JP2017214536A - Radical curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerization inhibitor which improves thermal stability and storage stability and suppresses a gel time drift even after long-term storage in a radical curable composition containing an accelerating agent, and can keep a gelation period time in the presence of a curing agent after the storage, and to provide a radical curable composition containing the polymerization inhibitor.SOLUTION: A radical curable composition contains a radical curable compound (A), a polymerization inhibitor (B) and an accelerating agent (C), and contains a naphthoquinone compound represented by general formula (1) and a phenolic compound represented by general formula (2), as the polymerization initiator (B).SELECTED DRAWING: None

Description

The present invention relates to a radically curable composition and a method for curing the same. More specifically, the present invention relates to a radical curable composition containing an accelerator and a polymerization inhibitor and a curing method thereof.

A radical curable composition containing a radical curable compound typified by unsaturated polyester and vinyl ester is generally easy to handle because it can be handled as a liquid, and also has performance such as mechanical strength and durability of the cured product. Because it is good, it is used for hulls, bathtubs, vehicles, tanks, electrical parts, etc., especially as glass fiber and carbon fiber reinforced plastic products, as well as resin concrete, gel coat, putty, decorative boards, anchor bolts, paint, building materials, etc. It is used for various purposes.

A radical curable composition containing such a radical curable compound is composed of, for example, a radical curable oligomer such as unsaturated polyester or vinyl ester and a radical curable monomer such as styrene or methyl methacrylate. Then, by adding a radical polymerization initiator such as an organic peroxide as a curing agent to the radical curable composition, a polymerization reaction is started, and a cured resin product is formed. That is, it is generally handled with two liquids of a radical curable composition and a curing agent.

In so-called room temperature curing type radical curable compositions that are used at room temperature without heating, the addition of an accelerator is indispensable in order to advance the reaction of the curing agent, and an accelerator is added to the radical curable composition in advance. A curing agent is added to the cake later and cured (Patent Document 1). At this time, the radical curable composition to which the accelerator is added has a problem that the storage stability is poor. In some cases, the radical curable composition is handled with three liquids of the radical curable composition, the accelerator and the curing agent.

A polymerization inhibitor is added to the radical curable composition both when the accelerator is added to the radical curable composition in advance and when the accelerator is added separately at the time of curing. One of the purposes is to prevent spontaneous polymerization of radical curable oligomers and radical curable monomers. That is, a polymerization inhibitor is added to improve the storage stability of the radical curable composition. Even if the radical curable composition is in a “semi-finished product” state in which the curable compound is polymerized to a certain degree of fluidity, it remains in the fluid semi-cured state. Is added.

Further, in the production process of the radical curable composition, in order to prevent a polymerization reaction when a high-viscosity radical curable oligomer is mixed with the radical curable monomer at a high temperature, an accelerator or the like is further added to the radical curable compound. A polymerization inhibitor is added in order to prevent the polymerization reaction of the radical curable oligomer or radical curable monomer in the step of adding or transferring the radical curable composition, that is, to improve thermal stability. Furthermore, in order to secure an induction period (casting time; gelation time) from the mixing of the curing agent to the start of curing, or from the heating to the start of curing, that is, the gelation time corresponding to the working time. A polymerization inhibitor is used to ensure the resistance.

Thus, the polymerization inhibitor added to the radical curable composition mainly has the following three roles, and a plurality of polymerization inhibitors according to the purpose and characteristics are used. 1) Improvement of storage stability 2) Improvement of thermal stability 3) Ensuring gelation time.

It is difficult to formulate a polymerization inhibitor that satisfies all three required roles. For example, even if you want to add a lot of polymerization inhibitor to improve storage stability and thermal stability, if you add a large amount, the gelation time becomes too long when you try to cure by adding a curing agent. Trouble may occur during molding.

Therefore, a polymerization inhibitor that hardly changes the gelation time, that is, a polymerization inhibitor that improves thermal stability and storage stability without substantially affecting the curing characteristics of the radically curable composition is particularly demanded. . Radical curable composition mainly composed of unsaturated polyester using 2,6-di-t-butyl-p-cresol (BHT), which is a phenolic polymerization inhibitor, as a polymerization inhibitor having such properties. Has been proposed (Patent Document 2). However, although phenol-based polymerization inhibitors certainly improve storage stability, a phenomenon (gel time drift) in which the gelation time after long-term storage fluctuates as compared to before storage is observed. Fluctuation of gelation time causes problems during molding. In general, when a cobalt accelerator such as cobalt naphthenate is used, the gelation time is delayed, and when an amine accelerator such as dimethylaniline is used, the gelation time is shortened. It is done.

When cobalt naphthenate is used as an accelerator, a method of adding hydroxylamine oxide or hydroxylamine as a method for stabilizing the gelation time (Patent Document 3), a method of adding N, N′-dimethylacetamide (Patent Document 4), a method using N, N′-dimethylacetamide and tolhydroquinone (Patent Document 5) is known. These methods are intended to prevent inactivation due to complex formation of free acid present in the radical curable composition and cobalt as an accelerator, but the effect is satisfactory. It wasn't possible. In addition, the stability of the radically curable composition during storage is not sufficient, and the cured product is colored, and there is a problem that it is effective only for cobalt naphthenate as an accelerator.

In addition, when an amine accelerator is used, a method of adding a non-phenolic inhibitor and a phenolic inhibitor is known as a method for stabilizing the gelation time (Patent Documents 6 and 7). This method is a method in which a phenothiazine compound or an organic nitroxyl radical is added as a non-phenolic inhibitor, and hydroquinone or 2,6-di-t-butylphenol is used as a phenolic inhibitor in some cases. Although it is characterized by using a phenothiazine compound that is a non-phenolic inhibitor or an organic nitroxyl radical in combination with a conventional phenolic inhibitor, the effect of suppressing gel time drift in an amine accelerator has been reported, The effect of cobalt naphthenate is not known.

Furthermore, the present inventors improve storage stability by adding a dihydroxynaphthalene compound or a naphthoquinone compound in addition to a phenothiazine compound or an organic nitroxyl radical when using a cobalt accelerator or an amine accelerator. Has proposed a polymerization inhibitor (Patent Documents 8 and 9). However, there is room for further improvement in curing properties, particularly gel time drift.

In addition, there are some documents in which naphthoquinone is listed as having the same action as hydroquinone as a phenol-based polymerization inhibitor, but the hydroquinone compound and the naphthoquinone compound have different effects in the polymerization inhibition action, There is no description about the special effect which arises by using together a hydroquinone compound and a naphthoquinone compound (patent documents 7, 10, 11, 12).

JP-A-8-157544 JP-A-5-222281 JP 2004-225045 A JP 2006-265336 A JP 2007-91998 A JP 2009-541540 A JP, 2006-501933, A JP-A-2014-14103 JP, 2006-56283, A JP 11-29740 A Japanese Patent Laid-Open No. 9-302046 JP2013-228758A

The present invention has been made in view of the above circumstances, and its purpose is to improve the thermal stability and storage stability of a radical-curable composition containing an accelerator, and to suppress gel time drift even after long-term storage. Another object of the present invention is to provide a polymerization inhibitor capable of maintaining the gelation time in the presence of a curing agent even after storage, and a radically curable composition containing the polymerization inhibitor.

As a result of intensive studies by the present inventors, it is possible to solve the above problems by using a naphthoquinone compound and a phenol polymerization inhibitor in combination as a polymerization inhibitor in a radical curable composition to which an accelerator is added. As a result, the present invention was completed.

First, the first invention is a radical curable composition containing a radical curable compound (A), a polymerization inhibitor (B) and an accelerator (C), and the polymerization inhibitor (B) has the following general formula ( The radical curable composition comprises a naphthoquinone compound represented by 1) and a phenol compound represented by the following general formula (2).

In the general formula (1), X, Y and Z may be the same or different, and each is a hydrogen atom, a hydroxyl group, a halogen atom, an acyl group having 2 to 9 carbon atoms, or 1 carbon atom. ˜8 alkyl group, C 6-10 aryl group, C 6-10 aralkyl group, C 2-10 alkoxyalkyl group, amino group, C 1-8 alkylamino group, glycidyl group, It represents either a hydroxyalkyl group having 1 to 8 carbon atoms or an aryloxyalkyl group having 6 to 10 carbon atoms, among which X and Y may be bonded to each other to form a saturated or unsaturated ring, You may form a ring on both sides of a hetero atom.

