the twenty-second to twenty-fourth aspects of the present invention, wherein the ultraviolet rays to be irradiated are light having a peak wavelength in a wavelength range of 300nm to 410 nm.

A twenty-sixth aspect of the present invention is a photopolymerization sensitizer containing a compound having a polycyclic aromatic skeleton represented by the following general formula (6).

[ solution 25]

In the general formula (6), T represents an alkylene group having 1 to 20 carbon atoms, which may have an alkyl branch; r³、R⁴Represents an alkyl group having 1 to 20 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

A twenty-seventh aspect of the present invention is the photopolymerization sensitizer according to the twenty-sixth aspect of the present invention, wherein T is a methylene group in the compound having a polycyclic aromatic skeleton represented by the general formula (6).

The twenty-eighth invention resides in a photopolymerization initiator composition comprising the photopolymerization sensitizer of the twenty-sixth or twenty-seventh invention and a photopolymerization initiator.

A twenty-ninth invention resides in a photopolymerizable composition comprising the photopolymerization initiator composition according to the twenty-eighth invention and a photo radical polymerizable compound.

A thirtieth invention resides in a polymerization method of polymerizing the photopolymerizable composition according to the twenty-ninth invention by irradiating energy rays containing light having a wavelength in a range of 300nm to 500 nm.

A thirty-first invention resides in the polymerization method according to the thirty-second invention, characterized in that the irradiation source of the energy ray containing light in a wavelength range of 300nm to 500nm is an ultraviolet LED or a 405nm semiconductor laser having a central wavelength of 365nm, 375nm, 385nm, 395nm or 405 nm.

Effects of the invention

The present invention provides a novel radical polymerization initiator, which is a cyclic aromatic skeleton-containing endoperoxide compound, in radical polymerization of a radical polymerizable compound.

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

Drawings

FIG. 1 is a graph showing the light absorption spectrum in the ultraviolet region and the visible region of 9, 10-dibutoxyanthracene-9, 10-endoperoxide (9, 10-dibutoxy-9, 10-dihydro-9, 10-cyclodioxyanthracene) (DBAEPO) synthesized in example 1 of the present invention. The vertical axis represents absorbance, and the horizontal axis represents wavelength (nm). The solid line in the graph indicates the absorbance at each wavelength when DBAEPO is 100ppm, and the broken line indicates the absorbance at DBAEPO10 ppm.

FIG. 2 is a graph showing the light absorption spectrum in the ultraviolet region and the visible region of 9, 10-bis (ethoxycarbonylmethyleneoxy) anthracene-9, 10-endoperoxide (ECMAEPO) synthesized in example 2 of the present invention. The vertical axis represents absorbance, and the horizontal axis represents wavelength (nm). The solid line in the graph indicates the absorbance at each wavelength for ECMAEPO 100ppm, and the dashed line indicates the absorbance at ECMAEPO 10 ppm.

Detailed Description

(endoperoxide Compound having polycyclic aromatic skeleton)

The endoperoxide compound having a polycyclic aromatic skeleton of the present invention has the structures of the general formulae (1), (3) and (5).

First, an endoperoxide compound having a polycyclic aromatic skeleton represented by the following general formula (3) will be described. In the general formula (1), when R is an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms or an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms, the compound is an endoperoxide compound having a polycyclic aromatic skeleton represented by the general formula (3).

[ solution 26]

In the general formula (3), R¹、R²Represents any one of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, or an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

In the general formula (3), as R¹、R²Examples of the alkyl group having 1 to 20 carbon atoms include a linear, branched or cyclic alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, and an n-decyl group. Examples of the alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms include a methoxymethyl group, an ethoxymethyl group, a n-propoxymethyl group, an isopropoxymethyl group, a n-butoxymethyl group, an isobutoxymethyl group, a n-pentoxymethyl group, and an isopentoxymethyl group. Examples of the aryl group having 6 to 10 carbon atoms include a substituted or unsubstituted phenyl group, tolyl group, naphthyl group, and the like. Examples of the alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms include an acetyl group, a propionyl group, an n-butyryl group, an isobutyryl group, an n-pentanoyl group, an n-hexanoyl group, an n-heptanoyl group, an n-octanoyl group, a 2-ethylhexanoyl group, an n-nonanoyl group, and an n-decanoyl group. Examples of the arylcarbonyl group having an aryl group having 6 to 20 carbon atoms include a benzoyl group and a naphthoyl group. Examples of the alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, a n-butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, a n-pentyloxycarbonyl group, a 2, 2-dimethylpropoxycarbonyl group, a cyclopentyloxycarbonyl group, a n-hexyloxycarbonyl group, a cyclohexyloxycarbonyl group, a n-heptyloxycarbonyl groupA phenyl group, a 2-methylpentyloxycarbonyl group, a n-octyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, a n-nonyloxycarbonyl group, a n-decyloxycarbonyl group and the like. Examples of the aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group and the like.

In the general formula (3), as Y¹、Y²Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Specific examples of the endoperoxide compound having a polycyclic aromatic skeleton of the present invention represented by the general formula (3) are shown below. First, R in the general formula (3) is exemplified¹、R²An alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms.

Examples thereof include 9, 10-diethoxyanthracene-9, 10-endoperoxide, 9, 10-di (n-propoxy) anthracene-9, 10-endoperoxide, 9, 10-di (isopropoxy) anthracene-9, 10-endoperoxide, 9, 10-di (n-butoxy) anthracene-9, 10-endoperoxide, 9, 10-di (isobutoxy) anthracene-9, 10-endoperoxide, 9, 10-di (n-pentyloxy) anthracene-9, 10-endoperoxide, 9, 10-di (isopentyloxy) anthracene-9, 10-endoperoxide, 9, 10-di (n-hexyloxy) anthracene-9, 10-endoperoxide, 9, 10-di (n-heptyloxy) anthracene-9, 10-endoperoxide, 9, 10-di (n-octyloxy) anthracene-9, 10-endoperoxide, 9, 10-di (2-ethylhexyloxy) anthracene-9, 10-endoperoxide, 9, 10-di (n-nonyloxy) anthracene-9, 10-endoperoxide, 9, 10-dimethoxymethyloxyanthracene-9, 10-endoperoxide, 9, 10-diethoxymethyloxyanthracene-9, 10-endoperoxide, 9, 10-dipropoxymethyloxyanthracene-9, 10-endoperoxide, 9, 10-dibutoxymethyloxyanthracene-9, 10-endoperoxide, 9, 10-diphenoxyanthracene-9, 10-endoperoxide, 9, 10-ditolyoxyanthracene-9, 10-endoperoxides, and the like.

Further, there may be mentioned 2-methyl-9, 10-diethoxy anthracene-9, 10-endoperoxide, 2-methyl-9, 10-di (n-propoxy) anthracene-9, 10-endoperoxide, 2-methyl-9, 10-di (isopropoxy) anthracene-9, 10-endoperoxide, 2-methyl-9, 10-di (n-butoxy) anthracene-9, 10-endoperoxide, 2-methyl-9, 10-di (isobutoxy) anthracene-9, 10-endoperoxide, 2-methyl-9, 10-dimethoxymethyloxyanthracene-9, 10-endoperoxide, 2-methyl-9, 10-diethoxymethyloxyanthracene-9, 10-endoperoxide, 2-methyl-9, 10-dipropoxymethyloxyanthracene-9, 10-endoperoxide, 2-methyl-9, 10-dibutoxymethyloxyanthracene-9, 10-endoperoxide, 2-methyl-9, 10-diphenoxyanthracene-9, 10-endoperoxide, 2-methyl-9, 10-ditolyloxyacanthrene-9, 10-endoperoxide, 2-pentyl-9, 10-dimethoxyanthracene-9, 10-endoperoxide, 2-pentyl-9, 10-diethoxyanthracene-9, 10-endoperoxide, 2-pentyl-9, 10-di (n-propoxy) anthracene-9, 10-endoperoxide, 2-pentyl-9, 10-di (isopropoxy) anthracene-9, 10-endoperoxide, 2-pentyl-9, 10-di (n-butoxy) anthracene-9, 10-endoperoxide, 2-pentyl-9, 10-di (isobutoxy) anthracene-9, 10-endoperoxide, and the like.

Further, there may be mentioned 2-chloro-9, 10-diethoxyanthracene-9, 10-endoperoxide, 2-chloro-9, 10-di (n-propoxy) anthracene-9, 10-endoperoxide, 2-chloro-9, 10-di (isopropoxy) anthracene-9, 10-endoperoxide, 2-chloro-9, 10-di (n-butoxy) anthracene-9, 10-endoperoxide, 2-chloro-9, 10-di (isobutoxy) anthracene-9, 10-endoperoxide and the like, which are further substituted with a halogen atom.

Next, R in the general formula (3) is exemplified¹、R²Is the case of an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms.

The following substances can be mentioned as specific examples. Examples thereof include 9, 10-diacetyloxyanthracene-9, 10-endoperoxide, 9, 10-dipropionyloxyanthracene-9, 10-endoperoxide, 9, 10-bis (n-butyryloxy) anthracene-9, 10-endoperoxide, 9, 10-bis (isobutyryloxy) anthracene-9, 10-endoperoxide, 9, 10-bis (n-valeryloxy) anthracene-9, 10-endoperoxide, 9, 10-bis (n-hexanoyloxy) anthracene-9, 10-endoperoxide, 9, 10-bis (n-heptanoyloxy) anthracene-9, 10-endoperoxide, 9, 10-bis (n-octanoyloxy) anthracene-9, 10-endoperoxide, 9, 10-bis (2-ethylhexanoyloxy) anthracene-9, 10-endoperoxide, 9, 10-bis (n-nonanoyloxy) anthracene-9, 10-endoperoxide, 9, 10-bis (n-decanoyloxy) anthracene-9, 10-endoperoxide, 9, 10-bis (n-dodecanoyloxy) anthracene-9, 10-endoperoxide, and the like.

Next, there may be mentioned 1-methyl-9, 10-diacetyloxyanthracene-9, 10-endoperoxide, 1-methyl-9, 10-dipropionyloxyanthracene-9, 10-endoperoxide, 1-methyl-9, 10-bis (n-butyryloxy) anthracene-9, 10-endoperoxide, 1-methyl-9, 10-bis (isobutyryloxy) anthracene-9, 10-endoperoxide, 1-methyl-9, 10-bis (n-hexanoyloxy) anthracene-9, 10-endoperoxide, 1-methyl-9, 10-bis (n-heptanoyloxy) anthracene-9, 10-endoperoxide, 1-methyl-9, 10-bis (n-octanoyloxy) anthracene-9, 10-endoperoxide, 2-methyl-9, 10-diacetyloxyanthracene-9, 10-endoperoxide, 2-methyl-9, 10-dipropionyloxyanthracene-9, 10-endoperoxide, 2-methyl-9, 10-bis (n-butanoyloxy) anthracene-9, 10-endoperoxide, 2-methyl-9, 10-bis (isobutyryloxy) anthracene-9, 10-endoperoxide, 2-methyl-9, 10-bis (n-hexanoyloxy) anthracene-9, 10-endoperoxide, 2-methyl-9, 10-bis (n-heptanoyloxy) anthracene-9, 10-endoperoxide, 2-methyl-9, 10-diacetylanthracene-9, 10-endoperoxide, 2-methyl-9, 10-di (n-octanoyloxy) anthracene-9, 10-ylperoxide, 2-bis (n-butanoyloxy) anthracene-9, 10-endoperoxide, 10-one, 2-bis (n-butanoyloxy) anthracene-9, 10-hydroperoxide, 2-n-9, 10-n-oxide, n-9, n-oxide, n-9, n-oxide, n-9, n-9, n-, 2-methyl-9, 10-bis (n-octanoyloxy) anthracene-9, 10-endoperoxide, 1-ethyl-9, 10-diacetyloxyanthracene-9, 10-endoperoxide, 1-ethyl-9, 10-dipropionyloxyanthracene-9, 10-endoperoxide, 1-ethyl-9, 10-bis (n-butanoyloxy) anthracene-9, 10-endoperoxide, 1-ethyl-9, 10-bis (isobutyryloxy) anthracene-9, 10-endoperoxide, 1-ethyl-9, 10-bis (n-hexanoyloxy) anthracene-9, 10-endoperoxide, 1-ethyl-9, 10-bis (n-heptanoyloxy) anthracene-9, 10-endoperoxide, 1-ethyl-9, 10-bis (n-octanoyloxy) anthracene-9, 10-endoperoxide, 2-ethyl-9, 10-diacetyloxyanthracene-9, 10-endoperoxide, 2-ethyl-9, 10-dipropanoyloxy anthracene-9, 10-endoperoxide, 2-ethyl-9, 10-bis (n-butanoyloxy) anthracene-9, 10-endoperoxide, 2-ethyl-9, 10-bis (isobutyryloxy) anthracene-9, 10-endoperoxide, 2-ethyl-9, 10-bis (n-hexanoyloxy) anthracene-9, 10-endoperoxide, 2-ethyl-9, 10-bis (n-heptanoyloxy) anthracene-9, 10-endoperoxide, 2-ethyl-9, 10-bis (n-octanoyloxy) anthracene-9, 10-endoperoxide, and the like.

Further examples of the antioxidant include 2, 3-dimethyl-9, 10-diacetyloxyanthracene-9, 10-endoperoxide, 2, 3-dimethyl-9, 10-dipropionyloxyanthracene-9, 10-endoperoxide, 2, 3-dimethyl-9, 10-bis (n-butyryloxy) anthracene-9, 10-endoperoxide, 2, 3-dimethyl-9, 10-bis (isobutyryloxy) anthracene-9, 10-endoperoxide, 2, 3-dimethyl-9, 10-bis (n-hexanoyloxy) anthracene-9, 10-endoperoxide, 2, 3-dimethyl-9, 10-bis (n-heptanoyloxy) anthracene-9, 10-endoperoxide, 2, 3-di (n-deacyloxy) anthracene-9, 10-one, 2, 3-di (n-deacyloxy) anthracene-9, 10-endoperoxide, 2, 3-di (n-deacyloxy) anthracene-9, 10-one, 10-bis (n-naphthoyloxy anthracene-9, 10-endoperoxide, 2, 3-bis (n-naphthoyloxy) anthracene-9, 10-n-hydroperoxide, n-oxide, n-p-oxide, n-p-n-p-oxide, n-p-n-p-n-p-n-p, 2, 3-dimethyl-9, 10-bis (n-octanoyloxy) anthracene-9, 10-endoperoxide, 2, 6-dimethyl-9, 10-diacetyloxyanthracene-9, 10-endoperoxide, 2, 6-dimethyl-9, 10-dipropanoyloxyanthracene-9, 10-endoperoxide, 2, 6-dimethyl-9, 10-bis (n-butanoyloxy) anthracene-9, 10-endoperoxide, 2, 6-dimethyl-9, 10-bis (isobutyryloxy) anthracene-9, 10-endoperoxide, 2, 6-dimethyl-9, 10-bis (n-hexanoyloxy) anthracene-9, 10-endoperoxide, 10-bis (n-heptanoyloxy) anthracene-9, 10-endoperoxide, 2, 6-dimethyl-9, 10-bis (n-octanoyloxy) anthracene-9, 10-endoperoxide, and the like.

Furthermore, R in the general formula (3) is illustrated below¹、R²Is the case of an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having an aryl group having 6 to 20 carbon atoms.

The following substances can be mentioned as specific examples. Examples thereof include 9, 10-bis (methoxycarbonyloxy) anthracene-9, 10-endoperoxide, 9, 10-bis (ethoxycarbonyloxy) anthracene-9, 10-endoperoxide, 9, 10-bis (n-propoxycarbonyloxy) anthracene-9, 10-endoperoxide, 9, 10-bis (isopropoxycarbonyloxy) anthracene-9, 10-endoperoxide, 9, 10-bis (n-butoxycarbonyloxy) anthracene-9, 10-endoperoxide, 9, 10-bis (isobutoxycarbonyloxy) anthracene-9, 10-endoperoxide and the like.

