Radical polymerization control agent and radical polymerization control method

文档序号：1431760 发布日期：2020-03-17 浏览：35次中文

阅读说明：本技术 自由基聚合控制剂和自由基聚合控制方法 (Radical polymerization control agent and radical polymerization control method ) 是由桧森俊一井内启太于 2018-06-27 设计创作，主要内容包括：现有的阻聚剂是为了捕捉例如在自由基聚合性化合物的保存中产生的自由基、稳定地处理自由基聚合性化合物而使用的试剂,但其是一旦使该自由基聚合性化合物进行自由基聚合反应时则不需要的添加剂,是在自由基聚合反应时优选被除去的化合物。本发明的目的在于消除在该自由基聚合时将其除去的这种不便。本发明的含有在自由基聚合性组合物中的自由基聚合控制剂例如在暗处保存时作为自由基聚合阻聚剂发挥作用,在聚合时,通过在照射某一特定波长的光的同时引发聚合而失去自由基聚合阻止效果,从而能够在不增加自由基聚合引发剂的量的情况下容易地引发自由基聚合性化合物的自由基聚合。即,本发明的自由基聚合控制剂是具有阻止自由基聚合性化合物的自由基聚合的效果的化合物,其特征在于,在含有300nm～500nm的波长范围的光的光线的照射下,该自由基聚合阻止效果消失。(The conventional polymerization inhibitor is a reagent used for trapping radicals generated during storage of a radically polymerizable compound and stably treating the radically polymerizable compound, but it is an additive which is not required when the radically polymerizable compound is subjected to radical polymerization reaction, and is preferably removed during radical polymerization reaction. The present invention aims to eliminate such inconvenience of removing the radical polymerization. The radical polymerization controlling agent contained in the radical polymerizable composition of the present invention functions as a radical polymerization inhibitor, for example, when stored in a dark place, and when polymerized, the radical polymerization inhibiting effect is lost by initiating polymerization while irradiating light of a certain specific wavelength, so that radical polymerization of the radical polymerizable compound can be easily initiated without increasing the amount of the radical polymerization initiator. That is, the radical polymerization controlling agent of the present invention is a compound having an effect of inhibiting radical polymerization of a radical polymerizable compound, and is characterized in that the radical polymerization inhibiting effect disappears by irradiation with light containing light having a wavelength range of 300nm to 500 nm.)

1. A radical polymerization controlling agent represented by the following general formula (1), which is a compound having an effect of inhibiting radical polymerization of a radical polymerizable compound, characterized in that the radical polymerization inhibiting effect disappears under irradiation of light containing light in a wavelength range of 300nm to 500nm,

[ solution 1]

In the formula (1), R independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, an alkoxyalkyl group having 1 to 15 carbon atoms, a glycidyl group, a hydroxyalkyl group having 1 to 15 carbon atoms, an aryloxyalkyl group having 7 to 14 carbon atoms, an acyl group having 2 to 13 carbon atoms, or a substituted carbonyl group having 2 to 13 carbon atoms, and X independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 12 carbon atoms, but adjacent groups of X may be bonded to each other to form a saturated or unsaturated 6-membered ring instead of the substituent; the 6-membered ring formed by the adjacent group X may be further substituted with an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or a halogen atom.

2. A radical polymerization controlling agent represented by the following general formula (2) which is a compound having an effect of inhibiting radical polymerization of a radical polymerizable compound, characterized in that the radical polymerization inhibiting effect disappears under irradiation of light containing light in a wavelength range of 300nm to 500nm,

[ solution 2]

In the formula (2), R independently represents alkyl with 1-15 carbon atoms, aryl with 6-12 carbon atoms, aralkyl with 6-12 carbon atoms, alkoxyalkyl with 1-15 carbon atoms, glycidyl, hydroxyalkyl with 1-15 carbon atoms or aryloxyalkyl with 7-14 carbon atoms, acyl with 2-13 carbon atoms or substituted carbonyl with 2-13 carbon atoms, and X independently represents hydrogen, alkyl with 1-15 carbon atoms or aryl with 6-12 carbon atoms.

3. A radical polymerization controlling agent represented by the following general formula (3) which is a compound having an effect of inhibiting radical polymerization of a radical polymerizable compound, characterized in that the radical polymerization inhibiting effect disappears under irradiation of light containing light in a wavelength range of 300nm to 500nm,

[ solution 3]

In the formula (3), R represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, an alkoxyalkyl group having 1 to 15 carbon atoms, a glycidyl group, a hydroxyalkyl group having 1 to 15 carbon atoms, an aryloxyalkyl group having 7 to 14 carbon atoms, an acyl group having 2 to 13 carbon atoms, or a substituted carbonyl group having 2 to 13 carbon atoms, and X each independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

4. A radical polymerization controlling agent represented by the following general formula (4), which is a compound having an effect of inhibiting radical polymerization of a radical polymerizable compound, characterized in that the radical polymerization inhibiting effect disappears under irradiation of light containing light in a wavelength range of 300nm to 500nm,

[ solution 4]

In the formula (4), X independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or a halogen atom, Y and Z independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an amino group or a halogen atom, but Y and Z may be bonded to each other not to the substituent to form a saturated or unsaturated 6-membered ring; the 6-membered ring formed by Y and Z may be further substituted with an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or a halogen atom.

5. The radical polymerization control agent according to claim 4, wherein in the general formula (4), X is a hydrogen atom, and Y and Z are hydrogen atoms.

6. The control agent for radical polymerization according to claim 4, wherein in the general formula (4), X represents a hydrogen atom, Y represents a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an amino group or a halogen atom, and Z represents a hydrogen atom.

7. The radical polymerization control agent according to claim 4, wherein in the general formula (4), X is a hydrogen atom, Y is a hydroxyl group or a methyl group, and Z is a hydrogen atom.

8. The control agent for radical polymerization according to claim 4, wherein in the general formula (4), X is a hydrogen atom, Y is a chlorine atom, and Z is a chlorine atom or an amino group.

9. A radical polymerization controlling agent represented by the following general formula (5) or (6), which is a compound having an effect of inhibiting radical polymerization of a radical polymerizable compound, characterized in that the radical polymerization inhibiting effect disappears under irradiation of light containing light in a wavelength range of 300nm to 500nm,

[ solution 5]

In the formula (5), X independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or a halogen atom, Q represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or a halogen atom,

[ solution 6]

In the formula (6), X independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or a halogen atom, and Q represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or a halogen atom.

10. A radically polymerizable composition comprising the radically polymerizable compound and the radically polymerization control agent according to any one of claims 1 to 9.

11. The radically polymerizable composition according to claim 10, wherein the radically polymerizable compound is (meth) acrylic acid, (meth) acrylate, or styrene, or an oligomer thereof.

12. A radically polymerizable composition according to claim 10 or 11, further comprising a radical polymerization initiator.

13. The radically polymerizable composition according to claim 12, wherein the radical polymerization initiator is a thermal radical polymerization initiator.

14. The radically polymerizable composition according to claim 12, wherein the radical polymerization initiator is a photo radical polymerization initiator.

15. A method for controlling radical polymerization, which comprises applying thermal energy to the radical polymerizable composition according to claim 13 under irradiation with light containing light having a wavelength ranging from 300nm to 500nm to initiate radical polymerization.

16. A method for controlling radical polymerization, comprising irradiating a substrate with light having a wavelength of 300 to 500nm in a state where the radical polymerizable composition according to claim 13 is applied to the substrate and a part of the obtained coating film is masked, and applying thermal energy to the substrate to perform radical polymerization, thereby polymerizing only the portion irradiated with the light.

17. A method for controlling radical polymerization, comprising irradiating a specific region with light containing light having a wavelength ranging from 300nm to 500nm, thereby causing radical polymerization only in the specific region, when radical polymerization is performed by applying thermal energy to the radical polymerizable composition according to claim 13.

18. A method for controlling radical polymerization, characterized in that radical polymerization is initiated by applying light energy for initiating polymerization to the radical polymerizable composition according to claim 14 under irradiation of light containing light in a wavelength range of 300nm to 500 nm.

19. A method for controlling radical polymerization, comprising applying the radical polymerizable composition according to claim 14 to a substrate, and in a state where a part of the obtained coating film is masked, irradiating light having a wavelength ranging from 300nm to 500nm, and simultaneously applying light energy for initiating polymerization to cause radical polymerization, thereby polymerizing only a portion irradiated with the light having a wavelength ranging from 300nm to 500 nm.

20. A method for controlling radical polymerization, comprising irradiating a specific region with light containing light having a wavelength ranging from 300nm to 500nm to cause radical polymerization only in the specific region, when the radical polymerizable composition according to claim 14 is subjected to radical polymerization by irradiation with light energy for initiating polymerization.

Technical Field

The present invention relates to a radical polymerization control agent for a radical polymerizable compound and a radical polymerization control method. In particular, the present invention relates to a radical polymerization control agent and a radical polymerization control method capable of controlling radical polymerization of a radical polymerizable compound in a light state and a dark state.

Background

The radical polymerization controlling agent of the present invention is a brand new type of polymerization controlling agent which has a radical polymerization inhibiting effect in a state where light irradiation is not performed, and loses the radical polymerization inhibiting effect in a state where light of a certain specific wavelength is irradiated; and a method for controlling radical polymerization using the radical control agent.

In general, a radical polymerization inhibitor is contained as a storage stabilizer in a radical polymerizable compound. For example, in the case of an aromatic vinyl compound or the like, in order to prevent the monomer from polymerizing by light, heat, air or the like during storage, an o-dihydroxybenzene compound such as p-tert-butylcatechol or p-methylcatechol is added; hydroquinone compounds such as hydroquinone and methoxyhydroquinone; azine ring compounds such as pyrazine, p-thiazine, 1,3, 5-triazine and phenothiazine; hydrazine compounds such as 1, 2-diphenylhydrazine and diphenylpicrylhydrazide; and a polymerization inhibitor such as a phenol compound such as nitrophenol and bisphenol A. However, when polymerization is carried out using such an aromatic vinyl compound or the like, the radical polymerization inhibitor acts as a radical polymerization inhibitor and delays the polymerization reaction. Therefore, the reaction is usually carried out after removing the added polymerization inhibitor by distillation, adsorption, washing, or the like. In addition, when not removed, the amount of the radical polymerization initiator added needs to be increased so as to exceed the radical polymerization inhibiting effect of the radical polymerization inhibitor.

For example, styrene contains about 1 to several hundred ppm of a radical polymerization inhibitor such as a catechol compound or a hydroquinone compound in order to prevent polymerization during storage. When such styrene containing a radical polymerization inhibitor is homopolymerized or copolymerized to obtain a polymer, the radical polymerization inhibitor reacts with a polymerization catalyst or a polymerization initiator, and formation of a desired polymer is inhibited. Therefore, polymerization is carried out by using purified styrene by removing a polymerization inhibitor in styrene (for example, patent documents 1 and 2). Removal of such radical polymerization inhibitors takes time and cost.

Therefore, a radical polymerization inhibitor which has an ability to trap radicals generated in a radical polymerizable compound during storage and which is harmless when a radical polymerizable compound is subjected to radical polymerization, and a radical polymerization method using the same are required.