In the general formula (2), n is 0 or 1, and m represents an integer of 0 to 4. Moreover, R represents a C1-C8 alkyl group or a C1-C8 alkoxy group, and when there are a plurality of Rs, they may be the same or different.

The second invention is the radical curable composition according to the first invention, wherein the curing agent (D) is added immediately after the radical curable composition is prepared and polymerized at 25 ° C. Gelation time (GT ₀ ) of the curable composition and radical curable composition when the curing agent (D) is added and polymerized at 25 ° C. after storage at 60 ° C. for 2 days after preparation of the radical curable composition It exists in the radical curable composition characterized by the ratio with the gel time (GT) of a thing being represented with the following numerical formula.

In a third invention, the naphthoquinone compound represented by the general formula (1) is 1,4-naphthoquinone, 2methyl-1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, and the general formula The phenol compound represented by (2) is 1,4-dihydroxybenzene, 4-t-butyl-1,2-dihydroxybenzene, 2,6-di-t-butyl-p-cresol, It exists in the radically curable composition as described in 2nd invention.

A fourth invention resides in the radically curable composition according to any one of the first to third inventions, wherein the accelerator (C) is a cobalt compound and / or an amine compound. .

In the fifth invention, the addition ratio of the naphthoquinone compound represented by the general formula (1) and the phenol compound represented by the general formula (2) is 10/90 or more and less than 90/10 in weight ratio. The radical curable composition according to any one of the first to fourth inventions.

The sixth invention is cured by radical polymerization of the radically curable composition according to any one of the first to fifth inventions with active energy rays and / or heat in the presence of the curing agent (D). Lies in the curing method.

The “accelerator” in the present invention is a compound that can accelerate the curing of the radical curable compound, and is a compound that functions to promote the radical polymerization reaction by the curing agent.

The “gelation time” in the present invention refers to the time from the addition of the curing agent to the gelation of the radical curable composition when the radical curable composition is cured using a curing agent. The measurement of the gelation time is performed according to the method defined in 5.9 Room temperature curing characteristics (exothermic method) of JIS K6901 (2008) “Testing method of liquid unsaturated polyester resin”.

According to the radically curable composition of the present invention, the progress of polymerization in the storage / transport process, etc. caused by the addition of an accelerator is suppressed, and the thermal stability and storage stability are improved. Thus, the gelation time in the presence of the curing agent can be maintained even after long-term storage.

Hereinafter, the present invention will be described in detail.

In the radical curable composition containing the radical curable compound (A), the polymerization inhibitor (C) and the accelerator (C), the present invention is represented by the general formula (1) as the polymerization inhibitor (C). The radical curable composition characterized by using the naphthoquinone compound and the phenol compound represented by the general formula (2).

[Radical curable compound (A)]
The radical curable compound (A) used in the radical curable composition of the present invention is not particularly limited as long as it has one or more polymerizable groups in the molecule, and examples thereof include radical curable oligomers and radicals. A curable monomer is mentioned. Two or more kinds of these radically curable compounds may be used.

Examples of the radical curable oligomer include unsaturated polyester, vinyl ester, urethane (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate.

The unsaturated polyester is obtained, for example, by reacting an unsaturated polycarboxylic acid and a polyhydric alcohol by a known method, and is modified with a compound having a polymerizable group such as dicyclopentadiene. May be.

Examples of the unsaturated polyvalent carboxylic acid used as an unsaturated polyester production raw material include ester derivatives such as maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid and their anhydrides and methyl esters. . Also, saturated polyvalent carboxylic acids that can be used at the same time include aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, and tetrachlorophthalic acid, and their anhydrides. Derivatives such as succinic acid, adipic acid, sebacic acid, cyclohexanedicarboxylic acid, tetrahydrophthalic acid, het acid and their anhydrides, halides and methyl Examples include ester derivatives such as esters. Two or more kinds of these polycarboxylic acids may be used.

Examples of the polyhydric alcohol used as an unsaturated polyester production raw material include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propanediol, butanediol, pentanediol, and hexanediol. Dihydric alcohols such as cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A and isomers thereof, trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, and these ethylene oxides, Examples include alkylene oxide adducts such as propylene oxide. Two or more kinds of these polyhydric alcohols may be used.

As vinyl ester, it is a thing obtained by making an epoxy oligomer and unsaturated carboxylic acid react by a well-known method, for example.

Examples of the epoxy oligomer used as a vinyl ester production raw material include bisphenol A, hydrogenated bisphenol A, bisphenol F, novolac, and resole, each of which includes 1,6-hexanediol diglycidyl ether, Obtained by reaction with diglycidyl ether type epoxy compounds such as neopentyl glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, (di) glycerin (poly) glycidyl ether, (poly) tetramethylene glycol diglycidyl ether Is. Two or more of these epoxy oligomers may be used.

Examples of the unsaturated carboxylic acid used as a vinyl ester production raw material include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, α-phenylacrylic acid, methoxyacrylic acid, itaconic acid, and halogenated acrylic acid. Two or more of these unsaturated carboxylic acids may be used.

Urethane (meth) acrylate is obtained by reacting polyisocyanate, (meth) acrylate having a hydroxyl group and, if necessary, polyol with a known method.

Examples of the polyisocyanate used as a raw material for producing urethane (meth) acrylate include aromatic polyisocyanates such as diphenylmethane diisocyanate, tolylene diisocyanate, polyphenylene polymethylene polyisocyanate, xylylene diisocyanate, naphthalene diisocyanate and modified products thereof, hexa Examples include aliphatic polyisocyanates such as methylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate and modified products thereof. Two or more kinds of these polyisocyanates may be used.

Examples of the (meth) acrylate having a hydroxyl group used as a raw material for producing urethane (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, Monovalent (meth) acrylates such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate, multivalents such as tris (hydroxyethyl) isocyanuric acid di (meth) acrylate and pentaerythritol tri (meth) acrylate ( And (meth) acrylate. Two or more kinds of these (meth) acrylates having a hydroxyl group may be used.

Examples of the polyol used as a raw material for producing urethane (meth) acrylate include polyethylene glycol, polypropylene glycol, polyether polyol, polyester polyol, polycarbonate polyol, and polybutadiene polyol. Two or more of these polyols may be used.

The polyester (meth) acrylate is obtained by reacting an unsaturated carboxylic acid with a polyvalent carboxylic acid or a polyhydric alcohol by a known method.

Examples of the unsaturated carboxylic acid used as a raw material for producing polyester (meth) acrylate include those used in the above vinyl esters, and ester derivatives such as halides and methyl esters thereof. Moreover, what is used with said unsaturated polyester as a polyhydric carboxylic acid and a polyhydric alcohol is mentioned. Any of these may use two or more types.

The polyether (meth) acrylate used as a raw material for producing the polyester (meth) acrylate is obtained by reacting an unsaturated carboxylic acid and a polyhydric alcohol by a known method.

Examples of the unsaturated carboxylic acid used as a raw material for producing polyester (meth) acrylate include those used in the above vinyl esters, and ester derivatives such as halides and methyl esters thereof. Examples of the polyhydric alcohol include those used in the above unsaturated polyester and polyols used in the above urethane (meth) acrylate.

Examples of the radical curable monomer include monofunctional vinyl monomers and polyfunctional vinyl monomers.

Monofunctional vinyl monomers include, for example, monofunctional aromatic vinyl monomers such as styrene, α-methylstyrene, α-ethylstyrene, p-chlorostyrene, hydroxystyrene, vinyltoluene, (meth) acrylic acid, (meth) Methyl acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic acid-2 -Ethylhexyl, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylic acid Glycidyl, tetrahydrofurfuryl (meth) acrylate, ( Allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (meth) Dimethylaminoethyl acrylate, dimethylaminoethyl methyl chloride (meth) acrylate, dimethylaminoethyl benzyl chloride (meth) acrylate, diethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, (meth) Monofunctional like heptadecafluorodecyl acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate (Meta) Acry Acid monomers.

