JP2002327032A - Radical curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radical curable resin composition having an N-vinyl compound and a radical curable resin which can be stored for a long time and which has an excellent characteristic for the stability of the contained N-vinyl compound. SOLUTION: The composition is obtained by containing, in a composition comprising (A) the radical curable resin and (B) N-vinyl compound represented by the formula (I) [wherein, R<1> -R<3> are each independently a hydrogen or a hydrocarbon group; X and Y are each independently a hydrogen, an organic group of forming an organic group by being bound to each other directly which may contain a hetero atom], (C) a radical polymerization inhibitor of 10-10,000 ppm and (D) an organic base compound of 10-10,000 ppm each with respect to the N-vinyl compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an adhesive, a pressure-sensitive adhesive,
Dental materials, optical materials, information recording materials, optical fiber materials, resist materials, sealing materials, printing inks, paints, casting materials, decorative boards, WPCs, coating materials, lining materials, civil engineering and building materials, putty, repair materials, The present invention relates to a radical curable resin composition useful for applications such as flooring materials, pavement materials gel coat, overcoat, hand lay-up, spray-up, pultrusion molding, filament winding, SMC, BMC and other molding materials and sheets.

[0002]

2. Description of the Related Art Generally, a radical-curable resin composition comprises
It is widely used for molding materials, woodwork, building materials, paper, paints such as various plastics, printed boards, and the like. Conventionally, a radical-curable resin composition is a composition in which a radical-curable resin such as an acrylic oligomer or unsaturated polyester and a monomer as a reactive diluent are blended, and a curing agent and various additives are blended as necessary. is there. In general, radical-curable resins are difficult to handle because of their high viscosity,
It is necessary to mix a reactive diluent to lower the viscosity. This reactive diluent is required to have properties such as low viscosity, fast curability, low toxicity, and physical properties of a cured product. However, at present, few compounds satisfy all of these properties.

[0003] For example, acrylate-based reactive diluents are generally highly irritating to the skin and various derivatives having low irritation have been developed. However, since these derivatives have high viscosity, they are formulated in large amounts as reactive diluents. And the physical properties of the resin composition are impaired.

On the other hand, N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam and N-vinylformamide are used as reactive diluents. These compounds have excellent characteristics such as low viscosity and high curability as compared with conventional reactive diluents. However, as described above
When an N-vinyl compound is mixed with a radical-curable resin, it gels for a short time, and thus has a problem in storage stability. further,
These N-vinyl compounds are inferior in stability, particularly hydrolysis resistance, as compared with acrylate-based reaction diluents, and have a problem of causing a hydrolysis reaction under acidic conditions.
JP-A-2000-319308 discloses that storage stability is improved by blending a specific compound into a composition comprising N-vinylformamide and a polymerizable oligomer. However, this method does not improve the stability of the N-vinyl compound, although the short-term gelation by the combination of the N-vinyl compound and the radical-curable resin is improved.

[0005]

The problem to be solved by the present invention is that a radical-curable resin composition of an N-vinyl compound and a radical-curable resin can be stored for a long period of time, and An object of the present invention is to provide a radical-curable resin composition having excellent characteristics in the stability of an N-vinyl compound contained therein.

[0006]

Means for Solving the Problems The present inventor has made intensive studies to solve the above-mentioned problems. As a result, they have found that the above objects can be achieved by combining and compounding specific compounds, and have completed the present invention. That is, the radical-curable resin composition according to the present invention comprises (A) a radical-curable resin and (B) the following general formula (1):

[0007]

Embedded image

(However, in the formula (1), R ^{1 to} R ³ each independently represent a hydrogen or a hydrocarbon group, and X and Y each independently represent a hydrogen or an organic group, or directly bond to each other. And an organic group represented by the formula (1):
In the above, the organic groups directly bonded to each other may contain a hetero atom. More specifically, the hetero atom is at least one or more selected from O, S, and N. In the composition comprising an N-vinyl compound represented by the formula (C), the radical polymerization inhibitor (C) contains 10 to 10000 ppm and the organic basic compound (D) contains 10 to 10000 ppm based on the N-vinyl compound. It is characterized by the following.

Further, in the radical-curable resin composition according to the present invention, the radical polymerization inhibitor may comprise a phenolic compound, a quinone-based compound, a phenothiazine-based compound and an N-
It is characterized by being at least one or more selected from oxyl compounds.

The radical-curable resin composition according to the present invention is characterized in that (D) the organic basic compound has the following general formula (2):

[0011]

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(Wherein, in the formula (2), R ^{4 to} R ⁷ each independently represent hydrogen or an organic group), which is a radically curable resin composition. I have. Further, in the radical-curable resin composition according to the present invention, the (B) N-vinyl compound is represented by the following general formula (3):

[0013]

Embedded image

(However, in the formula (3), R ^{8 to} R ¹⁰ are
Represents hydrogen or a hydrocarbon group each independently, also R ¹¹
To R ¹⁴ each independently represent hydrogen or an organic group. )
It is characterized by being.

The radical-curable resin composition according to the present invention is characterized in that the (B) N-vinyl compound is N-vinylpyrrolidone.

Further, a method for curing a radical-curable resin composition according to the present invention is characterized in that the radical-curable resin composition is cured with an active energy ray. Specifically, the radical-curable resin composition of the present invention is a radical-curable resin composition for active energy ray curing.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below.

