JP2014201614A - Radical curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a polymerization inhibitor enabling thermal stability and storage stability of a radical curable composition to be improved without changing the curing property of the radical curable composition; and a radical curable composition using the polymerization inhibitor.SOLUTION: There is provided the radical curable composition which is obtained by using as a raw material, at least a radical curable oligomer (A) and a polymerization inhibitor (C). In the radical curable composition, a compound having a condensed polycyclic aromatic skeleton represented by the general formula (1) is used as the polymerization inhibitor (C). (1), where n represents an integer of 1 to 4, R represents any of a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, a glycidyl group, a hydroxyalkyl group or an aryloxyalkyl group, R may be same or different when there are a plurality of OR groups.

Description

The present invention relates to a radical curable composition, a production method thereof, and a cured product thereof. More specifically, a polymerization inhibitor capable of improving thermal stability and storage stability without changing the curing characteristics by adding, a radical curable composition using the same, a production method thereof, and a cured product thereof About.

Radical curable oligomers typified by unsaturated polyesters and vinyl esters are generally excellent in workability because they can be handled as liquids, and also have excellent performance such as mechanical strength and durability of cured products. As a fiber and carbon fiber reinforced plastic product, it is used in various applications such as resin concrete, gel coat, putty, decorative board, anchor bolt, etc. in addition to being used in hulls, bathtubs, vehicles, tanks, electrical parts and the like.

The composition (radical curable composition) containing such a radical curable oligomer is, for example, a radical curable oligomer such as unsaturated polyester or vinyl ester and a radical polymerizable monomer such as styrene or methyl methacrylate. It is comprised, A radical polymerization initiator, such as an organic peroxide, is added to this radical curable composition as a hardening | curing agent, a polymerization reaction is started, and a resin hardened | cured material is shape | molded.

The product form of a general radical curable composition is liquid, and is molded by adding a curing agent separately prepared by the user later. In addition, there are semi-finished products that are impregnated with a liquid radical curable composition obtained by adding a curing agent to chip-like or sheet-like glass fibers, and handled in a clay-like or sheet-like form in a semi-cured state. It is shape | molded by heating using.

In any case, a polymerization inhibitor is often added to the radical curable composition. Its purpose is to prevent spontaneous polymerization of radically curable oligomers and radically polymerizable monomers, and in the case of semi-finished products, to keep the polymerization in a semi-cured state, that is, to improve storage stability. Inhibitors are added. On the other hand, in the production process of the radical curable composition, the polymerization reaction is prevented during the production or transfer of the radical curable oligomer and when the high viscosity radical curable oligomer is mixed with the radical polymerizable monomer at a high temperature. Therefore, a polymerization inhibitor is added 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 for the extension of the above.

As described above, the polymerization inhibitor in this application mainly has the following three roles, and a plurality of polymerization inhibitors depending on the purpose and characteristics are used. 1) Improvement of storage stability 2) Improvement of thermal stability 3) Extension of gelation time. Therefore, even if you want to add a large amount 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 add and harden the curing agent. Trouble may occur during molding.

For example, in SMC (Sheet Molding Compound) and BMC (Bulk Molding Compound) used for automotive outer panels, exterior parts, etc., high-speed curability is required to improve the molding cycle, that is, to improve productivity. Therefore, it is difficult to use a large amount of a polymerization inhibitor. In practice, the gelation time is appropriately set according to the manufacturing equipment and production capacity of each user, and is controlled by the addition amount of the polymerization inhibitor.

Moreover, although molding materials, such as SMC, are stored at room temperature until they are press-molded, they become hard because the gelation of the unsaturated polyester as a raw material gradually proceeds during the storage period. In this case, there is a problem that the fluidity of the molding material is reduced during press molding, and molding defects such as poor filling occur. In order to prevent this, a hydroquinone polymerization inhibitor is usually blended (for example, Patent Documents 1, 2, and 3).

In particular, in this application, there is a demand for a polymerization inhibitor that improves the thermal stability and storage stability without substantially affecting the gelation time, that is, the curing characteristics of the radical curable composition in the presence of the curing agent. It can be said. As a polymerization inhibitor having such properties, a radical curable composition mainly composed of an unsaturated polyester using bis-t-butylhydroxytoluene (BHT) has been proposed. However, although BHT has a characteristic that does not change the gelation time so much, the thermal stability and the storage stability are never satisfactory (Patent Document 3).

On the other hand, it is already known that the compound having a condensed polycyclic aromatic skeleton used in the present invention has an action as a polymerization inhibitor (Patent Documents 4 and 5). However, examples used for radically curable compositions such as unsaturated polyesters in the present invention are not described, and further, the thermal stability and storage stability are improved, and the gelation time is affected in the presence of a curing agent. The property of not being described is not described.

JP-A-4-372649 JP-A-5-320275 JP-A-5-222281 JP 2012-111741 A JP 2005-336082 A

The present invention has been made in view of the above circumstances, and its purpose is to improve thermal stability and storage stability in a radical curable composition without changing the curing characteristics of the radical curable composition in the presence of a curing agent. Another object of the present invention is to provide a radical curable composition containing a polymerization inhibitor that can be produced and a method for producing a radical curable composition using the same.

As a result of intensive studies by the present inventors, it is possible to solve the above problems by using a compound having a condensed polycyclic aromatic skeleton having specific structural characteristics as a polymerization inhibitor in a radical curable composition. Knowledge was obtained and the present invention was completed.

That is, the first gist of the present invention is a radical curable composition containing at least a radical curable oligomer (A) and a polymerization inhibitor (C), and is represented by the following general formula (1) as a polymerization inhibitor (C). The radical curable composition is characterized by using a compound having a condensed polycyclic aromatic skeleton represented.