Next, there may be mentioned 1-methyl-9, 10-bis (methoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1-methyl-9, 10-bis (ethoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1-methyl-9, 10-bis (n-propoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1-methyl-9, 10-bis (isopropoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1-methyl-9, 10-bis (n-butoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1-methyl-9, 10-bis (isobutoxycarbonyloxy) anthracene-9, 10-endoperoxide, further alkyl-substituted, 2-methyl-9, 10-bis (methoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2-methyl-9, 10-bis (ethoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2-methyl-9, 10-bis (n-propoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2-methyl-9, 10-bis (isopropoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2-methyl-9, 10-bis (n-butoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2-methyl-9, 10-bis (isobutoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1-ethyl-9, 10-bis (methoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1-ethyl-9, 10-bis (ethoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1-ethyl-9, 10-bis (n-propoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1-ethyl-9, 10-bis (isopropoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1-ethyl-9, 10-bis (n-butoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1-ethyl-9, 10-bis (isobutoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2-ethyl-9, 10-bis (methoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2-ethyl-9, 10-bis (ethoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2-ethyl-9, 10-bis (n-propoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2-ethyl-9, 10-bis (isopropoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2-ethyl-9, 10-bis (n-butoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2-ethyl-9, 10-bis (isobutoxycarbonyloxy) anthracene-9, 10-endoperoxide, and the like.

Further, there may be mentioned 2, 3-dimethyl-9, 10-bis (methoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 3-dimethyl-9, 10-bis (ethoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 3-dimethyl-9, 10-bis (n-propoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 3-dimethyl-9, 10-bis (isopropoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 3-dimethyl-9, 10-bis (n-butoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 3-dimethyl-9, 10-bis (isobutoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 6-dimethyl-9, 10-bis (methoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 6-dimethyl-9, 10-bis (ethoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 6-dimethyl-9, 10-bis (n-propoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 6-dimethyl-9, 10-bis (isopropoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 6-dimethyl-9, 10-bis (n-butoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 6-dimethyl-9, 10-bis (isobutoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 7-dimethyl-9, 10-bis (methoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 7-dimethyl-9, 10-bis (ethoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 7-dimethyl-9, 10-bis (n-propoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 7-dimethyl-9, 10-bis (isopropoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 7-dimethyl-9, 10-bis (n-butoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 7-dimethyl-9, 10-bis (isobutoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1, 5-dimethyl-9, 10-bis (methoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1, 5-dimethyl-9, 10-bis (ethoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1, 5-dimethyl-9, 10-bis (n-propoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1, 5-dimethyl-9, 10-bis (isopropoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1, 5-dimethyl-9, 10-bis (n-butoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1, 5-dimethyl-9, 10-bis (isobutoxycarbonyloxy) anthracene-9, 10-endoperoxides, and the like.

Further, there may be mentioned 2, 3-diethyl-9, 10-bis (methoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 3-diethyl-9, 10-bis (ethoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 3-diethyl-9, 10-bis (n-propoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 3-diethyl-9, 10-bis (isopropoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 3-diethyl-9, 10-bis (n-butoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 3-diethyl-9, 10-bis (isobutoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 6-diethyl-9, 10-bis (methoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 6-diethyl-9, 10-bis (ethoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 6-diethyl-9, 10-bis (n-propoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 6-diethyl-9, 10-bis (isopropoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 6-diethyl-9, 10-bis (n-butoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 6-diethyl-9, 10-bis (isobutoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 7-diethyl-9, 10-bis (methoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 7-diethyl-9, 10-bis (ethoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 7-diethyl-9, 10-bis (n-propoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 7-diethyl-9, 10-bis (isopropoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 7-diethyl-9, 10-bis (n-butoxycarbonyloxy) anthracene-9, 10-endoperoxide, 2, 7-diethyl-9, 10-bis (isobutoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1, 5-diethyl-9, 10-bis (methoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1, 5-diethyl-9, 10-bis (ethoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1, 5-diethyl-9, 10-bis (n-propoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1, 5-diethyl-9, 10-bis (isopropoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1, 5-diethyl-9, 10-bis (n-butoxycarbonyloxy) anthracene-9, 10-endoperoxide, 1, 5-diethyl-9, 10-bis (isobutoxycarbonyloxy) anthracene-9, 10-endoperoxides, and the like.

Next, an endoperoxide compound having a polycyclic aromatic skeleton represented by the following general formula (5) will be described. In the general formula (1), when R is an alkyloxycarbonylmethyl group having an alkyl group having 1 to 12 carbon atoms or an aryloxycarbonylmethyl group having an aryl group having 6 to 12 carbon atoms, it is a compound of the general formula (5).

[ solution 27]

In the general formula (5), T represents an alkylene group having 1 to 20 carbon atoms, which may have an alkyl branch; r³、R⁴Represents an alkyl group having 1 to 20 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

In the general formula (5), examples of the alkylene group having 1 to 20 carbon atoms represented by T 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, a nonylene group, 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 nonadecylene group, and a eicosylene group, and the alkylene group may have an alkyl branch.

In the general formula (5), as R³、R⁴Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and an n-eicosyl group.

In the general formula (5), as Y¹、Y²Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Specific examples of the endoperoxide compound having a polycyclic aromatic skeleton of the present invention represented by the general formula (5) are shown below. Specific examples thereof include 9, 10-bis (methoxycarbonylmethylenoxy) anthracene-9, 10-endoperoxide, 9, 10-bis (ethoxycarbonylmethylenoxy) anthracene-9, 10-endoperoxide, 9, 10-bis (isopropoxycarbonylmethylenoxy) anthracene-9, 10-endoperoxide, 9, 10-bis (tert-butoxycarbonylmethyloxy) anthracene-9, 10-endoperoxide, 9, 10-bis (n-butoxycarbonylmethyloxy) anthracene-9, 10-endoperoxide, 9, 10-bis (methoxycarbonylpropyleneoxy) anthracene-9, 10-endoperoxide, 9, 10-bis (ethoxycarbonylpropyleneoxy) anthracene-9, 10-endoperoxide, 9, 10-bis (ethoxycarbonylpropyleneoxy) anthracene-9, 10-one, 9, 10-endoperoxide, and the like, 9, 10-bis (isopropoxycarbonylpropyleneoxy) anthracene-9, 10-endoperoxide, 9, 10-bis (tert-butoxycarbonylpropyleneoxy) anthracene-9, 10-endoperoxide, 9, 10-bis (n-butoxycarbonylpropyleneoxy) anthracene-9, 10-endoperoxide, and the like.

In addition, as Y¹、Y²Specific examples of the alkyl group include 2-ethyl-9, 10-bis (methoxycarbonylmethylenoxy) anthracene-9, 10-endoperoxide, 2-ethyl-9, 10-bis (ethoxycarbonylmethylenoxy) anthracene-9, 10-endoperoxide, 2-ethyl-9, 10-bis (isopropoxycarbonylmethyleneoxy) anthraceneMethyloxy) anthracene-9, 10-endoperoxide, 2-ethyl-9, 10-bis (tert-butoxycarbonylmethylenoxy) anthracene-9, 10-endoperoxide, 2-ethyl-9, 10-bis (n-butoxycarbonylmethyloxy) anthracene-9, 10-endoperoxide, 2-ethyl-9, 10-bis (methoxycarbonylpropyleneoxy) anthracene-9, 10-endoperoxide, 2-ethyl-9, 10-bis (ethoxycarbonylpropyleneoxy) anthracene-9, 10-endoperoxide, 2-ethyl-9, 10-bis (isopropoxycarbonylpropyleneoxy) anthracene-9, 10-endoperoxide, 2-ethyl-9, 10-bis (tert-butoxycarbonylpropyleneoxy) anthracene-9, 10-endoperoxide, 2-ethyl-9, 10-bis (n-butyloxycarbonylpropyleneoxy) anthracene-9, 10-endoperoxide, and the like.

In addition, as Y¹、Y²Specific examples of the halogen atom include 2-chloro-9, 10-bis (methoxycarbonylmethylenoxy) anthracene-9, 10-endoperoxide, 2-chloro-9, 10-bis (ethoxycarbonylmethyloxy) anthracene-9, 10-endoperoxide, 2-chloro-9, 10-bis (isopropoxycarbonylmethyloxy) anthracene-9, 10-endoperoxide, 2-chloro-9, 10-bis (tert-butoxycarbonylmethyloxy) anthracene-9, 10-endoperoxide, 2-chloro-9, 10-bis (n-butoxycarbonylmethyloxy) anthracene-9, 10-endoperoxide, 2-chloro-9, 10-bis (methoxycarbonylpropylenoxy) anthracene-9, 10-endoperoxide, 2-chloro-9, 10-bis (ethoxycarbonylpropyleneoxy) anthracene-9, 10-endoperoxide, 2-chloro-9, 10-bis (isopropoxycarbonylpropyleneoxy) anthracene-9, 10-endoperoxide, 2-chloro-9, 10-bis (tert-butoxycarbonylpropyleneoxy) anthracene-9, 10-endoperoxide, 2-chloro-9, 10-bis (n-butoxycarbonylpropyleneoxy) anthracene-9, 10-endoperoxide, and the like.

(method for producing endoperoxide compound having polycyclic aromatic skeleton)

Next, a method for producing the endoperoxide compound having a polycyclic aromatic skeleton of the present invention will be described. The endoperoxide compound having a polycyclic aromatic skeleton of the present invention is produced by reacting a corresponding compound having a polycyclic aromatic skeleton with singlet oxygen.

(Compound having polycyclic aromatic skeleton)

The compound having a polycyclic aromatic skeleton used as a raw material in the present invention is a compound having a structure of general formula (2), general formula (4) or general formula (6). In the general formula (2), when R is an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, or an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms, the compound is a compound having a polycyclic aromatic skeleton represented by the general formula (4). First, a compound having a polycyclic aromatic skeleton represented by the following general formula (4) will be described.

[ solution 28]

In the general formula (4), R¹、R²Represents any one of an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, or an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

R in the general formula (4)¹、R²、Y¹、Y²Specific examples of (3) and R illustrated in the general formula (3)¹、R²、Y¹、Y²The same applies to specific examples of (1).

Specific examples of the general formula (4) include, for example, 9, 10-diethoxyanthracene, 9, 10-di (n-propoxy) anthracene, 9, 10-di (isopropoxy) anthracene, 9, 10-di (n-butoxy) anthracene, 9, 10-di (isobutoxy) anthracene, 9, 10-di (n-pentoxy) anthracene, 9, 10-di (isopentoxy) anthracene, 9, 10-di (n-hexoxy) anthracene, 9, 10-di (n-heptoxy) anthracene, 9, 10-di (n-octoxy) anthracene, 9, 10-di (2-ethylhexoxy) anthracene, 9, 10-di (n-nonyloxy) anthracene, 9, 10-dimethoxymethyloxyanthracene, 9, 10-diethoxymethyloxyanthracene, 9, 10-dipropoxymethyloxyanthracene, 9, 10-dibutoxymethyloxyanthracene, 9, 10-di (n-propoxymethyloxyanthracene), 9, 10-n-propoxymethyloxyanthracene, 9, 10-di (n-propoxymethyloxyanthracene, 9, 10-n-propoxymethyloxyanthracene, 9, 10-n-propoxymethyloxyanthracene, and the like, 9, 10-diphenoxyanthracene, 9, 10-xylyloxyanthracene, and the like.

Further, there may be mentioned 2-methyl-9, 10-diethoxyanthracene, 2-methyl-9, 10-di (n-propoxy) anthracene, 2-methyl-9, 10-di (isopropoxy) anthracene, 2-methyl-9, 10-di (n-butoxy) anthracene, 2-methyl-9, 10-di (isobutoxy) anthracene, 2-methyl-9, 10-dimethoxymethyloxyanthracene, 2-methyl-9, 10-diethoxymethyloxyanthracene, 2-methyl-9, 10-dipropoxymethyloxyanthracene, 2-methyl-9, 10-dibutoxymethyloxyanthracene, 2-methyl-9, 10-diphenoxyanthracene, 2-methyl-9, 10-ditolyl oxyanthracene, 2-pentyl-9, 10-dimethoxy anthracene, 2-pentyl-9, 10-diethoxy anthracene, 2-pentyl-9, 10-di (n-propoxy) anthracene, 2-pentyl-9, 10-di (isopropoxy) anthracene, 2-pentyl-9, 10-di (n-butoxy) anthracene, 2-pentyl-9, 10-di (isobutoxy) anthracene, 2-pentyl-9, 10-dimethoxy methyloxyanthracene, 2-pentyl-9, 10-diethoxymethyloxyanthracene, 2-pentyl-9, 10-dipropoxymethyloxyanthracene, 2-pentyl-9, 10-dibutoxymethyloxyanthracene, 2-pentyl-9, 10-diphenoxyanthracene, 2-pentyl-9, 10-xylyloxyanthracene, and the like.

Further, there may be mentioned 2-chloro-9, 10-dimethoxyanthracene, 2-chloro-9, 10-diethoxyanthracene, 2-chloro-9, 10-di (n-propoxy) anthracene, 2-chloro-9, 10-di (isopropoxy) anthracene, 2-chloro-9, 10-di (n-butoxy) anthracene, 2-chloro-9, 10-di (isobutoxy) anthracene, 2-chloro-9, 10-dimethoxymethyloxyanthracene, 2-chloro-9, 10-diethoxymethyloxyanthracene, 2-chloro-9, 10-dipropoxymethyloxyanthracene, 2-chloro-9, 10-dibutoxymethyloxyanthracene, 2-chloro-9, 10-diphenoxyanthracene, further substituted with a halogen atom, 2-chloro-9, 10-ditolyloxyacnthracene, and the like.

Next, R in the general formula (4) is exemplified¹、R²Is the case of an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms, an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms.

The following substances can be mentioned as specific examples. Examples thereof include 9, 10-diacetyloxyanthracene, 9, 10-dipropionyloxyanthracene, 9, 10-bis (n-butyryloxy) anthracene, 9, 10-bis (isobutyryloxy) anthracene, 9, 10-bis (n-valeryloxy) anthracene, 9, 10-bis (n-hexanoyloxy) anthracene, 9, 10-bis (n-heptanoyloxy) anthracene, 9, 10-bis (n-octanoyloxy) anthracene, 9, 10-bis (2-ethylhexanoyloxy) anthracene, 9, 10-bis (n-nonanoyloxy) anthracene, 9, 10-bis (n-decanoyloxy) anthracene, 9, 10-bis (n-dodecanoyloxy) anthracene and the like.

Next, there may be mentioned 1-methyl-9, 10-diacetoxyanthracene, 1-methyl-9, 10-dipropionyloxyanthracene, 1-methyl-9, 10-bis (n-butyryloxy) anthracene, 1-methyl-9, 10-bis (isobutyryloxy) anthracene, 1-methyl-9, 10-bis (n-hexanoyloxy) anthracene, 1-methyl-9, 10-bis (n-heptanoyloxy) anthracene, 1-methyl-9, 10-bis (n-octanoyloxy) anthracene, 2-methyl-9, 10-diacetoxyanthracene, 2-methyl-9, 10-dipropionyloxyanthracene, 2-methyl-9, 10-bis (n-butyryloxy) anthracene, further alkyl-substituted 1-methyl-9, 10-diacetoxyanthracene, 1-methyl-9, 10-bis (n-butyryloxy) anthracene, 1-methyl-9, 10-bis (isobutyryloxy) anthracene, 1-methyl-9, 10-bis (n-butyryloxy) anthracene, and the like, 2-methyl-9, 10-bis (isobutyryloxy) anthracene, 2-methyl-9, 10-bis (n-hexanoyloxy) anthracene, 2-methyl-9, 10-bis (n-heptanoyloxy) anthracene, 2-methyl-9, 10-bis (n-octanoyloxy) anthracene, 1-ethyl-9, 10-diacetyloxyanthracene, 1-ethyl-9, 10-dipropionyloxyanthracene, 1-ethyl-9, 10-bis (n-butanoyloxy) anthracene, 1-ethyl-9, 10-bis (isobutyryloxy) anthracene, 1-ethyl-9, 10-bis (n-hexanoyloxy) anthracene, 1-ethyl-9, 10-bis (n-heptanoyloxy) anthracene, 1-ethyl-9, 10-bis (n-octanoyloxy) anthracene, 2-ethyl-9, 10-diacetyloxyanthracene, 2-ethyl-9, 10-dipropionyloxyanthracene, 2-ethyl-9, 10-bis (n-butanoyloxy) anthracene, 2-ethyl-9, 10-bis (isobutyryloxy) anthracene, 2-ethyl-9, 10-bis (n-hexanoyloxy) anthracene, 2-ethyl-9, 10-bis (n-heptanoyloxy) anthracene, 2-ethyl-9, 10-bis (n-octanoyloxy) anthracene, and the like.