[(A) Radical curable resin] The radical curable resin in the present invention may be used in the presence of a radical generator such as a curing agent, or an ultraviolet ray, an electron beam, an excimer laser,
The resin is not particularly limited as long as it is a radical-curable resin that is cured by radical polymerization under irradiation of radiation such as γ-rays, X-rays, infrared rays, or visible light. Examples of such a radical-curable resin include a resin containing a radical-curable polymer such as unsaturated polyester, epoxy (meth) acrylate, urethane (meth) acrylate, and polyester (meth) acrylate, and a reactive diluent. And
A resin containing (meth) acrylic syrup containing a reactive diluent is exemplified. In addition, other examples include a resin containing a polymer having no radical curability such as saturated polyester or poly (methyl methacrylate) and a reactive diluent. One of these radical curable resins may be used alone, or two or more of them may be appropriately mixed and used.

Among the radical-curable polymers exemplified above, the unsaturated polyester is obtained by condensation polymerization of a polybasic acid containing an α, β-unsaturated dibasic acid and a polyhydric alcohol. Things.

Among the polybasic acids used as raw materials for the unsaturated polyester, the α, β-unsaturated dibasic acid is not particularly limited, but specific examples include maleic acid and fumaric acid. Acids or their anhydrides,
Alkyl ester products and the like can be mentioned. The above α,
Examples of polybasic acids other than β-unsaturated dibasic acids include, for example,
Malonic acid, succinic acid, methyl succinic acid, 2,2-dimethyl succinic acid, 2,3-dimethyl succinic acid, hexyl succinic acid, glutaric acid, 2-methyl glutaric acid, 3-methyl glutaric acid, 2,2-dimethyl glutar Acid, 3,3-dimethylglutaric acid, 3,3-diethylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, aliphatic saturated polybasic acids such as sebacic acid; phthalic acid, isophthalic acid, terephthalic acid, Trimellitic acid, pyromellitic acid,
Aromatic polybasic acids such as 2,6-naphthalenedicarboxylic acid;
Alicyclic polybasic acids such as nadic acid, 1,2-hexahydrophthalic acid, tetrahydrophthalic acid, and 1,4-cyclohexanedicarboxylic acid; and anhydrides and alkyl esterified products of these acids. These polybasic acids are
One type may be used alone, or two or more types may be appropriately mixed and used.

The polyhydric alcohol used as a raw material of the unsaturated polyester is not particularly limited, but specific examples thereof include ethylene glycol, diethylene glycol, propylene glycol,
1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, dipropylene glycol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-1,4-butanediol, 1,7-
Heptanediol, 1,8-octanediol, 1,9
-Nonanediol, 1,10-decanediol, 1,4
-Cyclohexanediol, 1,4-dimethylolcyclohexane, 2,2-diethyl-1,3-propanediol, 3-methyl-1,4-pentanediol, 2,2
-Diethyl-1,3-butanediol, 4,5-nonanediol, triethylene glycol, tetraethylene glycol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, hydrogenated bisphenol A, alkylene oxide of hydrogenated bisphenol A Adducts and alkylene oxide adducts of bisphenol A may be mentioned. Further, as the polyhydric alcohol, an epoxy compound which is a precursor of the polyhydric alcohol may be used. Specific examples of the epoxy compound include ethylene oxide, propylene oxide, styrene oxide, glycidyl (meth) acrylate, and allyl glycidyl ether. One of these polyhydric alcohols may be used alone, or two or more of them may be appropriately mixed and used.

The unsaturated polyester may be modified with dicyclopentadiene, if necessary, for the purpose of improving the appearance, surface smoothness, dimensional stability, heat resistance and the like of the obtained cured product. Dicyclopentadiene is, for example, the condensation polymerization by mixing the polybasic acid and polyhydric alcohols and dicyclopentadiene used for ordinary unsaturated polyester, or the polybasic acid and polyhydric alcohols To start the condensation polymerization by adding dicyclopentadiene,
You only need to introduce it.

Among the radical-curable polymers exemplified above, epoxy (meth) acrylate is (meth) acrylate.
It is obtained by an addition reaction between acrylic acid and a compound having at least one epoxy group in the molecule. Also,
If necessary, a basic acid other than (meth) acrylic acid may be used as a part of the raw material.

The compound having an epoxy group used as a raw material of the epoxy (meth) acrylate includes:
Although not particularly limited, specifically, for example,
Bisphenol-type epoxy resin which is a reaction product of a bisphenol such as bisphenol A or bisphenol F with epihalohydrin; Novolak-type epoxy resin which is a reaction product of novolak resin with epihalohydrin; Glycidyl ester compounds which are reactants; glycidyl ether compounds which are reactants of alcohols such as neopentyl glycol and polypropylene glycol with epihalohydrin; One of these compounds having an epoxy group may be used alone, or two or more of them may be appropriately mixed and used.

The basic acid other than (meth) acrylic acid, which is optionally used as a raw material of the epoxy (meth) acrylate, is not particularly limited.
Specifically, for example, aliphatic acids such as maleic acid, fumaric acid, succinic acid, adipic acid, suberic acid, azelaic acid, tetrahydrophthalic acid, a polymer of unsaturated fatty acids having 18 carbon atoms such as dimer acid and trimer acid Polybasic acids; aromatic polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, trimellitic acid, and pyromellitic acid; Furthermore, obtained by performing a condensation reaction between a polyhydric alcohol and a polybasic acid,
Polyesters in which at least one of the terminal groups is a carboxyl group can also be used as a basic acid other than (meth) acrylic acid. One of these basic acids may be used alone, or two or more of them may be used as an appropriate mixture.