In the formula, n represents an integer of 1 to 4, R represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, a glycidyl group, a hydroxyalkyl group, or an aryloxyalkyl group, and OR When there are a plurality of groups, Rs may be the same or different. X, Y, and Z each represent a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, or an alkoxy group, and may be the same or different from each other. X and Y are bonded to each other to be saturated or unsaturated. A saturated ring may be formed, or a ring may be formed across an oxygen atom.

The second gist is a condensation represented by the following general formula (2) as a polymerization inhibitor (C) in a radical curable composition containing at least a radical curable oligomer (A) and a polymerization inhibitor (C). The radical curable composition is characterized by using a compound having a polycyclic aromatic skeleton.

In the formula, R ¹ and R ^{2 each} represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, a glycidyl group, a hydroxyalkyl group, or an aryloxyalkyl group, and R ¹ and R ² are respectively It may be the same or different. X, Y, and Z each represent a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, or an alkoxy group, and may be the same or different, and X and Y are bonded to each other to be saturated or unsaturated. A ring may be formed, or a ring may be formed across an oxygen atom.

The third gist lies in the radical curable composition according to the second gist, wherein R ¹ is a hydrogen atom and R ² is a methyl group.

The fourth gist lies in the radical curable composition according to the third gist, wherein R ¹ is a hydrogen atom, R ² is a methyl group, and X, Y, and Z are all hydrogen atoms. .

A fifth aspect of the present invention is the radical curable composition according to any one of the first to fourth aspects, further comprising a radical polymerizable monomer (D). Exist.

A sixth aspect resides in a radical curable composition according to any one of the first to fifth aspects, further comprising a curing agent (B).

A seventh aspect is characterized in that 0.05% by weight to 10% by weight of a curing agent (B) is further mixed with the radically curable composition according to any one of the first to fifth aspects. It exists in the manufacturing method of the radical curable composition made into.

An eighth aspect resides in a cured product obtained by radical polymerization of the radical curable composition according to any one of the first to sixth aspects.

In the description of the present invention, the range of numerical values connected by “to” represents a range that is greater than or equal to the numerical value described before “to” and less than the numerical value described after “to”.

According to the radical curable composition of the present invention, thermal stability and storage stability can be improved without substantially changing the curing characteristics when the radical curable composition is cured.

Hereinafter, the present invention will be described in detail.

The present invention relates to a condensed polycycle represented by the following general formula (1) as a polymerization inhibitor (C) in a radical curable composition containing at least a radical curable oligomer (A) and a polymerization inhibitor (C). A compound having an aromatic skeleton is used.

In the formula, n represents an integer of 1 to 4, R represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, a glycidyl group, a hydroxyalkyl group, or an aryloxyalkyl group, and OR When there are a plurality of groups, Rs may be the same or different. X, Y, and Z each represent a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, or an alkoxy group, and may be the same or different, and X and Y are bonded to each other to be saturated or unsaturated. A ring may be formed, or a ring may be formed across an oxygen atom.

The radical curable oligomer (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. For example, unsaturated polyester, vinyl ester , Urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, and the like. Two or more kinds of these radical curable oligomers may be used.

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, and each includes 1,6-hexanediol diglycidyl ether. 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, polytetramethylene glycol diglycidyl ether It 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 kinds 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.

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.

Next, examples of the curing agent (B) used in the radical curable composition of the present invention include t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1 , 1,3,3-tetramethylbutyl hydroperoxide, hydroperoxide, methyl ethyl ketone peroxide, ketone peroxide such as acetylacetone peroxide, diacyl peroxide such as benzoyl peroxide, dicumyl peroxide, t-butyl cumi Dialkyl peroxides such as ruperoxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxide Alkyl peresters such as xylbenzoate, peroxides such as bis (4-tert-butylcyclohexyl) peroxydicarbonate; 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyrate Examples thereof include azo compounds such as ronitrile. Two or more kinds of these curing agents may be used.

The curing agent (B) may include 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% by weight or less with respect to 100% by weight of the curing agent.

Although it does not specifically limit as the usage-amount of the said hardening | curing agent (B), When the total amount of a radical-curable oligomer (A) and a radically polymerizable monomer (D) is 100 weight part, it is 0.05-10 weight normally. Parts, preferably 0.1 to 7 parts by weight, and more preferably 0.15 to 5 parts by weight. In any case, the curing agent is the weight as an active ingredient excluding the solvent.

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

In addition to the curing agent (B), an accelerator may be used as necessary to improve curability at low temperatures and to make a radically curable composition such as SMC or BMC semi-cured. . Examples of such an accelerator include metal soaps such as cobalt naphthenate, manganese naphthenate, copper naphthenate, potassium naphthenate, calcium naphthenate, cobalt octylate, manganese octylate, cobalt acetylacetonate, vanadium acetylacetate. Metal chelate compounds such as nate, amine compounds such as dimethylaniline, N, N′-dimethylaniline, N, N-dimethyltoluidine, N, N-diethylaniline, N, N-di (hydroxy) -4-methylaniline, Examples include acyl group-containing lactone compounds such as acetylacetone and ethyl acetoacetate, acetoacetamide compounds, β-diketones, β-ketoesters, β-ketoamides, etc., all of which may contain a solvent. Two or more kinds of these accelerators may be used.

Although it does not specifically limit as the usage-amount of the said hardening accelerator, When the total amount of a radical curable oligomer (A) and a radically polymerizable monomer (D) is 100 weight part, 0.1-10 weight part normally, Preferably it is 0.15-7 weight part, More preferably, it is 0.2-5 weight part, and all are a weight as an active ingredient except a hardening accelerator except a solvent.

As the polymerization inhibitor (C), a compound having a condensed polycyclic aromatic skeleton represented by the following general formula (1) is used.

In the formula, n represents an integer of 1 to 4, R represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, a glycidyl group, a hydroxyalkyl group, or an aryloxyalkyl group, and OR When there are a plurality of groups, Rs may be the same or different. X, Y, and Z each represent a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, or an alkoxy group, and may be the same or different, and X and Y are bonded to each other to be saturated or unsaturated. A ring may be formed, or a ring may be formed across an oxygen atom.