Further examples thereof include 2, 3-dimethyl-9, 10-diacetoxyanthracene, 2, 3-dimethyl-9, 10-dipropionoxyanthracene, 2, 3-dimethyl-9, 10-bis (n-butyryloxy) anthracene, 2, 3-dimethyl-9, 10-bis (isobutyryloxy) anthracene, 2, 3-dimethyl-9, 10-bis (n-hexanoyloxy) anthracene, 2, 3-dimethyl-9, 10-bis (n-heptanoyloxy) anthracene, 2, 3-dimethyl-9, 10-bis (n-octanoyloxy) anthracene, 2, 6-dimethyl-9, 10-diacetoxyanthracene, 2, 6-dimethyl-9, 10-dipropionoxyanthracene, 2, 6-dimethyl-9, 10-bis (n-butyryloxy) anthracene, 2, 6-dimethyl-9, 10-bis (isobutyryloxy) anthracene, 2, 6-dimethyl-9, 10-bis (n-hexanoyloxy) anthracene, 2, 6-dimethyl-9, 10-bis (n-heptanoyloxy) anthracene, 2, 6-dimethyl-9, 10-bis (n-octanoyloxy) anthracene, 2, 7-dimethyl-9, 10-diacetoxyanthracene, 2, 7-dimethyl-9, 10-dipropionyloxyanthracene, 2, 7-dimethyl-9, 10-bis (n-butyryloxy) anthracene, 2, 7-dimethyl-9, 10-bis (isobutyryloxy) anthracene, 2, 7-dimethyl-9, 10-bis (n-hexanoyloxy) anthracene, 2, 7-dimethyl-9, 10-bis (n-heptanoyloxy) anthracene, 2, 7-dimethyl-9, 10-bis (n-octanoyloxy) anthracene, and the like.

Furthermore, the following examples illustrate R in the general formula (4)¹、R²Is the case of an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having an aryl group having 6 to 20 carbon atoms.

The following substances can be mentioned as specific examples. Examples thereof include 9, 10-bis (methoxycarbonyloxy) anthracene, 9, 10-bis (ethoxycarbonyloxy) anthracene, 9, 10-bis (n-propoxycarbonyloxy) anthracene, 9, 10-bis (isopropoxycarbonyloxy) anthracene, 9, 10-bis (n-butoxycarbonyloxy) anthracene, 9, 10-bis (isobutoxycarbonyloxy) anthracene, 9, 10-bis (n-pentyloxycarbonyloxy) anthracene, 9, 10-bis (isopentoxycarbonyloxy) anthracene, 9, 10-bis (n-hexyloxycarbonyloxy) anthracene, 9, 10-bis (n-heptyloxycarbonyloxy) anthracene, 9, 10-bis (n-octyloxycarbonyloxy) anthracene and the like.

Next, there may be mentioned 1-methyl-9, 10-bis (methoxycarbonyloxy) anthracene, 1-methyl-9, 10-bis (ethoxycarbonyloxy) anthracene, 1-methyl-9, 10-bis (n-propoxycarbonyloxy) anthracene, 1-methyl-9, 10-bis (isopropoxycarbonyloxy) anthracene, 1-methyl-9, 10-bis (n-butoxycarbonyloxy) anthracene, 1-methyl-9, 10-bis (isobutoxycarbonyloxy) anthracene, 1-methyl-9, 10-bis (n-pentyloxycarbonyloxy) anthracene, 1-methyl-9, 10-bis (isopentyloxycarbonyloxy) anthracene, 1-methyl-9, 10-bis (n-hexyloxycarbonyloxy) anthracene, further alkyl-substituted, 1-methyl-9, 10-bis (n-heptyloxycarbonyloxy) anthracene, 1-methyl-9, 10-bis (n-octyloxycarbonyloxy) anthracene, 2-methyl-9, 10-bis (methoxycarbonyloxy) anthracene, 2-methyl-9, 10-bis (ethoxycarbonyloxy) anthracene, 2-methyl-9, 10-bis (n-propoxycarbonyloxy) anthracene, 2-methyl-9, 10-bis (isopropoxycarbonyloxy) anthracene, 2-methyl-9, 10-bis (n-butoxycarbonyloxy) anthracene, 2-methyl-9, 10-bis (isobutoxycarbonyloxy) anthracene, 2-methyl-9, 10-bis (n-pentyloxycarbonyloxy) anthracene, 2-methyl-9, 10-bis (isopentoxycarbonyloxy) anthracene, 2-methyl-9, 10-bis (n-hexyloxycarbonyloxy) anthracene, 2-methyl-9, 10-bis (n-heptyloxycarbonyloxy) anthracene, 2-methyl-9, 10-bis (n-octyloxycarbonyloxy) anthracene, 1-ethyl-9, 10-bis (methoxycarbonyloxy) anthracene, 1-ethyl-9, 10-bis (ethoxycarbonyloxy) anthracene, 1-ethyl-9, 10-bis (n-propoxycarbonyloxy) anthracene, 1-ethyl-9, 10-bis (isopropoxycarbonyloxy) anthracene, 1-ethyl-9, 10-bis (n-butoxycarbonyloxy) anthracene, 1-ethyl-9, 10-bis (isobutoxycarbonyloxy) anthracene, 1-ethyl-9, 10-bis (n-pentyloxycarbonyloxy) anthracene, 1-ethyl-9, 10-bis (isopentoxycarbonyloxy) anthracene, 1-ethyl-9, 10-bis (n-hexyloxycarbonyloxy) anthracene, 1-ethyl-9, 10-bis (n-heptoxycarbonyloxy) anthracene, 1-ethyl-9, 10-bis (n-octyloxycarbonyloxy) anthracene, 2-ethyl-9, 10-bis (methoxycarbonyloxy) anthracene, 2-ethyl-9, 10-bis (ethoxycarbonyloxy) anthracene, 2-ethyl-9, 10-bis (n-propoxycarbonyloxy) anthracene, 2-ethyl-9, 10-bis (isopropoxycarbonyloxy) anthracene, 2-ethyl-9, 10-bis (n-butyloxycarbonyloxy) anthracene, 2-ethyl-9, 10-bis (isobutoxycarbonyloxy) anthracene, 2-ethyl-9, 10-bis (n-pentyloxycarbonyloxy) anthracene, 2-ethyl-9, 10-bis (isopentoxycarbonyloxy) anthracene, 2-ethyl-9, 10-bis (n-hexyloxycarbonyloxy) anthracene, 2-ethyl-9, 10-bis (n-heptyloxycarbonyloxy) anthracene, 2-ethyl-9, 10-bis (n-octyloxycarbonyloxy) anthracene, and the like.

Further, there may be mentioned 2, 3-dimethyl-9, 10-bis (methoxycarbonyloxy) anthracene, 2, 3-dimethyl-9, 10-bis (ethoxycarbonyloxy) anthracene, 2, 3-dimethyl-9, 10-bis (n-propoxycarbonyloxy) anthracene, 2, 3-dimethyl-9, 10-bis (isopropoxycarbonyloxy) anthracene, 2, 3-dimethyl-9, 10-bis (n-butoxycarbonyloxy) anthracene, 2, 3-dimethyl-9, 10-bis (isobutoxycarbonyloxy) anthracene, 2, 3-dimethyl-9, 10-bis (n-pentyloxycarbonyloxy) anthracene, 2, 3-dimethyl-9, 10-bis (isopentoxycarbonyloxy) anthracene, 2, 3-dimethyl-9, 10-bis (n-hexyloxycarbonyloxy) anthracene, 2, 3-dimethyl-9, 10-bis (n-heptyloxycarbonyloxy) anthracene, 2, 3-dimethyl-9, 10-bis (n-octyloxycarbonyloxy) anthracene, 2, 6-dimethyl-9, 10-bis (methoxycarbonyloxy) anthracene, 2, 6-dimethyl-9, 10-bis (ethoxycarbonyloxy) anthracene, 2, 6-dimethyl-9, 10-bis (n-propoxycarbonyloxy) anthracene, 2, 6-dimethyl-9, 10-bis (isopropoxycarbonyloxy) anthracene, 2, 6-dimethyl-9, 10-bis (n-butoxycarbonyloxy) anthracene, 2, 6-dimethyl-9, 10-bis (isobutoxycarbonyloxy) anthracene, 2, 6-dimethyl-9, 10-bis (n-pentyloxycarbonyloxy) anthracene, 2, 6-dimethyl-9, 10-bis (isopentoxycarbonyloxy) anthracene, 2, 6-dimethyl-9, 10-bis (n-hexyloxycarbonyloxy) anthracene, 2, 6-dimethyl-9, 10-bis (n-heptyloxycarbonyloxy) anthracene, 2, 6-dimethyl-9, 10-bis (n-octyloxycarbonyloxy) anthracene, 2, 7-dimethyl-9, 10-bis (methoxycarbonyloxy) anthracene, 2, 7-dimethyl-9, 10-bis (ethoxycarbonyloxy) anthracene, 2, 7-dimethyl-9, 10-bis (n-propoxycarbonyloxy) anthracene, 2, 7-dimethyl-9, 10-bis (isopropoxycarbonyloxy) anthracene, 2, 7-dimethyl-9, 10-bis (n-butoxycarbonyloxy) anthracene, 2, 7-dimethyl-9, 10-bis (isobutoxycarbonyloxy) anthracene, 2, 7-dimethyl-9, 10-bis (n-pentyloxycarbonyloxy) anthracene, 2, 7-dimethyl-9, 10-bis (isopentoxycarbonyloxy) anthracene, 2, 7-dimethyl-9, 10-bis (n-hexyloxycarbonyloxy) anthracene, 2, 7-dimethyl-9, 10-bis (n-heptyloxycarbonyloxy) anthracene, 2, 7-dimethyl-9, 10-bis (n-octyloxycarbonyloxy) anthracene, 1, 5-dimethyl-9, 10-bis (methoxycarbonyloxy) anthracene, 1, 5-dimethyl-9, 10-bis (ethoxycarbonyloxy) anthracene, 1, 5-dimethyl-9, 10-bis (n-propoxycarbonyloxy) anthracene, 1, 5-dimethyl-9, 10-bis (isopropoxycarbonyloxy) anthracene, 1, 5-dimethyl-9, 10-bis (n-butoxycarbonyloxy) anthracene, 1, 5-dimethyl-9, 10-bis (isobutoxycarbonyloxy) anthracene, 1, 5-dimethyl-9, 10-bis (n-pentyloxycarbonyloxy) anthracene, 1, 5-dimethyl-9, 10-bis (isopentoxycarbonyloxy) anthracene, 1, 5-dimethyl-9, 10-bis (n-hexyloxycarbonyloxy) anthracene, 1, 5-dimethyl-9, 10-bis (n-heptyloxycarbonyloxy) anthracene, 1, 5-dimethyl-9, 10-bis (n-octyloxycarbonyloxy) anthracene, and the like.

Further, there may be mentioned 2, 3-diethyl-9, 10-bis (methoxycarbonyloxy) anthracene, 2, 3-diethyl-9, 10-bis (ethoxycarbonyloxy) anthracene, 2, 3-diethyl-9, 10-bis (n-propoxycarbonyloxy) anthracene, 2, 3-diethyl-9, 10-bis (isopropoxycarbonyloxy) anthracene, 2, 3-diethyl-9, 10-bis (n-butoxycarbonyloxy) anthracene, 2, 3-diethyl-9, 10-bis (isobutoxycarbonyloxy) anthracene, 2, 3-diethyl-9, 10-bis (n-pentyloxycarbonyloxy) anthracene, 2, 3-diethyl-9, 10-bis (isopentoxycarbonyloxy) anthracene, 2, 3-diethyl-9, 10-bis (n-hexyloxycarbonyloxy) anthracene, 2, 3-diethyl-9, 10-bis (n-heptyloxycarbonyloxy) anthracene, 2, 3-diethyl-9, 10-bis (n-octyloxycarbonyloxy) anthracene, 2, 6-diethyl-9, 10-bis (methoxycarbonyloxy) anthracene, 2, 6-diethyl-9, 10-bis (ethoxycarbonyloxy) anthracene, 2, 6-diethyl-9, 10-bis (n-propoxycarbonyloxy) anthracene, 2, 6-diethyl-9, 10-bis (isopropoxycarbonyloxy) anthracene, 2, 6-diethyl-9, 10-bis (n-butoxycarbonyloxy) anthracene, 2, 6-diethyl-9, 10-bis (isobutoxycarbonyloxy) anthracene, 2, 6-diethyl-9, 10-bis (n-pentyloxycarbonyloxy) anthracene, 2, 6-diethyl-9, 10-bis (isopentoxycarbonyloxy) anthracene, 2, 6-diethyl-9, 10-bis (n-hexyloxycarbonyloxy) anthracene, 2, 6-diethyl-9, 10-bis (n-heptyloxycarbonyloxy) anthracene, 2, 6-diethyl-9, 10-bis (n-octyloxycarbonyloxy) anthracene, 2, 7-diethyl-9, 10-bis (methoxycarbonyloxy) anthracene, 2, 7-diethyl-9, 10-bis (ethoxycarbonyloxy) anthracene, 2, 7-diethyl-9, 10-bis (n-propoxycarbonyloxy) anthracene, 2, 7-diethyl-9, 10-bis (isopropoxycarbonyloxy) anthracene, 2, 7-diethyl-9, 10-bis (n-butoxycarbonyloxy) anthracene, 2, 7-diethyl-9, 10-bis (isobutoxycarbonyloxy) anthracene, 2, 7-diethyl-9, 10-bis (n-pentyloxycarbonyloxy) anthracene, 2, 7-diethyl-9, 10-bis (isopentyloxycarbonyloxy) anthracene, 2, 7-diethyl-9, 10-bis (n-hexyloxycarbonyloxy) anthracene, 2, 7-diethyl-9, 10-bis (n-heptyloxycarbonyloxy) anthracene, 2, 7-diethyl-9, 10-bis (n-octyloxycarbonyloxy) anthracene, 1, 5-diethyl-9, 10-bis (methoxycarbonyloxy) anthracene, 1, 5-diethyl-9, 10-bis (ethoxycarbonyloxy) anthracene, 1, 5-diethyl-9, 10-bis (n-propoxycarbonyloxy) anthracene, 1, 5-diethyl-9, 10-bis (isopropoxycarbonyloxy) anthracene, 1, 5-diethyl-9, 10-bis (n-butoxycarbonyloxy) anthracene, 1, 5-diethyl-9, 10-bis (isobutoxycarbonyloxy) anthracene, 1, 5-diethyl-9, 10-bis (n-pentyloxycarbonyloxy) anthracene, 1, 5-diethyl-9, 10-bis (isopentoxycarbonyloxy) anthracene, 1, 5-diethyl-9, 10-bis (n-hexyloxycarbonyloxy) anthracene, 1, 5-diethyl-9, 10-bis (n-heptyloxycarbonyloxy) anthracene, 1, 5-diethyl-9, 10-bis (n-octyloxycarbonyloxy) anthracene, and the like.

(method for producing Compound having polycyclic aromatic skeleton represented by the general formula (4))

The compound having a polycyclic aromatic skeleton represented by the general formula (4),in the case of, for example, an anthracene compound, R¹、R²The 9, 10-dialkoxyanthracene compound which is an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms can be produced, for example, by the method described in Japanese patent laid-open No. 2003-104925. That is, the compound is produced by allowing an etherifying agent to act on a 9, 10-dihydroxyanthracene compound corresponding to a 9, 10-dialkoxyanthracene compound represented by general formula (2). In the compound having a polycyclic aromatic skeleton represented by the general formula (2), R¹、R²The 9, 10-bis (substituted acyloxy) anthracene compound which is an alkylcarbonyl group having an alkyl group having 1 to 10 carbon atoms or an arylcarbonyl group having an aryl group having 6 to 20 carbon atoms can be produced, for example, by the method described in Japanese patent application laid-open No. 2014-101442. That is, the compound is produced by allowing an acylating agent to act on a 9, 10-dihydroxyanthracene compound corresponding to a 9, 10-bis (substituted acyloxy) anthracene compound represented by general formula (2) in the presence of a basic compound. In addition, R¹、R²9, 10-bis (substituted carbonyloxy) anthracene compounds which are an alkyloxycarbonyl group having an alkyl group having 1 to 10 carbon atoms and an aryloxycarbonyl group having an aryl group having 6 to 20 carbon atoms can be produced, for example, by allowing a carbonating agent to act on a 9, 10-dihydroxyanthracene compound corresponding to a 9, 10-bis (substituted carbonyloxy) anthracene compound in the presence of a basic compound as described in Japanese patent laid-open Nos. 2011-42743 and 2014-70203.