Examples of the polyfunctional vinyl monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, di Propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2-hydroxy-1 , 3-propanediol di (meth) acrylate, butanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate n = 8,9), neopentyl glycol di (meth) acrylate, pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol di (meth) acrylate, dipentol di (meth) acrylate, sorbitol di (meth) acrylate, trishydroxyethyl isocyanurate, nonane Diol di (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, 2,2-bis [4-((meth) acryloxyethoxy) phenyl] propane, 2,2-bis [4-((meth) acryloxydiethoxy) phenyl] propane, 2,2-bis [4-((meth) acryloxypolyethoxy) phenyl] propane, 2-hydroxy-1-acryloxy- Examples thereof include polyfunctional (meth) acrylic monomers such as 3-methacryloxypropane, polyfunctional aromatic vinyl monomers such as divinylbenzene, and polyfunctional allyl monomers such as diallyl phthalate and triallyl cyanurate.

These radical curable oligomers and radical curable monomers may be used in any combination of two or more.

The mixing ratio of the radical curable oligomer and the radical curable monomer is preferably 10% by mass or more and 90% by mass or less, more preferably 15% by mass with respect to 100% by mass in total of the radical curable oligomer and the radical curable monomer. % To 80% by mass, and most preferably 20% to 70% by mass. When it exceeds 90% by mass, the performance of the obtained cured product is not sufficient, and when it is less than 10% by mass, the viscosity cannot be sufficiently reduced and the workability may not be excellent.

[Polymerization inhibitor (B)]
The polymerization inhibitor (B) of the present invention is a naphthoquinone compound represented by the general formula (1) and a phenol compound represented by the general formula (2). By using a naphthoquinone compound and a phenol compound in combination, a synergistic effect can be obtained.

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

In the general formula (1), X, Y and Z may be the same or different, and each is a hydrogen atom, a hydroxyl group, a halogen atom, an acyl group having 2 to 9 carbon atoms, or 1 carbon atom. ˜8 alkyl group, C 6-10 aryl group, C 6-10 aralkyl group, C 2-10 alkoxyalkyl group, amino group, C 1-8 alkylamino group, glycidyl group, It represents either a hydroxyalkyl group having 1 to 8 carbon atoms or an aryloxyalkyl group having 6 to 10 carbon atoms, among which X and Y may be bonded to each other to form a saturated or unsaturated ring, You may form a ring on both sides of a hetero atom.

Examples of the halogen atom represented by X, Y and Z in the general formula (1) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the acyl group having 2 to 9 carbon atoms include an acetyl group and propionyl. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n- Examples include pentyl group, n-hexyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group, 2-methoxyethyl group, 2-ethoxyethyl group and the like. Examples of the aralkyl group having 6 to 10 carbon atoms include a benzyl group and a phenethyl group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a p-tolyl group, an o-tolyl group, and a naphthyl group. It is done. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a tert-butoxy group, and the like. Includes a methoxymethyl group, an ethoxymethyl group, and the like. Examples of the alkylamino group having 1 to 8 carbon atoms include a methylamino group, an ethylamino group, and an n-propylamino group. Examples of the hydroxyalkyl group include a hydroxymethyl group and 1-hydroxyethyl group, and examples of the aryloxyalkyl group having 6 to 10 carbon atoms include a phenoxymethyl group. In addition to those described above, there may be mentioned substituents containing oxygen, nitrogen and sulfur. However, a structure composed of carbon, oxygen, and hydrogen is desirable from the viewpoints of improving the handleability and reducing the environmental load.

Specific examples of the naphthoquinone compound of the present invention include the following compounds.

In the general formula (1), as specific examples in the case where X and Y are not bonded to each other to form a saturated or unsaturated 6-membered ring, for example, 1,4-naphthoquinone, 2-fluoro-1,4 -Naphthoquinone, 2-chloro-1,4-naphthoquinone, 2-bromo-1,4-naphthoquinone, 2-iodo-1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone, 2-ethyl-1,4 -Naphthoquinone, 2-n-propyl-1,4-naphthoquinone, 2-i-propyl-1,4-naphthoquinone, 2-n-butyl-1,4-naphthoquinone, 2-i-butyl 1,4-naphthoquinone, 2-sec-butyl-1,4-naphthoquinone, 2-tert-butyl 1,4-naphthoquinone, 2-n-pentyl-1,4-naphthoquinone 2-n-hexyl-1,4-naphthoquinone, 2- ( 4-methylpentyl)- , 4-naphthoquinone, 2-n-heptyl-1,4-naphthoquinone, 2-n-octyl-1,4-naphthoquinone, 2-sec-octyl-1,4-naphthoquinone, 2-n-nonyl-1,4 -Naphthoquinone, 2-n-decyl-1,4-naphthoquinone, 2-n-undecyl-1,4-naphthoquinone, 2-n-dodecyl-1,4-naphthoquinone, 2-n-tridecyl-1,4-naphthoquinone 2-n-tetradecyl-1,4-naphthoquinone, 2-n-pentadecyl-1,4-naphthoquinone, 2-cyclopropyl-1,4-naphthoquinone, 2-cyclopentyl-1,4-naphthoquinone, 2-cyclohe Xyl-1,4-naphthoquinone, 2-cyclopropylmethyl-1,4-naphthoquinone, 2-cyclopentylmethyl-1,4-naphthoquinone, 2-cyclohexylmethyl-1,4- Examples include naphthoquinone, 2- (2-cyclopropylethyl) -1,4-naphthoquinone, 2- (2-cyclopentylethyl-1,4-naphthoquinone, 2- (2-cyclohexylethyl) -1,4-naphthoquinone, and the like. .

Also, 2-benzyl-1,4-naphthoquinone, 2- (2-fluorobenzyl) -1,4-naphthoquinone, 2- (3-fluorobenzyl) -1,4-naphthoquinone, 2- (4-fluorobenzyl) 1,4-naphthoquinone, 2- (2-chlorobenzyl) -1,4-naphthoquinone, 2- (3-chlorobenzyl) -1,4-naphthoquinone, 2- (4-chlorobenzyl) -1,4- Naphthoquinone, 2- (2-methylbenzyl) -1,4-naphthoquinone, 2- (3-methylbenzyl) -1,4-naphthoquinone, 2- (4-methylbenzyl) -1,4-naphthoquinone, 2- ( 2-methoxybenzyl) -1,4-naphthoquinone, 2- (3-methoxybenzyl) -1,4-naphthoquinone, 2- (4-methoxybenzyl) -1,4-naphthoquinone, 2- (2-trifluoromethyl) Be Ndyl) -1,4-naphthoquinone, 2- (3-trifluoromethylbenzyl) -1,4-naphthoquinone, 2- (4-trifluoromethylbenzyl) -1,4-naphthoquinone, 2- (2-methylthiobenzyl) ) -1,4-naphthoquinone, 2- (3-methylthiobenzyl) -1,4-naphthoquinone, 2- (4-methylthiobenzyl) -1,4-naphthoquinone, 2- (2-nitrobenzyl) -1,4 -Naphthoquinone, 2- (3-nitrobenzyl) -1,4-naphthoquinone, 2- (4-nitrobenzyl) -1,4-naphthoquinone, 2- (2-phenethyl) -1,4-naphthoquinone, 2- ( 1-phenethyl) -1,4-naphthoquinone, 2- (3-phenylpropyl) -1,4-naphthoquinone, 2- (2-phenylpropyl) -1,4-naphthoquinone, 2- (1-phenylpropyl) (Lopyl) -1,4-naphthoquinone, 2-diphenylmethyl-1,4-naphthoquinone, 2- (1,1-diphenylethyl) -1,4-naphthoquinone, 2- (2,2-diphenylethyl) -1, 4-naphthoquinone, 2-chloromethyl-1,4-naphthoquinone, 2-bromomethyl-1,4-naphthoquinone, 2-iodomethyl-1,4-naphthoquinone, 2-trifluoromethyl-1,4-naphthoquinone, 2-dichloro Methyl-1,4-naphthoquinone, 2-trichloromethyl-1,4-naphthoquinone, 2- (2-chloroethyl) -1,4-naphthoquinone, 2- (2-bromoethyl) -1,4-naphthoquinone, 2-penta Fluoroethyl-1,4-naphthoquinone, 2-hydroxymethyl-1,4-naphthoquinone, 2- (1-hydroxyethyl) -1,4-naphthoquinone, 2- (2 Hydroxyethyl) -1,4-naphthoquinone, 2-methoxymethyl-1,4-naphthoquinone, 2-ethoxymethyl-1,4-naphthoquinone, 2-n-propoxymethyl-1,4-naphthoquinone, 2-i-propoxy Methyl-1,4-naphthoquinone, 2-n-butyloxymethyl-1,4-naphthoquinone, 2-i-butyloxymethyl-1,4-naphthoquinone, 2-sec-butyloxymethyl-1,4-naphthoquinone, 2-tert-butyloxymethyl-1,4-naphthoquinone, 2- (1-methoxyethyl) -1,4-naphthoquinone, 2- (2-methoxyethyl) -1,4-naphthoquinone, 2- (1-ethoxy Ethyl) -1,4-naphthoquinone, 2- (2-ethoxyethyl) -1,4-naphthoquinone, 2-dimethoxymethyl-1,4-naphthoquinone, 2-die Kishimechiru-1,4-naphthoquinone, and the like.