On the other hand, as well as the above-mentioned radical polymerization inhibitors, naphthalene-based and naphthoquinone-based radical polymerization inhibitors are known. For example, alkylated naphthoquinone compounds (for example, patent document 3), 2-hydroxy-1, 4-naphthoquinone (for example, patent document 4), and the like are known as polymerization inhibitors for aromatic vinyl compounds. Further, 1, 4-naphthoquinone and the like are known as a polymerization inhibitor for vinyl acetate (for example, patent document 5), and 1, 2-naphthoquinone is known as a polymerization inhibitor for (meth) acrylic acid and esters (for example, patent document 6). Alkoxynaphthol is known as a polymerization inhibitor for radical polymerization of (meth) acrylic acid, (meth) acrylic acid esters, styrene, and the like (patent document 7). However, these polymerization inhibitors are merely radical polymerization inhibitors for capturing generated radicals, and are not required additives in the radical polymerization reaction, and are preferably removed in the radical polymerization reaction.

Disclosure of Invention

Problems to be solved by the invention

The purpose of the present invention is to provide a radical polymerization control agent having radical polymerization inhibiting ability, which is capable of capturing radicals generated during storage of a radical polymerizable compound, thereby improving stability of radical polymerizability, etc., and exerting an action of inhibiting unexpected polymerization, and is completely harmless when the radical polymerizable compound is polymerized; and a method for controlling radical polymerization using the radical polymerization control agent.

Means for solving the problems

The radical polymerization control agent of the present invention is the following compound: free radicals are trapped in the ground state (dark reaction) and act as a radical polymerization inhibitor, but when light of a specific wavelength is irradiated, the radical polymerization inhibitor becomes excited, loses the radical trapping ability, and is harmless to the radical polymerization reaction. Further, the energy in the excited state is transferred to, for example, a radical polymerization initiator, and the like, and instead, is a compound having a function of promoting radical polymerization.

That is, the radical polymerization controller contained in the radical polymerizable composition of the present invention captures radicals generated by heat or decomposition when stored in a dark place, for example, and functions as a radical polymerization inhibitor for the polymerizable compound; however, in the polymerization (which may be thermal polymerization or photopolymerization), the radical polymerization inhibiting effect is lost by initiating the polymerization while irradiating light of a certain specific wavelength, and the radical polymerization of the radical polymerizable compound can be easily initiated without increasing the amount of the radical polymerization initiator.

That is, a first aspect of the present invention resides in a radical polymerization control agent represented by the following general formula (1), which is a compound having an effect of inhibiting radical polymerization of a radical polymerizable compound, wherein the radical polymerization inhibiting effect disappears upon irradiation with light containing light having a wavelength ranging from 300nm to 500 nm.

[ solution 1]

In the formula (1), R independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, an alkoxyalkyl group having 1 to 15 carbon atoms, a glycidyl group, a hydroxyalkyl group having 1 to 15 carbon atoms, an aryloxyalkyl group having 7 to 14 carbon atoms, an acyl group having 2 to 13 carbon atoms or a substituted carbonyl group having 2 to 13 carbon atoms, and X independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or an aryl group having 6 to 12 carbon atoms, but adjacent groups X may be bonded to each other to form a saturated or unsaturated 6-membered ring instead of the above-mentioned substituents. The 6-membered ring formed by the adjacent group X may be further substituted with an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or a halogen atom.

The second invention is a radical polymerization control agent represented by the following general formula (2) which has an effect of inhibiting radical polymerization of a radical polymerizable compound, and is characterized in that the radical polymerization inhibiting effect disappears under irradiation of light containing light in a wavelength range of 300nm to 500 nm.

[ solution 2]

In the formula (2), R independently represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, an alkoxyalkyl group having 1 to 15 carbon atoms, a glycidyl group, a hydroxyalkyl group having 1 to 15 carbon atoms, an aryloxyalkyl group having 7 to 14 carbon atoms, an acyl group having 2 to 13 carbon atoms or a substituted carbonyl group having 2 to 13 carbon atoms, and X independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or an aryl group having 6 to 12 carbon atoms.

The third invention is a radical polymerization control agent represented by the following general formula (3) which has an effect of inhibiting radical polymerization of a radical polymerizable compound, wherein the radical polymerization inhibiting effect disappears by irradiation with light containing light having a wavelength ranging from 300nm to 500 nm.

[ solution 3]

A fourth aspect of the present invention is a radical polymerization control agent represented by the following general formula (4), which is a compound having an effect of inhibiting radical polymerization of a radical polymerizable compound, wherein the radical polymerization inhibiting effect is eliminated by irradiation with light containing light having a wavelength ranging from 300nm to 500 nm.

[ solution 4]

In the formula (4), X independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or a halogen atom, Y and Z independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an amino group or a halogen atom, but Y and Z may be bonded to each other not to the above-mentioned substituents to form a saturated or unsaturated 6-membered ring. The 6-membered ring formed by Y and Z may be further substituted with an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or a halogen atom.

A fifth invention is a radical polymerization controller according to claim 4, wherein X is a hydrogen atom, and Y and Z are hydrogen atoms in the general formula (4).

A sixth invention is a radical polymerization control agent according to claim 4, wherein in the general formula (4), X represents a hydrogen atom, Y represents a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an amino group or a halogen atom, and Z represents a hydrogen atom.

A seventh invention is a radical polymerization controller according to claim 4, wherein in the general formula (4), X is a hydrogen atom, Y is a hydroxyl group or a methyl group, and Z is a hydrogen atom.

An eighth invention is a radical polymerization controller according to claim 4, wherein in the general formula (4), X is a hydrogen atom, Y is a chlorine atom, and Z is a chlorine atom or an amino group.

A ninth invention is a radical polymerization control agent represented by the following general formula (5) or (6), which is a compound having an effect of inhibiting radical polymerization of a radical polymerizable compound, characterized in that the radical polymerization inhibiting effect disappears under irradiation of light containing light in a wavelength range of 300nm to 500 nm.

[ solution 5]

In the formula (5), X independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or a halogen atom, and Q represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or a halogen atom.

[ solution 6]

A tenth aspect of the present invention is a radically polymerizable composition comprising the radically polymerizable compound and the radically polymerization control agent according to any one of the first to ninth aspects of the present invention.

An eleventh aspect of the present invention is the radical polymerizable composition according to the tenth aspect, wherein the radical polymerizable compound is (meth) acrylic acid, (meth) acrylate, or styrene, or an oligomer thereof.

A twelfth aspect of the present invention is a radical polymerizable composition, wherein the radical polymerizable composition according to the tenth or eleventh aspect further contains a radical polymerization initiator.

A thirteenth aspect of the invention is the radical polymerizable composition according to the twelfth aspect of the invention, wherein the radical polymerization initiator is a thermal radical polymerization initiator.

A fourteenth aspect of the present invention is the radical polymerizable composition according to the twelfth aspect of the present invention, wherein the radical polymerization initiator is a photo radical polymerization initiator.

A fifteenth aspect of the present invention is a method for controlling radical polymerization, wherein radical polymerization is initiated by applying heat energy to the radical polymerizable composition of the thirteenth aspect of the present invention under irradiation with light containing light having a wavelength in the range of 300nm to 500 nm.

A sixteenth aspect of the present invention is a method for controlling radical polymerization, wherein the radical polymerizable composition according to the thirteenth aspect of the present invention is applied to a substrate, and a part of the obtained coating film is masked, and is irradiated with light having a wavelength range of 300nm to 500nm, and is subjected to radical polymerization by applying thermal energy, thereby polymerizing only the portion irradiated with the light.

A seventeenth aspect of the present invention is a method for controlling radical polymerization, wherein, when radical polymerization is performed by applying thermal energy to the radical polymerizable composition according to the thirteenth aspect of the present invention, a specific region is irradiated with light containing light having a wavelength ranging from 300nm to 500nm, thereby causing radical polymerization only in the specific region.

The eighteenth invention is a method for controlling radical polymerization, wherein the radical polymerization is initiated by applying light energy for initiating polymerization to the radical polymerizable composition according to the fourteenth invention under irradiation of light containing light in a wavelength range of 300nm to 500 nm.

A nineteenth aspect of the present invention is a method for controlling radical polymerization, wherein a substrate is coated with the radical polymerizable composition according to the fourteenth aspect of the present invention, and a part of the obtained coating film is masked, and radical polymerization is performed by applying light energy for initiating polymerization while irradiating light in a wavelength range of 300nm to 500nm, thereby polymerizing only a portion irradiated with the light in the wavelength range of 300nm to 500 nm.

A twentieth aspect of the present invention is a method for controlling radical polymerization, wherein in radical polymerization of the radical polymerizable composition according to the fourteenth aspect of the present invention by irradiating the composition with light energy for initiating polymerization, light including light having a wavelength in a range of 300nm to 500nm is irradiated onto a specific region, thereby causing radical polymerization only in the specific region.

ADVANTAGEOUS EFFECTS OF INVENTION

In the radical polymerizable composition containing the radical polymerization control agent of the present invention, the radical polymerization control agent functions as a radical polymerization inhibitor when stored in a dark place, for example, but by initiating polymerization while irradiating light of a certain specific wavelength at the time of polymerization of the radical polymerizable composition, the radical polymerization inhibiting effect of the radical polymerization control agent is lost, and radical polymerization can be easily performed without increasing the amount of the radical polymerization initiator. That is, the radical polymerization control agent of the present invention initiates radical polymerization of the radical polymerizable compound under irradiation of light of a certain specific wavelength (bright portion), and blocks radical polymerization of the radical polymerizable compound under a condition where light of a certain specific wavelength is not irradiated (dark portion). That is, the light and shade control of the initiation of radical polymerization of the radical polymerizable compound can be performed.

Detailed Description

[ radical polymerization controllers ]

The radical polymerization controller of the present invention is a compound represented by the following general formulae (1) to (6).

[ solution 7]

In the formula (1), R independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, an alkoxyalkyl group having 1 to 15 carbon atoms, a glycidyl group, a hydroxyalkyl group having 1 to 15 carbon atoms, an aryloxyalkyl group having 7 to 14 carbon atoms, an acyl group having 2 to 13 carbon atoms or a substituted carbonyl group having 2 to 13 carbon atoms, and X independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or an aryl group having 6 to 12 carbon atoms, but adjacent groups X may be bonded to each other to form a saturated or unsaturated 6-membered ring instead of the above-mentioned substituents. The 6-membered ring formed by the adjacent group X may be further substituted with an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or a halogen atom.

[ solution 8]

[ solution 9]

[ solution 10]

In the formula (4), X independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or a halogen atom, Y and Z independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an amino group or a halogen atom, but Y and Z may be bonded to each other not to the above-mentioned substituents to form a saturated or unsaturated 6-membered ring. The 6-membered ring formed by Y and Z may be further substituted with an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or a halogen atom.

[ solution 11]

In the formula (5), X independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or a halogen atom, and Q represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or a halogen atom.

[ solution 12]

In the general formulae (1) to (3), examples of the alkyl group represented by R include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-decyl, n-dodecyl and the like, examples of the aryl group include phenyl, p-tolyl, o-tolyl, naphthyl and the like, examples of the aralkyl group include benzyl, phenethyl, phenylpropyl, naphthylmethyl, naphthylethyl and the like, and examples of the alkoxyalkyl group include 2-methoxyethyl, 2-ethoxyethyl, 2-methoxyethoxyethyl and the like. Examples of the glycidyl group include a glycidyl group and a 2-methylglycidyl group. Examples of the hydroxyalkyl group include a hydroxymethyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 2-hydroxybutyl group, and a 3-hydroxybutyl group. Examples of the aryloxyalkyl group include a phenoxyethyl group and a tolyloxyethyl group.