After the completion of the above reaction, if necessary, unreacted raw materials, solvent and catalyst may be removed by washing, distillation under reduced pressure, filtration or a combination of 2 or more thereof, or may be separated and purified by column chromatography. When the product is a solid, or when crystals precipitate during concentration, the product may be recrystallized using a poor solvent such as alcohol or hexane, or directly dried to obtain crystals. When the product is a liquid, it may be dried as it is and purified by distillation or the like as necessary. Further, the internal peroxide may be used without purification or separation.

Next, a raw material for production of the general formula (5), that is, a compound having a polycyclic aromatic skeleton represented by the following general formula (6), will be described. In the general formula (2), when R is an alkyloxycarbonylmethyl group having an alkyl group having 1 to 12 carbon atoms or an aryloxycarbonylmethyl group having an aryl group having 6 to 12 carbon atoms, the compound is represented by the general formula (6).

[ solution 29]

In the general formula (6), T represents an alkylene group having 1 to 20 carbon atoms, which may have an alkyl branch; r³、R⁴Represents an alkyl group having 1 to 20 carbon atoms; y is¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

R in the general formula (6)³、R⁴、T、Y¹、Y²Specific examples of (3) and R illustrated in the general formula (5)³、R⁴、T、Y¹、Y²The same applies to specific examples of (1).

Next, specific examples of the compound having a polycyclic aromatic skeleton of the present invention represented by the general formula (6) will be given. Specific examples thereof include 9, 10-bis (methoxycarbonylmethylenoxy) anthracene, 9, 10-bis (ethoxycarbonylmethylenoxy) anthracene, 9, 10-bis (isopropoxycarbonylmethyloxy) anthracene, 9, 10-bis (tert-butoxycarbonylmethyloxy) anthracene, 9, 10-bis (n-butoxycarbonylmethyloxy) anthracene, 9, 10-bis (methoxycarbonylpropylenoxy) anthracene, 9, 10-bis (ethoxycarbonylpropylenoxy) anthracene, 9, 10-bis (isopropoxycarbonylpropylenoxy) anthracene, 9, 10-bis (tert-butoxycarbonylpropylenoxy) anthracene, 9, 10-bis (n-butoxycarbonylpropylenoxy) anthracene, 9, 10-bis (methoxycarbonylmethylmethyleneoxy) anthracene, 9, 10-bis (ethoxycarbonylmethylmethyleneoxy) anthracene, 9, 10-bis (ethoxycarbonylethylmethylmethylmethylmethylmethylenoxy) anthracene, 9, 10-bis (isopropoxycarbonylmethylmethylmethylmethylmethylenoxy) anthracene, 9, 10-bis (tert-butoxycarbonylmethylmethylmethylmethylmethylmethylmethylenoxy) anthracene, 9, 10-bis (methoxycarbonylbutyloxy) anthracene, 9, 10-bis (ethoxycarbonylbutyloxy) anthracene, 9, 10-bis (isopropoxycarbonylbutyloxy) anthracene, 9, 10-bis (tert-butoxycarbonylbutyloxy) anthracene, 9, 10-bis (n-butoxycarbonylbutyloxy) anthracene, and 9, 10-bis (n-butoxycarbonylbutyloxy) anthracene.

Further examples thereof include 9, 10-bis (methoxycarbonylpentyloxy) anthracene, 9, 10-bis (ethoxycarbonylpentyloxy) anthracene, 9, 10-bis (isopropoxycarbonylpentyloxy) anthracene, 9, 10-bis (tert-butoxycarbonylpentyloxy) anthracene, 9, 10-bis (n-butoxycarbonylpentyloxy) anthracene, 9, 10-bis (methoxycarbonylhexyloxy) anthracene, 9, 10-bis (ethoxycarbonylhexyloxy) anthracene, 9, 10-bis (isopropoxycarbonylhexyloxy) anthracene, 9, 10-bis (tert-butoxycarbonylhexyloxy) anthracene, 9, 10-bis (n-butoxycarbonylhexyloxy) anthracene, 9, 10-bis (methoxycarbonylheptyloxy) anthracene, 9, 10-bis (ethoxycarbonylheptyloxy) 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-butoxycarbonylnonyloxy) anthracene, 9, 10-bis (methoxycarbonyldecylenoxy) anthracene, 9, 10-bis (ethoxycarbonyldecylenoxy) anthracene, 9, 10-bis (isopropoxycarbonyldecylenoxy) anthracene, 9, 10-bis (tert-butoxycarbonyldecylenoxy) anthracene, 9, 10-bis (n-butoxycarbonyldecylenoxy) anthracene, 9, 10-bis (methoxycarbonylundecyloxy) anthracene, 9, 10-bis (ethoxycarbonylundecyloxy) anthracene, 9, 10-bis (isopropoxycarbonylundecyloxy) anthracene, 9, 10-bis (tert-butoxycarbonylundecyloxy) anthracene, 9, 10-bis (n-butoxycarbonylundecyloxy) anthracene, 9, 10-bis (methoxycarbonyldodecyloxy) anthracene, 9, 10-bis (ethoxycarbonyldodecyloxy) anthracene, 9, 10-bis (isopropoxycarbonyldodecyloxy) anthracene, 9, 10-bis (tert-butoxycarbonyldodecyloxy) anthracene, 9, 10-bis (n-butoxycarbonyldodecyloxy) anthracene, 9, 10-bis (methoxycarbonyltridecyloxy) anthracene, 9, 10-bis (ethoxycarbonyltridecyloxy) anthracene, 9, 10-bis (isopropoxycarbonyltridecyloxy) anthracene, 9, 10-bis (tert-butoxycarbonyltridecyloxy) anthracene, 9, 10-bis (n-butoxycarbonyltridecyloxy) anthracene, 9, 10-bis (methoxycarbonyltetradecyloxy) anthracene, 9, 10-bis (ethoxycarbonyltetradecyloxy) anthracene, 9, 10-bis (isopropoxycarbonyltetradecyloxy) anthracene, 9, 10-bis (tert-butoxycarbonyltetradecyloxy) anthracene, 9, 10-bis (n-butoxycarbonyltetradecyloxy) anthracene, 9, 10-bis (methoxycarbonylpentadecyloxy) anthracene, 9, 10-bis (ethoxycarbonylpentadecyloxy) anthracene, 9, 10-bis (isopropoxycarbonylpentadecyloxy) anthracene, 9, 10-bis (tert-butoxycarbonylpentadecyloxy) anthracene, 9, 10-bis (n-butoxycarbonylpentadecyloxy) anthracene, 9, 10-bis (methoxycarbonylhexadecyloxy) anthracene, 9, 10-bis (ethoxycarbonylhexadecyloxy) anthracene, 9, 10-bis (isopropoxycarbonylhexadecyloxy) anthracene, 9, 10-bis (tert-butoxycarbonylhexadecyloxy) anthracene, 9, 10-bis (n-butoxycarbonylhexadecyloxy) anthracene, 9, 10-bis (methoxycarbonylheptadecyloxy) anthracene, 9, 10-bis (ethoxycarbonylheptadecyloxy) anthracene, 9, 10-bis (isopropoxycarbonylheptadecyloxy) anthracene, 9, 10-bis (tert-butoxycarbonylheptadecyloxy) anthracene, 9, 10-bis (n-butoxycarbonylheptadecyloxy) anthracene, 9, 10-bis (methoxycarbonyloctadecyloxy) anthracene, 9, 10-bis (ethoxycarbonyloctadecyloxy) anthracene, 9, 10-bis (isopropoxycarbonyloctadecyloxy) anthracene, 9, 10-bis (tert-butoxycarbonyloctadecyloxy) anthracene, 9, 10-bis (n-butoxycarbonyloctadecyleneoxy) anthracene, 9, 10-bis (methoxycarbonylnonadecyleneoxy) anthracene, 9, 10-bis (ethoxycarbonylnonadecyleneoxy) anthracene, 9, 10-bis (isopropoxycarbonylnonadecyleneoxy) anthracene, 9, 10-bis (tert-butoxycarbonylnonadecyleneoxy) anthracene, 9, 10-bis (n-butoxycarbonylnonadecyleneoxy) anthracene, 9, 10-bis (methoxycarbonyleicosyleneoxy) anthracene, 9, 10-bis (ethoxycarbonyleicosyleneoxy) anthracene, 9, 10-bis (isopropoxycarbonyleicosyleneoxy) anthracene, 9, 10-bis (tert-butoxycarbonyleicosyleneoxy) anthracene, 9, 10-bis (n-butoxycarbonyleicosyleneoxy) anthracene, and the like.

In addition, as Y¹、Y²Specific examples of the alkyl group include, for example, 2-ethyl-9, 10-bis (methoxycarbonylmethylenoxy) anthracene, 2-ethyl-9, 10-bis (ethoxycarbonylmethyloxy) anthracene, 2-ethyl-9, 10-bis (isopropoxycarbonylmethyloxy) anthracene, 2-ethyl-9, 10-bis (tert-butoxycarbonylmethyloxy) anthracene, 2-ethyl-9, 10-bis (n-butoxycarbonylmethyloxy) anthracene, 2-ethyl-9, 10-bis (methoxycarbonylpropylenoxy) anthracene, 2-ethyl-9, 10-bis (ethoxycarbonylpropylenoxy) anthracene, 2-ethyl-9, 10-bis (isopropoxycarbonylpropylenoxy) anthracene, n-butyloxycarbonyl methylenoxy) anthracene, n-butyloxycarbonyl methyloxy (n-butyloxy) anthracene, n-butyloxycarbonyl (n-butyloxycarbonyl-methyloxy) anthracene, n-butyloxycarbonyl (n-butyloxy) anthracene, n-butyloxycarbonyl (n-butyloxy) anthracene, n-carbonyl (n-carbonylpropylenoxy) anthracene, n-carbonyl (n-carbonyl) anthracene, n-ethyl-9, n-carbonyl (n-carbonyl) anthracene, n-carbonyl (n-carbonyl) anthracene), n-carbonyl (n-carbonyl) anthracene, n-carbonyl (n-carbonyl) anthracene, n-methyl (n-methyl) and (n-methyl) anthracene), n-methyl) n-methyl (n-methyl) n, n-methyl) n-methyl (n-methyl) n-ethyl-methyl) n-9, n-ethyl-methyl) n-methyl (n-ethyl-9, n-methyl) n-methyl) n-ethyl-methyl) n-9, n-ethyl-methyl-9, n-ethyl-9, n-ethyl-9, n-ethyl-methyl-ethyl-n-ethyl-9, n-n, 2-ethyl-9, 10-bis (tert-butoxycarbonylpropylenoxy) anthracene, 2-ethyl-9, 10-bis (n-butoxycarbonylpropylenoxy) anthracene, and the like.

Further, 2-pentyl-9, 10-bis (methoxycarbonylmethylenoxy) anthracene, 2-pentyl-9, 10-bis (ethoxycarbonylmethylenoxy) anthracene, 2-pentyl-9, 10-bis (isopropoxycarbonylmethylenoxy) anthracene, 2-pentyl-9, 10-bis (tert-butoxycarbonylmethyloxy) anthracene, 2-pentyl-9, 10-bis (n-butoxycarbonylmethyloxy) anthracene, 2-pentyl-9, 10-bis (methoxycarbonylpropylenoxy) anthracene, 2-pentyl-9, 10-bis (ethoxycarbonylpropyleneoxy) anthracene, 2-pentyl-9, 10-bis (isopropoxycarbonylpropyleneoxy) anthracene, 10-bis (tert-butoxycarbonylpropyleneoxy) anthracene, 2-pentyl-9, 10-bis (n-butoxycarbonylpropyleneoxy) anthracene, and the like.

In addition, as Y¹、Y²Specific examples of the halogen atom include 2-chloro-9, 10-bis (methoxycarbonylmethylenoxy) anthracene, 2-chloro-9, 10-bis (ethoxycarbonylmethyloxy) anthracene, 2-chloro-9, 10-bis (isopropoxycarbonylmethyloxy) anthracene, 2-chloro-9, 10-bis (tert-butoxycarbonylmethyloxy) anthracene, 2-chloro-9, 10-bis (n-butoxycarbonylmethyloxy) anthracene, and 2-chloro-9, 10-bis (n-butoxycarbonylmethyloxy) anthraceneBis (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, and the like.

(method for producing Compound having polycyclic aromatic skeleton represented by the general formula (6))

The compound having a polycyclic aromatic skeleton represented by the above general formula (6) can be obtained by reacting a corresponding 9, 10-dihydroxyanthracene compound represented by the following general formula (7) with a halogenated ester compound such as methyl chloroacetate, ethyl chloroacetate, n-propyl chloroacetate, isopropyl chloroacetate, n-butyl chloroacetate, methyl bromoacetate, ethyl bromoacetate, n-propyl bromoacetate, isopropyl bromoacetate, n-butyl bromoacetate, t-butyl bromoacetate, methyl 2-bromopropionate, or ethyl 4-bromobutyrate, in the presence of a basic compound.

[ solution 30]

In the general formula (7), Y¹、Y²Represents any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

The amount of the halogenated ester compound to be used is preferably 2.0 times by mole or more and less than 10.0 times by mole, and more preferably 2.2 times by mole or more and less than 5.0 times by mole, based on the 9, 10-dihydroxyanthracene compound. If the amount is less than 2.0 times by mole, the reaction cannot be completed, and if the amount is 10.0 times by mole or more, side reactions occur and the yield and purity are lowered, which is not preferable.

Examples of the basic compound to be used include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, lithium hexamethyldisilazane, lithium diisopropylamide, triethylamine, tributylamine, trihexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dimethylaniline, pyridine, 4-dimethylaminopyridine, piperidine, γ -methylpyridine, and lutidine.

The amount of the basic compound to be added is preferably 2.0 times by mole or more and less than 10.0 times by mole, and more preferably 2.2 times by mole or more and less than 5.0 times by mole, based on the 9, 10-dihydroxyanthracene compound. If the amount is less than 2.0 times by mole, the reaction cannot be completed, and if the amount is 10.0 times by mole or more, side reactions occur and the yield and purity are lowered, which is not preferable.

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

When the 9, 10-dihydroxyanthracene compound is dissolved in an aqueous solution of an inorganic base to react 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, trioctylbutylammonium bromide, benzyldimethyloctadecylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, trioctylmethylammonium chloride, trioctylethylammonium chloride, trioctylpropylammonium chloride, trioctylbutylammonium chloride, and benzyldimethyloctadecylammonium chloride.

The amount of the phase transfer catalyst to be added is preferably 0.01 times by mole or more and less than 1.0 times by mole, and more preferably 0.05 times by mole or more and less than 0.5 times by mole, based on the 9, 10-dihydroxyanthracene compound. When the amount is less than 0.01 times by mol, the reaction rate is slow, and when the amount is 1.0 times by mol or more, the purity of the product is lowered, which is not preferable.

The reaction temperature of the reaction is usually 0 ℃ to 200 ℃, preferably 10 ℃ to 100 ℃. When the temperature is less than 0 ℃ and the reaction time is too long, the impurities increase and the purity of the objective compound decreases when the temperature is heated to more than 100 ℃, which is not preferable.

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

After the completion of the reaction, if necessary, unreacted raw materials, solvents and catalysts are removed by washing, distillation under reduced pressure, filtration or other operations alone or a combination of 2 or more thereof. The extract may be purified by column chromatography. When the product is a solid, crystals precipitate during the reaction, and therefore, solid-liquid separation is performed by filtration, and the product is recrystallized in a poor solvent such as alcohol or hexane as necessary. Or may be directly dried to obtain crystals. When the product is a liquid, it may be dried as it is and, if necessary, purified by distillation or the like to obtain a compound having a polycyclic aromatic skeleton represented by the general formula (6).