Furthermore, 2-mercaptomethyl-1,4-naphthoquinone, 2- (1-mercaptoethyl) -1,4-naphthoquinone, 2- (2-mercaptoethyl) -1,4-naphthoquinone, 2-methylthiomethyl 2- (1-mercaptoethyl) -1,4-naphthoquinone, 2-ethylthiomethyl-1,4-naphthoquinone, 2-n-propiothiomethyl-1,4-naphthoquinone, 2-i-propylthiomethyl-1, 4-naphthoquinone, 2-n-butylthiomethyl-1,4-naphthoquinone, 2-i-butylthiomethyl-1,4-naphthoquinone, 2-sec-butylthiomethyl-1,4-naphthoquinone, 2-tert- Butylthiomethyl-1,4-naphthoquinone, 2- (1-methylthioethyl) -1,4-naphthoquinone, 2- (2-methylthioethyl) -1,4-naphthoquinone, 2 -(1-ethylthioethyl) -1,4-naphthoquinone, 2- (2-ethylthioethyl) -1,4-naphthoquinone, 2-chloromethoxymethyl-1,4-naphthoquinone, 2-trifluoromethoxymethyl- 1,4-naphthoquinone, 2- (1-chloromethoxyethyl) -1,4-naphthoquinone, 2- (2-chloromethoxyethyl) -1,4-naphthoquinone, 2-chloromethylthiomethyl-1,4-naphthoquinone, 2-trifluoromethylthiomethyl-1,4-naphthoquinone, 2- (1-chloromethylthioethyl) -1,4-naphthoquinone, 2- (2-chloromethylthioethyl) -1,4-naphthoquinone, 2-phenoxymethyl- 1,4-naphthoquinone, 2- (1-phenoxyethyl) -1,4-naphthoquinone, 2- (2-phenoxyethyl) -1,4-naphthoquinone 2- (1-phenoxypropyl) -1,4-naphthoquinone, 2- (2-phenoxypropyl) -1,4-naphthoquinone, 2- (3-phenoxypropyl) -1,4-naphthoquinone, 2- (1 -Phenoxy-1-methylethyl) -1,4-naphthoquinone, 2- (2-chlorophenoxymethyl) -1,4-naphthoquinone, 2- (3-chlorophenoxymethyl) -1,4-naphthoquinone, 2- ( 4-chlorophenoxymethyl) -1,4-naphthoquinone, 2- (2-methylphenoxymethyl) -1,4-naphthoquinone, 2- (3-methylphenoxymethyl) -1,4-naphthoquinone, 2- (4- Methylphenoxymethyl) -1,4-naphthoquinone, 2- (2-fluorophenoxymethyl) -1,4-naphthoquinone, 2- (3-fluorophenoxymethyl) -1,4- Phtoquinone, 2- (4-fluorophenoxymethyl) -1,4-naphthoquinone, 2- (2-trifluoromethylphenoxymethyl) -1,4-naphthoquinone, 2- (3-trifluoromethylphenoxymethyl) -1, 4-naphthoquinone, 2- (4-trifluoromethylphenoxymethyl) -1,4-naphthoquinone, 2- (2-nitrophenoxymethyl) -1,4-naphthoquinone, 2- (3-nitrophenoxymethyl) -1, 4-naphthoquinone, 2- (4-nitrophenoxymethyl) -1,4-naphthoquinone, 2-benzyloxymethyl-1,4-naphthoquinone, 2- (2-fluorobenzyloxymethyl) -1,4-naphthoquinone, 2 -(3-Fluorobenzyloxymethyl) -1,4-naphthoquinone, 2- (4-Fluorobenzyloxymethyl) -1,4 -Naphthoquinone, 2- (2-chlorobenzyloxymethyl) -1,4-naphthoquinone, 2- (3-chlorobenzyloxymethyl) -1,4-naphthoquinone, 2- (4-chlorobenzyloxymethyl) -1, 4-naphthoquinone, 2- (2-methoxybenzyloxymethyl) -1,4-naphthoquinone, 2- (3-methoxybenzyloxymethyl) -1,4-naphthoquinone, 2- (4-methoxybenzyloxymethyl) -1 , 4-naphthoquinone, 2- (2-trifluoromethylbenzyloxymethyl) -1,4-naphthoquinone, 2- (3-trifluoromethylbenzyloxymethyl) -1,4-naphthoquinone, 2- (4-trifluoro Methylbenzyloxymethyl) -1,4-naphthoquinone, 2- (2-nitrobenzyloxymethyl) -1,4-naphthoquinone, 2 -(3-nitrobenzyloxymethyl) -1,4-naphthoquinone, 2- (4-nitrobenzyloxymethyl) -1,4-naphthoquinone, 2- (2-phenethyloxymethyl) -1,4-naphthoquinone, 2 -(1-phenethyloxymethyl) -1,4-naphthoquinone, 2- (1-benzyloxyethyl) -1,4-naphthoquinone, 2- (2-benzyloxyethyl) -1,4-naphthoquinone, 2- ( 1-benzyloxy-1-methylethyl) -1,4-naphthoquinone, 2-benzoyloxymethyl) -1,4-naphthoquinone, 2- (2-fluorobenzoyloxymethyl) -1,4-naphthoquinone, 2- ( 3-fluorobenzoyloxymethyl) -1,4-naphthoquinone, 2- (4-fluorobenzoyloxymethyl) -1,4-naphthoquinone, 2- (2-meso Rubenzoyloxymethyl) -1,4-naphthoquinone, 2- (3-methylbenzoyloxymethyl) -1,4-naphthoquinone, 2- (4-methylbenzoyloxymethyl) -1,4-naphthoquinone, 2- (2 -Chlorobenzoyloxymethyl) -1,4-naphthoquinone, 2- (3-chlorobenzoyloxymethyl) -1,4-naphthoquinone, 2- (4-chlorobenzoyloxymethyl) -1,4-naphthoquinone, 2- ( 2-trifluoromethylbenzoyloxymethyl) -1,4-naphthoquinone, 2- (3-trifluoromethylbenzoyloxymethyl) -1,4-naphthoquinone, 2- (4-trifluoromethylbenzoyloxymethyl) -1, 4-naphthoquinone, 2-acetoxymethyl-1,4-naphthoquinone, 2-propionyloxymethyl-1,4- Phtoquinone, 2-phenylthiomethyl-1,4-naphthoquinone, 2-benzylthiomethyl-1,4-naphthoquinone, 2-benzoylthiomethyl-1,4-naphthoquinone, 2-acetylthiomethyl-1,4-naphthoquinone, 2-carboxymethyl-1,4-naphthoquinone, 2-cyanomethyl-1,4-naphthoquinone, 2-methoxycarbonylmethyl-1,4-naphthoquinone, 2-ethoxycarbonylmethyl-1,4-naphthoquinone, 2-methylthiocarbonylmethyl -1,4-naphthoquinone, 2-vinyl-1,4-naphthoquinone, 2-allyl-1,4-naphthoquinone, 2- (2-butenyl) -1,4-naphthoquinone, 2- (3-methyl-2- Butenyl) -1,4-naphthoquinone, 2-ethyl-1,4-naphthoquinone, 2-propargyl-1,4-naphthoquinone, 2 Phenyl-1,4-naphthoquinone, 2- (2-fluorophenyl) -1,4-naphthoquinone, 2- (3-fluorophenyl) -1,4-naphthoquinone, 2- (4-fluorophenyl) -1,4 -Naphthoquinone, 2- (2-chlorophenyl) -1,4-naphthoquinone, 2- (3-chlorophenyl) -1,4-naphthoquinone, 2- (4-chlorophenyl) -1,4-naphthoquinone, 2- (2- Methylenyl) -1,4-naphthoquinone, 2- (3-methylenyl) -1,4-naphthoquinone, 2- (4-methylenyl) -1,4-naphthoquinone, 2- (2-trifluoromethylphenyl) -1, 4-naphthoquinone, 2- (2-trifluoromethylphenyl) -1,4-naphthoquinone, 2- (3-trifluoromethylphenyl) -1,4-naphthoquinone, 2- (4-trimethyl) Fluoromethylphenyl) -1,4-naphthoquinone, 2- (2-methoxyphenyl) -1,4-naphthoquinone, 2- (3-methoxyphenyl) -1,4-naphthoquinone, 2- (4-methoxyphenyl) 1,4-naphthoquinone, 2- (2-nitrophenyl) -1,4-naphthoquinone, 2- (3-nitrophenyl) -1,4-naphthoquinone, 2- (4-nitrophenyl) -1,4- Examples thereof include naphthoquinone and 2- (1 ′, 4′-naphthoquinone-2′-yl) -1,4-naphthoquinone.