Among the radical-curable polymers exemplified above, urethane (meth) acrylate is a urethanization reaction between a hydroxyl group-containing (meth) acrylate and a compound having at least one isocyanate group in the molecule. Is obtained by Also, if necessary,
A polyhydric alcohol may be used as a part of the raw material.

Specific examples of the hydroxyl group-containing (meth) acrylate used as a raw material of the urethane (meth) acrylate include, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. ) Acrylate,
Examples include polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate, but are not particularly limited. One of these hydroxyl group-containing (meth) acrylic esters may be used alone, or two or more thereof may be appropriately mixed and used.

Examples of the compound having an isocyanate group used as a raw material of the urethane (meth) acrylate include, for example, 2,4-tolylene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate And xylylene diisocyanate. One of these compounds having an isocyanate group may be used alone, or two or more of them may be appropriately mixed and used.

The polyhydric alcohol optionally used as a raw material of the urethane (meth) acrylate is not particularly limited, but specific examples thereof include ethylene glycol, diethylene glycol, polyethylene glycol, and propylene. Glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, trimethylolpropane, glycerin, pentaerythritol and the like. Further, polyether polyols or polyester polyols obtained by adding ethylene oxide or propylene oxide to these polyhydric alcohols can also be used as the polyhydric alcohol. One of these polyhydric alcohols may be used alone, or two or more of them may be appropriately mixed and used.

Among the radical-curable polymers exemplified above, polyester (meth) acrylate is obtained by an esterification reaction between (meth) acrylic acid and a polyhydric alcohol. If necessary, a polybasic acid other than (meth) acrylic acids may be used as a part of the raw material.

The (meth) acrylic acid used as a raw material of the polyester (meth) acrylate is not particularly limited, but specific examples thereof include (meth) acrylic acid and alkyl (meth) acrylate. (Meth) acrylic acid and its derivatives capable of forming an ester bond with a hydroxyl group, such as an ester and a (meth) acrylic halide. These (meth) acrylic acids are 1
Only the types may be used, or two or more types may be appropriately mixed and used.

The polyhydric alcohol used as a raw material of the polyester (meth) acrylate is not particularly limited, but specifically, for example, the polyhydric alcohols described above (for example, the unsaturated polyester or urethane ( Polyhydric alcohol used for meth) acrylate.

Examples of the basic acid other than (meth) acrylic acid used as a raw material for the polyester (meth) acrylate include, for example, the above-mentioned basic acids, and more specifically, the unsaturated polyester. Examples of the raw materials include α, β-unsaturated dibasic acids, aliphatic saturated polybasic acids, aromatic polybasic acids, and alicyclic polybasic acids. One of these basic acids may be used alone, or two or more of them may be used as an appropriate mixture.

The (meth) acryl syrup exemplified above is a resin comprising a (meth) acrylic polymer and a reactive diluent. The (meth) acrylic polymer is a polymer obtained by polymerizing monomer components including (meth) acrylic acid, (meth) acrylic acid ester, and other vinyl monomers as necessary. Examples thereof include polymethyl methacrylate-based polymers and copolymers thereof. Further, a modified (meth) acryl syrup composed of a polymer obtained by reacting a (meth) acrylic polymer with an epoxy compound or an isocyanate compound capable of reacting with a functional group of the (meth) acrylic polymer. Can also be used as a radical curable resin. The modified (meth) acryl syrup can be obtained, for example, by using glycidyl methacrylate having an unsaturated group as an epoxy compound and introducing a (meth) acryloyl group having a radical polymerizable bond into a side chain. When an isocyanate compound also having an unsaturated group is used as the isocyanate compound, a similar modified (meth) acryl syrup can be obtained by introducing a hydroxyl group into the (meth) acrylic polymer.

The (meth) acrylic ester used as a raw material of the (meth) acrylic polymer is not particularly limited, but specifically, for example, methyl (meth) acrylate, ethyl ( (Meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, hydroxyethyl (meth)
Acrylate and the like. One of these (meth) acrylates may be used alone, or two or more of them may be appropriately mixed and used.

The other vinyl monomer optionally used as a raw material of the (meth) acrylic polymer is not particularly limited.
For example, styrene, α-methylstyrene, vinyl toluene, vinyl acetate and the like can be mentioned. One of these vinyl monomers may be used alone, or two or more thereof may be appropriately mixed and used.

The reaction pressure, reaction time, reaction temperature, etc., for synthesizing the unsaturated polyester, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, and (meth) acrylic polymer. The reaction conditions are not particularly limited. Further, the molecular weight of each radical-curable polymer constituting the radical-curable resin is not particularly limited.

In the radical-curable resin composition, the radical-curable resin such as the unsaturated polyester, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, and (meth) acrylic polymer is used. The content of each radical-curable polymer is not particularly limited, but is usually preferably 1 to 99.
%, More preferably 5 to 95% by weight, even more preferably 10 to 90% by weight. If the amount of the radical polymerizable resin is too small, distortion due to shrinkage accompanying the curing reaction is likely to occur, and the physical properties after curing are apt to become brittle. Conversely, if the amount of the radically polymerizable resin is too large, the viscosity of the composition may not be sufficiently reduced to impair workability or a uniform composition may not be obtained.

[(B) N-vinyl compound] The N-vinyl compound in the present invention is represented by the following general formula (1):

[0040]

Embedded image

(However, in the formula (1), R ^{1 to} R ³ each independently represent a hydrogen or a hydrocarbon group, and X and Y each independently represent a hydrogen or an organic group, or directly bond to each other. And an organic group represented by the formula (1):
In the above, the organic groups directly bonded to each other may contain a hetero atom. Specifically, the hetero atom is at least one or more selected from O, S, and N. ).