Examples of the alkyl group represented by X in the general formulae (1) to (6) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, 2-ethylhexyl, 4-methylpentyl, and 4-methyl-3-pentenyl, and examples of the aryl group include phenyl, p-tolyl, o-tolyl, and naphthyl. Examples of the aralkyl group represented by X in the general formulae (3) to (6) include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group, and examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group. Examples of the glycidyl group include a glycidyl group and a 2-methylglycidyl group. Examples of the aryloxy group include a phenoxy group and a tolyloxy group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Examples of the alkyl group represented by Y and Z in the general formula (4) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a pentyl group, a 2-ethylhexyl group, a 4-methylpentyl group, and a 4-methyl-3-pentenyl group, examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group, and examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

In the formula (4), as an example of the mutual bonding of Y and Z, Y and Z are CH₂CH₂A compound in which the group Y and Z are bonded by a single bond,the compound is represented by general formula (6). With Y and Z being CH₂A compound in which CH group, Y and Z are bonded by a double bond, the compound being represented by the general formula (5). The 6-membered ring formed by Y and Z may be further substituted with an alkyl group, an aryl group, an aralkyl group, a hydroxyl group, an alkoxy group, an aryloxy group or a halogen atom.

In the general formulae (5) and (6), examples of the alkyl group represented by Q include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-decyl, n-dodecyl and the like, and examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Specific examples of the radical polymerization controller of the present invention are shown below.

First, specific examples of the compound represented by the following general formula (1) will be described.

[ solution 13]

In the formula (1), R independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, an alkoxyalkyl group having 1 to 15 carbon atoms, a glycidyl group, a hydroxyalkyl group having 1 to 15 carbon atoms, an aryloxyalkyl group having 7 to 14 carbon atoms, an acyl group having 2 to 13 carbon atoms or a substituted carbonyl group having 2 to 13 carbon atoms, and X independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or an aryl group having 6 to 12 carbon atoms, but adjacent groups X may be bonded to each other to form a saturated or unsaturated 6-membered ring instead of the above-mentioned substituents. The 6-membered ring formed by the adjacent group X may be further substituted with an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or a halogen atom.

Examples of the compound represented by the general formula (1) include the following compounds. Examples thereof include 1, 4-dihydroxynaphthalene, 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4- (n-propoxy) -1-naphthol, 4- (n-butoxy) -1-naphthol, 4- (n-pentyloxy) -1-naphthol, 4- (n-hexyloxy) -1-naphthol, 4- (n-heptyloxy) -1-naphthol, 4- (n-octyloxy) -1-naphthol, 4- (2-ethylhexyloxy) -1-naphthol, 4- (n-nonyloxy) -1-naphthol, 4-benzyloxy-1-naphthol, 4-phenethyloxy-1-naphthol, 4-glycidyloxy-1-naphthol, 4-methyloxyphenyl-1-naphthol, and the like, 4- (2-Methyloxypropoxy) -1-naphthol, 1, 4-dimethoxynaphthalene, 1, 4-diethoxynaphthalene, 1, 4-di-n-propoxytalene, 1, 4-diisopropoxytalene, 1, 4-di-n-butoxynaphthalene, 1, 4-dihexyloxynaphthalene, 1, 4-bis (2-ethylhexyloxy) naphthalene, 1, 4-di-dodecyloxy) naphthalene, 1, 4-diphenylethyloxynaphthalene, 1, 4-bis (2-methoxyethoxy) naphthalene, 1, 4-bis (2-phenoxyethoxy) naphthalene, 1, 4-diepoxyloxynaphthalene, 1, 4-bis (2-hydroxyethoxy) naphthalene, 1, 4-bis (2-hydroxypropoxy) naphthalene, 1-methoxy-4-ethoxynaphthalene, 1-methoxy-4-butoxynaphthalene and the like.

Further examples thereof include 2-methyl-1, 4-dimethoxynaphthalene, 2-methyl-1, 4-diethoxynaphthalene, 2-methyl-1, 4-di-n-propoxaphthalene, 2-methyl-1, 4-diisopropoxytalene, 2-methyl-1, 4-di-n-butoxynaphthalene, 2-methyl-1, 4-dihexonaphthalene, 2-methyl-1, 4-bis (2-ethylhexyloxy) naphthalene, 2-methyl-1, 4-di (dodecyloxy) naphthalene, 2-methyl-1, 4-diphenylethyloxynaphthalene, 2-methyl-1, 4-bis (2-methoxyethoxy) naphthalene, 2-methyl-1, 4-bis (2-phenoxyethoxy) naphthalene, 2-methyl-1, 4-diepoxyloxynaphthalene, 2-methyl-1, 4-bis (2-hydroxyethoxy) naphthalene, 2-methyl-1, 4-bis (2-hydroxypropoxy) naphthalene, 2-ethyl-1, 4-diethoxynaphthalene, 6-methyl-1, 4-dimethoxynaphthalene, 6-methyl-1, 4-diethoxynaphthalene, 6-methyl-1, 4-di-n-propoxaphthalene, 6-methyl-1, 4-diisopropoxaphthalene, 6-methyl-1, 4-di-n-butoxynaphthalene, 6-methyl-1, 4-dihexyloxynaphthalene, 6-methyl-1, 4-bis (2-ethylhexyloxy) naphthalene, 2-methyl-1, 4-bis (2-hydroxyethoxy) naphthalene, 2-methyl-1, 4-dimethoxynaphthalene, 6-methyl-1, 4-diethoxyn, 6-methyl-1, 4-di (dodecyloxy) naphthalene, 6-methyl-1, 4-diphenylethyloxynaphthalene, 6-methyl-1, 4-bis (2-methoxyethoxy) naphthalene, 6-methyl-1, 4-bis (2-phenoxyethoxy) naphthalene, 6-methyl-1, 4-diepoxyloxynaphthalene, 6-methyl-1, 4-bis (2-hydroxyethoxy) naphthalene, 6-methyl-1, 4-bis (2-hydroxypropoxy) naphthalene, 6-ethyl-1, 4-diethoxynaphthalene, 2, 3-dimethyl-1, 4-dimethoxynaphthalene, 2, 3-dimethyl-1, 4-diethoxynaphthalene, 6-methyl-1, 4-diethoxynaphthalene, and mixtures thereof, 2, 3-dimethyl-1, 4-di-n-propoxytalene, 2, 3-dimethyl-1, 4-diisopropoxytalene, 2, 3-dimethyl-1, 4-di-n-butoxynaphthalene, 2, 3-dimethyl-1, 4-dihexyloxynaphthalene, 2, 3-dimethyl-1, 4-bis (2-ethylhexyloxy) naphthalene, 2, 3-dimethyl-1, 4-di (dodecyloxy) naphthalene, 2, 3-dimethyl-1, 4-diphenylethyloxynaphthalene, 2, 3-dimethyl-1, 4-bis (2-methoxyethoxy) naphthalene, 2, 3-dimethyl-1, 4-bis (2-phenoxyethoxy) naphthalene, 2, 3-dimethyl-1, 4-diepoxyloxynaphthalene, 2, 3-dimethyl-1, 4-bis (2-hydroxyethoxy) naphthalene, 2, 3-dimethyl-1, 4-bis (2-hydroxypropoxy) naphthalene and the like.

In the general formula (1), specific examples of the compound wherein R is an acyl group having 2 to 13 carbon atoms include the following compounds. That is, examples of the case where X is a hydrogen atom include 1, 4-bis (acetyloxy) naphthalene, 1, 4-bis (propionyloxy) naphthalene, 1, 4-bis (n-butyryloxy) naphthalene, 1, 4-bis (isobutyryloxy) naphthalene, 1, 4-bis (n-valeryloxy) naphthalene, 1, 4-bis (n-hexanoyloxy) naphthalene, 1, 4-bis (n-heptanoyloxy) naphthalene, 1, 4-bis (n-octanoyloxy) naphthalene, 1, 4-bis (2-ethylhexanoyloxy) naphthalene, 1, 4-bis (n-nonanoyloxy) naphthalene, 1, 4-bis (n-decanoyloxy) naphthalene, 1, 4-bis (n-undecanoyloxy) naphthalene, 1, 4-bis (n-dodecanoyloxy) naphthalene, and the like.

Further, examples of X as an alkyl group include 2-methyl-1, 4-bis (acetyloxy) naphthalene, 2-methyl-1, 4-bis (propionyloxy) naphthalene, 2-methyl-1, 4-bis (n-butyryloxy) naphthalene, 2-methyl-1, 4-bis (isobutyryloxy) naphthalene, 2-methyl-1, 4-bis (n-valeryloxy) naphthalene, 2-methyl-1, 4-bis (n-hexanoyloxy) naphthalene, 2-methyl-1, 4-bis (n-heptanoyloxy) naphthalene, 2-methyl-1, 4-bis (n-octanoyloxy) naphthalene, 2-methyl-1, 4-bis (2-ethylhexanoyloxy) naphthalene, 2-methyl-1, 4-bis (n-nonanoyloxy) naphthalene, 2-methyl-1, 4-bis (n-decanoyloxy) naphthalene, 2-methyl-1, 4-bis (n-undecanoyloxy) naphthalene, 2-methyl-1, 4-bis (n-dodecanoyloxy) naphthalene, 2-ethyl-1, 4-bis (acetyloxy) naphthalene, 2-ethyl-1, 4-bis (propionyloxy) naphthalene, 2-ethyl-1, 4-bis (n-butanoyloxy) naphthalene, 2-ethyl-1, 4-bis (isobutyryloxy) naphthalene, 2-ethyl-1, 4-bis (n-pentanoyloxy) naphthalene, 2-ethyl-1, 4-bis (n-hexanoyloxy) naphthalene, 2-ethyl-1, 4-bis (n-heptanoyloxy) naphthalene, 2-ethyl-1, 4-bis (n-octanoyloxy) naphthalene, 2-ethyl-1, 4-bis (2-ethylhexanoyloxy) naphthalene, 2-ethyl-1, 4-bis (n-nonanoyloxy) naphthalene, 2-ethyl-1, 4-bis (n-decanoyloxy) naphthalene, 2-ethyl-1, 4-bis (n-undecanoyloxy) naphthalene, 2-ethyl-1, 4-bis (n-dodecanoyloxy) naphthalene, and the like.

In the general formula (1), specific examples of the compound in which R is a substituted carbonyl group having 2 to 13 carbon atoms include 1, 4-bis (methoxycarbonyloxy) naphthalene, 1, 4-bis (ethoxycarbonyloxy) naphthalene, 1, 4-bis (n-propoxycarbonyloxy) naphthalene, 1, 4-bis (isopropoxycarbonyloxy) naphthalene, 1, 4-bis (n-butoxycarbonyloxy) naphthalene, 1, 4-bis (n-pentyloxycarbonyloxy) naphthalene, 1, 4-bis (n-hexyloxycarbonyloxy) naphthalene, 1, 4-bis (n-heptyloxycarbonyloxy) naphthalene, 1, 4-bis (n-octyloxycarbonyloxy) naphthalene, 1, 4-bis (2-ethylhexyloxycarbonyloxy) naphthalene, 1, 4-bis (n-nonyloxycarbonyloxy) naphthalene, 1, 4-bis (n-decyloxycarbonyloxy) naphthalene, 1, 4-bis (n-undecyloxycarbonyloxy) naphthalene, 1, 4-bis (n-dodecyloxycarbonyloxy) naphthalene, and the like.