Examples of the alkyl group represented by R in the formula 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. As the aryl group, phenyl group, p-tolyl group, o- A tolyl group, a naphthyl group, and the like. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group. Examples of the alkoxyalkyl group include a methoxyethyl group and an ethoxyethyl group. And a methoxyethoxyethyl group. Examples of the glycidyl group include a glycidyl group and a 2-methylglycidyl group. Examples of the hydroxyalkyl group include a hydroxymethyl group, a 2-hydroxyethoxy group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 2-hydroxybutyl group, and a 3-hydroxybutyl group. Examples of the aryloxyalkyl group include phenoxyethyl and triloxyethyl.

Examples of the alkyl group represented by X, Y and Z in the formula 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 aryl group includes phenyl group, p-tolyl. Group, o-tolyl group, naphthyl group and the like. Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, tert-butoxy group and the like. Is mentioned.

In general formula (1), a compound in which n is 2 and two OR groups are substituted at positions 1 and 4 of the naphthalene skeleton is a compound of general formula (2).

In the formula, R ¹ and R ^{2 each} represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, a glycidyl group, a hydroxyalkyl group, or an aryloxyalkyl group, and R ¹ and R ² are respectively It may be the same or different. X, Y, and Z each represent a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, or an alkoxy group, and may be the same or different, and X and Y are bonded to each other to be saturated or unsaturated. A ring may be formed, or a ring may be formed across an oxygen atom.

Examples of the alkyl group represented by R ¹ and R ² in the formula 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 aryl group includes phenyl group, p-tolyl. Group, o-tolyl group, naphthyl group, and the like. Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, naphthylethyl group, and the like. Examples of the alkoxyalkyl group include methoxyethyl group. Ethoxyethyl group, methoxyethoxyethyl group and the like. Examples of the glycidyl group include a glycidyl group and a 2-methylglycidyl group. Examples of the hydroxyalkyl group include a hydroxymethyl group, a 2-hydroxyethoxy group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 2-hydroxybutyl group, and a 3-hydroxybutyl group. Examples of the aryloxyalkyl group include phenoxyethyl and triloxyethyl.

Examples of the alkyl group represented by X, Y and Z in the formula 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 aryl group includes phenyl group, p-tolyl. Group, o-tolyl group, naphthyl group and the like. Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, tert-butoxy group and the like. Is mentioned.

Specific examples of the compound having such a structure include the following compounds.

First, in the general formula (2), when X and Y are not bonded to each other to form a ring, for example, 1,4-dimethoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-di-n- Propoxynaphthalene, 1,4-diisopropoxynaphthalene, 1,4-di-n-butoxynaphthalene, 1,4-dihexyloxynaphthalene, 1,4-bis (2-ethylhexyloxy) naphthalene, 1,4-bis ( 2-methoxyethoxy) naphthalene, 1,4-bis (2-phenoxyethoxy) naphthalene, 1,4-diglycidyloxynaphthalene, 1,4-bis (2-hydroxyethoxy) naphthalene, 1,4-bis (2- Hydroxypropoxy) naphthalene, 1-methoxy-4-ethoxynaphthalene, 1-methoxy-4-butoxynaphthalene, 2-methyl 1,4-diethoxynaphthalene, 2-ethyl-1,4-diethoxynaphthalene, 1-hydroxy-4-methoxynaphthalene, 1-hydroxy-4-ethoxynaphthalene, 1-hydroxy-4-n-propoxynaphthalene, 1 -Hydroxy-4-isopropoxynaphthalene, 1-hydroxy-4-n-butoxynaphthalene, 1-hydroxy-4-hexyloxynaphthalene, 1-hydroxy-4- (2-ethylhexyloxy) naphthalene, 1-hydroxy-4- (2-methoxyethoxy) naphthalene, 1-hydroxy-4- (2-phenoxyethoxy) naphthalene 1-hydroxy-4-glycidyloxynaphthalene, 1-hydroxy-4- (2-hydroxyethoxy) naphthalene, 1-hydroxy-4 -(2-Hydroxypropoxy) naphth Ren, 2-methyl-1-hydroxy-4-ethoxy-naphthalene, 2-ethyl-1-hydroxy-4-ethoxy-naphthalene, 1,4-dihydroxy naphthalene.

In the general formula (2), as specific examples in which X and Y are bonded to each other to form a saturated 6-membered ring, 9,10-dimethoxy-1,2,3,4-tetrahydroanthracene, 9 , 10-diethoxy-1,2,3,4-tetrahydroanthracene, 9,10-di-n-propoxy-1,2,3,4-tetrahydroanthracene, 9,10-diisopropoxy-1,2,3 , 4-tetrahydroanthracene, 9,10-di-n-butoxy-1,2,3,4-tetrahydroanthracene, 9,10-bis (2-ethylhexyloxy) -1,2,3,4-tetrahydroanthracene, 9,10-bis (2-methoxyethoxy) -1,2,3,4-tetrahydroanthracene, 9,10-bis (2-phenoxyethoxy) -1,2,3,4-tetrahydro Loanthracene, 9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydroanthracene, 9-methoxy-10-ethoxy-1,2,3,4-tetrahydroanthracene, 9-methoxy-10 -Butoxy-1,2,3,4-tetrahydroanthracene, 2-methyl-9,10-diethoxy-1,2,3,4-tetrahydroanthracene, 2-ethyl-9,10-diethoxy-1,2,3 , 4-tetrahydroanthracene, 9-hydroxy-10-methoxy-1,2,3,4-tetrahydroanthracene, 9-hydroxy-10-ethoxy-1,2,3,4-tetrahydroanthracene, 9-hydroxy-10- n-propoxy-1,2,3,4-tetrahydroanthracene, 9-hydroxy-10-isopropoxy-1 2,3,4-tetrahydroanthracene, 9-hydroxy-10-n-butoxy-1,2,3,4-tetrahydroanthracene, 9-hydroxy-10- (2-ethylhexyloxy) -1,2,3,4 -Tetrahydroanthracene, 9-hydroxy-10- (2-methoxyethoxy) -1,2,3,4-tetrahydroanthracene, 9-hydroxy-10- (2-phenoxyethoxy) -1,2,3,4-tetrahydro Anthracene, 9-hydroxy-10- (2-hydroxyethoxy) -1,2,3,4-tetrahydroanthracene, 2-methyl-9-hydroxy-10-ethoxy-1,2,3,4-tetrahydroanthracene, 2 -Ethyl-9-hydroxy-10-ethoxy-1,2,3,4-tetrahydroanthracene The