In the general formula (1), examples of the hydrocarbon group as examples of R ^{1 to} R ³ include an alkyl group, a cycloalkyl group, an alkenyl group and a phenyl group. Among them, a methyl group, an ethyl group, a propyl group, and a butyl group are preferable. As the N-vinyl compound of the present invention, specifically, N-vinylpyrrolidone, N-vinylcaprolactam, N-
Vinylformamide, N-vinylacetamide, N-methyl-N-vinylacetamide, N-vinylphthalimide, N-vinylsuccinimide, N-vinyl-5-methyl-2-oxazolidone, N-vinyl-2-oxazolidone and the like Can be
Further, among the N-vinyl compounds in the present invention, the following general formula (3):

[0043]

Embedded image

(However, in the formula (3), R ^{8 to} R ¹⁰ are
Represents hydrogen or a hydrocarbon group each independently, also R ¹¹
To R ¹⁴ each independently represent hydrogen or an organic group. )
Are preferred.

In the general formula (3), the organic group which is an example of R ^{11 to} R ¹⁴ is not particularly limited.
Saturated or unsaturated aliphatic, cycloaliphatic, or aromatic hydrocarbon groups, halogen groups, hydroxyl groups, ether groups,
Sulfide group, nitrile group, aldehyde group, carboxylic acid group, sulfonic acid group, ester group, amide group and the like, among them, the hydrocarbon group, carboxylic acid group,
An ester group, an amide group and the like are preferable, and an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group is more preferable.

As the N-vinyl compound represented by the general formula (3), specifically, N-vinyl-5-methyl-2-oxazolidone, N-vinyl-2-oxazolidone, N-vinyl- 4-methyl-2-oxazolidone, N-vinyl-5-ethyl-4
-Methyl-2-oxazolidone, N-vinyl-5-butyl-2-oxazolidone, N-vinyl-4-propyl-2-oxazolidone,
N-vinyl-4,4-diethyl-5,5-dimethyl-2-oxazolidone and the like. Among them, N-vinyl-5-methyl-2-oxazolidone and N-vinyl-2-oxazolidone are particularly preferred. Further, among the N-vinyl compounds in the present invention, N-vinylpyrrolidone is particularly preferred from the viewpoint of physical properties of the cured product.

In the radical-curable resin composition, the N-
The content of the vinyl compound is not particularly limited, but usually,
It is preferably 99 to 1% by weight, more preferably 95 to 5% by weight, and still more preferably 90 to 10% by weight. If the amount of the vinyl compound is too large, distortion due to shrinkage accompanying the curing reaction is likely to occur, and the physical properties after curing are likely to be brittle. On the other hand, if the amount of the N-vinyl compound is too small, the viscosity of the composition may not be sufficiently reduced to impair workability, or a uniform composition may not be obtained.

[(C) Radical polymerization inhibitor] The radical polymerization inhibitor in the present invention is an agent which generally inhibits or suppresses radical polymerization, and specifically includes phenol compounds, quinone compounds, phenothiazine compounds, N-oxyl compounds are mentioned, and phenol compounds and quinone compounds are particularly preferable.

The phenolic compound has the following general formula:
(4):

[0050]

Embedded image

(However, in the formula (4), R ^{15 to} R ¹⁹ each independently represent hydrogen, a hydroxyl group or an organic group.)
There is no particular limitation as long as it has a structure represented by

In the general formula (4), the organic group which is an example of R ^{15 to} R ¹⁹ is not particularly limited.
Saturated or unsaturated aliphatic, cycloaliphatic, or aromatic hydrocarbon groups, halogen groups, hydroxyl groups, ether groups,
Examples include a sulfide group, a nitrile group, an aldehyde group, a carboxylic acid group, a sulfonic acid group, an ester group, an amide group and the like and a combination of two or more of them.

Specific examples of the phenolic compound represented by the general formula (4) include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone,
Catechol, t-butylcatechol, 2,6-di-tert-butyl-4-methylphenol, 2,4-dimethyl-6
Examples thereof include, but are not limited to, t-butylphenol, cresol, and 2,2′-methylenebis (4-methyl-6-tert-butylphenol). Among these, hydroquinone, hydroquinone monomethyl ether, catechol, t-butylcatechol, and 2,6-di-tert-butyl-4-methylphenol are preferred from the viewpoint of cost and the like.

The quinone compound is not particularly limited, but specifically, benzoquinone, methylbenzoquinone and the like are preferable.

The phenothiazine compound is not particularly limited, but specific examples include phenothiazine, bis- (α-methylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, bis- (α-dimethylbenzyl) phenothiazine and the like. Among them, phenothiazine is particularly preferred.