Next, examples of the alkyl group as X include 2-methyl-1, 4-bis (methoxycarbonyloxy) naphthalene, 2-methyl-1, 4-bis (ethoxycarbonyloxy) naphthalene, 2-methyl-1, 4-bis (n-propoxycarbonyloxy) naphthalene, 2-methyl-1, 4-bis (isopropoxycarbonyloxy) naphthalene, 2-methyl-1, 4-bis (n-butoxycarbonyloxy) naphthalene, 2-methyl-1, 4-bis (n-pentyloxycarbonyloxy) naphthalene, 2-methyl-1, 4-bis (n-hexyloxycarbonyloxy) naphthalene, 2-methyl-1, 4-bis (n-heptyloxycarbonyloxy) naphthalene, 2-methyl-1, 4-bis (n-octyloxycarbonyloxy) naphthalene, 2-methyl-1, 4-bis (2-ethylhexyloxycarbonyloxy) naphthalene, 2-methyl-1, 4-bis (n-nonyloxycarbonyloxy) naphthalene, 2-methyl-1, 4-bis (n-decyloxycarbonyloxy) naphthalene, 2-methyl-1, 4-bis (n-undecyloxycarbonyloxy) naphthalene, 2-methyl-1, 4-bis (n-dodecyloxycarbonyloxy) naphthalene, 2-ethyl-1, 4-bis (methoxycarbonyloxy) naphthalene, 2-ethyl-1, 4-bis (ethoxycarbonyloxy) naphthalene, 2-ethyl-1, 4-bis (n-propoxycarbonyloxy) naphthalene, 2-ethyl-1, 4-bis (isopropoxycarbonyloxy) naphthalene, 2-ethyl-1, 4-bis (n-butoxycarbonyloxy) naphthalene, 2-ethyl-1, 4-bis (n-pentyloxycarbonyloxy) naphthalene, 2-ethyl-1, 4-bis (n-hexyloxycarbonyloxy) naphthalene, 2-ethyl-1, 4-bis (n-heptyloxycarbonyloxy) naphthalene, 2-ethyl-1, 4-bis (n-octyloxycarbonyloxy) naphthalene, 2-ethyl-1, 4-bis (2-ethylhexyloxycarbonyloxy) naphthalene, 2-ethyl-1, 4-bis (n-nonyloxycarbonyloxy) naphthalene, 2-ethyl-1, 4-bis (n-decyloxycarbonyloxy) naphthalene, 2-ethyl-1, 4-bis (n-undecyloxycarbonyloxy) naphthalene, 2-ethyl-1, 4-bis (n-dodecyloxycarbonyloxy) naphthalene and the like.

In general formula (1), specific examples of the case where adjacent groups of R are bonded to each other to form a saturated 6-membered ring include 9, 10-dimethoxy-1, 2,3, 4-tetrahydroanthracene, 9, 10-diethoxy-1, 2,3, 4-tetrahydroanthracene, 9, 10-di-n-propoxy-1, 2,3, 4-tetrahydroanthracene, 9, 10-diisopropoxy-1, 2,3, 4-tetrahydroanthracene, 9, 10-di-n-butoxy-1, 2,3, 4-tetrahydroanthracene, 9, 10-bis (2-ethylhexyloxy) -1,2,3, 4-tetrahydroanthracene, 9, 10-di (dodecyloxy) -1,2,3, 4-tetrahydroanthracene, 9, 10-diphenylethyloxy-1, 2,3, 4-tetrahydroanthracene, 9, 10-bis (2-methoxyethoxy) -1,2,3, 4-tetrahydroanthracene, 9, 10-bis (2-phenoxyethoxy) -1,2,3, 4-tetrahydroanthracene, 9, 10-bis (2-hydroxyethoxy) -1,2,3, 4-tetrahydroanthracene, 9-methoxy-10-ethoxy-1, 2,3, 4-tetrahydroanthracene, 9-methoxy-10-butoxy-1, 2,3, 4-tetrahydroanthracene, 2-methyl-9, 10-diethoxy-1, 2,3, 4-tetrahydroanthracene, 2-ethyl-9, 10-diethoxy-1, 2,3, 4-tetrahydroanthracene, and the like.

In the general formula (1), when an unsaturated 6-membered ring is formed by bonding adjacent groups of R to each other, specific examples of the case where the 6-membered ring is non-aromatic include 9, 10-dimethoxy-1, 4-dihydroanthracene, 9, 10-diethoxy-1, 4-dihydroanthracene, 9, 10-di-n-propoxy-1, 4-dihydroanthracene, 9, 10-diisopropoxy-1, 4-dihydroanthracene, 9, 10-di-n-butoxy-1, 4-dihydroanthracene, 9, 10-bis (2-ethylhexyloxy) -1, 4-dihydroanthracene, 9, 10-di-dodecyloxy) -1, 4-dihydroanthracene, 9, 10-diphenylethyloxy-1, 4-dihydroanthracene, and the like, 9, 10-bis (2-methoxyethoxy) -1, 4-dihydroanthracene, 9, 10-bis (2-phenoxyethoxy) -1, 4-dihydroanthracene, 9, 10-bis (2-hydroxyethoxy) -1, 4-dihydroanthracene, 9-methoxy-10-ethoxy-1, 4-dihydroanthracene, 9-methoxy-10-butoxy-1, 4-dihydroanthracene, 2-methyl-9, 10-diethoxy-1, 4-dihydroanthracene, 2-ethyl-9, 10-diethoxy-1, 4-dihydroanthracene, and the like.

Next, specific examples of the compound represented by the following general formula (2) will be described.

[ solution 14]

In the general formula (2), in the compound represented by the formula (2), wherein R is an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, an alkoxyalkyl group having 1 to 15 carbon atoms, a glycidyl group, a hydroxyalkyl group having 1 to 15 carbon atoms or an aryloxyalkyl group having 7 to 14 carbon atoms, specific examples of the case where X is a hydrogen atom include 9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 9, 10-di-n-propoxylanthracene, 9, 10-diisopropoxylanthracene, 9, 10-di-n-butoxyanthracene, 9, 10-bis (2-ethylhexyloxy) anthracene, 9, 10-di (dodecyloxy) anthracene, 9, 10-diphenylethyloxyanthracene, 9, 10-bis (2-methoxyethoxy) anthracene, 9, 10-bis (2-phenoxyethoxy) anthracene, 9, 10-bis (2-hydroxyethoxy) anthracene, 9, 10-diepoxy-propylanthracene, 9-methoxy-10-ethoxy anthracene, 9-methoxy-10-butoxyanthracene, and the like.

Further, examples of X as an alkyl group include 2-methyl-9, 10-dimethoxyanthracene, 2-methyl-9, 10-diethoxyanthracene, 2-methyl-9, 10-di-n-propoxylanthracene, 2-methyl-9, 10-diisopropoxylanthracene, 2-methyl-9, 10-di-n-butoxyanthracene, 2-methyl-9, 10-bis (2-ethylhexyloxy) anthracene, 2-methyl-9, 10-bis (dodecyloxy) anthracene, 2-methyl-9, 10-diphenylethyloxyanthracene, 2-methyl-9, 10-bis (2-methoxyethoxy) anthracene, 2-methyl-9, 10-bis (2-phenoxyethoxy) anthracene, 2-methyl-9, 10-bis (2-hydroxyethoxy) anthracene, 2-methyl-9, 10-diepoxyoxyanthracene, 9-methoxy-10-ethoxyanthracene, 9-methoxy-10-butoxyanthracene, 2-methyl-9, 10-diethoxyanthracene, 2-ethyl-9, 10-dimethoxyanthracene, 2-ethyl-9, 10-diethoxyanthracene, 2-ethyl-9, 10-di-n-propoxylanthracene, 2-ethyl-9, 10-diisopropoxylanthracene, 2-ethyl-9, 10-di-n-butoxyanthracene, di-n-butoxyanthracene, 2-ethyl-9, 10-bis (2-ethylhexyloxy) anthracene, 2-ethyl-9, 10-di (dodecyloxy) anthracene, 2-ethyl-9, 10-diphenylethyloxy anthracene, 2-ethyl-9, 10-bis (2-methoxyethoxy) anthracene, 2-ethyl-9, 10-bis (2-phenoxyethoxy) anthracene, 2-ethyl-9, 10-bis (2-hydroxyethoxy) anthracene, 2-ethyl-9, 10-diepoxy anthracene, 9-methoxy-10-ethoxyanthracene, 9-methoxy-10-butoxyanthracene, 2-methyl-2-ethyl-9, 10-diethoxyanthracene, 2-ethyl-9, 10-diethoxyanthrace, 2-ethyl-9, 10-diethoxyanthracene, and the like.

In the general formula (2), specific examples of the compound wherein R is an acyl group having 2 to 13 carbon atoms include the following compounds. That is, examples of the case where X is a hydrogen atom include 9, 10-bis (acetyloxy) anthracene, 9, 10-bis (propionyloxy) anthracene, 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-undecanoyloxy) anthracene, 9, 10-bis (n-dodecanoyloxy) anthracene, and the like.

Further, examples of X as an alkyl group include 2-methyl-9, 10-bis (acetyloxy) anthracene, 2-methyl-9, 10-bis (propionyloxy) anthracene, 2-methyl-9, 10-bis (n-butyryloxy) anthracene, 2-methyl-9, 10-bis (isobutyryloxy) anthracene, 2-methyl-9, 10-bis (n-valeryloxy) 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, 2-methyl-9, 10-bis (2-ethylhexanoyloxy) anthracene, 2-methyl-9, 10-bis (n-nonanoyloxy) anthracene, 2-methyl-9, 10-bis (n-decanoyloxy) anthracene, 2-methyl-9, 10-bis (n-undecanoyloxy) anthracene, 2-methyl-9, 10-bis (n-dodecanoyloxy) anthracene, 2-ethyl-9, 10-bis (acetyloxy) anthracene, 2-ethyl-9, 10-bis (propionyloxy) anthracene, 2-ethyl-9, 10-bis (n-butanoyloxy) anthracene, 2-ethyl-9, 10-bis (isobutyryloxy) anthracene, 2-ethyl-9, 10-bis (n-pentanoyloxy) 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, 2-ethyl-9, 10-bis (2-ethylhexanoyloxy) anthracene, 2-ethyl-9, 10-bis (n-nonanoyloxy) anthracene, 2-ethyl-9, 10-bis (n-decanoyloxy) anthracene, 2-ethyl-9, 10-bis (n-undecanoyloxy) anthracene, 2-ethyl-9, 10-bis (n-dodecanoyloxy) anthracene, and the like.

In the general formula (2), specific examples of the compound in which R is a substituted carbonyl group having 2 to 13 carbon atoms 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 (n-pentyloxycarbonyloxy) anthracene, 9, 10-bis (n-hexyloxycarbonyloxy) anthracene, 9, 10-bis (n-heptyloxycarbonyloxy) anthracene, 9, 10-bis (n-octyloxycarbonyloxy) anthracene, 9, 10-bis (2-ethylhexyloxycarbonyloxy) anthracene, 9, 10-bis (n-nonyloxycarbonyloxy) anthracene, 9, 10-bis (n-decyloxycarbonyloxy) anthracene, 9, 10-bis (n-undecyloxycarbonyloxy) anthracene, 9, 10-bis (n-dodecyloxycarbonyloxy) anthracene, and the like.

Next, examples of the alkyl group as X include 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 (n-pentyloxycarbonyloxy) 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, 2-methyl-9, 10-bis (2-ethylhexyloxycarbonyloxy) anthracene, 2-methyl-9, 10-bis (n-nonyloxycarbonyloxy) anthracene, 2-methyl-9, 10-bis (n-decyloxycarbonyloxy) anthracene, 2-methyl-9, 10-bis (n-undecyloxycarbonyloxy) anthracene, 2-methyl-9, 10-bis (n-dodecyloxycarbonyloxy) 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-butoxycarbonyloxy) anthracene, 2-ethyl-9, 10-bis (n-pentyloxycarbonyloxy) 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, 2-ethyl-9, 10-bis (2-ethylhexyloxycarbonyloxy) anthracene, 2-ethyl-9, 10-bis (n-nonyloxycarbonyloxy) anthracene, 2-ethyl-9, 10-bis (n-decyloxycarbonyloxy) anthracene, 2-ethyl-9, 10-bis (n-undecyloxycarbonyloxy) anthracene, 2-ethyl-9, 10-bis (n-dodecyloxycarbonyloxy) anthracene, and the like.