In the general formula (2), when X and Y are bonded to each other to form an unsaturated 6-membered ring and the 6-membered ring is non-aromatic, a specific example is 9,10-dimethoxy -1,4-dihydroanthracene, 9,10-diethoxy-1,4-dihydroanthracene, 9,10-di-n-propoxy-1,4-dihydroanthracene, 9,10-diisopropoxy-1,4- Dihydroanthracene, 9,10-di-n-butoxy-1,4-dihydroanthracene, 9,10-bis (2-ethylhexyloxy) -1,4-dihydroanthracene, 9,10-bis (2-methoxyethoxy) -1,4-dihydroanthracene, 9,10-bis (2-phenoxyethoxy) -1,4-dihydroanthracene, 9,10-bis (2-hydroxyethoxy) -1, -Dihydroanthracene, 9-methoxy-10-ethoxy-1,4-dihydroanthracene, 9-methoxy-10-butoxy-1,4-dihydroanthracene, 2-methyl-9,10-diethoxy-1,4-dihydroanthracene 2-ethyl-9,10-diethoxy-1,4-dihydroanthracene, 9-hydroxy-10-methoxy-1,4-dihydroanthracene, 9-hydroxy-10-ethoxy-1,4-dihydroanthracene, 9- Hydroxy-10-n-propoxy-1,4-dihydroanthracene, 9-hydroxy-10-isopropoxy-1,4-dihydroanthracene, 9-hydroxy-10-n-butoxy-1,4-dihydroanthracene, 9- Hydroxy-10- (2-ethylhexyloxy) -1,4-dihydride Anthracene, 9-hydroxy-10- (2-methoxyethoxy) -1,4-dihydroanthracene, 9-hydroxy-10- (2-phenoxyethoxy) -1,4-dihydroanthracene, 9-hydroxy-10- (2 -Hydroxyethoxy) -1,4-dihydroanthracene, 2-methyl-9-hydroxy-10-ethoxy-1,4-dihydroanthracene, 2-ethyl-9-hydroxy-10-ethoxy-1,4-dihydroanthracene, etc. Is mentioned.

In the general formula (2), when X and Y are bonded to each other to form an unsaturated 6-membered ring and the 6-membered ring is aromatic, a specific example is 9,10-dimethoxyanthracene 9,10-diethoxyanthracene, 9,10-di-n-propoxyanthracene, 9,10-diisopropoxyanthracene, 9,10-di-n-butoxyanthracene, 9,10-bis (2-ethylhexyloxy) ) Anthracene, 9,10-bis (2-methoxyethoxy) anthracene, 9,10-bis (2-phenoxyethoxy) anthracene, 9,10-bis (2-hydroxyethoxy) anthracene, 9-methoxy-10-ethoxyanthracene 9-methoxy-10-butoxyanthracene, 2-methyl-9,10-diethoxyanthracene, 2-ethy -9,10-diethoxyanthracene, 9-hydroxy-10-methoxyanthracene, 9-hydroxy-10-ethoxyanthracene, 9-hydroxy-10-n-propoxyanthracene, 9-hydroxy-10-isopropoxyanthracene, 9- Hydroxy-10-n-butoxyanthracene, 9-hydroxy-10- (2-ethylhexyloxy) anthracene, 9-hydroxy-10- (2-methoxyethoxy) anthracene, 9-hydroxy-10- (2-phenoxyethoxy) anthracene 9-hydroxy-10- (2-hydroxyethoxy) anthracene, 2-methyl-9-hydroxy-10-ethoxyanthracene, 2-ethyl-9-hydroxy-10-ethoxyanthracene and the like.

In the general formula (2), as a specific example in which X and Y are bonded to each other via an oxygen atom to form a ring, 3,4-dihydro-5,10-dimethoxy-2-methyl-2H -Naphtho [2,3-b] pyran-4-one, 4,9-dimethoxy-2,3-dihydronaphtho [2,3-b] furan, 2-methyl-4,9-dimethoxy-2,3- Dihydronaphtho [2,3-b] furan, 1,4-dimethoxy-2,3-methylenedioxynaphthalene, 9-methoxy-2,3-dihydronaphtho [2,3-b] furan-4-ol, 2 -Methyl-9-methoxy-2,3-dihydronaphtho [2,3-b] furan-4-ol and the like.