The N-oxyl compound is not particularly limited, but specific examples include 1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6, 6-tetramethylpiperidin-4-ol, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl- Acetate, 1-oxyl-2,2,6,6-
Tetramethylpiperidin-4-yl-2-ethylhexaate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-stearate, 1-oxyl-2,2,6,6-tetra Methylpiperidin-4-yl-benzoate, 1-oxyl-2,2,6,6-
Tetramethylpiperidin-4-yl- (4-t-butyl) benzoate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) -succinate, bis (1-oxyl-2, 2,6,6-
Tetramethylpiperidin-4-yl) -adipate, bis (1-
Oxyl-2,2,6,6-tetramethylpiperidin-4-yl) -sebacate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) -butylmalonate, bis ( 1-oxyl-
2,2,6,6-tetramethylpiperidin-4-yl) -phthalate, bis (1-oxyl-2,2,6,6-tetramethylpiperidine
-4-yl) -isophthalate, bis (1-oxyl-2,2,6,6-
(Tetramethylpiperidin-4-yl) -terephthalate, N,
N'-bis (1-oxyl-2,2,6,6-tetramethylpiperidine-
4-yl) -adipamide,-(N- (1-oxyl-2,2,6,6-
Tetramethylpiperidin-4-yl) -caprolactam, N
1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-
Dodecylsuccinimide, 2,4,6-tris- [N-butyl-N- (1
-Oxyl-2,2,6,6-tetramethylpiperidin-4-yl)]-
s-Triazine, 4,4'-ethylenebis (1-oxyl-2,2,
6,6-tetramethylpiperidin-3-one) and tris (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) -phosphite.

When an N-oxyl compound is used,
1,4-dihydroxy-2,2,6,6-tetramethylpiperidine, 1
N-hydroxy-2,2,6,6-tetramethylpiperidine, such as -hydroxy-2,2,6,6-tetramethylpiperidine, 2,2,6,6-
Having 2,2,6,6-tetramethylpiperidine such as tetramethylpiperidine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, ADK STAB LA-82, LA-87 (made by Asahi Denka) in the ester group Significant radical polymerization inhibition effect by using one or more 2,2,6,6-tetramethylpiperidine compounds such as (meth) acrylates, N-nitrosophenylhydroxyamine and its salt compounds in combination with N-oxyl compounds Is expressed.

Other examples of the radical polymerization inhibitor include a copper salt compound and a manganese salt compound.

The copper salt compound is not particularly limited, but may be any of an inorganic salt and an organic salt.
Examples thereof include copper dialkyldithiocarbamate, copper acetate, copper naphthenate, copper acrylate, copper sulfate, and copper chloride.

The manganese salt compound is not particularly limited, and may be manganese dialkyldithiocarbamate, manganese diphenyldithiocarbamate, manganese formate,
Manganese acetate, manganese octenoate, manganese naphthenate, manganese permanganate, manganese salts of ethylenediaminetetraacetic acid and the like can be mentioned.

Even if one kind of radical polymerization inhibitor is used,
More than one type may be used in combination. When two or more kinds are used in combination, a remarkable radical polymerization inhibiting effect may be exhibited. Radical polymerization inhibitors are used for N-vinyl compounds.
It is 10 to 10,000 ppm, preferably 10 to 5,000 ppm, more preferably 10 to 2,000 ppm. If the amount of the radical polymerization inhibitor is small, the stabilizing effect is low, and if it is too large, the curability in the radical-curable resin composition may be adversely affected.
Further, among the above radical polymerization inhibitors, compounds showing basicity may be used.

[(D) Organic Basic Compound] The organic basic compound in the present invention is an organic compound showing basicity in water or an organic solvent, and has an effect of improving the stability of the N-vinyl compound. is there. Specifically, nitrogen-containing compounds, particularly amine compounds, are preferred. As the amine compound,
Although not particularly limited, alkylamines such as methylamine, ethylamine, diethylamine, and triethylamine;
Examples thereof include hydroxyalkylamines such as ethanolamine, diethanolamine, and triethanolamine; cyclic amines such as pyrrolidine, piperazine, morpholine, and aniline; phenylamine; and phenylenediamine derivatives. Among the amine compounds, particularly, the following general formula (2):

[0063]

Embedded image

(Wherein, in the formula (2), R ^{4 to} R ⁷ each independently represent hydrogen or an organic group).

In the general formula (2), examples of the organic group which is an example of R ^{4 to} R ⁷ include, but are not particularly limited to, for example, a saturated or unsaturated aliphatic, cycloaliphatic, or aromatic hydrocarbon group. Hydrogen group, halogen group, hydroxyl group, ether group, sulfide group, nitrile group, aldehyde group, carboxylic acid group,
Sulfonic acid group, ester group, amide group and the like, among them, the hydrocarbon group, carboxylic acid group, ester group, amide group and the like are preferable, especially methyl group, ethyl group, propyl group, butyl group and the like Alkyl groups and phenyl groups are more preferred.

Examples of the phenylenediamine derivative represented by the general formula (2) include N, N'-dimethyl-p-phenylenediamine, N, N'-diethyl-p-phenylenediamine, N N, N'-diisopropyl-p-phenylenediamine, N, N'-diisobutyl-p-phenylenediamine, N, N'-di-n-butyl-p-phenylenediamine, N, N'-di-sec-butyl- p-phenylenediamine, N, N′-diphenyl-p-phenylenediamine,
N, N, N'-trimethyl-p-phenylenediamine, N, N,
N'-triethyl-p-phenylenediamine, N-phenyl-N'-methyl-p-phenylenediamine, N-phenyl-N'-ethyl-p-phenylenediamine, N-phenyl-N'-propyl-p-phenylene Diamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N
-Phenyl-N′-n-butyl-p-phenylenediamine,
N-phenyl-N'-isobutyl-p-phenylenediamine, N-phenyl-N'-sec-butyl-p-phenylenediamine, N-phenyl-N'-tert-butyl-p-phenylenediamine, N-phenyl- N'-n-pentyl-p-phenylenediamine, N-phenyl-N'-n-hexyl-p
-Phenylenediamine, N-phenyl-N '-(1-methylhexyl) -p-phenylenediamine, N-phenyl-
N ′-(1,3-dimethylbutyl) -p-phenylenediamine,
N-phenyl-N '-(1,4-dimethylpentyl) -p-phenylenediamine, N-phenyl-N, N'-dimethyl-p-
Phenylenediamine, N-phenyl-N, N'-diethyl-
p-phenylenediamine, N-phenyl-N, N'-di-n-
Butyl-p-phenylenediamine, N-phenyl-N, N '
-Di-sec-butyl-p-phenylenediamine, N-phenyl-N-methyl-N'-ethyl-p-phenylenediamine, especially N, N'-diisobutyl-p-phenylenediamine, N, N '-Di-sec-butyl-p-phenylenediamine, N-phenyl-N'-(1,3-dimethylbutyl)-
P-phenylenediamine and N-phenyl-N '-(1,4-dimethylpentyl) -p-phenylenediamine are preferred.