Next, specific examples of the compound represented by the following general formula (3) will be described.

[ solution 15]

In the general formula (3), in a compound wherein R is represented by an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, an alkoxyalkyl group having 1 to 15 carbon atoms, a glycidyl group, a hydroxyalkyl group having 1 to 15 carbon atoms, or an aryloxyalkyl group having 7 to 14 carbon atoms, specific examples of the case where X is a hydrogen atom include 9-methoxyanthracene, 9-ethoxyanthracene, 9-n-propoxylanthracene, 9-isopropoxyanthracene, 9-n-butoxyanthracene, 9- (2-ethylhexyloxy) anthracene, 9-dodecyloxyanthracene, 9-phenethyloxyanthracene, 9- (2-methoxyethoxy) anthracene, 9- (2-phenoxyethoxy) anthracene, 9, 10-bis (2-hydroxyethoxy) anthracene, 9-glycidoxyanthracene, and the like.

Further, examples of X as an alkyl group include 2-methyl-9-methoxyanthracene, 2-methyl-9-ethoxyanthracene, 2-methyl-9-n-propoxylanthracene, 2-methyl-9-isopropoxyanthracene, 2-methyl-9-n-butoxyanthracene, 2-methyl-9- (2-ethylhexyloxy) anthracene, 2-methyl-9-dodecyloxyanthracene, 2-methyl-9-phenethyloxyanthracene, 2-methyl-9- (2-methoxyethoxy) anthracene, 2-methyl-9- (2-phenoxyethoxy) anthracene, 9, 10-bis (2-hydroxyethoxy) anthracene, 2-methyl-9-glycidoxyanthracene, 2-methyl-9-epoxypropoxylanthracene, 2-methyl-9-ethoxyanthracene, 2-methyl-9-n-butoxyanthracene, 2-methyl-9- (2-, 2-ethyl-9-methoxyanthracene, 2-ethyl-9-ethoxyanthracene, 2-ethyl-9-n-propoxylanthracene, 2-ethyl-9-isopropoxyanthracene, 2-ethyl-9-n-butoxyanthracene, 2-ethyl-9- (2-ethylhexyloxy) anthracene, 2-ethyl-9-dodecyloxyanthracene, 2-ethyl-9-phenethyloxyanthracene, 2-ethyl-9- (2-methoxyethoxy) anthracene, 2-ethyl-9- (2-phenoxyethoxy) anthracene, 9, 10-bis (2-hydroxyethoxy) anthracene, 2-ethyl-9-glycidoxyanthracene, and the like.

In the general formula (3), specific examples of the compound wherein R is an acyl group having 2 to 13 carbon atoms include the following compounds. Examples of X as a hydrogen atom include 9, 10-bis (acetyloxy) anthracene, 9, 10-bis (propionyloxy) anthracene, 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-undecanoyloxy) anthracene, 9, 10-bis (n-dodecanoyloxy) anthracene, and the like.

Next, examples of X as an alkyl group include 2-methyl-9, 10-bis (acetyloxy) anthracene, 2-methyl-9, 10-bis (propionyloxy) anthracene, 2-methyl-9, 10-bis (n-butyryloxy) anthracene, 2-methyl-9, 10-bis (isobutyryloxy) anthracene, 2-methyl-9, 10-bis (n-valeryloxy) 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, 2-methyl-9, 10-bis (2-ethylhexanoyloxy) anthracene, 2-methyl-9, 10-bis (n-nonanoyloxy) anthracene, 2-methyl-9, 10-bis (n-decanoyloxy) anthracene, 2-methyl-9, 10-bis (n-undecanoyloxy) anthracene, 2-methyl-9, 10-bis (n-dodecanoyloxy) anthracene, 2-ethyl-9, 10-bis (acetyloxy) anthracene, 2-ethyl-9, 10-bis (propionyloxy) anthracene, 2-ethyl-9, 10-bis (n-butanoyloxy) anthracene, 2-ethyl-9, 10-bis (isobutyryloxy) anthracene, 2-ethyl-9, 10-bis (n-pentanoyloxy) 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, 2-ethyl-9, 10-bis (2-ethylhexanoyloxy) anthracene, 2-ethyl-9, 10-bis (n-nonanoyloxy) anthracene, 2-ethyl-9, 10-bis (n-decanoyloxy) anthracene, 2-ethyl-9, 10-bis (n-undecanoyloxy) anthracene, 2-ethyl-9, 10-bis (n-dodecanoyloxy) anthracene, and the like.

In the general formula (3), as a specific example of the compound wherein R is a substituted carbonyl group having 2 to 13 carbon atoms, a case where X is a hydrogen atom is exemplified, examples thereof include 9-methoxycarbonyloxyanthracene, 9-ethoxycarbonyloxyanthracene, 9- (n-propoxycarbonyloxy) anthracene, 9- (isopropoxycarbonyloxy) anthracene, 9- (n-butoxycarbonyloxy) anthracene, 9- (n-pentyloxycarbonyloxy) anthracene, 9- (n-hexyloxycarbonyloxy) anthracene, 9- (n-heptyloxycarbonyloxy) anthracene, 9- (n-octyloxycarbonyloxy) anthracene, 9- (2-ethylhexyloxycarbonyloxy) anthracene, 9- (n-nonyloxycarbonyloxy) anthracene, 9- (n-decyloxycarbonyloxy) anthracene, 9- (n-undecyloxycarbonyloxy) anthracene, and 9- (n-dodecyloxycarbonyloxy) anthracene.

Next, examples of the alkyl group as X include 2-methyl-9-methoxycarbonyloxyanthracene, 2-methyl-9-ethoxycarbonyloxyanthracene, 2-methyl-9- (n-propoxycarbonyloxy) anthracene, 2-methyl-9- (isopropoxycarbonyloxy) anthracene, 2-methyl-9- (n-butoxycarbonyloxy) anthracene, 2-methyl-9- (n-pentyloxycarbonyloxy) anthracene, 2-methyl-9- (n-hexyloxycarbonyloxy) anthracene, 2-methyl-9- (n-heptyloxycarbonyloxy) anthracene, 2-methyl-9- (n-octyloxycarbonyloxy) anthracene, 2-methyl-9- (2-ethylhexyloxycarbonyloxy) anthracene, 2-methyl-9- (n-nonyloxycarbonyloxy) anthracene, 2-methyl-9- (n-octyloxycarbonyloxy) anthracene, 2-methyl-9- (n-hexyl, 2-methyl-9- (n-decyloxycarbonyloxy) anthracene, 2-methyl-9- (n-undecyloxycarbonyloxy) anthracene, 2-methyl-9- (n-dodecyloxycarbonyloxy) anthracene, 2-ethyl-9-methoxycarbonyloxyanthracene, 2-ethyl-9-ethoxycarbonyloxyanthracene, 2-ethyl-9- (n-propoxycarbonyloxy) anthracene, 2-ethyl-9- (isopropoxycarbonyloxy) anthracene, 2-ethyl-9- (n-butoxycarbonyloxy) anthracene, 2-ethyl-9- (n-pentyloxycarbonyloxy) anthracene, 2-ethyl-9- (n-hexyloxycarbonyloxy) anthracene, 2-ethyl-9- (n-heptyloxycarbonyloxy) anthracene, n-hexyloxycarbonyloxy) anthracene, n-undecyloxycarbonyloxy anthracene, n-dodecyloxycarbonyloxy-substituted anthracene, n-ethyl, 2-ethyl-9- (n-octyloxycarbonyloxy) anthracene, 2-ethyl-9- (2-ethylhexyloxycarbonyloxy) anthracene, 2-ethyl-9- (n-nonyloxycarbonyloxy) anthracene, 2-ethyl-9- (n-decyloxycarbonyloxy) anthracene, 2-ethyl-9- (n-undecyloxycarbonyloxy) anthracene, 2-ethyl-9- (n-dodecyloxycarbonyloxy) anthracene, and the like.

Next, specific examples of the compound represented by the following general formula (4) will be described.

[ solution 16]

In the formula (4), X independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or a halogen atom, Y and Z independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an amino group or a halogen atom, but Y and Z may be bonded to each other not to the above-mentioned substituent to form a saturated or unsaturated 6-membered ring. The 6-membered ring formed by Y and Z may be further substituted with an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or a halogen atom.

As a specific example of the compound represented by the general formula (4), first, the following compounds are given as examples of compounds in which Y and Z are hydrogen atoms. Examples thereof include 1, 4-naphthoquinone, 5-methyl-1, 4-naphthoquinone, 6, 7-dimethyl-1, 4-naphthoquinone, 5-butyl-1, 4-naphthoquinone, 6, 7-dibutyl-1, 4-naphthoquinone, 5-pentyl-1, 4-naphthoquinone, 6-pentyl-1, 4-naphthoquinone, 5-chloro-1, 4-naphthoquinone, 6, 7-dichloro-1, 4-naphthoquinone, 5-hydroxy-1, 4-naphthoquinone, 6-hydroxy-1, 4-naphthoquinone, 5, 8-dihydroxy-1, 4-naphthoquinone, 5,6, 8-trihydroxy-1, 4-naphthoquinone, 5-methoxy-1, 4-naphthoquinone, 6-methoxy-1, 4-naphthoquinone, 5, 8-dimethoxy-1, 4-naphthoquinone, etc.