In the reaction of singlet oxygen with a compound having a polycyclic aromatic skeleton, it is known that the ring of the compound having a polycyclic aromatic skeleton acts as a diene, and the 1, 4-or 9, 10-position reacts with singlet oxygen to form an endoperoxide. Further, singlet oxygen exhibits electron-withdrawing behavior and is therefore rich in reactivity with an electron-rich substrate. Accordingly, the compound having a polycyclic aromatic skeleton used as a reaction raw material is preferably substituted with an electron donating group on the aromatic ring, and is preferably structured to have an electron donating group on the ring at the reaction position. In this sense, the compound having a polycyclic aromatic skeleton of the present invention substituted with an alkoxy group is more reactive with singlet oxygen than the compound having an alkyl group substituted on an anthracene ring, and thus is preferable.

(method for producing endoperoxide compound having polycyclic aromatic skeleton)

The endoperoxide compound having a polycyclic aromatic skeleton represented by the general formulae (1), (3) and (5) of the present invention is produced by reacting the corresponding compounds having a polycyclic aromatic skeleton represented by the general formulae (2), (4) and (6) with molecular oxygen under irradiation with light having a peak wavelength in a wavelength range of 300nm to 410 nm.

The compounds having a polycyclic aromatic skeleton represented by the general formulae (2), (4) and (6) of the present invention can be produced by, for example, dissolving the compounds having a polycyclic aromatic skeleton represented by the general formulae (1), (3) and (5) in a solvent, irradiating the solution with light having a peak wavelength in a wavelength range of 300nm to 410nm, and reacting the light with oxygen dissolved in the solution.

The reaction solvent may be any solvent as long as it dissolves the compound having a polycyclic aromatic skeleton and does not react with the generated endoperoxide, and ketone solvents such as acetone and methyl isobutyl ketone, ether solvents such as tetrahydrofuran, halogenated hydrocarbons such as methylene chloride, organic acid ester solvents such as ethyl acetate and butyl acetate, amide solvents such as N, N-dimethylformamide, and aromatic hydrocarbon solvents such as benzene and toluene can be used.

In addition, when the endoperoxide is used as a radical polymerization initiator after the endoperoxide is produced, a radical polymerizable compound may be used as a solvent. Examples of the radical polymerizable compound usable in the present invention include styrene, methylstyrene, divinylbenzene, p-hydroxystyrene, vinyl acetate, (meth) acrylic acid, acrylonitrile, methacrylonitrile, acrylamide, (meth) acrylate, fumarate, and the like, or oligomers thereof.

The reaction concentration also depends on the solvent and/or the radical polymerizable compound used, and the compound having a polycyclic aromatic skeleton is added in the range of 0.01 to 10 parts by weight relative to 100 parts by weight of the solvent and/or the radical polymerizable compound. Preferably in the range of 0.05 to 5 parts by weight, more preferably in the range of 0.1 to 3 parts by weight

The reaction temperature is also dependent on the endoperoxide compound having a polycyclic aromatic skeleton used and is carried out at a temperature ranging from-20 ℃ to 150 ℃. Preferably at 0 ℃ to 120 ℃.

Under stirring, the compound having a polycyclic aromatic skeleton dissolved in the solvent is irradiated with light having a peak wavelength in a wavelength range of 300nm to 410 nm. At this time, oxygen or air may be blown into the solution. Further, by irradiating the solution with light in the form of a film, the efficiency of contact with air on the surface of the solution can be improved, and the reaction can be performed without stirring or blowing air.

The intensity of light having a peak wavelength in a wavelength range of 300nm to 410nm may be 1 to 2000mW/cm²Left and right. The irradiation time also depends on the intensity of the light and may be from about 0.1 second to about 120 minutes.

As an irradiation source for irradiating light having a peak wavelength in a wavelength range of 300nm to 410nm, an ultraviolet LED having a central wavelength of 405nm, an ultraviolet LED having a central wavelength of 395nm, an ultraviolet LED having a central wavelength of 385nm, an ultraviolet LED having a central wavelength of 375nm, and an ultraviolet LED having a central wavelength of 365nm are preferable, but any lamp having an emission spectrum of 300nm to 410nm may be used, and an electrodeless lamp such as a laser, a D-tube manufactured by fuder, a V-tube, a xenon lamp, a black light lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a gallium-doped lamp, and the like may be used. In addition, curing may be performed by sunlight. In particular, when the compound having a polycyclic aromatic skeleton of the present invention is an anthracene compound, 385nm, 395nm, 405nm ultraviolet LEDs and 405nm lasers that emit light having a wavelength close to the absorption wavelength thereof are preferable.

The mechanism of formation of the endoperoxide compound having a polycyclic aromatic skeleton in the present invention is not yet determined, but it is considered that the compound having a polycyclic aromatic skeleton acts as a singlet oxygen generator. That is, the compound having a polycyclic aromatic skeleton absorbs irradiation light to become an excited state, and the excited state becomes a triplet excited state by intersystem crossing. It is considered that a triplet-triplet energy transfer reaction (triplet-triplet annihilation reaction) occurs between the triplet excited state and the triplet oxygen in the ground state of the compound having a polycyclic aromatic skeleton, and the compound having a polycyclic aromatic skeleton in the ground state and singlet oxygen are generated. It is considered that the ground-state compound having a polycyclic aromatic skeleton acts as a singlet oxygen scavenger for the singlet oxygen generated by the reaction. That is, it is considered that singlet oxygen reacts with an electron-rich diene structure of a compound having a polycyclic aromatic skeleton to generate an endoperoxide compound having a polycyclic aromatic skeleton.

In the reaction solution of the compound having a polycyclic aromatic skeleton, a singlet oxygen generating agent other than the compound having a polycyclic aromatic skeleton may be further coexistent and reacted as long as the effect of the present invention is not impaired. In the present invention, the compound having a polycyclic aromatic skeleton is used as a reaction reagent with singlet oxygen (singlet oxygen scavenger), but at the same time, it also functions as a singlet oxygen generator for generating singlet oxygen. In this reaction, a singlet oxygen generating agent other than the compound having a polycyclic aromatic skeleton may be present in order to further improve the efficiency of generation of singlet oxygen.

(singlet oxygen generators other than compounds having polycyclic aromatic skeleton)

Examples of singlet oxygen generators other than the compounds having polycyclic aromatic skeletons that can coexist include rose bengal, methylene blue, azurophil a, various porphyrins and metalloporphyrins (for example, zinc tetrahydroxyphenyl porphyrin, zinc tetracarboxylphenyl porphyrin, zinc uroporphyrin, zinc protoporphyrin, tetrasulfonated phenyl porphyrin Zn, tetramethylpyridinium porphyrin Zn, hematoporphyrin Zn, etc.), various phthalocyanines and metallophthalocyanines, luciferin such as thioxanthone, eosin Y, etc.

The amount of the singlet oxygen generating agent other than the compound having a polycyclic aromatic skeleton added is in the range of 1 to 200 parts by weight per 100 parts by weight of the compound having a polycyclic aromatic skeleton.

When a singlet oxygen generating agent other than the compound having a polycyclic aromatic skeleton is used, light having a wavelength most suitable for the singlet oxygen generating agent, for example, light having a longer wavelength such as 530nm may be added to the light used for the reaction in addition to light having a peak wavelength in a wavelength range of 300nm to 410 nm.

The compound having a polycyclic aromatic skeleton of the present invention may be used alone or in combination of 2 or more. For example, compounds of formula (2) and formula (4) may be used in combination.

After the completion of the above reaction, if necessary, the endoperoxide compound having a polycyclic aromatic skeleton formed in the solvent may be removed by an operation such as washing, distillation under reduced pressure, filtration or a combination of 2 or more of them, or may be separated and purified by column chromatography. When the product is a solid, it is crystallized during concentration, and thus, it can be recrystallized using a poor solvent such as alcohol or hexane, or directly dried to obtain crystals. When the product is a liquid, it may be dried as it is and purified as necessary. Further, it may be used as it is as a radical polymerization initiator without purification or isolation.

(first method of curing radical polymerizable composition)

The radical polymerizable composition can be prepared by adding the endoperoxide compound having a polycyclic aromatic skeleton of the present invention as a radical polymerization initiator to a radical polymerizable compound.

(photo radical polymerization initiator)

The endoperoxide compound having a polycyclic aromatic skeleton of the present invention is excited by irradiation with light having a specific wavelength range, and the excited substance becomes a radical substance having an ability to initiate radical polymerization of a radical polymerizable compound, and functions as a photo radical polymerization initiator for initiating radical polymerization of a radical polymerizable compound.

(thermal radical polymerization initiator)

The endoperoxide compound having a polycyclic aromatic skeleton of the present invention generates a radical species by thermal decomposition, and functions as a thermal radical polymerization initiator for initiating radical polymerization of a radical polymerizable compound.

(radical polymerizable Compound)

Examples of the radical polymerizable compound usable in the present invention include styrene, methylstyrene, divinylbenzene, p-hydroxystyrene, vinyl acetate, (meth) acrylic acid, acrylonitrile, methacrylonitrile, acrylamide, (meth) acrylate, fumarate, and the like, or oligomers thereof.

Specific examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, adamantane (meth) acrylate, 3-hydroxy-1-adamantane (meth) acrylate, 1-methyladamantane (meth) acrylate, 1-ethyladamantane (meth) acrylate, and mixtures thereof, 3, 5-dihydroxy-1-adamantane (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, methylphenoxyethyl (meth) acrylate, m-phenoxybenzyl (meth) acrylate, ethyl carbitol (meth) acrylate, methoxytriethylene (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-ethylhexyl diethylene glycol (meth) acrylate, n-butyl (meth) acrylate, phenoxyethyl (meth) acrylate, methylphenoxy ethyl (meth) acrylate, n-phenoxyethyl carbitol (meth) acrylate, n-butyl acrylate, n-2-acrylate, n-butyl acrylate, n-2-butyl acrylate, n-butyl acrylate, n-butyl acrylate, n-2-acrylate, n-butyl acrylate, n-2-butyl acrylate, n-2-acrylate, n-acrylate, Methoxy-dipropylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1, 4-cyclohexanedimethanol (meth) acrylate, glycerol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol-polytetramethylene glycol (meth) acrylate, polypropylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol-polytetramethylene glycol (meth) acrylate, polypropylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol-polypropylene glycol acrylate, polypropylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (propylene glycol-polypropylene glycol acrylate, polypropylene glycol-polypropylene glycol (polypropylene glycol-polypropylene glycol, polypropylene glycol-polypropylene glycol (propylene glycol copolymer, polypropylene glycol-polypropylene glycol copolymer, polypropylene glycol, Polyethylene glycol-polybutylene glycol (meth) acrylate, ethoxylated-o-phenylphenol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate (functional acrylate FA-314A, FA-318A manufactured by Hitachi chemical Co., Ltd.), octyloxypolyethylene glycol-polypropylene glycol (meth) acrylate, lauroxypolyethylene glycol (meth) acrylate, stearyloxypolyethylene glycol (meth) acrylate, phenoxy-polyethylene glycol-polypropylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol-polypropylene glycol (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, octylene glycol-polypropylene glycol (meth) acrylate, lauroxypolyethylene glycol (meth) acrylate, octylene glycol-polypropylene glycol (meth) acrylate, and the like, 2- (2-ethyleneoxyethoxy) ethyl (meth) acrylate, allyloxypolyethylene glycol-polypropylene glycol (meth) acrylate, undecoxy polyethylene glycol (meth) acrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tricyclo [5,2,1,02,6] decane dimethanol diacrylate, isobornyl methacrylate, epoxy acrylate, urethane acrylate, polyester acrylate, polybutadiene acrylate, polyol acrylate, polyether acrylate, silicone resin acrylate, imide acrylate, and the like.

Further, an unsaturated monomer having a bisphenol skeleton may be mentioned. Specific examples thereof include ethylene oxide-added bisphenol a (meth) acrylate, ethylene oxide-added tetrabromobisphenol a (meth) acrylate, propylene oxide-added bisphenol a (meth) acrylate, and propylene oxide-added tetrabromobisphenol a (meth) acrylate. Commercially available products of unsaturated monomers having such a structure include Biscoat #700, #540 (see above, manufactured by Osaka organic chemical Co., Ltd.), Aronix M-208, M-210 (see above, manufactured by Toyo chemical Co., Ltd.), NK ESTER BPE-100, BPE-200, BPE-500, and A-BPE-4 (see above, manufactured by Ninghamu chemical Co., Ltd.).

Examples of the fumarate compound include fumaric acid monoester compounds such as monomethyl fumarate, monoethyl fumarate, mono-n-propyl fumarate, dimonoisopropyl fumarate, mono-n-butyl fumarate, monoisobutyl fumarate, mono-tert-butyl fumarate, mono-n-pentyl fumarate, monoisopropyl fumarate, mono-n-hexyl fumarate, mono-n-heptyl fumarate, mono-n-octyl fumarate, and mono-2-ethylhexyl fumarate. Further, there may be mentioned fumaric acid diester compounds such as dimethyl fumarate, diethyl fumarate, di-n-propyl fumarate, diisopropyl fumarate, di-n-butyl fumarate, diisobutyl fumarate, di-t-butyl fumarate, di-n-pentyl fumarate, diisopentyl fumarate, di-n-hexyl fumarate, di-n-heptyl fumarate, di-n-octyl fumarate, bis (2-ethylhexyl) fumarate, ethylmethyl fumarate, ethyl-n-propyl fumarate, ethylisopropyl fumarate, ethyl-n-butyl fumarate, ethylisobutyl fumarate, ethyl-t-butyl fumarate, ethyl-n-pentyl fumarate, ethylisopropyl fumarate, ethyl-n-hexyl fumarate, ethyl-n-heptyl fumarate, ethyl-n-octyl fumarate and ethyl- (2-ethylhexyl) fumarate.

Among the above-mentioned radical polymerizable compounds, (meth) acrylic acid, (meth) acrylate, fumarate, styrene, or an oligomer thereof is preferable.

In the radical polymerizable composition of the present invention, the amount of the endoperoxide compound having a polycyclic aromatic skeleton of the present invention added is 0.01% by weight or more and less than 3.0% by weight, preferably 0.05% by weight or more and less than 1.0% by weight, based on the radical polymerizable compound. When the amount is less than 0.01 wt%, the curing rate may be lowered, while when the amount is 3.0 wt% or more, the physical properties of the cured product may be deteriorated, which is not preferable.

(curing method)

A method for radical-polymerizing the radical polymerizable composition of the present invention will be described.

(photo radical polymerization)

First, a case where the initiation energy of radical polymerization is light will be described. The radical polymerizable composition of the present invention can be polymerized and cured by irradiating light having a specific wavelength range.

The polymerization of the radical polymerizable composition may be carried out in the form of a film or may be cured into a block. When the polymerization is in the form of a film, the radical polymerizable composition is brought into a liquid state, and the radical polymerizable composition is applied to a substrate such as a polyester film or an adhesive film using, for example, a bar coater, and polymerized by irradiation with light having a specific wavelength range.

(coating)

As the substrate used when the polymerization is in the form of a film, paper, aluminum foil, metal, or the like is mainly used, but not particularly limited. As a material for the film as a substrate, polyester, triacetyl cellulose (TAC), polyvinyl alcohol (PVA), or the like is used. The thickness of the base film is generally less than 100. mu.m. The bar coater used for adjusting the film thickness of the coating film obtained by applying the radical polymerizable composition is not particularly specified, but a bar coater capable of adjusting the film thickness to 1 μm or more and less than 100 μm is used. On the other hand, a thinner film thickness or a thicker film thickness can be applied by a spin coating method or a screen printing method.

(irradiation source)

Irradiating an energy ray comprising light (the light comprising a wavelength range of 230nm to 330 nm) at 1 to 2000mW/cm²The coating film of the radical polymerizable composition thus prepared was irradiated with light at an intensity of about one hundred eighths (five) degrees, whereby a photo-cured product was obtained. As the irradiation source used, any irradiation source can be used as long as it can irradiate light including a wavelength range of 230nm to 330 nm. For example, a high-pressure mercury lamp, a low-pressure mercury lamp, an excimer lamp, a deep uv lamp, or the like can be used.