Specific examples of the compound represented by the general formula (1) other than the compound represented by the general formula (2) and n = 2 include the following compounds. That is, in the general formula (1), as specific examples in which X and Y are not bonded to each other to form a ring, 1,5-dimethoxynaphthalene, 1,6-dimethoxynaphthalene, 1,7-dimethoxynaphthalene 2,6-dimethoxynaphthalene, 2,7-dimethoxynaphthalene, 1,5-diethoxynaphthalene, 1,6-diethoxynaphthalene, 1,7-diethoxynaphthalene, 2,6-diethoxynaphthalene, 2,7 -Diethoxynaphthalene, 1,5-di-n-propoxynaphthalene, 1,5-diisopropoxynaphthalene, 1,6-di-n-propoxynaphthalene, 1,6-diisopropoxynaphthalene, 1,7-di -N-propoxynaphthalene, 1,7-diisopropoxynaphthalene, 2,6-di-n-propoxynaphthalene, 2,6-dii Propoxynaphthalene, 2,7-di-n-propoxynaphthalene, 2,7-diisopropoxynaphthalene, 1,5-di-n-butoxynaphthalene, 1,6-di-n-butoxynaphthalene, 1,7-di -N-butoxynaphthalene, 2,6-di-n-butoxynaphthalene, 2,7-di-n-butoxynaphthalene, 1,5-bis (2-ethylhexyloxy) naphthalene, 1,6-bis (2- Ethylhexyloxy) naphthalene, 1,7-bis (2-ethylhexyloxy) naphthalene, 2,6-bis (2-ethylhexyloxy) naphthalene, 2,7-bis (2-ethylhexyloxy) naphthalene, 1, 5-bis (2-methoxyethoxy) naphthalene, 1,6-bis (2-methoxyethoxy) naphthalene, 1,7-bis (2-methoxyethoxy) ) Naphthalene, 2,6-bis (2-methoxyethoxy) naphthalene, 2,7-bis (2-methoxyethoxy) naphthalene, 1,5-bis (2-hydroxyethoxy) naphthalene, 1,6-bis (2- Hydroxyethoxy) naphthalene, 1,7-bis (2-hydroxyethoxy) naphthalene, 2,6-bis (2-hydroxyethoxy) naphthalene, 2,7-bis (2-hydroxyethoxy) naphthalene, 1,5-bis ( 2-phenoxyethoxy) naphthalene, 1,6-bis (2-phenoxyethoxy) naphthalene, 1,7-bis (2-phenoxyethoxy) naphthalene, 2,6-bis (2-phenoxyethoxy) naphthalene, 2,7- Bis (2-phenoxyethoxy) naphthalene, 1-methoxy-5-ethoxynaphthalene, 1-methoxy-6- Ethoxynaphthalene, 1-methoxy-7-ethoxynaphthalene, 2-methoxy-6-ethoxynaphthalene, 2-methoxy-7-ethoxynaphthalene, 1-methoxy-5-n-butoxynaphthalene, 1-methoxy-6-n-butoxy Naphthalene, 1-methoxy-7-butoxynaphthalene, 2-methoxy-6-n-butoxynaphthalene, 2-methoxy-7-n-butoxynaphthalene, 2-methyl-1,5-dimethoxynaphthalene, 2-methyl-1, 6-dimethoxynaphthalene, 2-methyl-1,7-dimethoxynaphthalene, 2-ethyl-1,5-diethoxynaphthalene, 2-ethyl-1,6-diethoxynaphthalene, 2-ethyl-1,7-diethoxy And naphthalene.

Furthermore, 1-hydroxy-5-methoxynaphthalene, 1-hydroxy-6-methoxynaphthalene, 1-hydroxy-7-methoxynaphthalene, 2-hydroxy-6-methoxynaphthalene, 2-hydroxy-7-methoxynaphthalene, 1- Hydroxy-5-ethoxynaphthalene, 1-hydroxy-6-ethoxynaphthalene, 1-hydroxy-7-ethoxynaphthalene, 2-hydroxy-6-ethoxynaphthalene, 2-hydroxy-7-ethoxynaphthalene, 1-hydroxy-5-n -Propoxynaphthalene, 1-hydroxy-5-isopropoxynaphthalene, 1-hydroxy-6-n-propoxynaphthalene, 1-hydroxy-6-isopropoxynaphthalene, 1-hydroxy-7-n-propoxynaphthalene, 1-hydroxy- 7-Isop Poxynaphthalene, 2-hydroxy-6-n-propoxynaphthalene, 2-hydroxy-6-isopropoxynaphthalene, 2-hydroxy-7-n-propoxynaphthalene, 2-hydroxy-7-isopropoxynaphthalene, 1-hydroxy-5 -N-butoxynaphthalene, 1-hydroxy-6-n-butoxynaphthalene, 1-hydroxy-7-n-butoxynaphthalene, 2-hydroxy-6-n-butoxynaphthalene, 2-hydroxy-7-n-butoxynaphthalene, 1-hydroxy-5- (2-ethylhexyloxy) naphthalene, 1-hydroxy-6- (2-ethylhexyloxy) naphthalene, 1-hydroxy-7- (2-ethylhexyloxy) naphthalene, 2-hydroxy-6 -(2-ethylhexyloxy) naphthalene, 2 7-bis (2-ethylhexyloxy) naphthalene, 1-hydroxy-5- (2-methoxyethoxy) naphthalene, 1-hydroxy-6- (2-methoxyethoxy) naphthalene, 1-hydroxy-7- (2-methoxy Ethoxy) naphthalene, 2-hydroxy-6- (2-methoxyethoxy) naphthalene, 2-hydroxy-7- (2-methoxyethoxy) naphthalene, 1-hydroxy-5- (2-hydroxyethoxy) naphthalene, 1-hydroxy- 6- (2-hydroxyethoxy) naphthalene, 1-hydroxy-7- (2-hydroxyethoxy) naphthalene, 2-hydroxy-6- (2-hydroxyethoxy) naphthalene, 2-hydroxy-7- (2-hydroxyethoxy) Naphthalene, 1-hydroxy-5- (2-phenoxyethoxy) na Phthalene, 1-hydroxy-6- (2-phenoxyethoxy) naphthalene, 1-hydroxy-7- (2-phenoxyethoxy) naphthalene, 2-hydroxy-6- (2-phenoxyethoxy) naphthalene, 2-hydroxy-7- (2-phenoxyethoxy) naphthalene, 2-methyl-1-hydroxy-5-methoxynaphthalene, 2-methyl-1-hydroxy-6-methoxynaphthalene, 2-methyl-1-hydroxy-7-methoxynaphthalene, 2-ethyl Examples include -1-hydroxy-5-ethoxynaphthalene, 2-ethyl-1-hydroxy-6-ethoxynaphthalene, 2-ethyl-1-hydroxy-7-ethoxynaphthalene, and the like.