Next, in the general formula (4), examples of the compound in which Y is a hydroxyl group, an alkyl group, an alkoxy group, an amino group or a halogen atom, and Z is a hydrogen atom include the following compounds. Examples thereof include 2-methyl-1, 4-naphthoquinone, 2-ethyl-1, 4-naphthoquinone, 2-hydroxy-1, 4-naphthoquinone, 2-methoxy-1, 4-naphthoquinone, 2-chloro-1, 4-naphthoquinone, 2-amino-1, 4-naphthoquinone, 2, 5-dimethyl-1, 4-naphthoquinone, 2,6, 7-trimethyl-1, 4-naphthoquinone, 2-methyl-5-butyl-1, 4-naphthoquinone, 2-methyl-6, 7-dibutyl-1, 4-naphthoquinone, 2-methyl-6, 7-naphthoquinone, 2-ethyl-1, 4-naphthoquinone, 2-hydroxy-1, 4-naphthoquinone, 2-methoxy-1, 4-naphthoquinone, 2-methyl-1, 4-, 2-methyl-5-pentyl-1, 4-naphthoquinone, 2-methyl-6-pentyl-1, 4-naphthoquinone, 2-methyl-5-chloro-1, 4-naphthoquinone, 2-methyl-6, 7-dichloro-1, 4-naphthoquinone, 2-methyl-5-hydroxy-1, 4-naphthoquinone, 2-methyl-6-hydroxy-1, 4-naphthoquinone, 2-methyl-5, 8-dihydroxy-1, 4-naphthoquinone, 2-methyl-5, 6, 8-trihydroxy-1, 4-naphthoquinone, 2-methyl-5-methoxy-1, 4-naphthoquinone, 2-methyl-6-methoxy-1, 4-naphthoquinone, 2-methyl-5, 8-dimethoxy-1, 4-naphthoquinone, 2-hydroxy-5-methyl-1, 4-naphthoquinone, 2-ethyl-6, 7-dimethyl-1, 4-naphthoquinone, 2-ethyl-5-butyl-1, 4-naphthoquinone, 2-ethyl-6, 7-dibutyl-1, 4-naphthoquinone, 2-ethyl-6, 7-naphthoquinone, 2-methoxy-1, 4-naphthoquinone, 2-methyl-5, 8-dimethoxy-1, 4-naphthoquinone, 2-ethyl-6, 4-naphthoquinone, 2-, 2-ethyl-5-pentyl-1, 4-naphthoquinone, 2-ethyl-6-pentyl-1, 4-naphthoquinone, 2-ethyl-5-chloro-1, 4-naphthoquinone, 2-ethyl-6, 7-dichloro-1, 4-naphthoquinone, 2-ethyl-5-hydroxy-1, 4-naphthoquinone, 2-ethyl-6-hydroxy-1, 4-naphthoquinone, 2-ethyl-5, 8-dihydroxy-1, 4-naphthoquinone, 2-ethyl-5, 6, 8-trihydroxy-1, 4-naphthoquinone, 2-ethyl-5-methoxy-1, 4-naphthoquinone, 2-ethyl-6-methoxy-1, 4-naphthoquinone, 2-ethyl-5, 8-dimethoxy-1, 4-naphthoquinone, 2-hydroxy-6-methyl-1, 4-naphthoquinone, 2-hydroxy-6, 7-dimethyl-1, 4-naphthoquinone, 2-hydroxy-5-butyl-1, 4-naphthoquinone, 2-hydroxy-6, 7-dibutyl-1, 4-naphthoquinone, 2-hydroxy-5-pentyl-1, 4-naphthoquinone, 2-hydroxy-6-pentyl-1, 4-naphthoquinone, 2-dimethoxy-1, 4-naphthoquinone, 2-methoxy-, 2-hydroxy-5-chloro-1, 4-naphthoquinone, 2-hydroxy-6, 7-dichloro-1, 4-naphthoquinone, 2, 5-dihydroxy-1, 4-naphthoquinone, 2, 6-dihydroxy-1, 4-naphthoquinone, 2,5, 8-trihydroxy-1, 4-naphthoquinone, 2,5,6, 8-tetrahydroxy-1, 4-naphthoquinone, 2-hydroxy-5-methoxy-1, 4-naphthoquinone, 2-hydroxy-6-methoxy-1, 4-naphthoquinone, 2-hydroxy-5, 8-dimethoxy-1, 4-naphthoquinone, 2-hydroxy-6-methoxy-1, 4-naphthoquinone, 2-hydroxy-5, 8-dimethoxy-1, 4-naphthoquinone, 2-, 2-methoxy-5-methyl-1, 4-naphthoquinone, 2-methoxy-6, 7-dimethyl-1, 4-naphthoquinone, 2-methoxy-5-butyl-1, 4-naphthoquinone, 2-methoxy-6, 7-dibutyl-1, 4-naphthoquinone, 2-methoxy-5-pentyl-1, 4-naphthoquinone, 2-methoxy-6-pentyl-1, 4-naphthoquinone, 2-methoxy-5-chloro, 2-methoxy-6-chloro-1, 4-naphthoquinone, 2-methoxy-6, 7-dichloro-1, 4-naphthoquinone, 2-methoxy-5-hydroxy-1, 4-naphthoquinone, 2-methoxy-6-hydroxy-1, 4-naphthoquinone, 2-methoxy-5, 8-dihydroxy-1, 4-naphthoquinone, 2-methoxy-5, 6, 8-trihydroxy-1, 4-naphthoquinone, 2, 5-dimethoxy-1, 4-naphthoquinone, 2, 6-dimethoxy-1, 4-naphthoquinone, 2,5, 8-trimethoxy-1, 4-naphthoquinone, 2-chloro-5-methyl-1, 4-naphthoquinone, 2-chloro-6-methyl-1, 4-naphthoquinone, 2-chloro-6, 7-dimethyl-1, 4-naphthoquinone, 2-chloro-5-butyl-1, 4-naphthoquinone, 2-chloro-6, 7-dibutyl-1, 4-naphthoquinone, 2-chloro-5-pentyl-1, 4-naphthoquinone, 2-chloro-6-pentyl-1, 4-naphthoquinone, 2, 5-dichloro-1, 4-naphthoquinone, 2,6, 7-trichloro-1, 4-naphthoquinone, 2-chloro-6-pentyl-1, 4-naphthoquinone, 2,6, 7-trichloro-1, 4-naphthoquinone, 2,6, 7-naphthoquinone, 2, 2-chloro-5-hydroxy-1, 4-naphthoquinone, 2-chloro-6-hydroxy-1, 4-naphthoquinone, 2-chloro-5, 8-dihydroxy-1, 4-naphthoquinone, 2-chloro-5, 6, 8-trihydroxy-1, 4-naphthoquinone, 2-chloro-5-methoxy-1, 4-naphthoquinone, 2-chloro-6-methoxy-1, 4-naphthoquinone, 2-chloro-5, 8-dimethoxy-1, 4-naphthoquinone, 2-amino-5-methyl-1, 4-naphthoquinone, 2-amino-6, 7-dimethyl-1, 4-naphthoquinone, 2-amino-5-butyl-1, 4-naphthoquinone, 2-amino-6, 7-dibutyl-1, 4-naphthoquinone, 2-amino-5-pentyl-1, 4-naphthoquinone, 2-amino-6-pentyl-1, 4-naphthoquinone, 2-amino-5-chloro-1, 4-naphthoquinone, 2-amino-6, 7-dichloro-1, 4-naphthoquinone, 2-amino-5-hydroxy-1, 4-naphthoquinone, 2-amino-6-hydroxy-1, 4-naphthoquinone, 2-amino-5, 8-dihydroxy-1, 4-naphthoquinone, 2-amino-5, 6, 8-trihydroxy-1, 4-naphthoquinone, 2-amino-5-methoxy-1, 4-naphthoquinone, 2-amino-6-methoxy-1, 4-naphthoquinone, 2-amino-5, 8-dimethoxy-1, 4-naphthoquinone, and the like.

In the general formula (4), examples of the compound in which Y and Z are a hydroxyl group, an alkyl group, an alkoxy group, an amino group or a halogen atom include the following compounds. Examples thereof include 2, 3-dimethyl-1, 4-naphthoquinone, 2, 3-diethyl-1, 4-naphthoquinone, 2-methyl-3-hydroxy-1, 4-naphthoquinone, 2-methyl-3-methoxy-1, 4-naphthoquinone, 2, 3-dihydroxy-1, 4-naphthoquinone, 2, 3-dimethoxy-1, 4-naphthoquinone, 2, 3-dichloro-1, 4-naphthoquinone, 2-amino-3-chloro-1, 4-naphthoquinone, 2,3, 6-trimethyl-1, 4-naphthoquinone, 2,3,6, 7-tetramethyl-1, 4-naphthoquinone, 2, 3-dimethyl-5-butyl-1, 4-naphthoquinone, 2, 3-dimethyl-6-butyl-1, 4-naphthoquinone, 2, 3-dimethyl-6, 7-dibutyl-1, 4-naphthoquinone, 2, 3-dimethyl-5-pentyl-1, 4-naphthoquinone, 2, 3-dimethyl-6-pentyl-1, 4-naphthoquinone, 2, 3-dimethyl-5-chloro-1, 4-naphthoquinone, 2, 3-dimethyl-6, 7-dichloro-1, 4-naphthoquinone, 2, 3-dimethyl-5-hydroxy-1, 4-naphthoquinone, 2, 3-dimethyl-6-hydroxy-1, 4-naphthoquinone, 2, 3-dimethyl-5, 8-dihydroxy-1, 4-naphthoquinone, 2, 3-dimethyl-5, 6, 8-trihydroxy-1, 4-naphthoquinone, 2, 3-dimethyl-5-methoxy-1, 4-naphthoquinone, 2, 3-dimethyl-6-methoxy-1, 4-naphthoquinone, 2, 3-dimethyl-5, 8-dimethoxy-1, 4-naphthoquinone, 2, 6-dimethyl-3-hydroxy-1, 4-naphthoquinone, 2,6, 7-trimethyl-3-hydroxy-1, 4-naphthoquinone, 2-methyl-3-hydroxy-5-butyl-1, 4-naphthoquinone, 2-methyl-3-hydroxy-6-butyl-1, 4-naphthoquinone, 2-methyl-3-hydroxy-6, 7-dibutyl-1, 4-naphthoquinone, 2-methyl-3-hydroxy-5-pentyl-1, 4-naphthoquinone, 2-methyl-3-hydroxy-6-pentyl-1, 4-naphthoquinone, 2-methyl-3-hydroxy-5-chloro-1, 4-naphthoquinone, 2-methyl-3-hydroxy-6, 7-dichloro-1, 4-naphthoquinone, 2-methyl-3-hydroxy-6, 7-dichloro-1, 2-methyl-3, 5-dihydroxy-1, 4-naphthoquinone, 2-methyl-3, 6-dihydroxy-1, 4-naphthoquinone, 2-methyl-3, 5, 8-trihydroxy-1, 4-naphthoquinone, 2-methyl-3, 5,6, 8-tetrahydroxy-1, 4-naphthoquinone, 2-methyl-3-hydroxy-5-methoxy-1, 4-naphthoquinone, 2-methyl-3-hydroxy-6-methoxy-1, 4-naphthoquinone, 2-methyl-3-hydroxy-5, 8-dimethoxy-1, 4-naphthoquinone, 2, 3-dichloro-6-methyl-1, 4-naphthoquinone, 2, 3-dichloro-6, 7-dimethyl-1, 4-naphthoquinone, 2, 3-dichloro-5-butyl-1, 4-naphthoquinone, 2, 3-dichloro-6, 7-dibutyl-1, 4-naphthoquinone, 2, 3-dichloro-5-pentyl-1, 4-naphthoquinone, 2, 3-dichloro-6-pentyl-1, 4-naphthoquinone, 2,3, 5-trichloro-1, 4-naphthoquinone, 2,3,6, 7-tetrachloro-1, 4-naphthoquinone, 2, 3-dichloro-5-hydroxy-1, 4-naphthoquinone, 2, 3-dichloro-6-hydroxy-1, 4-naphthoquinone, 2, 3-dichloro-5, 8-dihydroxy-1, 4-naphthoquinone, 2, 3-dichloro-5, 6, 8-trihydroxy-1, 4-naphthoquinone, 2, 3-dichloro-5-methoxy-1, 4-naphthoquinone, 2, 3-dichloro-6-methoxy-1, 4-naphthoquinone, 2, 3-dichloro-5, 8-dimethoxy-1, 4-naphthoquinone, 2-amino-3-chloro-6-methyl-1, 4-naphthoquinone, 2-amino-3-chloro-6, 7-dimethyl-1, 4-naphthoquinone, 2-amino-3-chloro-5-butyl-1, 4-naphthoquinone, 2-amino-3-chloro-6, 7-dibutyl-1, 4-naphthoquinone, 2-amino-3-chloro-5-pentyl-1, 4-naphthoquinone, 2-amino-3-chloro-6-pentyl-1, 4-naphthoquinone, 2-amino-3-chloro-5-chloro-1, 4-naphthoquinone, 2-amino-3, 6-dichloro-1, 4-naphthoquinone, 2-amino-3, 4-naphthoquinone, 2-chloro-6-butyl-1, 4-naphtho, 2-amino-3, 6, 7-trichloro-1, 4-naphthoquinone, 2-amino-3-chloro-5-hydroxy-1, 4-naphthoquinone, 2-amino-3-chloro-6-hydroxy-1, 4-naphthoquinone, 2-amino-3-chloro-5, 8-dihydroxy-1, 4-naphthoquinone, 2-amino-3-chloro-5, 6, 8-trihydroxy-1, 4-naphthoquinone, 2-amino-3-chloro-5-methoxy-1, 4-naphthoquinone, 2-amino-3-chloro-6-methoxy-1, 4-naphthoquinone, 2-amino-3-chloro-5, 8-dimethoxy-1, 4-naphthoquinone, and the like.

