JP2002327031A - Radical curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radical curable resin composition containing 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 characterized by containing, in a composition containing (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 hydrocarbon group; X and Y are each independently a hydrogen, an organic group or 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 alkali metal compound and/or alkaline-earth metal compound of 10-5,000 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. The 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. . In general, radical-curable resins have high viscosity and are difficult to handle, so it is necessary to reduce the viscosity by adding a reactive diluent. 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. For example, acrylate-based reactive diluents are generally highly irritating to the skin, and various derivatives with low irritation have been developed. However, since such derivatives have high viscosity, they must be incorporated in large amounts as reactive diluents. There is a problem that the physical properties of the resin composition are impaired. On the other hand, as a reactive diluent, N-vinylpyrrolidone,
N-vinylcaprolactam, N-vinylformamide, etc.
N-vinyl compounds have been used. These compounds have excellent characteristics such as low viscosity and high curability as compared with conventional reactive diluents. However, when the N-vinyl compound as described above is mixed with a radical-curable resin, it gels for a short time, and thus has a problem in storage stability. In addition, these N-
Vinyl compounds are inferior in stability, particularly hydrolysis resistance, as compared with acrylate-based reaction diluents, and also have a problem of causing a hydrolysis reaction under acidic conditions. JP 20
JP-A-00-319308 discloses that storage stability is improved by blending a specific compound into a composition blended with 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.

[0003]

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

[0004]

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):

[0005]

Embedded image

(However, in the above formula (1), R ^{1 to} R
³ independently represent hydrogen or a hydrocarbon group; X, Y
Each independently represents hydrogen or an organic group or an organic group directly bonded to each other. In the formula (1), the organic groups directly bonded to each other may include a hetero atom. More specifically, the hetero atom is at least one selected from O, S, and N.
More than kind. In the composition containing an N-vinyl compound represented by the formula (C), the radical polymerization inhibitor (C) is 10 to 10000 ppm with respect to the N-vinyl compound, and (
D) An alkali metal compound and / or an alkaline earth metal compound containing 10 to 5000 ppm.

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

The radical-curable resin composition according to the present invention is characterized in that (D) the alkali metal compound and / or the alkaline earth metal compound is a hydroxide and / or hydrogen carbonate of the alkaline earth metal compound. Specifically, it is characterized by being one selected from sodium hydroxide, sodium hydrogen carbonate, potassium hydroxide, calcium hydroxide, and magnesium hydroxide.

The radical-curable resin composition according to the present invention is characterized in that the (B) N-vinyl compound is represented by the following general formula (2).

[0010]

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[0011] (wherein (2), ^R 4 ^{~R 6} represents hydrogen or a hydrocarbon group each independently, also ^R 7 to R
¹⁰ each independently represents hydrogen or an organic group. Further, the radical-curable resin composition according to the present invention,
(B) The N-vinyl compound is N-vinylpyrrolidone.

Further, the radical-curable resin composition according to the present invention is characterized in that it 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.

[0013]

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 a raw material for the unsaturated polyester, the α, β-unsaturated dibasic acid is not particularly limited, but specific examples thereof 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, and the like.
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 used as necessary 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.

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 the (meth) acrylic acid used as a raw material of the polyester (meth) acrylate include, for example, the above-mentioned basic acids, 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 above-mentioned (meth) acryl syrup is a resin containing 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) acrylic polymer containing 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. Syrups can also be used as radical curable resins. 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 are removed. 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, (meth) acrylic polymer, etc. 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).

[0036]

Embedded image

(However, in the above formula (1), R ^{1 to} R
³ independently represent hydrogen or a hydrocarbon group; X, Y
Each independently represents hydrogen or an organic group or an organic group directly bonded to each other. In the formula (1), the organic groups directly bonded to each other may include a hetero atom. More specifically, the hetero atom is at least one selected from O, S, and N.
More than kind. In the general formula (1), examples of the hydrocarbon group that is an example 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-vinyl
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 of the present invention,
The compound represented by (2) is a preferred form.

