JP7116866B2 - Radical curable composition - Google Patents

Description

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

Radically curable compositions containing radically curable compounds represented by unsaturated polyesters and vinyl esters generally can be handled as liquids, so they are excellent in workability, and the mechanical strength and durability of the cured products are also good. Because of its good properties, it is used especially as glass fiber and carbon fiber reinforced plastic products for hulls, bathtubs, vehicles, tanks, electrical parts, etc., as well as resin concrete, gel coat, putty, veneer, anchor bolts, paint, building materials, etc. are used for various purposes.

Radical-curable compositions containing such radical-curable compounds are composed of, for example, radical-curable oligomers such as unsaturated polyesters and vinyl esters and radical-curable monomers such as styrene and methyl methacrylate. A radical polymerization initiator such as an organic peroxide is added as a curing agent to this radical-curable composition to initiate a polymerization reaction and form a cured resin product. That is, it is common to handle two liquids, a radical curable composition and a curing agent.

In a so-called normal temperature curing type radical curable composition which is used at room temperature without heating, it is essential to add an accelerator to advance the reaction of the curing agent. A curing agent is added to the material afterward to cure it (Patent Document 1). In this case, a radical curing composition containing an accelerator has a problem of poor storage stability, and in some cases, it is handled as three liquids of a radical curing composition, an accelerator, and a curing agent.

A polymerization inhibitor is added to the radically curable composition in both cases where the accelerator is previously added to the radically curable composition and when the accelerator is separately added 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, a polymerization inhibitor is added in order to maintain the semi-cured state with fluidity. is added.

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

As described above, the polymerization inhibitor added to the radical curable composition mainly has the following three roles, and a plurality of polymerization inhibitors are used according to the purpose and characteristics. 1) improvement of storage stability, 2) improvement of thermal stability, and 3) securing of 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 large amount of a polymerization inhibitor to improve storage stability and thermal stability, if you add a large amount, when you add a curing agent and try to harden it, the gelation time becomes too long. Problems may occur during molding.

Therefore, there is a particular demand for a polymerization inhibitor that hardly changes the gelation time, that is, a polymerization inhibitor that improves the thermal stability and storage stability of the radical-curable composition while hardly affecting the curing properties of the composition. . Radical curable composition containing unsaturated polyester as a main component 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 varies from that before storage is observed. The variation in gelation time causes troubles during molding. In general, when a cobalt-based accelerator such as cobalt naphthenate is used, the gelation time is delayed, and when an amine-based accelerator such as dimethylaniline is used, the gelation time is shortened. be done.

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

Further, as a method for stabilizing the gelation time when using an amine-based accelerator, a method of adding a non-phenol-based inhibitor and a phenol-based inhibitor is known (Patent Documents 6 and 7). In this method, a phenothiazine compound and an organic nitroxyl radical are added as non-phenolic inhibitors, and hydroquinone, 2,6-di-t-butylphenol and the like are used as phenolic inhibitors in some cases. It is characterized by the use of a non-phenol inhibitor such as a phenothiazine compound or an organic nitroxyl radical in combination with a conventional phenol inhibitor. The effect in the cobalt naphthenate system is not known.

Furthermore, the present inventors have found that when a cobalt-based accelerator or an amine-based accelerator is used, the storage stability is improved by adding a dihydroxynaphthalene compound or a naphthoquinone compound in addition to the phenothiazine compound and the organic nitroxyl radical. (Patent Documents 8 and 9). However, there is room for further improvement in terms of curing properties, particularly gel time drift.

In addition, there are some literatures that list naphthoquinone as having the same action as hydroquinone etc. as a phenolic polymerization inhibitor. There is no description of a special effect produced by using a hydroquinone compound and a naphthoquinone compound in combination (Patent Documents 7, 10, 11 and 12).