Next, specific examples of the compound represented by the following general formula (5) will be described.

[ solution 17]

In the formula (5), X independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or a halogen atom, and Q represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or a halogen atom.

Specific examples of the general formula (5) include 1, 4-dihydro-9, 10-anthraquinone, 2-methyl-1, 4-dihydro-9, 10-anthraquinone, 2-chloro-1, 4-dihydro-9, 10-anthraquinone, 6-methyl-1, 4-dihydro-9, 10-anthraquinone, 2, 6-dimethyl-1, 4-dihydro-9, 10-anthraquinone, 2-chloro-6-methyl-1, 4-dihydro-9, 10-anthraquinone, and 2, 6-dichloro-1, 4-dihydro-9, 10-anthraquinone.

Next, specific examples of the compound represented by the following general formula (6) will be described.

[ solution 18]

Specific examples of the compound represented by the general formula (6) include 1,2,3, 4-tetrahydro-9, 10-anthraquinone, 2-methyl-1, 2,3, 4-tetrahydro-9, 10-anthraquinone, 2-chloro-1, 2,3, 4-tetrahydro-9, 10-anthraquinone, 6-methyl-1, 2,3, 4-tetrahydro-9, 10-anthraquinone, 2, 6-dimethyl-1, 2,3, 4-tetrahydro-9, 10-anthraquinone, 2-chloro-6-methyl-1, 2,3, 4-tetrahydro-9, 10-anthraquinone, 2, 6-dichloro-1, 2,3, 4-tetrahydro-9, 10-anthraquinone, etc.

The compounds represented by the general formulae (1) to (3) of the present invention can be easily synthesized by subjecting the corresponding hydroxynaphthalene compound or hydroxyanthracene compound to alkylation with an alkylating agent, arylation with an arylating agent, hydroxyalkylation with an alkylene oxide, acylation with an acylating agent, and substitution carbonylation with a substituted carbonylating agent.

Many of the naphthoquinone compounds having a substituent at the 2-position represented by the general formula (4) can be obtained as a reagent, or can be obtained by preparing a hydroquinone compound substituted at the 2-position by the reaction of a 1, 4-naphthoquinone compound with a corresponding nucleophile and then subjecting the hydroquinone compound to an oxidation treatment. For example, the synthesis can be carried out by the methods described in experimental chemistry, 5 th edition, synthesis of organic compounds (experiment chemistry, th edition, synthesis of III アルデヒド, ケトン, キノン, where 15 has the ability to inhibit growth of the compounds) (published by the society of chemistry, Japan), p 369, p 384.

In addition, the compounds of the general formulae (5) and (6) can be synthesized as follows: a cyclic adduct is synthesized by Diels-Alder reaction of a 1, 4-naphthoquinone compound with a corresponding butadiene compound, and then oxidized after isomerization, and this oxide is further subjected to catalytic hydrogen reduction.

Specific examples of the compounds represented by the above general formula (1) include 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 1, 4-dimethoxynaphthalene, 1, 4-diethoxynaphthalene, 1, 4-di-n-propoxytalene, 1, 4-diisopropoxytalene, 1, 4-di-n-butoxynaphthalene, 1, 4-dihexyloxynaphthalene and 1, 4-bis (2-ethylhexyloxy) naphthalene. Examples of the compound of the general formula (2) include 9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 9, 10-di-n-propoxylanthracene, 9, 10-diisopropoxylanthracene, 9, 10-di-n-butoxyanthracene, 9, 10-bis (2-ethylhexyloxy) anthracene, 9, 10-di (dodecyloxy) anthracene, 9, 10-bis (acetyloxy) anthracene, 9, 10-bis (propionyloxy) anthracene, 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-propoxylanthracene, 9, 10-di-propoxylanthracene, 9, 10-bis (n-nonanoyloxy) anthracene, 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 (n-pentyloxycarbonyloxy) anthracene, 9, 10-bis (n-hexyloxycarbonyloxy) anthracene, 9, 10-bis (n-heptyloxycarbonyloxy) anthracene, 9, 10-bis (n-octyloxycarbonyloxy) anthracene, 9, 10-bis (2-ethylhexyloxycarbonyloxy) anthracene, 9, 10-bis (n-nonyloxycarbonyloxy) anthracene. Examples of the compound of the general formula (3) include 9-methoxyanthracene, 9-ethoxyanthracene, 9-n-propoxylanthracene, 9-isopropoxyanthracene, 9-n-butoxyanthracene, 9- (2-ethylhexyloxy) anthracene and 9-dodecyloxyanthracene. Examples of the compound of the general formula (4) include 1, 4-naphthoquinone, 2-methyl-1, 4-naphthoquinone, 2-ethyl-1, 4-naphthoquinone, 2-hydroxy-1, 4-naphthoquinone, 2-methoxy-1, 4-naphthoquinone, and 2-chloro-1, 4-naphthoquinone. Examples of the compound of the general formula (5) include 1, 4-dihydro-9, 10-anthraquinone and 2-methyl-1, 4-dihydro-9, 10-anthraquinone, and examples of the compound of the general formula (6) include 1,2,3, 4-tetrahydro-9, 10-anthraquinone and 2-methyl-1, 2,3, 4-tetrahydro-9, 10-anthraquinone. Among these, from the viewpoint of ease of production, preferred are 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 1, 4-dimethoxynaphthalene, 1, 4-diethoxynaphthalene, 9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 9, 10-di-n-propoxylanthracene, 9, 10-diisopropoxylanthracene, 9, 10-di-n-butoxyanthracene, 9, 10-bis (n-butyryloxy) anthracene, 9, 10-bis (n-heptanoyloxy) anthracene, 9, 10-bis (n-octanoyloxy) anthracene, 9, 10-bis (n-butoxycarbonyloxy) anthracene, 9-isopropoxy anthracene, 9-n-butoxyanthracene, 1, 4-naphthoquinone, 2-methyl-1, 4-naphthoquinone, 2-hydroxy-1, 4-naphthoquinone and 2-methoxy-1, 4-naphthoquinone. Particularly preferred are 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 1, 4-diethoxynaphthalene, 9, 10-di-n-propoxylanthracene, 9, 10-di-n-butoxyanthracene, 9, 10-bis (n-octanoyloxy) anthracene, 1, 4-naphthoquinone, 2-methyl-1, 4-naphthoquinone, and 2-hydroxy-1, 4-naphthoquinone.

[ radically polymerizable composition ]

The radical polymerizable composition of the present invention contains the radical polymerization controller of the present invention and a radical polymerizable compound. When the radical polymerization control agent of the present invention is contained, when a radical species is generated in the radical polymerizable composition due to the influence of heat or the like, the radical polymerization control agent of the present invention traps the radical species and prevents initiation of radical polymerization of the radical polymerizable compound. Namely, the storage stability of the radical polymerizable compound is achieved. However, when the radical polymerizable compound is subjected to radical polymerization, the radical polymerization control agent of the present invention is harmless to radicals by irradiating light of a specific wavelength (light including light in a wavelength range of 300nm to 500 nm), and can initiate radical polymerization. That is, the radical polymerization control agent of the present invention can control initiation and termination of radical polymerization by irradiation with light of a specific wavelength. In addition, initiation and inhibition of polymerization can be controlled by the irradiated site and the non-irradiated site of light.

The radical polymerization control agent of the present invention is different from a photo radical polymerization initiator, which has an ability to initiate radical polymerization by irradiation with light of a specific wavelength (bright conditions), but is inert to radicals under dark conditions (conditions in which light of a specific wavelength is not irradiated). On the other hand, the radical polymerization control agent of the present invention is active against radicals under dark conditions (conditions where light of a specific wavelength is not irradiated), and has the ability to trap generated radicals, thereby functioning as a radical polymerization inhibitor, but loses the ability to trap radical polymerization by irradiation with light of a specific wavelength, and becomes inactive. Although the phenomenon of polymerization occurring under bright conditions without polymerization under dark conditions is the same, the content of the action is completely different.

The radical polymerization control agent of the present invention can be used as a storage stabilizer for a radical polymerizable compound by being added to the radical polymerizable compound in advance, but may be added to the radical polymerizable compound at the time of initiating radical polymerization to control polymerization caused by irradiation with light of a specific wavelength.

The amount of the radical polymerization control agent of the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the radical polymerizable compound, from the viewpoints of sufficient radical polymerization inhibiting effect and economy.

[ radically polymerizable Compound ]

The radical polymerizable compound in the present invention is not particularly limited as long as it has a polymerizable double bond in the molecule, and examples of such radical polymerizable compounds include α -unsaturated carboxylic acid compounds such as acrylic acid and methacrylic acid, α -unsaturated carboxylic acid ester compounds such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methyl methacrylate and butyl methacrylate, vinyl ester compounds such as vinyl acetate, acrylic compounds such as acrylonitrile and acrylamide, aromatic vinyl compounds such as styrene, α -methylstyrene, vinyltoluene and divinylbenzene, substituted vinyl compounds such as vinyl chloride and vinylidene chloride, ethylenically unsaturated compounds such as ethylene, propylene, butene, butadiene, isoprene, cyclopentadiene and pinene, and unsaturated organosilane compounds such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane and vinyltrimethoxysilane.

Among the radical polymerizable compounds, α -unsaturated carboxylic acid compound (meth) acrylic acid, (meth) acrylic acid ester α -unsaturated carboxylic acid ester, and aromatic vinyl compound (styrene) are preferable.

The form and content of the radical polymerizable compound contained in the radical polymerizable composition are not particularly limited. Examples thereof include the radical polymerizable compound itself and a solution of the radical polymerizable compound.

A radical polymerization initiator for initiating a radical reaction is added as necessary to the radical polymerizable composition containing the radical polymerization controller of the present invention as an essential component. Then, the polymerization is initiated by supplying initiation energy such as heat and light necessary for initiating the polymerization, whereby a polymer can be produced. Further, by irradiating light of a specific wavelength at the time of the polymerization reaction, the start and stop of the polymerization reaction can be controlled.

[ radical polymerization initiator ]

The radical polymerization initiator is not particularly limited as long as it generates a radical active on the radical polymerizable compound by supplying energy. So-called radical polymerization initiators which are generally commercially available can be used. For convenience, an initiator used to supply thermal energy is generally referred to as a thermal radical polymerization initiator, and an initiator to supply optical energy is generally referred to as a photo radical polymerization initiator. Both of the thermal radical polymerization initiator and the photo radical polymerization initiator can be used in the present invention.

The thermal radical polymerization initiator is not particularly limited, and a known compound can be used. Examples thereof include peroxides, hydrogen peroxide and azo compounds. Specific examples thereof include benzoyl peroxide, di-t-amyl peroxide, t-butyl peroxybenzoate, peroxides such as 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-di (t-butylperoxy) -3-hexyne and dicumyl peroxide, hydrogen peroxide such as t-amyl hydroperoxide, t-butyl hydroperoxide and hydrogen peroxide, (2,2 '-azobis (2, 4-dimethylvaleronitrile)), (2, 2' -azobis (2-methylpropionitrile)), (2,2 '-azobis (2-methylbutyronitrile)), (2, 2' -azobis (cyclohexanecarbonitrile)), and other azo compounds.