Furthermore, specific examples of the compound represented by the general formula (1) and n = 1 include the following compounds. First, specific examples when X and Y are not bonded to each other to form a ring include 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 1-ethoxynaphthalene, 1-n-propoxynaphthalene, 1- Isopropoxynaphthalene, 1-n-butoxynaphthalene, 1- (2-ethylhexyloxy) naphthalene, 2-methoxynaphthalene, 2-ethoxynaphthalene, 2-n-propoxynaphthalene, 2-isopropoxynaphthalene, 2-n-butoxynaphthalene , 2- (2-ethylhexyloxy) naphthalene and the like.

Furthermore, specific examples of the compound represented by the general formula (1) and n being 3 or more include the following compounds. First, specific examples in the case where X and Y are not bonded to each other to form a ring include 1,2,4-trimethoxynaphthalene, 1,2,4-triethoxynaphthalene, 1,2,4-trimethyl. Propoxynaphthalene, 1,2,4-tributoxynaphthalene, 1,4,5-trimethoxynaphthalene, 1,4,5-triethoxynaphthalene, 1,4,5-tri-n-propoxynaphthalene, 1,4 5-triisopropoxynaphthalene, 1,4,5-tri-n-butoxynaphthalene, 1,4,6-trimethoxynaphthalene, 1,4,6-triethoxynaphthalene, 1,4,6-tri-n- Propoxynaphthalene, 1,4,6-triisopropoxynaphthalene, 1,4,6-tri-n-butoxynaphthalene, 1,4,5,8-tetramethoxynaphthalene, 1,4,5 8-tetraethoxynaphthalene, 1,4,5,8-tetra-n-propoxynaphthalene, 1,4,5,8-tetraisopropoxynaphthalene, 1,4,5,8-tetra-n-butoxynaphthalene, 2, -Hydroxy-1,4-dimethoxynaphthalene, 2-hydroxy-1,4-diethoxynaphthalene, 2-hydroxy-1,4-dipropoxynaphthalene, 2-hydroxy-1,4-dibutoxynaphthalene, 2,3- Dihydroxy-1,4-dimethoxynaphthalene, 2,3-dihydroxy-1,4-diethoxynaphthalene, 2,3-dihydroxy-1,4-di-n-propoxynaphthalene, 2,3-dihydroxy-1,4- Examples thereof include diisopropoxynaphthalene and 2,3-dihydroxy-1,4-di-n-butoxynaphthalene.

In addition to the compounds exemplified here, for example, compounds specifically disclosed in JP2012-111741A can be used.

Among these exemplified compounds, OR ¹ group in the 1,4-position of the naphthalene skeleton, a compound of general OR ² group is substituted formula (2) is preferable because of high effects of the present invention, particularly, OR ¹ group is hydrogen A compound which is an atom and the OR ² group is a methyl group is preferred. Among these, compounds in which X, Y, and Z are hydrogen atoms are more preferable because they are highly effective and easy to produce.

These exemplified compounds can be easily synthesized by a method of alkylating the corresponding hydroxynaphthalene compound with an alkylating agent such as dialkyl sulfuric acid.

The amount of the polymerization inhibitor (C) used in the radical curable composition of the present invention is not particularly limited, but the radical curable oligomer (A) or the total amount of the radical curable oligomer (A) and the radical polymerizable monomer (D). Is usually 0.001 to 0.5 parts by weight, preferably 0.002 to 0.45 parts by weight, and more preferably 0.003 to 0.4 parts 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, 0.5 part by weight or more may be added, but it may precipitate beyond the solubility.

In addition to the polymerization inhibitor (C), a polymerization inhibitor other than the polymerization inhibitor (C) 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 hydroquinone such as hydroquinone, methylhydroquinone, 2-methylhydroquinone and t-butylhydroquinone, benzoquinone such as p-benzoquinone and methyl-p-benzoquinone, catechol, t -Catechol series such as butyl catechol, phenol series such as 2,6-di-t-butyl-4-methylphenol, 4-methoxyphenol, cresol, phenothiazine, ferdazyl, α, α-diphenyl-β-picrylhydrazyl And known polymerization inhibitors such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl. Two or more kinds of these polymerization inhibitors may be used.

The amount of the polymerization inhibitor that can be used in combination with the polymerization inhibitor (C) is not particularly limited, but the radical curable oligomer (A) or the total of the radical curable oligomer (A) and the radical polymerizable monomer (D). When the amount is 100 parts by weight, it is usually 0.001 to 0.3 parts by weight, preferably 0.002 to 0.25 parts by weight, and more preferably 0.003 to 0.2 parts by weight. When 0.3 part by weight or more is added, the gelation time may become too long, or the curing may be poor.

The radical polymerizable monomer (D) is not particularly limited as long as it has one or more polymerizable groups in the molecule, and examples thereof 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.

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 reinforcing material include glass fibers, organic fibers such as amide, aramid, vinylon, polyester, and phenol, and inorganic fibers such as carbon fibers, metal fibers, and ceramic fibers. Two or more kinds may be used. 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 amount of the filler or aggregate is not particularly limited, but when the total amount of the radical curable oligomer (A) or the radical curable oligomer (A) and the radical polymerizable monomer (D) is 100 parts by weight, Usually, it is 1 to 300 parts by weight.

The radical curable composition of the present invention includes a commercially available radical curable composition in which a polymerization inhibitor and a filler are mixed in advance, and a condensation polymer represented by the above general formula (1) as a polymerization inhibitor (C). It can also be prepared by adding a compound having a ring aromatic skeleton.

Examples of such commercially available radical curable compositions include unsaturated polyesters and vinyl esters in which fillers and the like are mixed in advance. These commercially available radically curable compositions include those in which the curing agent (B) is added before curing, or those in which the curing agent (B) is added in advance, such as SMC, BMC and the like. It is done.

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 Co., Ltd. (Polyhope is a registered trademark of Japan Composite Co., Ltd.) and Sandoma manufactured by DH Material Co., Ltd. (Sandoma is a registered trademark of DH Material Co., Ltd.).