JP-A-8-157544 JP-A-5-222281 JP 2004-225045 A JP 2006-265336 A JP-A-2007-91998 JP 2009-541540 A JP 2016-501933 A JP 2016-14103 A JP 2016-56283 A JP-A-11-29740 JP-A-9-302046 JP 2013-228758 A

The present invention has been made in view of the above circumstances, and its object is to improve the thermal stability and storage stability of a radical curable composition containing an accelerator, and to suppress the gel time drift even after long-term storage. It is an object of the present invention 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, the above problems can be solved by using a combination of a naphthoquinone compound and a phenol-based polymerization inhibitor as polymerization inhibitors in a radically curable composition to which an accelerator is added. The present invention was completed by obtaining the knowledge of

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

In the above general formula (1), X, Y and Z may be the same or different, and are each a hydrogen atom, a hydroxyl group, a halogen atom, an acyl group having 2 to 9 carbon atoms, and 1 carbon atom. ~8 alkyl group, aryl group having 6 to 10 carbon atoms, aralkyl group having 6 to 10 carbon atoms, alkoxyalkyl group having 2 to 10 carbon atoms, amino group, alkylamino group having 1 to 8 carbon atoms, glycidyl group, represents either a hydroxyalkyl group having 1 to 8 carbon atoms or an aryloxyalkyl group having 6 to 10 carbon atoms, wherein X and Y may be bonded to each other to form a saturated or unsaturated ring; A ring may be formed with a heteroatom in between.

In the above general formula (2), n is 0 or 1, and m represents an integer of 0-4. In addition, R represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and when there are multiple Rs, they may be the same or different.

A second invention is the radical-curable composition according to the first invention, wherein a curing agent (D) is added immediately after preparation of the radical-curable composition and polymerized at 25° C. for radical curing. The gelation time (GT ₀ ) of the curable composition, and the radical curable composition in the case where 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 resides in a radical curable composition characterized in that the ratio of the gelation time (GT) of the product to the product is represented by the following formula.

In a third invention, the naphthoquinone compound represented by the general formula (1) is 1,4-naphthoquinone, 2methyl-1,4-naphthoquinone, or 2-hydroxy-1,4-naphthoquinone, and The first or It resides in the radical curable composition according to the second invention.

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

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

A sixth invention is the radical-curable composition according to any one of the first to fifth inventions, cured by radical polymerization with active energy rays and/or heat in the presence of a curing agent (D). It resides in a curing method that allows

The "accelerator" in the present invention is a compound capable of speeding up the curing of the radical-curable compound, and is a compound that functions to accelerate the radical polymerization reaction by the curing agent.

The term "gelation time" as used 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 gelation time is measured according to the method specified in JISK6901 (2008) "Liquid Unsaturated Polyester Resin Test Method", 5.9 Curing Characteristics at Normal Temperature (Exothermic Method).

According to the radical curable composition of the present invention, the progress of polymerization during storage and transportation processes caused by the addition of an accelerator is suppressed, the thermal stability and storage stability are improved, and the gel time drifts even after long-term storage. does not occur, and the gelation time in the presence of the curing agent can be maintained even after long-term storage.

The present invention will be described in detail below.

The present invention provides a radical-curable composition containing a radical-curable compound (A), a polymerization inhibitor (C), and an accelerator (C), wherein the polymerization inhibitor (C) is represented by the above general formula (1). and a phenol compound represented by the above 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. Curable monomers can be mentioned. Two or more kinds of these radical-curable compounds may be used.

Examples of radical-curable oligomers include unsaturated polyesters, vinyl esters, urethane (meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates, and the like.

The unsaturated polyester is, for example, one obtained 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

Unsaturated polycarboxylic acids used as raw materials for producing unsaturated polyesters include, for example, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid and their anhydrides and ester derivatives such as methyl esters. . Saturated polycarboxylic acids that can be used at the same time include aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid and tetrachlorophthalic acid, and their anhydrides. and halides and ester derivatives such as methyl esters, aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, cyclohexanedicarboxylic acid, tetrahydrophthalic acid, het acid and their anhydrides and halides and methyl Ester derivatives such as esters are included. Two or more kinds of these polyvalent carboxylic acids may be used.

Examples of polyhydric alcohols used as raw materials for producing unsaturated polyesters include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propanediol, butanediol, pentanediol, and hexanediol. , cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A and their isomers, trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane and pentaerythritol, and their ethylene oxides, Alkylene oxide adducts such as propylene oxide are included. Two or more of these polyhydric alcohols may be used.