[0039]

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[0040] (wherein (2), ^R 4 ^{~R 6} represents hydrogen or a hydrocarbon group each independently, also ^R 7 to R
¹⁰ each independently represents hydrogen or an organic group. In the formula (2), examples of the organic group that is an example of R ^{4 to} R ¹⁰ include, but are not particularly limited to, for example, a saturated or unsaturated aliphatic, cycloaliphatic, or aromatic hydrocarbon group. , A halogen group, a hydroxyl group, an ether group, 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. Among these, the hydrocarbon group, the carboxylic acid group, and the ester Group,
Amide groups and the like are preferred, and alkyl groups such as methyl, ethyl, propyl and butyl are more preferred.

As the N-vinyl compound represented by the general formula (2), 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 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 and suppresses radical polymerization, and specifically includes phenolic 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 (3)
There is no particular limitation as long as it has a structure represented by

[0046]

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(However, in the formula (3), R ^{11 to} R ¹⁵ each independently represent hydrogen, a hydroxyl group or an organic group.) In the general formula (3), an organic group which is an example of R ¹¹ to R ¹⁵ Although not particularly limited, for example, a saturated or unsaturated aliphatic, cycloaliphatic, or aromatic hydrocarbon group, a halogen group, a hydroxyl group, an ether group, a sulfide group, a nitrile group, an aldehyde group, a carboxylic acid Groups, sulfonic acid groups, ester groups, amide groups and the like and combinations of two or more of these groups. Specific examples of the phenolic compound represented by the general formula (3) include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, catechol, t-butylcatechol, and 2,6-di-tert-butyl-4-. Methylphenol, 2,4-dimethyl-6-t-butylphenol, cresol, 2,2′-methylenebis (4-methyl-6-te
rt-butylphenol) and the like, but are not limited thereto. 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 and 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-tetramethylpiperidin-4-yl-benzoate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl- (4-t- Butyl) benzoate, bis (1-oxyl-2,2,6,6-tetramethylpiperidine
-4-yl) -succinate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) -adipate, bis (1-oxyl-2,2,6,6-tetramethylpiperidine -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- Tetramethylpiperidin-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-tetramethylpiperidine-4 -Il)]-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 restricted but includes 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.

One of the above radical polymerization inhibitors may be used alone, or two or more thereof may be used in combination. When two or more kinds are used in combination, a remarkable radical polymerization inhibiting effect may be exhibited. The radical polymerization inhibitor is used in an amount of 10 to 10,000 ppm, preferably 10 to 5,000 ppm, more preferably 10 to 2,000 ppm, based on the N-vinyl compound. 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.

Even if one kind of radical polymerization inhibitor is used,
More than one type may be used in combination. The radical polymerization inhibitor is 10 to 10,000 ppm, preferably 10 ppm, based on the N-vinyl compound.
5,000 ppm, more preferably 10-2,000 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.

[(D) Alkali metal compound and / or alkaline earth metal compound] In the present invention, the (D) alkali metal compound and / or alkaline earth metal compound is
It has the effect of improving the stability of the N-vinyl compound. Examples thereof include hydroxides, bicarbonates, carbonates, and phosphates of alkali metal compounds such as lithium, sodium, and potassium, and alkaline earth metal compounds such as beryllium, magnesium, potassium, strontium, and barium. Preferred are hydroxides and / or hydrogen carbonates of the alkaline earth metal compounds, and particularly preferred are sodium hydroxide, sodium hydrogen carbonate, potassium hydroxide, calcium hydroxide, and magnesium hydroxide.

The alkali metal compound and / or the alkaline earth metal compound may be used alone or in combination of two or more. The alkali metal compound and / or the alkaline earth metal compound is added to the N-vinyl compound by 10%.
-10,000 ppm, preferably 10-5,000 ppm, more preferably 10-2,000 ppm. When the amount of the alkali metal compound and / or the alkaline earth metal compound is small, the stabilizing effect is low. When the amount is too large, coloring may be caused or curability in the radical curable resin composition may be adversely affected.

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.

The polyfunctional compound is, for example, 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 amount of the photopolymerization initiator used is not particularly limited, but may be 0.1 to 100% by weight of the radical curable resin.
It is desirable to use within a range of 1 to 15% by weight, preferably 1 to 10% by weight.

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, etc., 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 or the like 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.