The above-mentioned organic basic compounds may be used alone or in combination of two or more. The content of the organic basic compound is 10 to 10,000 ppm with respect to the N-vinyl compound,
Preferably, 10 to 5,000 ppm, more preferably 10 to 2,000 p
pm. When the amount of the organic basic compound is small, the stabilizing effect is low, and when the amount is too large, there is a possibility that coloring or a curability in the radical curable resin composition may be adversely affected. Further, in the radical curable resin composition of the present invention, the above,
The form obtained by compounding (D) an organic basic compound with a resin composition containing a radical curable resin as an essential component is preferable.

The radical-curable resin composition of the present invention may optionally contain one or more reactive diluents other than the N-vinyl compound of the present invention. A reactive diluent is a compound having at least one polymerizable unsaturated bond in the molecule, and a monofunctional compound having one polymerizable unsaturated bond in the molecule and two or more polymerizable unsaturated bonds in the molecule. There are polyfunctional compounds having an unsaturated bond. Specific examples of the monofunctional compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, Propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, Hexyl (meth) acrylate, heptyl (meth)
Acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate,
Decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxy Ethylene glycol mono (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth Acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl ( (Meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7
-Amino-3,7-dimethyloctyl (meth) acrylate, (meth) acryloylmorpholine, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid,
2- (meth) acryloyloxypropyl phthalic acid,
2- (meth) acryloyloxypropyl tetrahydrophthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl succinic acid, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) Acrylate, hexafluoropropyl (meth) acrylate,
(Meth) acrylates such as octafluoropentyl (meth) acrylate and heptadecafluorodecyl (meth) acrylate; unsaturated carboxylic acids such as methyl crotonate, methyl cinnamate, dimethyl itaconate, dibutyl maleate, and dibutyl fumarate Esters, (meth)
Vinyl esters such as acrylonitrile, vinyl acetate and vinyl propionate; vinyl ethers such as isobutyl vinyl ether, cyclohexyl vinyl ether and methoxy polyethylene glycol monovinyl ether; propenyl ethers such as isobutyl propenyl ether; allyl ethers such as allyl glycidyl ether and hydroxybutyl allyl ether , Styrene, vinyltoluene, pt-butylstyrene, α-methylstyrene, p
And styrenes such as -chlorostyrene, p-methylstyrene and p-chloromethylstyrene.

Examples of the polyfunctional compound include ethylene glycol di (meth) acrylate,
Propylene glycol di (meth) acrylate, 1,
4-butanediol di (meth) acrylate, 1,6
-Hexanediol di (meth) acrylate, 1,9
-Nonanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate , Tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acryle Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropanetrioxyethyl (meth) acrylate, trimethylolpropanepolyoxyethyl (meth) acrylate, trimethylolpropanetrioxypropyl (meth) acrylate ) Acrylate, trimethylolpropane polyoxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene oxide-added bisphenol A di ( (Meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, propylene oxide-added bisphenol A di (meth) acryl And polyfunctional (meth) acrylates such as propylene oxide-added bisphenol F di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A diepoxy di (meth) acrylate, and bisphenol F diepoxy di (meth) acrylate. Examples thereof include divinyl ethers such as ethylene glycol divinyl ether, and divinyl benzene. The amount of these monofunctional and polyfunctional compounds is not particularly limited, but is usually 99 to 1% by weight, preferably 80 to 10% by weight, more preferably 50 to 20% by weight in the radical-curable resin composition. Can be used. The method for curing the radical-curable resin composition of the present invention is not particularly limited, and can be cured by irradiating with an active energy ray. Examples of the active energy ray include an ultraviolet ray, an electron beam, an excimer laser,
Radiation such as γ-rays and X-rays, infrared rays, and visible rays may be cured by irradiation with these active energy rays, or may be cured by adding a radical generator such as a curing agent.

When the composition is cured by irradiation with an active energy ray, the radical-curable resin composition of the present invention comprises:
In addition to the radical curable resin, a photopolymerization initiator may be further contained. By including a photopolymerization initiator, the radical-curable resin composition of the present invention becomes a photosensitive resin composition, which is one of the preferred embodiments in the present invention.