A vinyl ester is obtained, for example, by reacting an epoxy oligomer and an unsaturated carboxylic acid by a known method.

Examples of epoxy oligomers used as raw materials for vinyl ester production include bisphenol A-based, hydrogenated bisphenol A-based, bisphenol F-based, novolak-based, and resol-based oligomers. Obtained by reaction with a diglycidyl ether type epoxy compound such as neopentyl glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, (di)glycerin (poly)glycidyl ether, (poly)tetramethylene glycol diglycidyl ether It is. Two or more kinds of these epoxy oligomers may be used.

Examples of unsaturated carboxylic acids used as starting materials for vinyl ester production include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, α-phenylacrylic acid, methoxyacrylic acid, itaconic acid, and halogenated acrylic acid. Two or more kinds of these unsaturated carboxylic acids may be used.

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

Examples of polyisocyanates used as raw materials for producing urethane (meth)acrylate include aromatic polyisocyanates such as diphenylmethane diisocyanate, tolylene diisocyanate, polyphenylenepolymethylene polyisocyanate, xylylene diisocyanate and naphthalene diisocyanate, modified products thereof, hexa Aliphatic polyisocyanates such as methylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, and modified products thereof can be mentioned. Two or more kinds of these polyisocyanates may be used.

(Meth)acrylates having a hydroxyl group used as raw materials for producing urethane (meth)acrylates include, for example, 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, and polyvalent (meth) acrylates such as tris (hydroxyethyl) isocyanuric acid di (meth) acrylate and pentaerythritol tri (meth) acrylate meth)acrylates. Two or more kinds of (meth)acrylates having these hydroxyl groups may be used.

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

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

Unsaturated carboxylic acids used as starting materials for polyester (meth)acrylate production include those used in the vinyl esters described above, as well as their halides and ester derivatives such as methyl esters. Further, examples of the polyhydric carboxylic acid and polyhydric alcohol include those used in the unsaturated polyester described above. Two or more types may be used.

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.

Unsaturated carboxylic acids used as starting materials for polyester (meth)acrylate production include those used in the vinyl esters described above, as well as their halides and ester derivatives such as methyl esters. Examples of polyhydric alcohols include those used in the above unsaturated polyesters and the polyols used in the above urethane (meth)acrylates.

Radical-curable monomers include, for example, monofunctional vinyl monomers and polyfunctional vinyl monomers.

Monofunctional vinyl monomers include, for example, styrene, α-methylstyrene, α-ethylstyrene, p-chlorostyrene, hydroxystyrene, monofunctional aromatic vinyl monomers such as 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)acrylate-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, (meth) ) 2-ethoxyethyl acrylate, dimethylaminoethyl (meth)acrylate, dimethylaminoethylmethyl chloride (meth)acrylate, dimethylaminoethylbenzyl chloride (meth)acrylate, diethylaminoethyl (meth)acrylate, (meth) trifluoroethyl acrylate, heptadecafluorodecyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, ( monofunctional (meth)acrylic acid monomers such as methoxypolyethylene glycol meth)acrylate;

Examples of polyfunctional vinyl monomers 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 ) acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol di(meth)acrylate, dipentol di(meth)acrylate, sorbitol di(meth)acrylate, trishydroxyethyl isocyanurate, nonanediol di(meth)acrylate, tris(2 -(meth)acryloyloxyethyl)isocyanurate, 2,2-bis[4-((meth)acryloxyethoxy)phenyl]propane, 2,2-bis[4-((meth)acryloxydiethoxy)phenyl] Polyfunctional (meth)acrylic monomers such as propane, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, 2-hydroxy-1-acryloxy-3-methacryloxypropane, divinylbenzene, etc. and polyfunctional allyl monomers such as diallyl phthalate and triallyl cyanurate.

Two or more of these radical-curable oligomers and radical-curable monomers may be used in combination.

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, based on the total 100% by mass of the radical-curable oligomer and the radical-curable monomer. % or more and 80 mass % or less, and most preferably 20 mass % or more and 70 mass % or less. If it exceeds 90% by mass, the performance of the cured product obtained is not sufficient, and if it is less than 10% by mass, the viscosity cannot be sufficiently reduced, and workability may not be excellent.