The temperature at which the radical polymerizable composition of the present invention is irradiated with light energy is not problematic at room temperature, but it is also effective to heat the radical polymerizable composition in advance because the endoperoxide compound having a polycyclic aromatic skeleton of the present invention also functions as a thermal radical polymerization initiator. In the case of heating, the preferred temperature is 30 ℃ to 150 ℃. Particularly preferably from 50 ℃ to 130 ℃. By heating the radical polymerizable composition in advance, decomposition of the endoperoxide compound having a polycyclic aromatic skeleton can be promoted, and curing can be accelerated.

The heating treatment may be performed by a hot plate or the like, or may be performed by a halogen heater or a hot air heater.

The infrared irradiation may be performed simultaneously with or instead of the heat treatment. The infrared rays to be irradiated may be either near infrared rays or far infrared rays. In terms of efficiently initiating decomposition of peroxide internally, infrared irradiation is preferred over external heating. In addition, a microwave heating apparatus may be used which vibrates structural molecules in the system by microwave irradiation and utilizes frictional heat thereof. The frequency is mainly 2.45GHz or 915 MHz.

Further, a photo radical polymerization sensitizer for accelerating decomposition of the generated endoperoxide and curing may be further added to the radical polymerizable composition of the present invention as long as the effect of the present invention is not impaired. The effect as a photo radical polymerization sensitizer is: the photo radical polymerization sensitizer is first excited by the irradiated light, and the excitation energy thereof is transferred to the endoperoxide compound having a polycyclic aromatic skeleton, thereby promoting the decomposition of the endoperoxide compound having a polycyclic aromatic skeleton. As the photo radical polymerization sensitizer, a thioxanthone compound or the like can be used. Further, a compound having a polycyclic aromatic skeleton, which is a raw material for producing the endoperoxide compound having a polycyclic aromatic skeleton of the present invention, may be used. Further, the compound having a polycyclic aromatic skeleton which remains without being reacted in the production of the endoperoxide compound having a polycyclic aromatic skeleton may be used as it is as a photo radical polymerization sensitizer without separation.

Examples of thioxanthones that can be added include thioxanthone, 2-chlorothioxanthone, 2, 4-diethylthioxanthone, and 2, 4-diisopropylthioxanthone.

When the compound having a polycyclic aromatic skeleton, which is a raw material for producing the endoperoxide compound having a polycyclic aromatic skeleton of the present invention, is used as the photo radical polymerization sensitizer, the compound having a polycyclic aromatic skeleton of the general formula (6) is particularly preferably used. It is considered that the compound having a polycyclic aromatic skeleton of the general formula (6) has a specific ester group structure in its structure, and the compound having a polycyclic aromatic skeleton of the general formula (6) is more resistant to migration and blooming during curing or storage of a cured product and less likely to cause a problem of dusting and coloring of a cured product than the compound having a polycyclic aromatic skeleton of the general formula (4) and the thioxanthone compound, and therefore the compound having a polycyclic aromatic skeleton of the general formula (6) is particularly preferable.

The irradiation wavelength of light for curing the radical polymerizable composition may be made to coincide with the absorption wavelength of the photo radical polymerization sensitizer depending on the photo radical polymerization sensitizer used. In addition, 2 wavelengths of light may be irradiated: light of absorption wavelength of the photo radical polymerization sensitizer and light of wavelength of 230nm to 330 nm. For example, when the compound having a polycyclic aromatic skeleton or the thioxanthone compound of the present invention is used, a wavelength of 300nm to 410nm is used as the absorption wavelength of the photo radical polymerization sensitizer. As the irradiation source to be used, an ultraviolet LED having a light of 405nm as a center wavelength, an ultraviolet LED having a light of 395nm as a center wavelength, an ultraviolet LED having a light of 385nm as a center wavelength, an ultraviolet LED having a light of 375nm as a center wavelength, and an ultraviolet LED having a light of 365nm as a center wavelength are preferable, but any lamp having an emission spectrum at a wavelength of 300nm to 410nm may be used, and electrodeless lamps such as D-tubes and V-tubes manufactured by fuding corporation, xenon lamps, black lamps, ultra-high pressure mercury lamps, metal halide lamps, gallium-doped lamps, lasers, and the like may be used. In addition, curing may be performed by sunlight. 385nm, 395nm, 405nm ultraviolet LED, 405nm laser are particularly preferred.

When light of 405nm is used, formula(4) Among the compounds of (1), R¹、R²The compound having a polycyclic aromatic skeleton which is an alkyl group having 1 to 10 carbon atoms, an alkoxymethyl group having an alkoxy group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms or the compound having a polycyclic aromatic skeleton of the general formula (6) is preferable because it has strong ultraviolet absorption in the vicinity of 405 nm.

Furthermore, a reducing agent may be added as a decomposition accelerator for accelerating decomposition of the endoperoxide and accelerating curing. Examples of the reducing agent include transition metals such as iron and cobalt, amines such as dimethylaniline, and phosphines such as triphenylphosphine.

(thermal radical polymerization)

Next, a case where the initiation energy of radical polymerization is heat will be described. The radical polymerizable composition of the present invention can be polymerized and cured by heating to a predetermined temperature.

The polymerization of the radical polymerizable composition may be carried out in the form of a film or may be cured into a block. When the polymerization is a film, the radical polymerizable composition is made into a liquid state, and is applied to a substrate such as a polyester film or an adhesive film by using, for example, a bar coater or the like in the same manner as in the case of photo radical polymerization, and is heated and polymerized.

As a heating method, heating may be performed with a hot plate or the like, or a halogen heater or a hot air heater may be used. The heating temperature is preferably 30 ℃ to 150 ℃. Generally, an endoperoxide compound that is an anthracene skeleton is more stable to heat and requires a higher reaction temperature than an endoperoxide compound whose polycyclic aromatic skeleton is a naphthalene skeleton. For example, an endoperoxide compound having a naphthalene skeleton is carried out at a reaction temperature of about 40 ℃ as compared with an endoperoxide compound having an anthracene skeleton which is carried out at a reaction temperature of 100 ℃ or higher.

The infrared irradiation may be performed simultaneously with or instead of the heat treatment. The infrared rays to be irradiated may be either near infrared rays or far infrared rays. In order to efficiently initiate decomposition of the peroxide in the interior, infrared irradiation is preferred over external heating. Further, a microwave heating device may be used which vibrates structural molecules in the reaction system by microwave irradiation and utilizes frictional heat thereof. The frequency is mainly 2.45GHz or 915 MHz.

Further, an endoperoxide decomposition accelerator may be added. Examples of such a decomposition accelerator include transition metals such as iron and cobalt, for example, organic metal salts such as zinc naphthenate, cobalt naphthenate, stannous octoate, cobalt (II) bisacetylacetonate and cobalt (III) triacetylacetonate, imidazoles and derivatives thereof, organic phosphorus compounds such as phosphines and phosphonium salts such as triphenylphosphine, secondary amines and tertiary amines such as dimethylaniline, quaternary ammonium salts, and 1 kind or 2 or more kinds of these may be used alone or in combination.

The decomposition accelerator is a reducing agent, and among the reducing agents, a reducing agent having an oxidation-reduction potential of-0.2V or less is preferable, and transition metals having an oxidation-reduction potential of-0.5V or less are particularly preferable. By adding the decomposition accelerator, the polymerization initiation temperature can be lowered.

(curing method of radically polymerizable composition II)

One of the methods for curing the radically polymerizable composition of the present invention is a method of adding the endoperoxide compound having a polycyclic aromatic skeleton of the present invention as a radical polymerization initiator to the radically polymerizable compound as described above, and the radically polymerizable compound may be polymerized and cured while the endoperoxide compound having a polycyclic aromatic skeleton is produced in the radically polymerizable composition.

Namely, the following curing method: the radical polymerizable composition containing a compound having a polycyclic aromatic skeleton and a radical polymerizable compound is irradiated with ultraviolet rays in the presence of oxygen to produce a endoperoxide compound having a polycyclic aromatic skeleton, and the endoperoxide compound having a polycyclic aromatic skeleton is subjected to a radical polymerization reaction of the radical polymerizable compound with a radical polymerization initiator.

According to the present curing method, since the compound having a polycyclic aromatic skeleton converts oxygen present in the system into singlet oxygen and reacts with the singlet oxygen to become an initiator by itself, the compound can be polymerized in the presence of oxygen, that is, can be subjected to radical polymerization without being inhibited by oxygen.

Further, in the case of the second method for curing a radical polymerizable composition, it is preferable that the compound having a polycyclic aromatic skeleton, which is a raw material of the endoperoxide having a polycyclic aromatic skeleton, also functions as a radical polymerization sensitizer to accelerate decomposition of the radical polymerization initiator and further increase the polymerization rate.

In general, an anthracene compound is known to have an effect of inhibiting radical polymerization, but unlike anthracene, a 9, 10-dialkylanthracene compound, and the like, a compound having a polycyclic aromatic skeleton used as a raw material of the present invention has a remarkably low radical inhibiting effect under light irradiation, and does not inhibit radical polymerization even if it remains in a radical polymerizable composition. In particular, the compound having a polycyclic aromatic skeleton represented by the general formula (6) is preferable because the inhibitory effect is remarkably low.

In the curing method of the present invention, as the compound having a polycyclic aromatic skeleton, a single compound may be used, or 2 or more compounds having a polycyclic aromatic skeleton of the present invention may be used in combination.

In the second curing method, the curing may be carried out in the form of a bulk, but is preferably carried out in the form of a film or a film. The radical polymerizable composition is made into a liquid state, and for example, the radical polymerizable composition is applied to a substrate such as a polyester film or an adhesive film using a bar coater or the like, and polymerized by irradiation with light having a specific wavelength range. The coating method may be the same as the curing method.

In the second curing method, it is necessary to irradiate light having a wavelength capable of exciting the compound having a polycyclic aromatic skeleton, that is, 300nm to 410 nm. As the irradiation source to be used, an ultraviolet LED having a light of 405nm as a center wavelength, an ultraviolet LED having a light of 395nm as a center wavelength, an ultraviolet LED having a light of 385nm as a center wavelength, an ultraviolet LED having a light of 375nm as a center wavelength, and an ultraviolet LED having a light of 365nm as a center wavelength are preferable, but as long as the irradiation source is a lamp having an emission spectrum at a wavelength of 300nm to 410nm, a laser, a D-tube manufactured by fuding corporation, a electrodeless lamp such as a V-tube, a xenon lamp, a black light lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a gallium-doped lamp, or the like may be used. In addition, curing may be performed by sunlight. 385nm, 395nm, 405nm ultraviolet LED, 405nm laser are particularly preferred.

(atmosphere)

In the second curing method, the curing is carried out in the presence of oxygen to generate singlet oxygen. The presence of oxygen means that oxygen is not positively removed, and means that the atmosphere is not replaced with an atmosphere such as nitrogen or helium. Conversely, air or oxygen may be actively blown in.

Specifically, the surface of the radical polymerizable composition may be in contact with air. Even if the surface of the radical polymerizable composition is covered with a film, oxygen may be sufficiently dissolved in the radical polymerizable composition.

In the second curing method, the generated endoperoxide compound having a polycyclic aromatic skeleton uses light energy and/or heat energy as energy in decomposition, but when light energy is used, the remaining compound having a polycyclic aromatic skeleton absorbs light energy, and the light energy migrates to the endoperoxide compound having a polycyclic aromatic skeleton, and the endoperoxide compound having a polycyclic aromatic skeleton can be decomposed to generate a radical polymerization initiator substance. Thus, the wavelength of the light irradiated in the second curing method can polymerize and cure the radical polymerizable composition as long as the light has a wavelength that excites the compound having a polycyclic aromatic skeleton.

Thus, in this curing method, it is not necessary to add a new photo radical polymerization sensitizer, but a photo radical polymerization sensitizer other than the compound having a polycyclic aromatic skeleton, for example, thioxanthone, may be added as long as the effect of the present invention is not impaired.

Examples of thioxanthones that can be added include thioxanthone, 2-chlorothioxanthone, 2, 4-diethylthioxanthone, and 2, 4-diisopropylthioxanthone.

Further, in the radical polymerizable composition used in the curing method 2, a singlet oxygen generator other than the compound having a polycyclic aromatic skeleton may be caused to coexist and react, as long as the effect of the present invention is not impaired. In the present invention, the compound having a polycyclic aromatic skeleton is used as a reactive agent (singlet oxygen scavenger) for reacting with singlet oxygen, but at the same time, it also functions as a singlet oxygen generator for generating singlet oxygen. In this reaction, a singlet oxygen generating agent other than the compound having a polycyclic aromatic skeleton may be present in order to further improve the efficiency of generation of singlet oxygen.

(singlet oxygen generators other than compounds having polycyclic aromatic skeleton)

Examples of singlet oxygen generators other than the compounds having polycyclic aromatic skeletons that can coexist include rose bengal, methylene blue, azurophil a, various porphyrins and metalloporphyrins (for example, zinc tetrahydroxyphenyl porphyrin, zinc tetracarboxylphenyl porphyrin, zinc uroporphyrin, zinc protoporphyrin, tetrasulfonated phenyl porphyrin Zn, tetramethylpyridinium porphyrin Zn, hematoporphyrin Zn, etc.), various phthalocyanines and metallophthalocyanines, luciferin such as thioxanthone, eosin Y, etc.

The temperature at which the radical polymerizable composition of the present invention is irradiated with light energy is not problematic at room temperature, but it is also effective to heat the radical polymerizable composition in advance because the endoperoxide compound having a polycyclic aromatic skeleton of the present invention also functions as a thermal radical polymerization initiator. In the case of heating, the preferred temperature is 30 ℃ to 150 ℃. Particularly preferably from 50 ℃ to 130 ℃. By heating the radical polymerizable composition in advance, decomposition of the endoperoxide compound having a polycyclic aromatic skeleton can be promoted, and curing can be accelerated.

The heating treatment may be performed by a hot plate or the like, or may be performed by a halogen heater or a hot air heater.

The infrared irradiation may be performed simultaneously with or instead of the heat treatment. The infrared rays to be irradiated may be either near infrared rays or far infrared rays. In terms of efficiently initiating decomposition of peroxide internally, infrared irradiation is preferred over external heating. In addition, a microwave heating apparatus may be used which vibrates structural molecules in the system by microwave irradiation and utilizes frictional heat thereof. The frequency is mainly 2.45GHz or 915 MHz.

Further, an endoperoxide decomposition accelerator may be added. Examples of such a decomposition accelerator include transition metals such as iron and cobalt, for example, organic metal salts such as zinc naphthenate, cobalt naphthenate, stannous octoate, cobalt (II) bisacetylacetonate and cobalt (III) triacetylacetonate, imidazoles and derivatives thereof, organic phosphorus compounds such as phosphines and phosphonium salts such as triphenylphosphine, secondary amines and tertiary amines such as dimethylaniline, quaternary ammonium salts, and 1 kind or 2 or more kinds of these may be used alone or in combination.

The decomposition accelerator is a reducing agent, and among the reducing agents, a reducing agent having an oxidation-reduction potential of-0.2V or less is preferable, and transition metals having an oxidation-reduction potential of-0.5V or less are particularly preferable.

In addition, the first and second curing methods of the present invention are characterized in that the polymerization can be carried out without using a conventional photo radical polymerization initiator, but a conventional photo radical polymerization initiator may be used together as long as the effects of the present invention are not impaired. In the second curing method of the present invention, since oxygen is excited to singlet oxygen, oxygen inhibition does not occur even when a conventionally used photo radical polymerization initiator is used.

Examples of a conventional photo radical polymerization initiator include benzoin compounds, acetophenones, benzophenones, thioxanthones, α -acyloxime esters, glyoxylic acid phenyl esters, benzils, azo compounds, diphenyl sulfide compounds, acylphosphine oxide compounds, organic dye compounds, iron-phthalocyanine compounds, benzoins, benzoin ethers, and anthraquinones. Specific examples thereof include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenones such as acetophenone, 2-diethoxy-2-phenylacetophenone, 1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one; anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; thioxanthones such as 2, 4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzoin dimethyl ether; benzophenones such as benzophenone, 4-benzoyl-4 '-methyldiphenyl sulfide, and 4, 4' -bismethylaminobenzophenone; and phosphine oxides such as 2,4, 6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide. Examples of the photo-radical polymerization initiator include those described in publicly known documents such as journal of the society of organic Synthesis chemistry 66, 458 (2008).