In addition, 2-hydroxy-1,4-naphthoquinone, 2-methoxy-1,4-naphthoquinone, 2-ethoxy-1,4-naphthoquinone, 2-n-propoxy-1,4-naphthoquinone, 2-i-propoxy 1,4-naphthoquinone, 2-n-butoxy-1,4-naphthoquinone, 2-i-butoxy-1,4-naphthoquinone, 2-sec-butoxy-1,4-naphthoquinone, 2-i-butoxy-1 , 4-naphthoquinone, 2-tert-butoxy-1,4-naphthoquinone, 2- (2-hydroxyethoxy) -1,4-naphthoquinone, 2-cyclopropyloxy-1,4-naphthoquinone, 2-cyclopentyloxy-1 , 4-naphthoquinone, 2-cyclohexyl-1,4-naphthoquinone, 2-cyclopropylmethyloxy-1,4-naphthoquinone, 2-cyclopentylmethyl Xyl-1,4-naphthoquinone, 2-cyclohexylmethyloxy-1,4-naphthoquinone, 2-chloromethyloxy-1,4-naphthoquinone, 2-trifluoromethyloxy-1,4-naphthoquinone, 2-allyloxy-1 , 4-naphthoquinone, 2- (2-butenyloxy) -1,4-naphthoquinone, 2-propargyloxy-1,4-naphthoquinone, 2-phenoxy-1,4-naphthoquinone, 2- (4-fluorophenoxy) -1 , 4-naphthoquinone, 2- (4-chlorophenoxy) -1,4-naphthoquinone, 2- (4-methylphenoxy) -1,4-naphthoquinone, 2- (4-trifluoromethylphenoxy) -1,4- Naphthoquinone, 2- (4-methoxyphenoxy) -1,4-naphthoquinone, 2- (4-nitrophenoxy) -1,4-naphthoquinone, 2 -Benzyloxy-1,4-naphthoquinone, 2- (4-fluorobenzyloxy) -1,4-naphthoquinone, 2- (4-chlorobenzyloxy) -1,4-naphthoquinone, 2- (4-methylbenzyloxy) ) -1,4-naphthoquinone, 2- (4-methoxybenzyloxy) -1,4-naphthoquinone, 2- (4-trifluoromethylbenzyloxy) -1,4-naphthoquinone, 2- (4-methylthiobenzyloxy) ) -1,4-naphthoquinone, 2- (4-nitrobenzyloxy) -1,4-naphthoquinone, 2- (2-phenethyloxy) -1,4-naphthoquinone, 2-acetoxy-1,4-naphthoquinone and the like. Cited.

Furthermore, 2- (2-nitrophenyl) -1,4-naphthoquinone, 2-propionyloxy-1,4-naphthoquinone, 2-benzoyloxy-1,4-naphthoquinone, 2- (4-fluorobenzoyloxy)- 1,4-naphthoquinone, 2- (4-methylbenzoyloxy) -1,4-naphthoquinone, 2- (4-chlorobenzoyloxy) -1,4-naphthoquinone, 2- (4-trifluoromethylbenzoyloxy)- 1,4-naphthoquinone, 2-mercapto-1,4-naphthoquinone, 2-methylthio-1,4-naphthoquinone, 2-ethylthio-1,4-naphthoquinone, 2-n-propylthio-1,4-naphthoquinone, 2- i-propylthio-1,4-naphthoquinone, 2-n-butylthio-1,4-naphthoquinone, 2-i-butylthio-1,4-naphthoquinone, -Sec-butylthio-1,4-naphthoquinone, 2-tert-butylthio-1,4-naphthoquinone, 2-cyclopropylthio-1,4-naphthoquinone, 2-cyclopentylthio-1,4-naphthoquinone, 2-cyclohexylthio 1,4-naphthoquinone, 2-cyclopropylmethylthio-1,4-naphthoquinone, 2-cyclopentylmethylthio-1,4-naphthoquinone, 2-cyclohexylmethylthio-1,4-naphthoquinone, 2-chloromethylthio-1,4- Naphthoquinone, 2-trifluoromethylthio-1,4-naphthoquinone, 2-allylthio-1,4-naphthoquinone, 2- (2-butenylthio) -1,4-naphthoquinone, 2-propargylthio-1,4-naphthoquinone, 2 -Phenylthio-1,4-naphthoquinone, 2- (4-fluorophenylthio)- , 4-naphthoquinone, 2- (4-chlorophenylthio) -1,4-naphthoquinone, 2- (4-methylphenylthio) -1,4-naphthoquinone, 2- (4-trifluoromethylphenylthio) -1, 4-naphthoquinone, 2- (4-methoxyphenylthio) -1,4-naphthoquinone, 2- (4-nitrophenylthio) -1,4-naphthoquinone, 2-benzylthio-1,4-naphthoquinone, 2- (4 -Fluorobenzylthio) -1,4-naphthoquinone, 2- (4-chlorobenzylthio) -1,4-naphthoquinone, 2- (4-methylbenzylthio) -1,4-naphthoquinone, 2- (4-methoxy) Benzylthio) -1,4-naphthoquinone, 2- (4-trifluoromethylbenzylthio) -1,4-naphthoquinone, 2- (4-nitrobenzylthio) -1,4-naphthoquinone 2- (2-phenethylthio) -1,4-naphthoquinone, 2-acetylthio-1,4-naphthoquinone, 2-propionylthio-1,4-naphthoquinone, 2-benzoylthio-1,4-naphthoquinone, 2- ( 4-fluorobenzoylthio) -1,4-naphthoquinone, 2- (4-methylbenzoylthio) -1,4-naphthoquinone, 2- (4-chlorobenzoylthio) -1,4-naphthoquinone, 2- (4- Trifluoromethylbenzoylthio) -1,4-naphthoquinone, 2-methylsulfinyl-1,4-naphthoquinone, 2-ethylsulfinyl-1,4-naphthoquinone, 2-n-propylsulfinyl-1,4-naphthoquinone, 2- i-propylsulfinyl-1,4-naphthoquinone, 2-n-butylsulfinyl-1,4-naphthoquinone, 2-i-butylsulfy 1,4-naphthoquinone, 2-sec-butylsulfinyl-1,4-naphthoquinone, 2-tert-butylsulfinyl-1,4-naphthoquinone, 2-cyclopropylsulfinyl-1,4-naphthoquinone, 2-cyclopentylsulfinyl 1,4-naphthoquinone, 2-cyclohexylsulfinyl-1,4-naphthoquinone, 2- (hydroxymethylsulfinyl) -1,4-naphthoquinone, 2- (hydroxyethylsulfinyl) -1,4-naphthoquinone, 2-phenylsulfinyl 1,4-naphthoquinone, 2-benzylsulfinyl-1,4-naphthoquinone, 2-methylsulfonyl-1,4-naphthoquinone, 2-ethylsulfonyl-1,4-naphthoquinone, 2-n-propylsulfonyl-1,4 -Naphthoquinone, 2-i-propylsulfonyl-1, 4-naphthoquinone, 2-n-butylsulfonyl-1,4-naphthoquinone, 2-i-butylsulfonyl-1,4-naphthoquinone, 2-sec-butylsulfonyl-1,4-naphthoquinone, 2-tert-butylsulfonyl- 1,4-naphthoquinone, 2-cyclopropylsulfonyl-1,4-naphthoquinone, 2-cyclopentylsulfonyl-1,4-naphthoquinone, 2-cyclohexylsulfonyl-1,4-naphthoquinone, 2- (hydroxymethylsulfonyl) -1, 4-naphthoquinone, 2- (hydroxyethylsulfonyl) -1,4-naphthoquinone, 2-phenylsulfonyl-1,4-naphthoquinone, 2-benzylsulfonyl-1,4-naphthoquinone, 2-acetyl-1,4-naphthoquinone, 2-propanoyl-1,4-naphthoquinone, 2-chloroacetyl-1, -Naphthoquinone, 2-trifluoroacetyl-1,4-naphthoquinone, 2-methoxyacetyl-1,4-naphthoquinone, 2-benzoyl-1,4-naphthoquinone, 2- (2-fluorobenzoyl) -1,4-naphthoquinone 2- (3-fluorobenzoyl) -1,4-naphthoquinone, 2- (4-fluorobenzoyl) -1,4-naphthoquinone, 2- (2-methylbenzoyl) -1,4-naphthoquinone, 2- (3 -Methylbenzoyl) -1,4-naphthoquinone, 2- (4-methylbenzoyl) -1,4-naphthoquinone, 2- (2-chlorobenzoyl) -1,4-naphthoquinone, 2- (3-chlorobenzoyl)- 1,4-naphthoquinone, 2- (4-chlorobenzoyl) -1,4-naphthoquinone, 2- (2-trifluoromethylbenzoyl) -1,4-naphthoquinone 2- (3-trifluoromethylbenzoyl) -1,4-naphthoquinone, 2- (4-trifluoromethylbenzoyl) -1,4-naphthoquinone, 2-carboxy-1,4-naphthoquinone, 2-methoxycarbonyl-1 , 4-naphthoquinone, 2-ethoxycarbonyl-1,4-naphthoquinone, 2-carbamoyl-1,4-naphthoquinone, 2-dimethylaminocarbonyl-1,4-naphthoquinone, 2-cyano-1,4-naphthoquinone, 2- Examples thereof include nitro-1,4-naphthoquinone.