As the photopolymerization initiator, various known substances can be used. Specifically, 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, 4-t-butyl-trichloroacetophenone, Diethoxyacetophenone, 2-hydroxy-2-phenyl-1-phenylpropan-1-one, 1- (4-
Dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-isopropylphenyl)-
2-hydroxy-2-methylpropan-1-one, 4-
Acetophenone-based compounds such as (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether,
Benzoin-based compounds such as benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl 4'-methyldiphenyl sulfide, 3,3'-
Dimethyl-4-methoxybenzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 3,3 ', 4,4'-tetra (t-
Nobenzophenone compounds such as butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone, 1- Thioxanthone compounds such as chloro-4-propoxythioxanthone and 2,4-dichlorothioxanthone; α-acyloxime esters, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, dibenzosuberone, 2- Ketone compounds such as ethylanthraquinone and 4 ′, 4 ″ -diethylisophthalophenone;
'-Bis (2-chlorophenyl) -4,4', 5,5
Imidazole compounds such as'-tetraphenyl-1,2'-imidazole; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; and other carbazole compounds can be used. One of these photopolymerization initiators may be used alone, or two or more of them may be appropriately mixed and used. The use amount of the photopolymerization initiator is not particularly limited, but is used in the range of 0.1 to 15% by weight, preferably 1 to 10% by weight based on 100% by weight of the radical curable resin. Is desirable.

When the radical-curable resin composition of the present invention is cured by irradiation with radiation, in addition to the photopolymerization initiator, a curing agent described below (a so-called peroxide-based or azo-based thermal radical-curable initiator) may be used. ) May be used in combination.

In the case of curing by adding a radical generator such as a curing agent, the radical-curable resin composition of the present invention may further contain a conventionally known curing agent in addition to the radical-curable resin. You may leave.

Examples of the curing agent include organic peroxides and azo compounds. Specifically, examples of the organic peroxide include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide; hydroperoxides such as cumene hydroperoxide; diacyl peroxides such as benzoyl peroxide; dicumyl peroxide; Dialkyl peroxides such as -butylgumyl peroxide;
Bis (4-t-alkylperesters such as 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, and t-butylperoxybenzoate; Butylcyclohexyl) percarbonate such as peroxycarbonate; As the azo compound, 2,
2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile and the like can be mentioned. One of these curing agents may be used alone, or two or more of them may be appropriately mixed and used. The amount of the curing agent used may be appropriately set so that the gelation time suitable for the application is obtained,
Although not particularly limited, radical curable resin 1
It is desirable to use within the range of 0.1 to 10% by weight with respect to 00% by weight.

When curing is performed by adding a radical generator such as a curing agent, a conventionally known curing accelerator may be used in combination with the curing agent. The curing accelerator may be any compound having a redox effect, and is not particularly limited. Specifically,
For example, metal soaps such as cobalt octylate and manganese octylate; metal chelate compounds such as cobalt acetylacetonate and vanadium acetylacetonate; amine compounds such as dimethylaniline and dimethyltoluidine; ethyl acetoacetate; acetylacetone; it can. One of these curing accelerators may be used alone, or two or more of them may be appropriately mixed and used.

The amount of the curing accelerator used is appropriately set according to the composition of the radical-curable resin composition, the curing agent to be used, the type of the curing accelerator, and the like so that the gelation time is suitable for the intended use. Although it is not particularly limited, it is preferable to use 0.1 to 10% by weight based on 100% by weight of the radical curable resin.

The curing agent and the curing accelerator may be previously contained in the radical-curable resin composition, or may be mixed immediately before curing. In addition, the curing temperature when curing the radical curable resin composition using these curing agents and curing accelerators varies depending on the type and amount of these curing agents and curing accelerators and other conditions, and is particularly limited. -30 ° C to 15 ° C
It is in the range of 0 ° C, more preferably in the range of -30 ° C to 80 ° C.

The radical-curable resin composition of the present invention may further contain copper dibutyldithiocarbamate, a phosphorus compound, a sulfur compound, etc. for the purpose of improving the stability of the radical-curable resin composition. .

The radical-curable resin composition of the present invention may further comprise a conventionally known additive such as, for example,
Low shrinkage agents, coloring agents, paraffin waxes, organometallic soaps, silane coupling agents, thixotropic agents, thixotropic aids, thickeners, plasticizers, ultraviolet absorbers, antiaging agents, difficult Flame retardants, stabilizers, reinforcing fibers such as glass fibers and carbon fibers, and the like may be contained within a range that does not impair the effects of the present invention.

The radical-curable resin composition of the present invention has excellent curing speed and physical properties of the cured product.
Adhesives, adhesives, dental materials, optical components, information recording materials,
Optical fiber materials, resist materials, sealing materials, printing inks, paints, casting materials, decorative boards, WPCs, coating materials, waterproof materials, lining materials, civil engineering and building materials, putty, repair materials, flooring materials, pavement materials, gel coats, It can be suitably used in various applications such as gel coating for various applications such as overcoating, hand lay-up, spray-up, pultrusion molding, filament winding, molding materials such as SMC and BMC, and sheets.

[0081]

EXAMPLES Examples and comparative examples according to the present invention will be described below, but the present invention is not limited by these examples. In the following examples, “parts” means “parts by weight”.

Example 1 100 parts of N-vinyl-2-oxazolidone were mixed with 20 ppm of N, N'-di-sec-butyl-p-phenylenediamine and hydroquinone monomethyl ether 5
At room temperature, 00 ppm was added and dissolved uniformly to obtain an N-vinyl-2-oxazolidone preparation.

Next, 179 parts of acrylic acid as an unsaturated monobasic acid, and bisphenol A type epoxy compound as a polyfunctional epoxy compound (A) were placed in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and an air blowing tube. 1136 parts of "Epototo YD-901" (trade name, manufactured by Toto Kasei Co., Ltd., average epoxy equivalent: 454.2), 5.8 parts of triethylamine as an esterification catalyst, and 0.27 parts of hydroquinone were charged. Next, the mixture was stirred while blowing air into the flask, and an esterification reaction was performed at 115 ° C. for 5.5 hours to obtain an epoxy acrylate having a solid acid value of 7.4 mgKOH / g.