Further, there may be mentioned acylphosphine oxide compounds such as 1-hydroxycyclohexylphenylketone (Irgacure 184 manufactured by BASF corporation, Irgacure being a registered trademark of BASF corporation), (2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl) -1-propanone) (Irgacure 907), or bis (2,4, 6-trimethylbenzoyl) -diphenyl-phosphine oxide (Irgacure 819); bis (eta)⁵Titanocene compounds such as-2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (Irgacure 784); and tetracene quinone compounds such as 6, 12-bis (trimethylsiloxy) -1, 11-tetracene benzoquinone.

In addition, onium salt type photo radical polymerization initiators may be used. The onium salt type photo radical polymerization initiator is generally used as a photo cation polymerization initiator which generates a cationic substance by light irradiation, but it is found that the onium salt type photo radical polymerization initiator functions as a photo radical polymerization initiator by being added to the radical polymerizable composition of the present invention. Examples of the onium salt-based photo radical polymerization initiator include sulfonium salts, iodonium salts, pyridinium salts, and phosphonium salts, but from the viewpoint of sensitivity to light irradiation, sulfonium salts and iodonium salts are preferable.

Examples of the sulfonium salt include diphenylalkylsulfonium salts, dinaphthylalkylsulfonium salts, and triphenylsulfonium salts, but triphenylsulfonium salts are preferable from the viewpoint of sensitivity to emitted light and the like. Examples of the triphenylsulfonium salt include S, S ' -tetraphenyl-S, S ' - (4,4 ' -thiodiphenyl) disulfonium bis hexafluorophosphate, diphenyl- (4-phenylthio) phenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, and the like, and for example, UVI-6992{ compound name: s, S, S ', S' -tetraphenyl-S, S '- (4, 4' -thiodiphenyl) disulfonium bis hexafluorophosphate }.

On the other hand, the iodonium salt includes iodonium salts such as diphenyliodonium salt, phenylnaphthyliodonium salt, dinaphthylium salt and the like, and diphenyliodonium salt is preferable from the viewpoint of sensitivity to light irradiation and the like. Examples of the diphenyliodonium salt include 4-isobutylphenyl-4 '-methylphenyliodilium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, and 4-isopropylphenyl-4' -methylphenyliodilium tetrakis (pentafluorophenyl) borate, and for example, irgacure (irgaure)250{ compound name: 4-isobutylphenyl-4' -methylphenyliodilium hexafluorophosphate, 2074{ compound name: 4-isopropylphenyl-4' -methylphenyliodioniumtetrakis (pentafluorophenyl) borate }.

Among these onium salts, iodonium salts may have a problem of discoloration or the like during long-term storage because of their low storage stability as compared with sulfonium salts. Therefore, when long-term storage stability is required, it is more preferable to use a sulfonium salt as the onium salt.

It is known that the above-exemplified usual photo radical polymerization initiators used in the past are inhibited by oxygen during radical polymerization, and the curing method of the present invention is carried out in the presence of oxygen, and therefore it is conceivable that the inhibition by oxygen is caused, but the compound having a polycyclic aromatic skeleton of the present invention converts oxygen in the system into singlet oxygen which does not cause oxygen inhibition, and therefore these usual photo radical polymerization initiators can function as radical polymerization initiators which reduce oxygen inhibition even in a system in which oxygen is present.

Examples

The present invention will be described in detail below with reference to examples, but the present invention is shown for illustrative purposes. That is, the following examples are not exhaustive, and the present invention is not limited to the embodiments described. Therefore, the present invention is not limited to the following description examples as long as it does not depart from the gist thereof. In addition, all parts and percentages are on a weight basis unless otherwise indicated.

The compounds of the invention were identified using the following equipment.

Infrared (IR) spectrophotometer: model is50 FT-IR manufactured by Thermo corporation

Nuclear magnetic resonance apparatus (¹H-NMR): model number ECS-400 made by Japan Electron Ltd

(Synthesis example 1) Synthesis of 9, 10-bis (methoxycarbonylmethylenoxy) anthracene

In a 100ml four-necked flask equipped with a stirrer and a thermometer under a nitrogen atmosphere, 15g of methyl isobutyl ketone as a solvent, 0.8g (1.2 mmol) of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst, and 9.5g (62.1 mmol) of methyl bromoacetate were added. While the temperature of the reaction system was maintained at 20 to 25 ℃, 29.1g of a 17 wt% aqueous solution (24 mmol in terms of anthraquinone) of the disodium salt of 9, 10-anthracenediol was added dropwise over 1 hour. After the completion of the dropwise addition, the mixture was further stirred for 1 hour. Thereafter, a yellow crystal was obtained in a yield of 4.7g (crude yield: 55 mol%) by suction filtration.

(1) Melting point: 151 ℃ and 152 DEG C

(2)IR(cm^-1)：1745，1391，1363，1164，1093，774，705.

(3)¹H-NMR(400MHz，CDCl₃)：δ＝3.914(s，6H)，4.792(s，4H)，7.261-7.545(m，4H)，8.319-8.366(m，4H).

(Synthesis example 2) Synthesis of 9, 10-bis (ethoxycarbonylmethyleneoxy) anthracene

In a 100ml four-necked flask equipped with a stirrer and a thermometer, 15g of methyl isobutyl ketone as a solvent, 0.8g (1.2 mmol) of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst, and 10.4g (62.5 mmol) of ethyl bromoacetate were charged under a nitrogen atmosphere. While the temperature of the reaction system was maintained at 20 to 25 ℃, 29.1g of a 17 wt% aqueous solution (24 mmol in terms of anthraquinone) of the disodium salt of 9, 10-anthracenediol was added dropwise over 1 hour. After the completion of the dropwise addition, the mixture was further stirred for 1 hour. Thereafter, a light yellow crystal was obtained in a yield of 5.0g (crude yield: 55 mol%) by suction filtration.

(1) Melting point: 93-94 deg.C

(2)IR(cm^-1)：1754，1742，1382，1367，1241，1212，1168，1087，1034，1004，936，809，768，720，691，669，585.

(3)¹H-NMR(400MHz，CDCl₃)：δ＝1.370(t，J＝14Hz，6H)，4.376(k，J＝21.6Hz，4H)，4.777(s，4H)，7.261-7.540(m，4H).

(Synthesis example 3) Synthesis of 9, 10-bis (Isopropoxycarbonylmethylenoxy) anthracene

In a 100ml four-necked flask equipped with a stirrer and a thermometer, 15g of methyl isobutyl ketone as a solvent, 0.8g (1.2 mmol) of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst, and 11.3g (62.5 mmol) of isopropyl bromoacetate were added under a nitrogen atmosphere. While the temperature of the reaction system was maintained at 20 to 25 ℃, 29.1g of a 17 wt% aqueous solution (24 mmol in terms of anthraquinone) of the disodium salt of 9, 10-anthracenediol was added dropwise over 1 hour. After the completion of the dropwise addition, the mixture was further stirred for 1 hour. Thereafter, a light yellow crystal was obtained in a yield of 5.9g (crude yield: 60 mol%) by suction filtration.

(1) Melting point: 109 ℃ and 110 DEG C

(2)IR(cm^-1)：1744，1360，1210，1163，1086，1018，1004，776，768，671.

(3)¹H-NMR(400MHz，CDCl₃)：δ＝1.347(d，J＝6.4Hz，12H)，4.743(s，4H)，5.246-5.277(m，2H)，7.504-7.529(m，4H)，8.356-8.398(m，4H).

(Synthesis example 4) Synthesis of 9, 10-bis (tert-butoxycarbonylmethylenoxy) anthracene

In a 100ml four-necked flask equipped with a stirrer and a thermometer under a nitrogen atmosphere, 15g of methyl isobutyl ketone as a solvent, 0.8g (1.2 mmol) of a 50% aqueous tetrabutylammonium bromide solution as a catalyst, and 12.2g (62.5 mmol) of t-butyl bromoacetate were added. While the temperature of the reaction system was maintained at 20 to 25 ℃, 29.1g of a 17 wt% aqueous solution (24 mmol in terms of anthraquinone) of the disodium salt of 9, 10-anthracenediol was added dropwise over 1 hour. After the completion of the dropwise addition, the mixture was further stirred for 1 hour. Thereafter, the anthraquinone was removed by suction filtration, and the obtained filtrate was left overnight to precipitate crystals. The precipitated crystals were further filtered with suction, whereby a yield of 6.5g (crude yield: 61 mol%) of pale yellow crystals was obtained.

(1) Melting point: 131 ℃ C. and 132 ℃ C

(2)IR(cm^-1)：1742，1391，1358，1232，1151，1089，1021，1004，846，776，749，670.

(3)¹H-NMR(400MHz，CDCl₃)：δ＝1.575(s，18H)，4.659(s，4H)，7.260-7.530(m，4H)，8.359-8.400(m，4H).

(Synthesis example 5) Synthesis of 9, 10-bis (n-butoxycarbonylmethylenoxy) anthracene

In a 100ml four-necked flask equipped with a stirrer and a thermometer, 15g of methyl isobutyl ketone as a solvent, 3.1g (4.8 mmol) of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst, and 9.4g (62.5 mmol) of butyl chloroacetate were charged under a nitrogen atmosphere. While the temperature of the reaction system was maintained at 20 to 25 ℃, 29.1g of a 17 wt% aqueous solution (24 mmol in terms of anthraquinone) of the disodium salt of 9, 10-anthracenediol was added dropwise over 1 hour. After the completion of the dropwise addition, the mixture was further stirred for 1 hour. Thereafter, the anthraquinone was removed by suction filtration, and the obtained filtrate was washed with water 2 times. After the water washing operation, anthraquinone precipitated, and thus anthraquinone was removed by suction filtration. The filtrate was left overnight to precipitate crystals, which were collected by suction filtration to give a yellow crystal yield of 5.5g (crude yield: 52 mol%).

(1) Melting point: 71-72 deg.C

(2)IR(cm^-1)：1749，1411，1385，1364，1246，1226，1167，1085，1035，1018，957，768，721，669，587.

(3)¹H-NMR(400MHz，CDCl₃)：δ＝0.967(d，J＝15.2Hz，6H)，1.387-1.481(m，4H)，1.678-1.750(m，4H)，4.317(t，J＝13.2Hz，4H)，4.779(s，4H)，7.508-7.826(m，4H)，8.319-8.377(m，4H).

(Synthesis example 6) Synthesis of 9, 10-bis (methoxycarbonylmethylmethyleneoxy) anthracene

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

(1) Melting point: 130 ℃ and 131 DEG C

(2)IR(cm^-1)：1737，1366，1207，1134，1078，1061，1020，970，748，681.

(3)¹H-NMR(400MHz，CDCl₃)：δ＝1.644(d，J＝6.4Hz，6H)，3.770(s，6H)，4.904(k，J＝20.4Hz，2H)，7.464-7.489(m，4H)，8.292-8.332(m，4H).

(Synthesis example 7) Synthesis of 9, 10-bis (ethoxycarbonylpropyleneoxy) anthracene

In a 100ml four-necked flask equipped with a stirrer and a thermometer, 0.77g (1.19 mmol) of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst, 12.1g (61.8 mmol) of ethyl 4-bromobutyrate, 5.0g (23.8 mmol) of 9, 10-anthracenediol, 9.9g (71.4 mmol) of potassium carbonate, and 40g of N, N-dimethylformamide as a solvent were added under a nitrogen atmosphere. And keeping the temperature of the reaction system at 20-30 ℃, and stirring for 1 hour. Thereafter, the anthraquinone was removed by suction filtration, and the obtained filtrate was dissolved in toluene and washed with water 2 times. The solution was concentrated with an evaporator. After standing overnight, methanol was added and heated to 50 ℃ to dissolve the solution as it solidified throughout. Undissolved anthraquinone was removed by suction filtration, and the filtrate was cooled in a refrigerator to precipitate crystals. The precipitated crystals were further filtered with suction, whereby a yield of 5.4g (crude yield: 51 mol%) of yellow crystals was obtained.

(1) Melting point: 95-96 deg.C

(2)IR(cm^-1)：1721，1351，1312，1239，1183，1164，1081，1024，1015，913，767，742，669.

(3)¹H-NMR(400MHz，CDCl₃)：δ＝1.307(t，J＝14.0Hz，6H)，2.340-2.408(m，4H)，2.776(t，J＝14.8Hz，4H)，4.171-4.235(m，8H)，7.456-7.494(m，4H)，8.230-8.256(m，4H).

(Synthesis example 8) Synthesis of 9, 10-bis (ethoxycarbonylbutylidenyloxy) anthracene

In a 100ml four-necked flask equipped with a stirrer and a thermometer, 0.77g (1.19 mmol) of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst, 12.9g (61.8 mmol) of ethyl 5-bromovalerate, 5.0g (23.8 mmol) of 9, 10-anthracenediol, 9.9g (71.4 mmol) of potassium carbonate, and 40g of N, N-dimethylformamide as a solvent were added under a nitrogen atmosphere. And keeping the temperature of the reaction system at 20-30 ℃, and stirring for 1 hour. Thereafter, the anthraquinone was removed by suction filtration, and the obtained filtrate was dissolved in toluene and washed 2 times with water by a liquid separation operation. The solution was concentrated with an evaporator. After standing overnight, methanol was added and undissolved anthraquinone was removed by suction filtration. The filtrate was cooled in a refrigerator to precipitate crystals. The precipitated crystals were further filtered with suction, whereby an orange crystal was obtained in a yield of 6.2g (crude yield: 55 mol%).

(1) Melting point: 57-58 deg.C

(2)IR(cm^-1)：1722，1403，1337，1284，1269，1229，1178，1167，1068，1021，934，763，675.

(3)¹H-NMR(400MHz，CDCl₃)：δ＝1.286(t，J＝14.4Hz，6H)，2.018-2.103(m，8H)，2.496(t，J＝13.6Hz，4H)，4.151-4.205(m，8H)，7.463-7.487(m，4H)，8.243-8.268(m，4H).

(Synthesis example 9) Synthesis of 2-ethyl-9, 10-bis (isopropoxycarbonylmethylenoxy) anthracene

5.0g (21.2 mmol) of 2-ethylanthraquinone, 9.1g (86.4 mmol) of thiourea dioxide, 8.4g (211.6 mmol) of sodium hydroxide and 50g of ion-exchanged water were added to a 200ml four-necked flask equipped with a stirrer and a thermometer under a nitrogen atmosphere, and stirring was performed while gradually raising the temperature to 120 ℃. When the solution became reddish black, the stirring was stopped, and the solution was cooled at room temperature to prepare an aqueous solution of disodium salt of 2-ethyl-9, 10-anthracenediol. Next, in a separate 200ml four-necked flask equipped with a stirrer and a thermometer, 15g of methyl isobutyl ketone as a solvent, 2.7g (4.23 mmol) of a 50% aqueous solution of tetrabutylammonium bromide as a catalyst, and 10.0g (55.0 mmol) of isopropyl bromoacetate were added under a nitrogen atmosphere. The disodium salt aqueous solution of 2-ethyl-9, 10-anthracenediol prepared as above was added dropwise over 1 hour while maintaining the temperature of the reaction system at 20 to 25 ℃. After the completion of the dropwise addition, the mixture was further stirred for 1 hour. Thereafter, the aqueous layer was removed, and the organic layer was concentrated by an evaporator to obtain an orange oil in an amount of 4.5g (crude yield: 48 mol%).

(1) Melting point: is liquid at room temperature

(2)IR(cm^-1)：1728，1673，1454，1385，1373，1324，1286，1206，1085，962，931，901，825，772，750，712.

(3)¹H-NMR(400MHz，CDCl₃)：δ＝1.237-1.371(m，15H)，2.816-2.899(m，2H)，4.731(s，4H)，5.014-5.123(m，1H)，5.225-5.301(m，1H)，7.391(d，J＝9.2Hz，1H)，7.461-7.512(m，2H)，7.766-7.790(m，1H)，8.119(d，J＝7.6Hz，1H)，8.284-8.368(m，2H).

< optical DSC measurement >

In the present example, the optical DSC measurement was performed as follows. The DSC measurement apparatus used XDSC-7000 manufactured by hitachi high and new technologies, and an optical DSC measurement unit was attached thereto so as to perform DSC measurement while irradiating light.