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.) and Exdoma manufactured by DH Material Co., Ltd. (Exdoma is a registered trademark of DH Material Co., Ltd.).

(Method for producing radically 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 is produced by mixing the radical curable oligomer (A), the curing agent (B), the polymerization inhibitor (C) and the radical polymerizable monomer (D) as necessary, and then stirring and mixing until uniform. can do. It is also possible to add the curing agent (B) later.

The amount of the curing agent (B) used is usually 0.05 to 10 parts by weight, preferably 0 when the total amount of the radical curable oligomer (A) and the radical polymerizable monomer (D) is 100 parts by weight. 0.1-7 parts by weight, more preferably 0.15-5 parts by weight, and in all cases, the curing agent is the weight as an active ingredient excluding the solvent.

The method of molding the radical curable composition of the present invention is not particularly limited, 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, A vacuum forming 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.

In the radically curable composition of the present invention, by using a compound having a condensed polycyclic aromatic skeleton represented by the above general formula (1) as the polymerization inhibitor (C), heat is hardly changed. Stability and storage stability can be improved.

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 gist.

  Table 1 shows the types and abbreviations of the polymerization inhibitors used in the examples. In the table, MNT and DEN are compounds having a condensed polycyclic aromatic skeleton of the present invention, and BHT and HQ are compounds having a monocyclic aromatic skeleton used for comparison.

<Evaluation of Thermal Stability of Styrene> Examples 1, 2, 3 and Comparative Examples 1, 2, 3
A commercially available styrene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) was washed with a 0.5% aqueous sodium hydroxide solution and then distilled under reduced pressure to remove the pre-added polymerization inhibitor and a trace amount of polymer. 30 g of styrene thus purified was put in a test tube, and each polymerization inhibitor shown in Table 2 was added. Next, the inside temperature was heated to 100 ° C. in an oil bath while aeration of nitrogen at 20 ml / min. When the internal temperature reached 100 ° C., about 2 g was sampled every predetermined time, and the viscosity was measured after quenching with ice water. The results are also shown in Table 2. The viscosity was measured at 25 ° C. using a Viscomate VM-10A (vibrating viscometer manufactured by CBC Corporation).

<Evaluation of Storage Stability of Styrene> Examples 4, 5, 6 and Comparative Examples 4, 5, 6
In a nitrogen box, 30 g of styrene purified by the same method as above was put in a test tube, and each polymerization inhibitor shown in Table 3 was added. Next, nitrogen was vented at 20 ml / min for 3 minutes, and after deaeration, the cap was sealed and stored in an inert oven at 60 ° C. in which nitrogen was vented at 5 L / min. The change in viscosity over time was confirmed by shaking the sample bottle, and the number of days until an increase in viscosity was observed is also shown in Table 3.

<Evaluation of Curing Properties of Unsaturated Polyester> Examples 7, 8, 9 and Comparative Examples 7, 8, 9
Using a commercially available unsaturated polyester (Rigolac 158BQT manufactured by Showa Denko KK), a curing property test was carried out by a room temperature curing property (exothermic method) described in JIS K6901 (2008) “Test method for liquid unsaturated polyester resin”. Such a commercially available unsaturated polyester is preliminarily added with some polymerization inhibitor, but in this test, each polymerization inhibitor shown in Table 4 is further added, and the time required for gelation and curing are required. Time was measured and the results are shown in Table 4.

<Evaluation of Curing Properties of Vinyl Ester> Examples 10, 11, 12 and Comparative Examples 10, 11, 12
Using a commercially available vinyl ester (Lipoxy R-802, manufactured by Showa Denko KK), a curing property test was carried out by a room temperature curing property (exothermic method) described in JIS K6901 (2008) “Test method for liquid unsaturated polyester resin”. Such a commercially available vinyl ester has some kind of polymerization inhibitor added in advance, but in this test, each polymerization inhibitor shown in Table 5 was further added to carry out the time required for gelation and the time required for curing. Were measured, and the results are also shown in Table 5.

  From the above results, the following is mainly clear.

First, from Table 2, the following is clear. That is, in the evaluation of the thermal stability of styrene, in the case of Examples 1 and 2 using 4-methoxy-1-naphthol (MNT) which is a compound having a condensed polycyclic aromatic skeleton of the present invention, a polymerization inhibitor was used. It can be seen that the thermal stability is clearly improved as compared with Comparative Example 1 that was not used and Comparative Example 2 using bis-t-butylhydroxytoluene (BHT). Moreover, in Example 2 which increased the usage-amount of 4-methoxy-1-naphthol, the thermal stability substantially equivalent to the case where the hydroquinone (HQ) of the comparative example 3 is shown is shown. However, in the case of hydroquinone, the thermal stability is good, but there is a problem in the evaluation of the curing characteristics in the next item. From this, it can be said that 4-methoxy-1-naphthol, which is a compound having a condensed polycyclic aromatic skeleton of the present invention, exhibits an excellent thermal stability effect on a polymerizable monomer as a polymerization inhibitor.

Furthermore, in the case of Example 3 in which 1,4-diethoxynaphthalene (DEN) which is a compound having a condensed polycyclic aromatic skeleton of the present invention and hydroquinone are used in combination, the case of using only the hydroquinone of Comparative Example 3 is compared. However, the thermal stability is remarkably improved. And in the case of hydroquinone alone, even in the evaluation of the curing characteristics of the next item, which is a problem, the gelling time is not prolonged, and excellent performance is exhibited.