Next, the synthesized epoxy acrylate 6
The radical-curable resin composition was prepared by mixing 0 parts, 40 parts of the N-vinyl-2-oxazolidone adjustment liquid prepared above, and 1 part of Irgacure184 (manufactured by Ciba-Geigy) as a photoinitiator.

Example 2 N-vinyl in Example 1
N, N'-di-sec-butyl-p-
The addition amount of phenylenediamine is from 20 ppm to 50 pp
m, and the same operation was performed except that hydroquinone monomethyl ether was changed to hydroquinone to prepare a radical curable resin composition.

Example 3 The same operation as in Example 1 was carried out except that N-vinyl-2-oxazolidone used in the oxazolidone preparation solution was changed to N-vinyl-5-methyl-2-oxazolidone. Then, a radical-curable resin composition was prepared.

(Example 4) In the same manner, a radical curable resin composition was prepared in the same manner as in Example 1, except that N-vinylpyrrolidone was used instead of N-vinyl-2-oxazolidone. did.

Example 5 N-vinyl in Example 1
N, N'-di-sec-butyl-p-
The addition amount of phenylenediamine is from 20 ppm to 50 pp
m, and the same operation was performed except that hydroquinone monomethyl ether was changed to phenothiazine to prepare a radical curable resin composition.

Comparative Example 1 N, N'-di-s in Example 1
The addition amount of ec-butyl-p-phenylenediamine is 20 p.
The same operation was performed except that the pm was changed to 5 ppm.
A radical curable resin composition was prepared.

Comparative Example 2 The addition amount of hydroquinone monomethyl ether in Example 1 was changed from 500 ppm to 5 p.
Except having changed to pm, the same operation was performed and the radical curable resin composition was adjusted.

Comparative Example 3 N, N'-di-s in Example 1
The addition amount of ec-butyl-p-phenylenediamine is 20 p.
The same operation was performed except that the pm was changed to 15000 ppm to prepare a radical-curable resin composition.

Comparative Example 4 The addition amount of hydroquinone monomethyl ether in Example 1 was changed from 500 ppm to 15 ppm.
The same operation was performed except that the amount was changed to 000 ppm, to prepare a radical curable resin composition.

<Evaluation of Examples 1 to 4 and Comparative Examples 1 to 4> Each of the radical-curable resin compositions obtained in Examples and Comparative Examples was evaluated as follows. Table 1 shows the results.

[Stability A] 20 g of the radical-curable resin compositions prepared in Examples and Comparative Examples were placed in a 20 ml sample tube, stored at 50 ° C., gelled, and the number of days until the fluidity disappeared was measured. , Stability was evaluated. The longer the number of days until gelation, the better the stability.

[Stability B] 20 g of the radical-curable resin composition prepared in each of Examples and Comparative Examples was added.
After storage for one day, these resins were analyzed by gas chromatography, the amount of N-vinyl compound in the resin was measured, and the residual ratio of the N-vinyl compound before and after storage was evaluated.
[Residual rate (%) = (N-vinyl compound amount after storage / N-vinyl compound amount before storage * 100) (%)] The higher the residual rate, the better the stability.

[Curability] A radical resin curable composition is applied on a zinc phosphate treated steel sheet using a bar coater so as to have a wet thickness of 15 μm, and then an ultraviolet irradiation apparatus equipped with a 80 W / cm high pressure mercury lamp (Distance from light source: 1
0 cm), the line speed was 15 m / min, and the length of one irradiation was 1.4 m. The surface of the coating film was confirmed by finger touch, and the curability was evaluated by the number of ultraviolet light irradiations until the tackiness disappeared. A resin composition having a smaller number of irradiations of ultraviolet light means having better curability.

[0097]

[Table 1]

[0098]

According to the present invention, it is an object of the present invention to provide a radically curable resin composition which can be stored for a long period of time and has excellent curing speed and excellent properties of a cured product.

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Claims (6)

[Claims] 1. A radical-curable resin (A), and (B) a general formula (1) below: (However, in the formula (1), R ^{1 to} R ³ each independently represent a hydrogen or a hydrocarbon group, and X and Y each independently represent a hydrogen or an organic group, or may be directly bonded to each other. A composition comprising an N-vinyl compound represented by the formula (C):
A radical curable resin composition comprising 10 to 10000 ppm of a radical polymerization inhibitor and 10 to 10000 ppm of (D) an organic basic compound. 2. The radical according to claim 1, wherein said radical polymerization inhibitor is at least one member selected from the group consisting of phenol compounds, quinone compounds, phenothiazine compounds and N-oxyl compounds. Curable resin composition. (3) The organic basic compound (D) is represented by the following general formula (2): (Wherein, in the formula (2), R ^{4 to} R ⁷ each independently represent hydrogen or an organic group).
The radical-curable resin composition according to claim 1. (4) The above-mentioned (B) N-vinyl compound is represented by the following general formula (3): (However, in the formula (3), R ^{8 to} R ¹⁰ each independently represent a hydrogen or a hydrocarbon group, and R ^{11 to} R ¹⁴ represent
Each independently represents hydrogen or an organic group. The radical curable resin composition according to any one of claims 1 to 3, characterized in that: 5. The radical curable resin composition according to claim 1, wherein the (B) N-vinyl compound is N-vinylpyrrolidone. 6. The method for curing a radical-curable resin composition according to claim 1, wherein the radical-curable resin composition is cured with an active energy ray.