As the light source for light irradiation in the polymerization reaction, LA-410UV manufactured by Lin clock industries, Inc. was used. The irradiation light is a light having a wavelength of 405nm extracted by a full wavelength of a high-pressure mercury lamp or a band-pass filter. In the case of the full wavelength of the high-pressure mercury lamp, the illuminance of light was adjusted to 100mW/cm at 365nm²At 405nm, 50mW/cm². The light of the light source was guided to the upper part of the sample using a glass fiber, and the shutter of the light source was set to be capable of trigger control so that DSC measurement could be performed while light irradiation was started.

For the optical DSC measurement, about 1mg of a sample was accurately weighed in an aluminum pan for measurement, and after placing the sample in a DSC measurement portion, an optical DSC unit was attached. The DSC measurement unit was measured in a nitrogen atmosphere while flowing nitrogen at a rate of 100 mL/min. After the first measurement, the sample was directly re-measured under the same conditions, and the value obtained by subtracting the second measurement result from the first measurement result was taken as the measurement result of the sample. Unless otherwise stated, results were compared as total exotherm per 1mg sample. Since heat is generated as the polymerization reaction proceeds, the degree of progress of the polymerization reaction can be investigated by measuring the total heat generation amount.

On the other hand, DSC measurement for thermal analysis was also performed. For the DSC measurement, about 1mg of a sample was precisely weighed in an aluminum seal disk for measurement under a nitrogen atmosphere and placed in a DSC measurement section. The DSC measurement unit was measured in a nitrogen atmosphere while flowing nitrogen at a rate of 100 mL/min. Unless specifically stated otherwise, results were compared as total heat release per 1mg sample. The polymerization reaction proceeds while generating heat, and the degree of progress of the polymerization reaction can be investigated by measuring the total amount of heat generated. The measurement was carried out under a temperature-raising condition of raising the temperature from 30 ℃ to 170 ℃ at a rate of 5 ℃/min.

In addition, as for the conversion, trimethylolpropane triacrylate (TMPTA) (manufactured by tokyo chemical industries, ltd.) was sealed in an aluminum sealing disk, and thermal analysis measurement was performed by DSC under a temperature-raising condition of raising the temperature from 30 ℃ to 300 ℃ at a rate of 5 ℃/min, and the total heat release amount of the obtained heat-release peaks was calculated as 100%.

< Observation of polymerization behavior Using rheometer >

Whether the polymerization reaction proceeded or not can be observed by the presence or absence of the rise in viscosity. This is a method of confirming the progress of the polymerization reaction by measuring the change with time in the complex viscosity with a rheometer. As the rheometer, one manufactured by Anton-Paar corporation was usedMCR102 with optional H-PTD200 for temperature and atmosphere control. The assay is usingAt a strain: 100%, frequency: 1Hz, temperature: constant at 25 ℃, measurement interval: 0.33 min, space: 0.5 mm. When the complex viscosity of the monomer was measured using trimethylolpropane triacrylate (TMPTA), it was determined that polymerization occurred when the complex viscosity reached 10000Pa · s. The complex viscosity of trimethylolpropane triacrylate (TMPTA) as a monomer is usually about 0.1 to 0.6 pas.

Example 1 Synthesis of 9, 10-dibutoxyanthracene-9, 10-endoperoxide (DBAEPO, 9, 10-dibutoxy-9, 10-dihydro-9, 10-Cyclodioxoanthracene)

226mg (0.701 mmol) of 9, 10-dibutoxyanthracene was dissolved in 7.5ml of ethyl acetate (manufactured by Wako pure chemical industries, Ltd., for spectroscopic analysis) in a 50ml Erlenmeyer flask under air. Using 385nm, 122mW/cm²The LED lamp (LED 385/L-STND, manufactured by optocode corporation) was irradiated for 2 hours, dried under reduced pressure, and then separated by thin layer chromatography (silica gel, ethyl acetate: hexane: 1: 20, Rf value 0.31) to obtain 144mg (0.406 mmol) of colorless and transparent liquid 9, 10-dibutoxyanthracene-9, 10-endoperoxide. The yield of 9, 10-dibutoxyanthracene based on the starting material was 58.0 mol%.

(1) Melting point: 39-40 deg.C

(2) IR (liquid film method, cm)^-1)：2957，2872，1461，1298，1073，759.

(3)¹H-NMR(300MHz、CDCl₃)：δ＝1.01(t，J＝7.3Hz，6H)，1.48-1.64(m，4H)，1.78-1.90(m，4H)，4.27(t，J＝6.6Hz，4H)，7.28(dd，J＝5.3Hz，3.0Hz，4H)，7.52(dd，J＝5.7Hz，3.4Hz，4H).

Example 2 Synthesis of 9, 10-bis (ethoxycarbonylmethyleneoxy) anthracene-9, 10-endoperoxide (ECMAEPO)

In a 50ml Erlenmeyer flask, 97.3mg (0.254 mmol) of 9, 10-bis (ethoxycarbonylmethyleneoxy) anthracene synthesized in the same manner as in Synthesis example 2 and 4.9mg (7.6 mmol) of eosin Y as a singlet oxygen generating agent were added to the flask and dissolved in 10ml of N, N-dimethylformamide (available from Wako pure chemical industries, Ltd., for spectroscopic analysis). The solution was irradiated with 530nm condensing LED light (LED 530/L-STND, manufactured by optocode K.K.) from the top of the Erlenmeyer flask for 3.5 hours. Then, the mixture was washed with ethyl acetate and washing water 2 times, and ethyl acetate and pure water 1 time to extract an ethyl acetate layer, and sodium sulfate was added to remove water. Then, the ethyl acetate layer was concentrated, dried under reduced pressure, and separated by thin layer chromatography (ethyl acetate: hexane: 1: 2, Rf value: 0.7) to obtain 48.5mg (0.117 mmol) of colorless and transparent liquid 9, 10-bis (ethoxycarbonylmethylenoxy) anthracene-9, 10-endoperoxide. The yield of 9, 10-bis (ethoxycarbonylmethyleneoxy) anthracene based on the raw material was 46.1 mol%.

(1) Melting point: 80-81 deg.C

(2) IR (liquid film method, cm)^-1)：2988，2950，1763、1753、1200、1139、1086、1054、902、753.

(3)¹H-NMR(500MHz、CDCl₃)：δ＝1.30-1.33(t，J＝7.3Hz，6H)，4.28-4.32(q，J＝7.0Hz，4H)，4.78(s，4H)，7.28-7.32(dd，J＝5.5Hz，3.0Hz，4H)，7.55-7.58(dd，J＝5.5Hz，3.5Hz，4H).

(4)¹³C-NMR(125MHz、CDCl₃)：δ＝14.3，61.5，64.0，102.9，120.6，127.9，137.9，169.2.

Example 3 photo radical polymerization

A radical polymerizable composition was prepared by adding 1.5 parts by weight of 9, 10-dibutoxyanthracene-9, 10-endoperoxide (DBAEPO) obtained in the same manner as in example 1 as a photo radical polymerization initiator to 100 parts by weight of trimethylolpropane triacrylate (TMPTA) (manufactured by tokyo chemical industries, ltd.). 1mg of the radical polymerizable composition was precisely weighed in an aluminum pan for measurement, and placed in a DSC measurement portion, and then an optical DSC unit was attached. The sample was irradiated with a high-pressure mercury lamp at full wavelength for 30 seconds under a nitrogen atmosphere. The exotherm at this time was 470mJ/mg and the conversion was 83.9% (the results are set forth in Table 1).

Comparative example 1

The same measurement as in example 3 was carried out, except that 9, 10-dibutoxyanthracene-9, 10-endoperoxide (DBAEPO) was not added as a photo-radical polymerization initiator. The exotherm at this time was 26.3mJ/mg and the conversion was 7.4% (the results are set forth in Table 1).

Example 4 thermal radical polymerization

A radical polymerizable composition was prepared by adding 1.5 parts by weight of 9, 10-dibutoxyanthracene-9, 10-endoperoxide (DBAEPO) obtained in the same manner as in example 1 as a thermal radical polymerization initiator to 100 parts by weight of trimethylolpropane triacrylate (TMPTA) (manufactured by tokyo chemical industries, ltd.). 1mg of the radical polymerizable composition was precisely weighed in an aluminum sealing disk for measurement under a nitrogen atmosphere, placed in a DSC measurement portion, and then measured under conditions of increasing from 30 ℃ to 170 ℃ at a rate of 5 ℃/min. The exotherm at this time was 503mJ/mg and the conversion was 88.2% (the results are set forth in Table 1).

Comparative example 2

The same measurement as in example 4 was carried out, except that 9, 10-dibutoxyanthracene-9, 10-endoperoxide (DBAEPO) was not added as a thermal radical polymerization initiator. The exothermic amount at this time was 0mJ/mg, and the conversion was 0.0% (the results are shown in Table 1).

(example 5)

The measurement was carried out in the same manner as in example 3 except that 1.5 parts of 9, 10-bis (ethoxycarbonylmethyleneoxy) anthracene-9, 10-endoperoxide (ECMAEPO) synthesized in the same manner as in example 2 was added instead of 1.5 parts of 9, 10-dibutoxyanthracene-9, 10-endoperoxide (DBAEPO) of example 3. The exotherm at this time was 284mJ/mg, and the conversion was 49.8% (the results are set forth in Table 1).

[ Table 1]

DBAEPO: 9, 10-dibutoxyanthracene-9, 10-endoperoxide

ECMAEPO: 9, 10-bis (ethoxycarbonylmethyleneoxy) anthracene-9, 10-endoperoxides

(example 6)

5 parts by weight of a cobalt naphthenate mineral essential oil solution (Co: 6%) (Wako pure chemical industries, Ltd.) was added as a reducing agent for promoting decomposition of an endoperoxide to 100 parts by weight of trimethylolpropane triacrylate (TMPTA) (manufactured by Tokyo chemical Co., Ltd.) as a radical polymerizable compound. The spacing between the two parts is 0.5mm,The solution was loaded on a heating plate of the rheometer maintained at 25 c in the amount that the parallel plates could sandwich. To this solution, a small amount (about 50 mg) of 9, 10-dibutoxyanthracene-9, 10-endoperoxide (DBAEPO) obtained in the same manner as in example 1 as a thermal radical polymerization initiator was added, and the solution was immediately sandwiched between parallel plates to start measurement of complex viscosity by a rheometer. As a result, the complex viscosity increased after about 20 minutes of the measurement, and reached 10080 pas after 61 minutes of the measurement, and 44260 pas after 90 minutes. This confirmed that the polymerization reaction had proceeded in the solution (the results are shown in Table 2).

Comparative example 3

The same measurement as in example 6 was carried out, except that 9, 10-dibutoxyanthracene-9, 10-endoperoxide (DBAEPO) was not added as a thermal radical polymerization initiator. As a result, after 90 minutes, no increase in complex viscosity was observed, and the viscosity after 90 minutes was 0.3 pas. This confirmed that the polymerization reaction did not proceed in the solution (the results are shown in Table 2).

[ Table 2]

DBAEPO: 9, 10-dibutoxyanthracene-9, 10-endoperoxide

(example 7)

A radical polymerizable composition was prepared by adding 1.5 parts by weight of 9, 10-dibutoxyanthracene-9, 10-endoperoxide (DBAEPO) obtained in the same manner as in example 1 as a photo radical polymerization initiator and further adding 0.01 part by weight of DBA (9, 10-dibutoxyanthracene) as a photo radical polymerization sensitizer to 100 parts by weight of trimethylolpropane triacrylate (TMPTA) (manufactured by tokyo chemical industries, Ltd.) as a radical polymerizable compound. 1mg of the radical polymerizable composition was precisely weighed in an aluminum pan for measurement, and placed in a DSC measurement portion, and then an optical DSC unit was attached. The sample was irradiated with light at 405nm for 2 minutes under a nitrogen atmosphere. The exotherm at this time was 266mJ/mg and the conversion was 53.2% (the results are set forth in Table 3).

(example 8)

A radical polymerizable composition was prepared by adding 1.5 parts by weight of 9, 10-dibutoxyanthracene-9, 10-endoperoxide (DBAEPO) obtained in the same manner as in example 1 as a photo-radical polymerization initiator and further adding 0.5 parts by weight of OcA (9, 10-bis (octanoyloxy) anthracene) as a photo-radical polymerization sensitizer to 100 parts by weight of trimethylolpropane triacrylate (TMPTA) (manufactured by tokyo chemical industries, Ltd.) as a radical polymerizable compound. 1mg of the radical polymerizable composition was precisely weighed in an aluminum pan for measurement, and placed in a DSC measurement portion, and then an optical DSC unit was attached. The sample was irradiated with light at 405nm for 5 minutes under a nitrogen atmosphere. The exotherm at this time was 359mJ/mg and the conversion was 71.8% (the results are set forth in Table 3).

(example 9)

A radical polymerizable composition was prepared by adding 1.5 parts by weight of 9, 10-dibutoxyanthracene-9, 10-endoperoxide (DBAEPO) obtained in the same manner as in example 1 as a photo-radical polymerization initiator and further adding 0.5 parts by weight of ECMA (9, 10-bis (ethoxycarbonylmethyleneoxy) anthracene) synthesized in the same manner as in synthesis example 2 as a photo-radical polymerization sensitizer to 100 parts by weight of trimethylolpropane triacrylate (TMPTA) (manufactured by tokyo chemical industries, ltd.) as a radical polymerizable compound. 1mg of the radical polymerizable composition was precisely weighed in an aluminum pan for measurement, and placed in a DSC measurement portion, and then an optical DSC unit was attached. The sample was irradiated with light at 405nm for 2 minutes under a nitrogen atmosphere. The exotherm at this time was 400mJ/mg and the conversion was 70.1% (the results are set forth in Table 3).

[ Table 3]

DBAEPO: 9, 10-dibutoxyanthracene-9, 10-endoperoxide

DBA: 9, 10-dibutoxyanthracene

OcA: 9, 10-bis (octanoyloxy) anthracenes

ECMA: 9, 10-bis (ethoxycarbonylmethyleneoxy) anthracenes

By comparing examples 3,5 and 1, it was found that 9, 10-dibutoxyanthracene-9, 10-endoperoxide (DBAEPO) and 9, 10-bis (ethoxycarbonylmethyleneoxy) anthracene-9, 10-endoperoxide (ECMAEPO) generated initiating radicals for initiating radical polymerization by ultraviolet irradiation.

Further, as is clear from comparative example 4 and comparative example 2, 9, 10-dibutoxyanthracene-9, 10-endoperoxide (DBAEPO) also generates an initiating radical which initiates radical polymerization by the application of thermal energy.

It is understood from comparative example 6 and comparative example 3 that 9, 10-dibutoxyanthracene-9, 10-endoperoxide (DBAEPO) does not decompose at 25 ℃ and does not act as a radical polymerization initiator, but that it is possible to generate an initiating radical for initiating radical polymerization by redox reaction at that temperature by adding a decomposition accelerator cobalt naphthenate, and to perform radical polymerization reaction.

The following results were obtained from example 7, example 8 and example 9. That is, as shown in FIG. 1, 9, 10-dibutoxyanthracene-9, 10-endoperoxide (DBAEPO) does not absorb in the wavelength region of 330nm or more. Thus, in this example, the decomposition reaction did not occur under irradiation with light of 405nm, and therefore the polymerization reaction did not proceed. However, when a compound having a polycyclic aromatic skeleton of the present invention (DBA, OcA, ECMA) absorbing at 405nm is added as a photo radical polymerization sensitizer, the anthracene compound is excited by light of 405nm and energy thereof is conducted to DBAEPO, whereby DBAEPO is decomposed to generate an initiating radical for initiating radical polymerization.

Industrial applicability

The novel radical polymerization method in which the endoperoxide compound having a polycyclic aromatic skeleton of the present invention is produced from the compound having a polycyclic aromatic skeleton by actively utilizing oxygen that initiates oxygen inhibition in the polymerization reaction of the radical polymerizable compound, and the endoperoxide compound having a polycyclic aromatic skeleton is used as a radical polymerization initiator is a novel radical polymerizable composition using the compound having a polycyclic aromatic skeleton of the present invention and a polymerization method thereof, and provides a radical polymerizable composition that is industrially very useful.