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

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

In the above general formula (1), X, Y and Z may be the same or different, and are each a hydrogen atom, a hydroxyl group, a halogen atom, an acyl group having 2 to 9 carbon atoms, and 1 carbon atom. ~8 alkyl group, aryl group having 6 to 10 carbon atoms, aralkyl group having 6 to 10 carbon atoms, alkoxyalkyl group having 2 to 10 carbon atoms, amino group, alkylamino group having 1 to 8 carbon atoms, glycidyl group, represents either a hydroxyalkyl group having 1 to 8 carbon atoms or an aryloxyalkyl group having 6 to 10 carbon atoms, wherein X and Y may be bonded to each other to form a saturated or unsaturated ring; A ring may be formed with a heteroatom in between.

Halogen atoms represented by X, Y and Z in general formula (1) include fluorine atom, chlorine atom, bromine atom and iodine atom, and examples of acyl groups having 2 to 9 carbon atoms include acetyl group and propionyl. and the like, and examples of alkyl groups 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- 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 aralkyl groups having 6 to 10 carbon atoms include benzyl group and phenethyl group, and examples of aryl groups having 6 to 10 carbon atoms include phenyl group, p-tolyl group, o-tolyl group and naphthyl group. be done. Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, tert-butoxy, etc. Examples of alkoxyalkyl groups having 2 to 10 carbon atoms include includes methoxymethyl group, ethoxymethyl group and the like; examples of alkylamino groups having 1 to 8 carbon atoms include methylamino group, ethylamino group, n-propylamino group and the like; The hydroxyalkyl group includes hydroxymethyl group, 1-hydroxyethyl group and the like, and the aryloxyalkyl group having 6 to 10 carbon atoms includes phenoxymethyl group and the like. Substituents containing oxygen, nitrogen, and sulfur in addition to those listed above are included. However, a structure composed of carbon, oxygen, and hydrogen is desirable from the viewpoint of improving handling properties and reducing environmental load.

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

In general formula (1), when X and Y do not combine to form a saturated or unsaturated 6-membered ring, specific examples include 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)-1,4-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-cyclohexyl-1,4-naphthoquinone, 2-cyclopropylmethyl-1,4-naphthoquinone, 2-cyclopentylmethyl-1,4-naphthoquinone, 2-cyclohexylmethyl-1,4-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 benzyl)-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)- 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-dichloromethyl-1 ,4-naphthoquinone, 2-trichloromethyl-1,4-naphthoquinone, 2-(2-chloroethyl)-1,4-naphthoquinone, 2-(2-bromoethyl)-1,4-naphthoquinone, 2-pentafluoroethyl- 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-propoxymethyl-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-ethoxyethyl)-1,4-naphthoquinone, 2-(2-ethoxyethyl)-1,4-naphthoquinone, 2-dimethoxymethyl-1,4 -naphthoquinone, 2-diethoxymethyl-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 - naphthoquino 2-(3-fluorophenoxymethyl)-1,4-naphthoquinone, 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-trifluoromethylbenzyloxymethyl) )-1,4-naphthoquinone, 2-(2-nitrobenzyloxymethyl)-1,4-naphthoquinone, 2-(3-nitrobenzyloxymethyl)-1,4-naphthoquinone, 2-(4-nitrobenzyloxy methyl)-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-methylbenzoyloxymethyl)-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-trifluoromethylbenzoyloxy methyl)-1,4-naphthoquinone, 2-(4-trifluoromethylbenzoyloxymethyl)-1,4-naphthoquinone, 2-acetoxymethyl-1,4-naphthoquinone, 2-propionyloxymethyl-1,4-naphthoquinone , 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 non, 2-(2-trifluoromethylphenyl)-1,4-naphthoquinone, 2-(3-trifluoromethylphenyl)-1,4-naphthoquinone, 2-(4-trifluoromethylphenyl)-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-naphthoquinone, 2-(1′,4 '-naphthoquinone-2'-yl)-1,4-naphthoquinone and the like.

and also 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-cyclopentylmethyloxy-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.