Furthermore, 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-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-hi Roxy-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-chloro-1, 4-naphthoquinone, 2-methyl-3-hydroxy-6,7-dichloro-1,4-naphthoquinone, 2-methyl-3,5-dihydroxy-1,4-naphthoquinone, 2-me Til-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-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-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-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-3,6,7-trichloro-1,4-naphthoquinone, 2-amino-3-chloro-5-hydroxy-1,4-naphthoquinone, 2-amino-3-chloro -6-hydroxy Ci-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.

In the general formula (1), as specific examples when X and Y are bonded to each other to form a saturated or unsaturated 6-membered ring, 9,10-anthraquinone, 1-methyl-9,10-anthraquinone, 2-methyl-9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 1-methoxy-9,10-anthraquinone, 1-methoxy-4-methyl-9,10-anthraquinone, 1,4-dihydro- 9,10-anthraquinone, 1,2,3,4-tetrahydro-9,10-anthraquinone, 2-methyl-1,4-dihydro-9,10-anthraquinone, 2-methyl-1,2,3,4 And tetrahydro-9,10-anthraquinone.

Among these exemplified compounds of the general formula (1), compounds in which X and Y are each a hydrogen atom, an alkyl group or a hydroxy group are preferred, and 1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone, 2 -Hydroxy-1,4-naphthoquinone is preferred because it is highly effective and easy to produce. In particular, 1,4-naphthoquinone is preferable.

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

In the general formula (2), n is 0 or 1, and m represents an integer of 0 to 4. Moreover, R represents a C1-C8 alkyl group or a C1-C8 alkoxy group, and when there are a plurality of Rs, they may be the same or different.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R in the general formula (2) include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert- A butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group, 2-methoxyethyl group, 2-ethoxyethyl group and the like can be mentioned. Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, and tert-butoxy group.

Specific examples of the phenol compound of the present invention include the following compounds.

First, in the general formula (2), as the compound where n is 0, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol (BHT), 2,6-di- t-butyl-4-ethylphenol, 2,4-di-t-butylphenol, 2-t-butyl-4,6-dimethylphenol, 2,4,6-tri-t-butylphenol, 4-methoxyphenol (MEHQ ) And the like.

In addition, as a compound in which n is 1, 1,4-dihydroxybenzene (hydroquinone), 2-methyl-1,4-dihydroxybenzene, 2-t-butyl-1,4-dihydroxybenzene, 1,2-dihydroxybenzene (Catechol), 4-t-butyl-1,2-dihydroxybenzene (t-butylcatechol), 2,3,5-trimethyl-1,4-dihydroxybenzene, 2,3,5,6-tetramethyl-1 , 4-dihydroxybenzene and the like.

Among these exemplified phenol polymerization inhibitors, 1,4-dihydroxybenzene, 1,2-dihydroxybenzene, 4-t-butyl-1,2-dihydroxybenzene, 2,6-di-t-butylphenol, 2, 6-di-t-butyl-4-methylphenol and 4-methoxyphenol are preferred. In particular, 1,4-dihydroxybenzene is preferable.

As exemplified above, in the radical curable composition of the present invention, the polymerization inhibitor (B) is a combination of the naphthoquinone compound represented by the general formula (1) and the phenol compound represented by the general formula (2). Use. The combined use amount is not particularly limited, but when the radical curable compound (A) is 100 parts by weight, it is usually 0.001 or more and less than 1.0 part by weight, preferably 0.002 or more, 0 Less than 0.8 part by weight, more preferably 0.003 or more and less than 0.5 part by weight. When the amount is less than 0.001 part by weight, the effect of inhibiting the polymerization is reduced. On the other hand, it may be added in excess of 1.0 part by weight, but the solubility may be exceeded and precipitation may occur.

The addition ratio of the naphthoquinone compound represented by the general formula (1) and the phenol compound represented by the general formula (2) in the polymerization inhibitor (B) is usually 10/90 or more and less than 90/10 in weight ratio. , Preferably 15/85 or more and less than 85/15, more preferably 20/80 or more and less than 80/20. When the ratio of the naphthoquinone compound is less than 10, gel time drift tends to occur, and when the ratio of the naphthoquinone compound exceeds 90, the storage stability of the radical curable composition tends to deteriorate. As a polymerization inhibitor, it is important to use a naphthoquinone compound represented by the general formula (1) and a phenol compound represented by the general formula (2) in combination, and the combined use only increases the stability during storage. In addition, the gel time drift after storage can be kept small.

In addition to the polymerization inhibitor (B), a polymerization inhibitor other than the polymerization inhibitor (B) can be used in the radical curable composition of the present invention as long as the effects of the present invention are not impaired.

Examples of the polymerization inhibitor that can be used in combination include N-oxyl-based compounds such as 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol, phenothiazine, benzoquinone, methyl-p-benzoquinone, For example, copper naphthenate can be used. In addition, well-known polymerization inhibitors, such as ferdazil and α, α-diphenyl-β-picrylhydrazyl, may be mentioned. Two or more kinds of these polymerization inhibitors may be used.

[Accelerator (C)]
The accelerator (C) used in the radical curable composition of the present invention is a radical curable composition such as SMC (sheet molding compound) or BMC (bulk molding compound) in order to improve curability at low temperatures. Used to make a semi-cured state. Such accelerators include cobalt naphthenate, manganese naphthenate, copper naphthenate, potassium naphthenate, calcium naphthenate, cobalt octylate, manganese octylate, etc., cobalt acetylacetonate, vanadium acetylacetonate, etc. Metal chelate compounds, dimethylaniline, N, N′-dimethylaniline, N, N-dimethyltoluidine, N, N-diethylaniline, amine compounds such as N, N-di (hydroxy) -4-methylaniline, acetylacetone, Examples include acyl group-containing lactone compounds such as ethyl acetoacetate, acetoacetamide compounds, β-diketones, β-ketoesters, β-ketoamides, and the like. Two or more kinds of these accelerators may be used. Among these exemplified accelerators, cobalt compounds such as cobalt naphthenate and cobalt octylate and amine compounds are preferred. A plurality of accelerators, for example, a cobalt compound and an amine compound may be used in combination.