[0073]

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) To 100 parts of N-vinyl-2-oxazolidone, 10 ppm of sodium hydroxide and 500 ppm of hydroquinone monomethyl ether were added at room temperature and uniformly dissolved, and an N-vinyl-2-oxazolidone adjusted solution was added. Obtained. Then, in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and an air blowing tube, 179 parts of acrylic acid as an unsaturated monobasic acid and bisphenol A type epoxy compound as a polyfunctional epoxy compound (Toto Kasei ( Co., Ltd., trade name "Epototo YD-901", 1136 parts of average epoxy equivalent 454.2), 5.8 parts of triethylamine as an esterification catalyst, and 0.27 parts of hydroquinone. 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, 60 parts of the synthesized epoxy acrylate, 40 parts of the N-vinyl-2-oxazolidone preparation solution prepared above, and Irgacure 184 as a photoinitiator.
One part (Ciba-Geigy) was mixed to prepare a radical-curable resin composition.

Example 2 N-vinyl in Example 1
A radical curable resin composition was prepared in the same manner as above except that the amount of sodium hydroxide added to the 2-oxazolidone preparation liquid was changed from 10 ppm to 20 ppm, and hydroquinone monomethyl ether was changed to hydroquinone.

(Example 3) N-vinyl-2 in Example 1
The same operation was performed, except that N-vinyl-5-methyl-2-oxazolidone was added instead of -oxazolidone, to obtain an N-vinyl compound adjusting solution, and a radical curable resin composition was prepared.

(Example 4) N-vinyl-2 in Example 1
A radical curable resin composition was prepared in the same manner as above except that N-vinylpyrrolidone was added instead of -oxazolidone.

Example 5 N-vinyl in Example 1
A radical-curable resin composition was prepared in the same manner as above except that the amount of sodium hydroxide added to the 2-oxazolidone preparation liquid was changed from 10 ppm to 20 ppm, and that hydroquinone monomethyl ether was changed to phenothiazine.

Comparative Example 1 A radical-curable resin composition was prepared in the same manner as in Example 1, except that the amount of sodium hydroxide was changed from 10 ppm to 2 ppm.

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 A radical curable resin composition was prepared in the same manner as in Example 1, except that the amount of sodium hydroxide was changed from 10 ppm to 10,000 ppm. However, the insoluble sodium hydroxide became a precipitate and the system was non-uniform.

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> The radical curable resin compositions obtained in Examples and Comparative Examples were 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 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 high-pressure mercury lamp of 80 W / cm. (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.

[0087]

[Table 1]

[0088]

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.

Continued on the front page F term (reference) 4J011 NA13 NA14 NA17 NA18 NA20 NA23 NA24 NA26 NA27 NA34 NA35 NA36 NB01 QA01 QA33 QA34 QA36 QA38 QA39 QA40 QB02 QB03 QB12 QB19 QB20 QB22 QB24 SA03 SA05 SA06 SA07 SA22 SA34 SA64 SA76 SA78 SA79 SA84 TA01 4J027 AA01 AB02 AB10 AE02 AE03 AE04 AG04 AG09 AG13 AG14 AG15 AG23 AG24 BA13 BA15 CB04 CB09 CB10 CC03

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 an organic group directly bonded to each other. In the composition containing an N-vinyl compound represented by the formula (1), the organic groups directly bonded to each other may contain a hetero atom. (C) 10 to 10000 ppm of a radical polymerization inhibitor and (D) 10% of an alkali metal compound and / or an alkaline earth metal compound with respect to the compound.
A radical-curable resin composition characterized by containing -5000 ppm. 2. The method according to claim 1, wherein (C) the radical polymerization inhibitor is at least one selected from phenolic compounds, quinone compounds, phenothiazine compounds and N-oxyl compounds.
The radical curable resin composition according to claim 1, wherein the composition is at least one kind. 3. The method according to claim 1, wherein (D) the alkali metal compound and / or the alkaline earth metal compound is a hydroxide and / or hydrogen carbonate of an alkaline earth metal compound. The radical curable resin composition according to the above. 4. The radical curable resin composition according to claim 1, wherein the (B) N-vinyl compound is represented by the following general formula (2). Embedded image (However, in the formula (2), R ^{4 to} R ⁶ each independently represent hydrogen or a hydrocarbon group, and R ^{7 to} R ¹⁰ each independently represent hydrogen or an organic group.) 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.