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, 2-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-fluoro phenylthio)-1,4-naphthoquinone, 2-(4-chlorophenylthio)-1,4-naphthoquinone, 2-(4-methylphenylthio)-1,4-naphthoquinone, 2-(4-trifluoromethylphenyl thio)-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-methoxybenzylthio)-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-butylsulfinyl-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 quinone, 2-acetyl-1,4-naphthoquinone, 2-propanoyl-1,4-naphthoquinone, 2-chloroacetyl-1,4-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-nitro-1,4-naphthoquinone and the like.

and also 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-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-chloro-1,4- naphthoquinone, 2-methyl-3-hydroxy-6,7-dichloro-1,4-naphthoquinone, 2-methyl-3,5-dihydroxy-1,4-naphthoquinone, 2-methyl Chill-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 c-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 general formula (1), when X and Y are bonded to each other to form a saturated or unsaturated 6-membered ring, specific examples include 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 general formula (1), compounds in which X and Y are each a hydrogen atom, an alkyl group or a hydroxy group are preferred, such as 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 preferred.

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

In the above general formula (2), n is 0 or 1, and m represents an integer of 0-4. In addition, R represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and when there are multiple 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- 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. The alkoxy group having 1 to 8 carbon atoms includes methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, tert-butoxy and the like.

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

First, in the general formula (2), the compounds in which n is 0 include 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.

Compounds in which n is 1 include 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 phenol-based 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, 4-methoxyphenol are preferred. In particular, 1,4-dihydroxybenzene is preferred.

As exemplified above, in the radical-curable composition of the present invention, the polymerization inhibitor (B) is a combination of a naphthoquinone compound represented by the general formula (1) and a phenol compound represented by the general formula (2). use. The total amount used is not particularly limited. Less than 0.8 parts by weight, more preferably 0.003 or more and less than 0.5 parts by weight. If the amount is less than 0.001 part by weight, the effect of inhibiting polymerization is reduced, while if the amount exceeds 1.0 part by weight, 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 by weight. , 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 the naphthoquinone compound represented by the general formula (1) and the phenol compound represented by the general formula (2) in combination, and the combined use only increases the stability during storage. In addition, it is possible to suppress the gel time drift after storage.

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

Polymerization inhibitors that can be used together include, for example, N-oxyls such as 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol, phenothiazine, benzoquinone, methyl-p-benzoquinone, Copper naphthenate or the like can be used. In addition, known polymerization inhibitors such as feldazyl, α,α-diphenyl-β-picrylhydrazyl and the like can also be used. 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 used to improve the curability at low temperatures, and to improve the curability of the radical curable composition such as SMC (sheet molding compound) and BMC (bulk molding compound). Used for semi-curing. Examples of such accelerators include metal soaps such as cobalt naphthenate, manganese naphthenate, copper naphthenate, potassium naphthenate, calcium naphthenate, cobalt octylate, and manganese octylate, cobalt acetylacetonate, vanadium acetylacetonate, and the like. dimethylaniline, N,N'-dimethylaniline, N,N-dimethyltoluidine, N,N-diethylaniline, N,N-di(hydroxy)-4-methylaniline and other amine compounds, acetylacetone, Examples include acyl group-containing lactone compounds such as ethyl acetoacetate, acetoacetamide compounds, β-diketones, β-ketoesters, β-ketoamides, and the like, all of which may be in a form containing a solvent. Two or more of these accelerators may be used. Among these accelerators, cobalt compounds such as cobalt naphthenate and cobalt octylate and amine compounds are preferred. Moreover, a plurality of accelerators, for example, a cobalt-based compound and an amine-based compound may be used in combination.

The amount of the accelerator (C) to be used is not particularly limited. The amount is less than 7 parts by weight, more preferably 0.15 or more and less than 5 parts by weight.

These accelerators (C) are handled in a mixed state with the radically curable composition. The radical polymerization inhibitor (B ) is used.