The amount of the accelerator (C) used is not particularly limited. However, when the radical curable compound (A) is 100 parts by weight, it is usually 0.05 or more and less than 10 parts by weight, preferably 0.1 or more. The amount is less than 7 parts by weight, more preferably 0.15 or more and less than 5 parts by weight. In any case, the accelerator is a weight as an active ingredient excluding the solvent.

These accelerators (C) are handled in the state mixed with the radical curable composition. In order to improve the thermal stability and storage stability of the radical curable composition in the presence of the accelerator (C), and to prevent gel time drift after long-term storage, the radical polymerization inhibitor (B ) Is used.

[Curing agent (D)]
Examples of the curing agent (D) used in the radical curable composition of the present invention include t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,1, Hydroperoxide such as 3,3-tetramethylbutyl hydroperoxide, ketone peroxide such as methyl ethyl ketone peroxide, acetylacetone peroxide, diacyl peroxide such as benzoyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, etc. Dialkyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy Peroxides such as alkyl peresters such as benzoate and bis (4-t-butylcyclohexyl) peroxydicarbonate; 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyro Examples thereof include azo compounds such as nitrile. Two or more kinds of these curing agents may be used.

The curing agent (D) may be in a form containing a solvent. As the solvent, for example, organic solvents such as dioctyl phthalate, dimethyl phthalate, and xylene, water, and the like can be used, and two or more kinds may be used. Although the content of these solvents is not particularly limited, for example, it is preferably 90 parts by weight or less per 100 parts by weight of the curing agent.

Although it does not specifically limit as the usage-amount of the said hardening | curing agent (D), When a radically curable compound (A) is 100 weight part, it is 0.01 or more and less than 10 weight part normally, Preferably it is 0.05 or more, The amount is less than 7 parts by weight, more preferably 0.1 or more and less than 5 parts by weight. In any case, the curing agent is a weight as an active ingredient excluding the solvent.

These curing agents (D) are used by adding to the radical curable composition immediately before molding, but can be added to the radical curable composition from the beginning and treated as a compound such as SMC or BMC.

[Other additives]
In the radical curable composition of the present invention, fiber reinforcing agent, filler, thixotropic agent, thixotropic agent, coupling agent, colorant, ultraviolet absorber, acid value prevention within the range not impairing performance. Various additives such as an agent, a thickener, a thickener, an internal mold release agent, a low shrinkage agent, an antifoaming agent, a wax, a plasticizer, and a patterning agent may be appropriately blended.

Examples of the fiber reinforcement include organic fibers such as glass fiber, carbon fiber, amide, aramid, vinylon, polyester, and phenol, and inorganic fibers such as carbon fiber, metal fiber, and ceramic fiber. Also good. In consideration of workability and economy, glass fibers and organic fibers are preferable, and glass fibers are more preferable. The fiber form includes plain weave, satin weave, non-woven fabric, mat, roving, chop, knitted fabric, braided fabric, and a composite structure of these, and is selected according to the construction method and product form.

Examples of the filler include calcium carbonate, aluminum hydroxide, fly ash, barium sulfate, talc, clay, and glass powder. Examples of the aggregate include quartz sand, gravel, and crushed stone. When used for mortar applications, those having a particle size of about 5 mm or less are preferred. The blending amount of the filler or aggregate is not particularly limited, but is usually 1 part by weight or more and less than 300 parts by weight when the radical curable compound (A) is 100 parts by weight.

[Method for producing radical curable composition]
The radical curable composition of this invention can be manufactured with the manufacturing method similar to a well-known radical curable composition except the component differing. For example, it can be produced by mixing the radical curable compound (A), the polymerization inhibitor (B), and the accelerator (C) and then sufficiently stirring and mixing until uniform.

The radical curable composition of the present invention can be prepared by further adding the polymerization inhibitor (B) of the present invention to a commercially available radical curable composition in which a polymerization inhibitor and a filler are mixed in advance.

Examples of such commercially available radical curable compositions include unsaturated polyesters and vinyl esters in which fillers and the like are mixed in advance. For example, SMC, BMC, etc. are mentioned.

Commercially available unsaturated polyesters include, for example, Rigolac manufactured by Showa Denko Co., Ltd. (Rigorac is a registered trademark of Showa Denko Co., Ltd.), Iupika manufactured by NIPPON YUPICA CO., LTD. Polyhope manufactured by Poly Corporation (Polyhope is a registered trademark of Japan Composite Co., Ltd.), Sandoma manufactured by DH Material Co., Ltd. (Sandoma is a registered trademark of DH Material Co., Ltd.), and the like.

Examples of commercially available vinyl esters include Lipoxy manufactured by Showa Denko KK (Lipoxy is a registered trademark of Showa Denko KK), Neopole manufactured by Nippon Yupica Co., Ltd. Examples include Vine Star manufactured by the company (Vini Star is a registered trademark of Japan Composite Co., Ltd.), Exdoma manufactured by DH Material Co., Ltd. (Exdoma is a registered trademark of DH Material Co., Ltd.), and the like.

In the radical curable composition of the present invention, radical curing is achieved by using a naphthoquinone compound represented by the general formula (1) and a phenol compound represented by the general formula (2) in combination as the polymerization inhibitor (B). In addition to improving the thermal stability and storage stability of the adhesive composition, it is possible to prevent gel time drift after long-term storage.

(Curing method)
The radically curable composition of the present invention is more preferable for the purpose of suppressing the fluctuation of the gelation time by adding the curing agent (D) immediately after the addition of the accelerator (C) and suppressing the variation in gelation time. In consideration of the transport time and storage period of the radically curable composition, after 1 day or more and 180 days or less have passed at room temperature, it is usually molded by adding a curing agent (D) on site. Even in such a usage form, the radically curable composition of the present invention has a feature that the variation in gelation time can be suppressed.

After adding the curing agent (D), the radically curable composition of the present invention is radically polymerized by irradiating active energy rays, applying heat, or applying heat while irradiating active energy rays. Can be cured. The radical curable composition may be cured after being applied on the substrate, or may be cured in a lump.

The method for applying the radically curable composition on the substrate may be appropriately selected depending on the application. For example, dip coating, brush coating, spray coating, spin coating, dip coating, etc. may be employed. .

There are no particular restrictions on the molding method of the radical curable composition, but for example, hand lay-up molding method, spray-up molding method, filament winding molding method, resin injection molding method, resin transfer molding method, pultrusion molding method, vacuum molding method A pressure forming method, a compression forming method, an injection forming method, a casting method, a spray method and the like can be applied.

As a method for curing the radically curable composition, for example, it is preferable that the curing agent (D) is mixed with the radically curable composition and cured immediately before molding. The curing temperature is usually between 0 ° C and 100 ° C.

The gelation time is preferably from 1 minute to 180 minutes, but may be appropriately set depending on the application and the shape of the molded product. However, it is important that the set gelation time is reproduced, not that it is appropriate. In particular, since radically curable compositions are often molded after being stored for a long period of time, it is important that the set gelling time is reproduced even after the long-term storage.

In the gelation time, the gelation time when the curing agent (D) is added immediately after adjusting the radical curable composition and the gelation time when the curing agent (D) is added during actual use vary. There are things to do. This variation is called gel time drift. It is practically useful that the gel time drift is smaller. It is the present invention that the gel time drift can be kept small.

In the present invention, the gel time drift can be kept small over a long period of time. As an indicator, the radical curable composition is usually stored at room temperature, but as an accelerated test, it is stored at 60 ° C. for 2 days, and thereafter The gel time (GT) was measured and compared with the gel time (GT ₀ ) immediately after preparation of the radical curable composition, and the ratio (GT / GT ₀ ) was determined to determine the effect of suppressing gel time drift. . The gelation time was measured by adding the curing agent (D) under stirring under the condition of 25 ° C., and measuring the time from the addition until the radical curable composition gelled.