Next, the following is clear from Table 3. That is, in the evaluation of the storage stability of styrene, in the case of Examples 4 and 5 using 4-methoxy-1-naphthol which is a compound having a condensed polycyclic aromatic skeleton of the present invention, a polymerization inhibitor was not used. The storage stability is significantly improved as compared with Comparative Example 4 and Comparative Example 5 using bis-t-butylhydroxytoluene. Moreover, it turns out that it has an effect substantially equivalent to the storage stability at the time of using the hydroquinone of the comparative example 6. However, in the case of HQ, the storage stability is good, but there is a problem in the evaluation of the curing characteristics in the next item. Moreover, in Example 5, it turns out that storage stability can be improved further by increasing the usage-amount of 4-methoxy-1-naphthol. From this, it can be said that 4-methoxy-1-naphthol, which is a compound having a condensed polycyclic aromatic skeleton of the present invention, exhibits an excellent storage stability effect on a polymerizable monomer as a polymerization inhibitor.

Furthermore, in the case of Example 6 in which 1,4-diethoxynaphthalene, which is a compound having a condensed polycyclic aromatic skeleton of the present invention, and hydroquinone are used in combination, the storage stability is higher than in the case of using only the hydroquinone of Comparative Example 6. It can be seen that the property is remarkably improved. In the case of hydroquinone alone, the evaluation of the curing characteristics in the next item, which is a problem, shows an excellent performance that the gelation time is not prolonged.

Next, the following is clear from Table 4. That is, in the evaluation of the curing characteristics of the unsaturated polyester, Example 7 using 4-methoxy-1-naphthol, which is a compound having a condensed polycyclic aromatic skeleton of the present invention, and bis-t-butylhydroxytoluene were used. Compared to Comparative Example 8 and Comparative Example 9 using hydroquinone, the difference in gelation time from Example 7 with 32.0 minutes and Comparative Example 7 without using a polymerization inhibitor was 25.6 minutes. Compared to 4 minutes, the difference in Comparative Example 8 was 10.6 minutes, and in Comparative Example 9 was 21.3 minutes, which is a compound having a condensed polycyclic aromatic skeleton of the present invention. It can be seen that in the case of certain 4-methoxy-1-naphthol, the increase in gelation time is small.

Furthermore, in the case of Example 9 in which 1,4-diethoxynaphthalene, which is a compound having a condensed polycyclic aromatic skeleton of the present invention, and hydroquinone are used in combination, Comparative Example 9 is compared with the case where only hydroquinone is used. There is almost no change, and it can be seen that there is no increase in gelation time due to the addition of 1,4-diethoxynaphthalene, which is a compound having a condensed polycyclic aromatic skeleton of the present invention.

Next, the following is clear from Table 5. That is, in the evaluation of the curing characteristics of the vinyl ester, Example 10 using 4-methoxy-1-naphthol, which is a compound having a condensed polycyclic aromatic skeleton of the present invention, and comparison using bis-t-butylhydroxytoluene Compared to Example 11 and Comparative Example 12 using hydroquinone, the gelation time was 10.6 minutes in Example 10 and the difference from 9.1 minutes in Comparative Example 10 where no polymerization inhibitor was used was 1.5. On the other hand, in the case of Comparative Example 11, the difference is almost equal at 0.9 minutes, and in Comparative Example 12, it is as long as 4.0 minutes. In the case of 4-methoxy-1-naphthol, which is a compound having a group skeleton, it can be seen that the increase in gelation time is small.

Furthermore, in the case of Example 12 in which 1,4-diethoxynaphthalene, which is a compound having a condensed polycyclic aromatic skeleton of the present invention, and hydroquinone are used in combination, gelation is performed as compared with the case of using only the hydroquinone of Comparative Example 12. There is almost no change in time, and it can be seen that there is no increase in gelation time due to the addition of 1,4-diethoxynaphthalene, which is a compound having a condensed polycyclic aromatic skeleton of the present invention.

In summary, the radical curable composition containing the compound having a condensed polycyclic aromatic skeleton of the present invention has a good heat stability and storage stability before the addition of a curing agent, and a curing agent is added. It can be said that there is little extension of the subsequent gelation time and there is little delay in curing. Further, if the addition amount is increased, the thermal stability is further improved, but it can be said that the extension of the curing time such as the extension of the gelation time is slight.

Claims (8)

In the radical curable composition containing at least the radical curable oligomer (A) and the polymerization inhibitor (C), a condensed polycyclic aromatic skeleton represented by the following general formula (1) is used as the polymerization inhibitor (C). A radical curable composition characterized by using a compound having the same.

(In the formula, n represents an integer of 1 to 4, R represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, a glycidyl group, a hydroxyalkyl group, or an aryloxyalkyl group, When there are a plurality of OR groups, Rs may be the same or different, and X, Y, and Z each represent a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, or an alkoxy group, and are the same Or X and Y may be bonded to each other to form a saturated or unsaturated ring, or a ring may be formed with an oxygen atom in between. In the radical curable composition containing at least the radical curable oligomer (A) and the polymerization inhibitor (C), a condensed polycyclic aromatic skeleton represented by the following general formula (2) is used as the polymerization inhibitor (C). A radical curable composition characterized by using a compound having the same.

(In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, a glycidyl group, a hydroxyalkyl group or an aryloxyalkyl group, and R ¹ and R ² may be the same. X, Y, and Z each represent a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, or an alkoxy group, and may be the same or different, and X and Y are bonded to each other. A saturated or unsaturated ring may be formed, or a ring may be formed across an oxygen atom.) The radical curable composition according to claim 2, wherein R ¹ is a hydrogen atom and R ² is a methyl group. The radical curable composition according to claim 3, wherein R ¹ is a hydrogen atom, R ² is a methyl group, and X, Y, and Z are each a hydrogen atom. The radical curable composition according to any one of claims 1 to 4, further comprising a radical polymerizable monomer (D). The radical curable composition according to any one of claims 1 to 5, further comprising a curing agent (B). The radical curable composition according to any one of claims 1 to 5, wherein 0.05% by weight to 10% by weight of a curing agent (B) is further mixed with the radical curable composition according to any one of claims 1 to 5. Manufacturing method. A cured product obtained by curing the radical curable composition according to any one of claims 1 to 6 by radical polymerization.