[Curing agent (D)]
Examples of the curing agent (D) used in the radically curable composition of the present invention include t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,1, Hydroperoxides such as 3,3-tetramethylbutyl hydroperoxide, ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, etc. dialkyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxybenzoate and other alkyl peresters , peroxides such as bis(4-t-butylcyclohexyl) peroxydicarbonate; azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, etc. is mentioned. Two or more kinds of these curing agents may be used.

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

The amount of the curing agent (D) used is not particularly limited. It is less than 7 parts by weight, more preferably 0.1 or more and less than 5 parts by weight.

These curing agents (D) are added to the radical curable composition immediately before molding and used, but they can also be added to the radical curable composition from the beginning and treated as compounds such as SMC and BMC.

[Other additives]
In the radically curable composition of the present invention, a fiber reinforcing agent, a filler, a thixotropic agent, a thixotropic agent, a coupling agent, a coloring agent, an ultraviolet absorber, and an acid value inhibitor are used within a range that does not impair the performance of the composition. Various additives such as agents, thickeners, viscosity reducers, internal mold release agents, low shrinkage agents, antifoaming agents, waxes, plasticizers, patterning agents, etc. may be added as appropriate.

Examples of the fiber reinforcing material 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. good too. Glass fibers and organic fibers are preferred from the viewpoint of workability and economy, and glass fibers are particularly preferred. The form of fiber includes plain weave, satin weave, non-woven fabric, mat, roving, chopped, knitted, braided, composite structure of these, etc., and is selected according to the construction method and product form.

Examples of fillers include calcium carbonate, aluminum hydroxide, fly ash, barium sulfate, talc, clay, and glass powder. Aggregates include, for example, silica sand, gravel, and crushed stone. When used for mortar applications, those having a particle size of about 5 mm or less are preferable. Although the amount of the filler or aggregate to be added is not particularly limited, it is usually 1 part by weight or more and less than 300 parts by weight when the radical curing compound (A) is 100 parts by weight.

[Method for producing radical curable composition]
The radical-curable composition of the present invention can be produced in the same manner as for known radical-curable compositions, except that the components are different. For example, it can be produced by blending the radical curable compound (A), the polymerization inhibitor (B), and the accelerator (C), and then thoroughly stirring and mixing them until they become uniform.

The radically curable composition of the present invention can also be prepared by adding the polymerization inhibitor (B) of the present invention to a commercially available radically curable composition previously mixed with a polymerization inhibitor and a filler.

Examples of such commercially available radically curable compositions include unsaturated polyesters, vinyl esters and the like premixed with fillers and the like. Examples include SMC and BMC.

Commercially available unsaturated polyesters include, for example, Rigolac manufactured by Showa Denko K.K. Polyhope manufactured by Co., Ltd. (Polyhope is a registered trademark of Japan Composite Co., Ltd.), Sundoma manufactured by DH Materials Co., Ltd. (Sundoma is a registered trademark of DH Materials Co., Ltd.), and the like.

Commercially available vinyl esters include, for example, Lipoxy manufactured by Showa Denko K.K. Viniester manufactured by the company (Viniester is a registered trademark of Japan Composite Co., Ltd.), Exdoma manufactured by DH Materials Co., Ltd. (Exdoma is a registered trademark of DH Materials Co., Ltd.), and the like.

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

(Curing method)
The radical curable composition of the present invention is more preferably used in such a manner that the curing agent (D) is added immediately after the accelerator (C) is added, and the curing agent (D) is added for molding and curing in order to suppress variations in the gelation time. Taking into consideration the transport time and storage period of the radical curable composition, it is usual to add the curing agent (D) on site after 1 day or more and 180 days or less at room temperature for molding. Even in such a mode of use, the radical curable composition of the present invention is characterized by being able to suppress variation in gelation time.

After adding the curing agent (D), the radical-curable composition of the present invention undergoes radical polymerization by irradiating with active energy rays, by applying heat, or by applying heat while irradiating with active energy rays. , can be cured. The radical-curable composition may be cured after being applied onto the substrate, or may be cured in bulk.

The method of applying the radical-curable composition onto the substrate may be appropriately selected depending on the application. For example, dip coating, brush coating, spray coating, spin coating, dip coating, etc. can be employed. .