In the case of the radical curable composition of the present invention, the gel time ratio (GT / GT ₀ ) is in the following value range, and the gel time drift is suppressed to a small value.

The radically curable composition of the present invention is generally unsaturated as described in “Plastics / Functional Polymer Material Dictionary” (Industry Research Committee, First Edition, August 1, 2005, pages 466 to 482). It can be used for the production of polyester resins.

Hereinafter, specific embodiments of the present invention will be described in more detail by way of examples. However, the present invention is not limited by these examples unless it exceeds the invention. In addition,% and ppm as addition amount of the polymerization inhibitor etc. in an Example are the ratios of the weight on the basis of a radical curable compound (A) unless there is particular notice.

(Synthesis Example 1) Synthesis of the radical curable compound (A) The radical curable compound (A) was synthesized according to a conventional synthesis method. That is, a glass reactor equipped with a stirrer, a heating device, a cooler, a vacuum pump, a thermometer, a pressure gauge, etc., and having a volume of 2 liters, 459 g of phthalic anhydride, 202 g of maleic anhydride, 432 g of propylene glycol, 1, 4 -Dihydroxybenzene 0.1g was prepared, the inside was replaced with nitrogen gas, and then heating was started. The reaction temperature was initially 180 ° C. and increased to 210 ° C. as the reaction proceeded. On the other hand, the pressure in the reactor was initially reduced to normal pressure and to -76 kPa as the reaction proceeded. The reaction was allowed to proceed for 8 hours from the time when the reaction temperature was 180 ° C., then cooled to 120 ° C., and 667 g of styrene was added to synthesize a radical curable compound (A).

Example 1
50 g of a radical curable compound prepared in the same manner as in Synthesis Example 1 was taken in a 100 ml sample tube (made of glass (cover PP), diameter 36 mm, height 120 mm), and 1,4- Naphthoquinone 500 ppm and 1,4-dihydroxybenzene 250 ppm were added. Each polymerization inhibitor was added after being dissolved in diethylene glycol dimethyl ether (reagent special grade manufactured by Wako Pure Chemical Industries, Ltd.) to a concentration of 5 wt%. The addition amount of 1,4-naphthoquinone and 1,4-dihydroxybenzene is the addition amount of 1,4-naphthoquinone and 1,4-dihydroxybenzene itself. Then, 1.0% of cobalt naphthenate (cobalt content: 6%) was added to the mixture as an accelerator (C), and dissolved by stirring to prepare a radical curable composition.

Inert set with a plurality of sample tubes containing the radical curable composition thus prepared in a 20 L SUS bucket, covered with air in the space, and set at 60 ° C. for a predetermined time. Stored in oven.

After storing for a predetermined time, gelation time was measured for each sample. The gelation time was measured according to 5.9 normal temperature curing characteristics (exothermic method) of JIS K6901 (2008) “Testing method for liquid unsaturated polyester resin”. That is, a sample tube containing a radical curable composition stored in an oven at 60 ° C. for a predetermined time is held in a constant temperature water bath set at 25 ° C. by a prescribed method, and the radical curable composition has a curing agent (D ) And 2.0% of methyl ethyl ketone peroxide was added to initiate polymerization. And the raise of the internal temperature of the said radical curable composition was measured, and time (gelation time) until an internal temperature became 30 degreeC after adding a hardening | curing agent (D) was measured. The results are shown in Table 1.

(Example 2)
As the radical polymerization inhibitor (B), the amount of 1,4-naphthoquinone added was reduced from 500 ppm to 250 ppm, and 100 ppm of 4-tert-butyl-1,2-dihydroxybenzene was used instead of 250 ppm of 1,4-dihydroxybenzene. Except for this, a radical curable composition was prepared in the same manner as in Example 1, and after storing for a certain period of time in the same manner as in Example 1, the gelation time was measured in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
As the radical polymerization inhibitor (B), a radical curable composition was prepared in the same manner as in Example 1 except that 1,4-naphthoquinone was not added and only 1,4-dihydroxybenzene was added at 500 ppm. After storage for a certain time in the same manner as in Example 1, the gelation time was measured in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)
Example 1 except that 1,4-naphthoquinone was not added as the radical polymerization inhibitor (B), and 250 ppm of 4-t-butyl-1,2-dihydroxybenzene was added instead of 250 ppm of 1,4-dihydroxybenzene. A radical curable composition was prepared in the same manner as in No. 1, and stored for a certain period of time in the same manner as in Example 1. Then, the gelation time was measured in the same manner as in Example 1. The results are shown in Table 1.

In addition, the abbreviations used in the table and the manufacturers of the reagents are as follows.
HQ: 1,4-dihydroxybenzene (hydroquinone) Wako Pure Chemical Industries, Ltd. reagent special grade NQ: 1,4-naphthoquinone Kawasaki Chemical Industries, Ltd. TBC: 4-t-butyl-1,2-dihydroxybenzene (4-t -Butylcatechol) Wako Pure Chemicals Co., Ltd. reagent special grade Co-Nap: Cobalt naphthenate (cobalt content 6%) Wako Pure Chemical Industries, Ltd. reagent special grade MEKPO: Methyl ethyl ketone peroxide Arukuma Yoshitomi Corporation LUPEROX, DDM-9

From Examples 1 and 2 and Comparative Examples 1 and 2 and Table 1, the following is clear. That is, when cobalt naphthenate is used as an accelerator, the gelation time is increased when 1,4-dihydroxybenzene or 4-t-butyl-1,2-dihydroxybenzene, which is conventionally used as a polymerization inhibitor, is used alone. When it is used in combination with 1,4-naphthoquinone of the present invention, it increases to 3.75 times and 2.42 times after storage at 60 ° C. for 48 hours, whereas it is 1.93 times, 1.54 times. It can be seen that the gel time drift is suppressed.

When an amine accelerator such as dimethylaniline is used as the accelerator (C), the gelation time tends to be shortened as the storage time is increased, contrary to cobalt naphthenate. Even in that case, gel time drift can be suppressed by using the polymerization inhibitor (B) of the present invention.

Claims (6)

A radical curable composition containing a radical curable compound (A), a polymerization inhibitor (B) and an accelerator (C), and represented by the following general formula (1) as the polymerization inhibitor (B) A radical curable composition comprising a naphthoquinone compound and a phenol compound represented by the following general formula (2).

(In the general formula (1), X, Y and Z may be the same or different, and each is a hydrogen atom, a hydroxyl group, a halogen atom, an acyl group having 2 to 9 carbon atoms, or a carbon number. An alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 6 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an amino group, an alkylamino group having 1 to 8 carbon atoms, and a glycidyl group Represents a hydroxyalkyl group having 1 to 8 carbon atoms or an aryloxyalkyl group having 6 to 10 carbon atoms, among which X and Y may be bonded to each other to form a saturated or unsaturated ring. And a ring may be formed with a hetero atom in between.

(In said general formula (2), n is 0 or 1, m represents the integer of 0-4. Moreover, R represents a C1-C8 alkyl group or a C1-C8 alkoxy group. In the case where there are a plurality of R, they may be the same or different.) The radical curable composition according to claim 1,
The gelation time (GT ₀ ) of the radical curable composition when the curing agent (D) is added and polymerized at 25 ° C. immediately after the preparation of the radical curable composition, and after the preparation of the radical curable composition The ratio with the gelation time (GT) of the radical curable composition when the curing agent (D) is added and polymerized at 25 ° C. after being stored at 60 ° C. for 2 days is represented by the following formula: A radical curable composition.
The naphthoquinone compound represented by the general formula (1) is 1,4-naphthoquinone, 2methyl-1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, and is represented by the general formula (2). The radical according to claim 1 or 2, wherein the phenol compound is 1,4-dihydroxybenzene, 4-t-butyl-1,2-dihydroxybenzene, 2,6-di-t-butyl-p-cresol. Curable composition. The radically curable composition according to any one of claims 1 to 3, wherein the accelerator (C) is a cobalt compound and / or an amine compound. The addition ratio of the naphthoquinone compound represented by the general formula (1) and the phenol compound represented by the general formula (2) is 10/90 or more and less than 90/10 in weight ratio. The radically curable composition as described in any one of thru | or 4. A curing method in which the radically curable composition according to any one of claims 1 to 5 is cured by radical polymerization with active energy rays and / or heat in the presence of a curing agent (D).