In order to use the thermal radical polymerization initiator at a relatively low temperature, a so-called redox initiator system may be used in which a reducing agent such as a transition metal or an amine is combined with an oxidizing agent initiator such as a peroxide, hydrogen peroxide, or ascorbic acid.

Examples of the photo radical polymerization initiator include benzoin-based compounds, acetophenone-based compounds, benzophenone-based compounds, thioxanthones, α -acyloxime esters, glyoxylic acid phenyl esters, benzil-based compounds, azo-based compounds, benzophenone-based compounds, acylphosphine oxide-based compounds, organic dye-based compounds, iron-phthalocyanine-based compounds, benzoin ethers and anthraquinones, specifically benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether and other benzoin-based compounds, acetophenone-based compounds, 2-diethoxy-2-phenylacetophenone, 1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxy benzophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one and the like, 2-ethyl-phenylketal, 2-diethoxy benzophenone-1-one, 2-hydroxycyclohexylphenylbenzophenone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-ethyl-phenylketal, 2-trimethyl-benzoylbenzophenone-4' -benzoylbenzophenone-6, 2-methyl-4- (methylthio) benzophenone-methyl-benzoylbenzophenone-2-methyl-4-methyl-2-benzoylbenzophenone, 2-methyl-4-methyl-benzoylbenzophenone, 2-4-methyl-2-methyl-4-2-methyl-benzoylbenzophenone, 6-methyl-4-methyl-phenyl-benzoylbenzophenone, etc., and the like, 4-methyl-benzoylbenzophenone, and the like, and.

Further, as a photo radical polymerization initiator available on the market, there can be mentioned: 1-Hydroxycyclohexylphenyl methanone (Irgac, product of Ciba Specialty Chemicals Inc.)ure 184, Irgacure is a registered trademark of Ciba specialty Chemicals Inc., (2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl) -1-propanone) (Irgacure 907), and an acylphosphine oxide compound such as bis (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide (Irgacure 819), bis (η)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.

These radical polymerization initiators may be used alone or in combination of 2 or more. A thermal radical polymerization initiator may also be used in combination with a photo radical polymerization initiator. The amount of the radical polymerization initiator to be added is determined by the radical polymerizable compound and the radical polymerization control agent to be used, and is preferably in the range of 0.0001 to 10 parts by mass relative to 100 parts by mass of the total amount of the radical polymerizable compounds.

[ energy of initiation of polymerization ]

The polymerization initiation energy may be any energy that can generate a radical from the radical initiator added. Generally, the thermal energy and the ionization wave energy can be appropriately selected. Specific examples of the energy source include electromagnetic wires such as heat, light, Electron Beam (EB), microwave, and radiation, and are called thermal polymerization, electromagnetic wire polymerization (photopolymerization, electron beam polymerization, microwave polymerization, and radiation polymerization), and the like depending on the energy source used.

[ thermal polymerization ]

In the case of thermal polymerization, the temperature range used for polymerization varies depending on the radical polymerizable compound used and the mode thereof, but is usually-20 to 200 ℃, preferably 0 to 150 ℃, and more preferably 10 to 120 ℃.

Further, as one of the thermal polymerization, redox polymerization using a redox (redox) initiator (described later) can be mentioned. In this case, the temperature range used is lower than that of ordinary thermal polymerization, and is-40 to 100 ℃, preferably-20 to 80 ℃, and more preferably 0 to 60 ℃.

The radical polymerization initiator is added to the radical polymerizable composition containing the radical polymerization control agent of the present invention and the radical polymerizable compound, and an initiation energy is supplied to initiate polymerization of the radical polymerizable compound. When the initiation energy is applied, the radical polymerization initiator generates radicals which are trapped by the radical polymerization controller of the present invention in the absence of irradiation with light having a wavelength of 300 to 500nm, and polymerization is inhibited. Therefore, in order to initiate radical polymerization, it is necessary to add a radical polymerization initiator more than necessary to generate radicals exceeding the trapping ability of the radical polymerization control agent. However, when the radical polymerization is initiated by irradiation with light having a wavelength in the range of 300 to 500nm, the radical trapping ability of the radical polymerization controller is lost, and the radical polymerization can be initiated by adding a small amount of the radical polymerization initiator.

Further, a radical polymerizable composition containing a thermal radical polymerization initiator and the radical polymerization control agent of the present invention is applied in a film form, a light-shielding film having a pattern is covered on the applied film, and the radical polymerizable composition is heated under irradiation of light having a wavelength range of 300 to 500nm, whereby polymerization occurs only at the portion irradiated with light, and a polymerization reaction does not sufficiently proceed at the portion not irradiated with light, whereby a polymer pattern can be formed. That is, the pattern of the polymer, which is generally formed using the photopolymerization initiator, may be formed using a thermal polymerization initiator.

In addition, when radical polymerization is performed by applying thermal energy to a radical polymerizable composition containing a thermal radical polymerization initiator and the radical polymerization control agent of the present invention, a specific region of the radical polymerizable composition is irradiated with light containing light having a wavelength ranging from 300nm to 500nm, whereby only the specific region can be radical polymerized.

The light having a specific wavelength range irradiated during the polymerization reaction is a light having a wavelength range of 300 to 500 nm. The light source may be any light source capable of emitting light having a wavelength in the range of 300 to 500 nm. For example, an LED (light emitting diode), a lamp may be used. Examples of the LED include a UV-LED, a blue LED, and a white LED. Examples of the lamp include a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, and a metal halide lamp.

Among the light beams containing light in the wavelength range of 300 to 500nm, the light beams containing light in the wavelength range of 300 to 370nm are preferable in the case of the radical polymerization control agent of the present invention represented by the above general formulae (1), (4) to (6), and the light beams containing light in the wavelength range of 350 to 500nm are preferable in the case of the radical polymerization control agent of the present invention represented by the general formulae (2) or (3).

The intensity of the irradiation is 1 to 2000mW/cm²Light irradiation was performed at left and right intensities.

[ photopolymerization ]

The polymerization reaction using the radical polymerization control agent of the present invention can also be used for photopolymerization. In photopolymerization, ultraviolet rays, visible rays, infrared rays, and the like can be used as light to be irradiated. In addition to the radical polymerization control agent of the present invention, a photo radical polymerization initiator may be used, and a photo polymerization sensitizer may be used. Specifically, a radical polymerizable composition containing the radical polymerization control agent of the present invention, a radical polymerizable compound, and a photo radical polymerization initiator is prepared, and polymerization can be initiated by irradiating light such as ultraviolet light or visible light as polymerization initiation energy. In this case, the radical polymerization control agent of the present invention can be rendered harmless by simultaneously irradiating light having a wavelength in the range of 300 to 500nm, and an additional photo radical polymerization initiator does not need to be added.

In the case of ultraviolet rays or visible rays to be irradiated, the wavelength range is, for example, 300 to 800 nm. As the light source, an LED (light emitting diode) or a lamp capable of irradiating light having a wavelength in the range of 300 to 800nm is used. Examples of the LED include a UV-LED, a blue LED, and a white LED. Examples of the lamp include a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, and a metal halide lamp.

The electron beam polymerization is performed by electron beam irradiation. In the electron beam irradiation, any method may be used without particular limitation as long as it can act on the electron beam polymerizable compound to cause polymerization of the polymerizable substance. The amount of the electron beam to be irradiated is preferably adjusted to a range of about 1 to 300kGy in absorbed dose. When the dose is less than 1kGy, a sufficient irradiation effect cannot be obtained, and when the dose is more than 300kGy, the substrate may be deteriorated, which is not preferable. As a method of irradiating an electron beam, for example, a scanning method, a curtain beam method, a wide beam method, or the like is used, and an acceleration voltage when irradiating an electron beam needs to be controlled according to the thickness of the substrate on the side to be irradiated, and is preferably about 20 to 100 kV.

The microwave polymerization can be carried out by a method known in Strauss et al (Aust. J.chem.,48,1665-1692 (1995)). The microwaves may be generated using any of a variety of methods known in the microwave art. Generally, these methods rely on klystrons or magnetrons that function as microwave generating sources. The frequency of generation is typically in the range of about 300MHz to 30GHz, corresponding to a wavelength of about 1m to 1 mm. In theory, any of these ranges can be effectively used, but it is preferred to use a commercially available range of frequencies including about 850 to 950MHz or about 2300 to 2600 MHz.

In radiation polymerization, polymerization is performed by irradiation with gamma rays, X rays, α rays, β rays, and gamma ray irradiation with cobalt 60 is generally used in many cases.

In the case of using a photo radical polymerization initiator, a radical polymerizable composition containing a photo radical polymerization initiator and the radical polymerization control agent of the present invention is coated in a film form, a light-shielding film having a pattern is coated on the coated film, and the radical polymerizable composition is irradiated with light energy (electromagnetic energy) for activating the photo radical polymerization initiator under irradiation of light having a wavelength range of 300 to 500nm to initiate polymerization, whereby only the portion irradiated with light having a wavelength range of 300 to 500nm is polymerized, and the portion not irradiated with light having a wavelength range of 300 to 500nm does not sufficiently undergo a polymerization reaction, and a pattern of a polymer can be formed.

In the case where the wavelength of light of the light energy irradiated during the photopolymerization is in the wavelength range of 300 to 500nm, initiation of photopolymerization and detoxification of the radical polymerization control agent of the present invention can be carried out simultaneously.

For example, a radical polymerizable composition containing a photo radical polymerization initiator and the radical polymerization control agent of the present invention is applied in a film form, a light-shielding film having a pattern is covered on the applied film, and the radical polymerizable composition is initiated by irradiation of light having a wavelength in the range of 300 to 500nm, whereby only the portion irradiated with light is polymerized, and a polymer pattern can be formed. This reaction can be carried out without including the radical polymerization control agent of the present invention, but in this reaction, when the radical polymerizable compound includes not the radical polymerization control agent of the present invention but a general radical polymerization inhibitor, the lead time (lead time) of radical polymerization is extended, or the polymerization reaction cannot be carried out well without increasing the amount of the photo radical polymerization initiator added. However, by containing the radical polymerization controlling agent of the present invention instead of the polymerization inhibitor, the following effects are produced: the radical polymerization can be smoothly performed while ensuring the storage stability of the radical polymerizable compound, and the amount of the photo radical polymerization initiator to be added may be small. Further, at the same time, when the portion irradiated with light is narrowed or when photopolymerization is performed with a part of the portion shielded, the radical polymerization control agent of the present invention functions as a radical polymerization inhibitor in the portion not irradiated with light, and therefore has a characteristic that the boundary between the portion irradiated with light and the portion not irradiated with light becomes clear.

In addition, when a radical polymerizable composition containing a photo-radical polymerization initiator and the radical polymerization control agent of the present invention is radical polymerized by irradiation with light energy, a specific region of the radical polymerizable composition is irradiated with light containing light in a wavelength range of 300nm to 500nm, and thus only the specific region can be radical polymerized.

[ other ingredients ]

In the radical polymerization of the radical polymerizable composition containing the radical polymerization control agent and the radical polymerizable compound of the present invention, other components may be contained as necessary in addition to the radical polymerization control agent, the radical polymerizable compound, and the radical polymerization initiator of the present invention within the range not impairing the effects of the present invention, and a solvent, a colorant, a plasticizer, an adhesion promoter, an antioxidant, various stabilizers, a filler, a surfactant, a coupling agent, an antistatic agent, an ultraviolet absorber, and the like may be added.

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