The molding method of the radical curable composition is not particularly limited, but examples include hand lay-up molding, spray-up molding, filament winding molding, resin injection molding, resin transfer molding, pultrusion molding, and vacuum molding. , air pressure molding, compression molding, injection molding, casting, spraying, and the like can be applied.

As a method for curing the radical-curable composition, for example, it is suitable to mix the curing agent (D) with the radical-curable composition immediately before molding and cure the composition. Moreover, the curing temperature is usually between 0°C and 100°C.

The gelation time is preferably 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, rather than just being appropriate. In particular, since the radical curable composition is often molded after being stored for a long period of time after being prepared, it is important that the set gelation time is reproduced even after long-term storage.

In the gelation time, the gelation time when the curing agent (D) is added immediately after preparing the radical curable composition and the gelation time when the curing agent (D) is added during actual use vary. I have something to do. This variation is called gel time drift. A smaller gel time drift is more practically useful. The present invention can suppress the gel time drift.

In the present invention, the gel time drift can be kept small over a long period of time. 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 obtained to measure the effect of suppressing the gel time drift. . The gelation time was measured by adding the curing agent (D) to the radical-curable composition at 25° C. while stirring, 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 gelation time ratio (GT/GT ₀ ) falls within the following value range, and the gel time drift is kept small.

The radical-curable composition of the present invention is generally an unsaturated polymer described in "Plastic/Functional Polymer Material Dictionary" (Industry Research Association, first edition, August 1, 2005, pp. 466-482). It can be used in the production of polyester resins.

Specific embodiments of the present invention will be described in more detail below with reference to examples, but the present invention is not limited by these examples as long as it does not exceed the scope of the invention. In addition, % and ppm as the addition amount of the polymerization inhibitor and the like in the examples are weight ratios based on the radical curable compound (A) unless otherwise specified.

(Synthesis Example 1) Synthesis of Radical Curable Compound (A) A radical curable compound (A) was synthesized according to a conventional method. Specifically, 459 g of phthalic anhydride, 202 g of maleic anhydride, 432 g of propylene glycol, 432 g of propylene glycol, 432 g of - Dihydroxybenzene 0.1 g was charged, and after the inside was replaced with nitrogen gas, heating was started. The reaction temperature was initially 180° C., and increased to 210° C. as the reaction progressed. On the other hand, the pressure inside the reactor was initially normal pressure, and decreased to -76 kPa as the reaction progressed. After the reaction was allowed to proceed for 8 hours from the time the reaction temperature reached 180°C, the mixture was 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 placed in a 100 ml sample tube (made of glass (cover PP), diameter 36 mm, height 120 mm), and 1,4- 500 ppm of naphthoquinone and 250 ppm of 1,4-dihydroxybenzene 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 amounts of 1,4-naphthoquinone and 1,4-dihydroxybenzene added are the amounts of 1,4-naphthoquinone and 1,4-dihydroxybenzene themselves. Then, 1.0% of cobalt naphthenate (cobalt content: 6%) was added to the mixture as an accelerator (C) and dissolved with stirring to prepare a radical curable composition.

A plurality of sample tubes containing the radical curable composition prepared in this way were placed in a 20 L SUS bucket, the air in the space was left as it was, and the inert was set to 60 ° C. for a predetermined time. Stored in oven.

After storage for a predetermined period of time, gelation time measurements were performed on each sample. The gelation time was measured according to JISK6901 (2008) "Liquid Unsaturated Polyester Resin Test Method", 5.9 Normal temperature curing characteristics (exothermic method). That is, a sample tube containing a radical curable composition stored in an oven at 60° C. for a predetermined time was held in a constant temperature water bath set at 25° C. by a prescribed method, and the radical curable composition was added with a curing agent (D ) was added at 2.0% methyl ethyl ketone peroxide to initiate polymerization. Then, the increase in internal temperature of the radical curable composition was measured, and the time (gelation time) from the addition of the curing agent (D) until the internal temperature reached 30°C 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-t-butyl-1,2-dihydroxybenzene was used instead of 250 ppm of 1,4-dihydroxybenzene. A radically curable composition was prepared in the same manner as in Example 1, except that it was stored for a certain period of time. The results are shown in Table 1.

(Comparative example 1)
A radical curable composition was prepared in the same manner as in Example 1 except that 500 ppm of 1,4-dihydroxybenzene alone was added without adding 1,4-naphthoquinone as the radical polymerization inhibitor (B), After storage 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 2)
As the radical polymerization inhibitor (B), 1,4-naphthoquinone was not added, 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 Example 1, stored for a certain period of time in the same manner as in Example 1, and then measured in the same manner as in Example 1 for gelation time. The results are shown in Table 1.

The abbreviations used in the table and the manufacturers of the reagents are as follows.
HQ: 1,4-dihydroxybenzene (hydroquinone) Reagent special grade manufactured by Wako Pure Chemical Industries, Ltd. NQ: 1,4-naphthoquinone manufactured by Kawasaki Chemical Industry Co., Ltd. TBC: 4-t-butyl-1,2-dihydroxybenzene (4-t -Butyl catechol) Reagent special grade Co-Nap manufactured by Wako Pure Chemical Industries, Ltd.: Cobalt naphthenate (cobalt content 6%) Reagent special grade manufactured by Wako Pure Chemical Industries, Ltd. MEKPO: Methyl ethyl ketone peroxide LUPEROX, DDM-9 manufactured by Arkema Yoshitomi Co., Ltd.

From Examples 1 and 2, 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 After storage at 60° C. for 48 hours, it increases to 3.75 times and 2.42 times, whereas when used in combination with the 1,4-naphthoquinone of the present invention, it increases to 1.93 times and 1.54 times. It can be seen that the gel time drift is suppressed by being doubled.

When an amine-based accelerator such as dimethylaniline is used as the accelerator (C), unlike cobalt naphthenate, the longer the storage time, the shorter the gelling time. Even in that case, gel time drift can be suppressed by using the polymerization inhibitor (B) of the present invention.

Claims (3)

A radical-curable composition that cures using a peroxide-based curing agent (D), the radical-curable composition containing a radical-curable compound (A), a polymerization inhibitor (B), and an accelerator (C). wherein the polymerization inhibitor (B) is a naphthoquinone compound represented by the following general formula (1) and a phenol compound represented by the following general formula (2), represented by the general formula (1) The addition ratio of the naphthoquinone compound and the phenol compound represented by the general formula (2) is 20/80 or more and less than 80/20 by weight, and the accelerator (C) is a cobalt compound and / or an amine is a system compound, does not contain a curing agent (D) added to cure the radical curable composition, the curing agent (D) is added immediately after the preparation of the radical curable composition and polymerized at 25 ° C. The gelling time (GT0) of the radical curable composition in the case where the radical curable composition was prepared and stored at 60 ° C. for 2 days, then the curing agent (D) was added and polymerized at 25 ° C. A radically curable composition, wherein the ratio of the gelation time (GT) of the radically curable composition in is represented by the following formula.

(In the above 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, 1 to 8 alkyl group, aryl group having 6 to 10 carbon atoms, aralkyl group having 6 to 10 carbon atoms, alkoxyalkyl group having 2 to 10 carbon atoms, amino group, alkylamino group having 1 to 8 carbon atoms, glycidyl group , represents either a hydroxyalkyl group having 1 to 8 carbon atoms or an aryloxyalkyl group having 6 to 10 carbon atoms, wherein X and Y may be bonded to each other to form a saturated or unsaturated ring , may form a ring with a heteroatom in between.)

(In the above general formula (2), n is 0 or 1, m represents an integer of 0 to 4, and R represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. , R may be the same or different when there is more than one.)

The naphthoquinone compounds represented by the above general formula (1) are 1,4-naphthoquinone, 2methyl-1,4-naphthoquinone, and 2-hydroxy-1,4-naphthoquinone, and are represented by the above general formula (2). 2. The radical curable composition according to claim 1, wherein the phenolic compound is 1,4-dihydroxybenzene, 4-t-butylcatechol, 2,6-di-t-butyl-p-cresol. 3. A curing method of curing the radically curable composition according to claim 1 or 2 by radical polymerization with active energy rays and/or heat in the presence of a curing agent (D).