JP3377455B2 - Resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is capable of room temperature curing, and the cured product has excellent corrosion resistance, chemical resistance, and
The present invention relates to a resin composition that not only exhibits water resistance, heat resistance, mechanical properties, etc., but can be stored for a long period of time while being mixed with a redox active organic cobalt compound.

[0002]

BACKGROUND OF THE INVENTION Ester (meth) acrylate resins, vinyl ester resins, urethane acrylate resins, and other resins are known for their excellent corrosion resistance, chemical resistance, water resistance, heat resistance, and mechanical properties when cured. Has been. When curing these resins at room temperature, for example, a redox active organic cobalt compound is used as a curing accelerator.

[0003]

However, the above resin is
If the redox-active organic cobalt compound is stored as it is in the resin, it will gel and become unusable in a short period of time. That is, the storage stability is poor. Therefore, it is impossible to stably supply the resin containing the redox-active organic cobalt compound, and therefore, the time to mix the redox-active organic cobalt compound into the resin was limited immediately before use. .

Therefore, the problem to be solved by the present invention is that it can be cured at room temperature, and the cured product exhibits the excellent corrosion resistance, chemical resistance, water resistance, heat resistance, mechanical properties, etc. inherent to the resin. It is another object of the present invention to provide a resin composition which can be stored for a long period of time while being blended with a redox active organic cobalt compound.

[0005]

Means for Solving the Problems The present inventor has conducted extensive studies and experiments in order to solve the above problems. As a result, when a resin composition containing a resin and a redox active organic cobalt compound was blended with a hydroquinone having two or more alkyl substituents and an N-oxyl compound as a polymerization inhibitor, room temperature curability and In addition, it is possible to prevent the gelation of the resin and improve the storage stability of the resin composition without impairing the performance such as the excellent corrosion resistance, chemical resistance, water resistance, heat resistance and mechanical properties of the resin. They have found the present invention and completed the present invention.

That is, the resin composition according to the present invention is
(A) comprises a compound (A) having a (meth) acryloyl group at the terminal and / or side chain of a molecular chain and a radically polymerizable compound (B), wherein the compound (A) is solid at 25 ° C. or The compound (B) has a viscosity of 100 poise or higher, the viscosity of 10 poise or lower at 25 ° C., and the mutual weight ratio of the compound (A) to the compound (B) (compound (A) / compound ( B)) is 10/90 to 90
/ 10 resin, (b) redox active organic cobalt compound, (c) hydroquinone having two or more alkyl substituents, and (d) N-oxyl compound.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The essential component constituting the resin composition according to the present invention is a resin (a) containing the compound (A) having a (meth) acryloyl group and the radically polymerizable compound (B). A redox-active organic cobalt compound (b), a hydroquinone having two or more alkyl substituents (c), and an N-oxyl compound (d). Therefore, in the following, these will be sequentially described, and then the composition of the entire composition will be described. [Resin (a)] The resin (a) used in the present invention contains a compound (A) having a (meth) acryloyl group at the terminal and / or side chain of the molecular chain, and a radically polymerizable compound (B). It is a radical-curable resin. The compound (A) is a component that has a solid state or a viscosity of 100 poise or more at 25 ° C. and is a component that builds a three-dimensional network structure in a cured product of the resin composition, and has excellent corrosion resistance in the cured product of the resin composition. , Chemical resistance, water resistance, heat resistance, mechanical properties and the like. Since the compound (A) is in a high-viscosity state or a solid state at room temperature, it is often unsuitable for operations such as coating and molding. Therefore, the compound (B) is used. The compound (B) has a viscosity of 10 poise or less at 25 ° C. and serves as a diluting component for diluting the compound (A) and adjusting it to an optimum working viscosity. In some cases, the compound (A) may join a part of the three-dimensional network structure mainly formed and become a part thereof.

Specific examples of such a resin (a) include:
Although not particularly limited, vinyl ester resin, urethane (meth) acrylate resin, ester (meth) acrylate resin and the like can be mentioned. These resins may be used alone or in combination of two or more. The vinyl ester resin is, for example, a vinyl ester compound which can be obtained by reacting an epoxy compound with (meth) acrylic acid as a compound (A) using an esterification catalyst. ) Is a mixture.

The above-mentioned epoxy compound used as a raw material for the vinyl ester compound is not particularly limited as long as it is a compound having at least one epoxy group in the molecule, and specifically, bisphenol A is used. , Bisphenol F, bisphenol S, tetrabromobisphenol A, and other epibishydric glycidyl ether type epoxy resins obtained by condensation reaction with epihalohydrin; novolak and epihalohydrin, which are condensates of phenol, cresol, and bisphenol with formalin Novolac type glycidyl ether type epoxy resin obtained by the condensation reaction of
Glycidyl ester type epoxy resin obtained by condensation reaction of tetrahydrophthalic acid, hexahydrophthalic acid, benzoic acid and epihalohydrin; Glycidyl ether type epoxy resin obtained by condensation reaction of water-added bisphenol and glycols with epihalohydrin; Hydantoin and cyanur Examples thereof include amine-containing glycidyl ether type epoxy resins obtained by a condensation reaction of an acid and epihalohydrin. In this case, the epoxy compound may be a compound having an epoxy group in the molecule by an addition reaction between an epoxy resin and polybasic acids and / or bisphenols. These epoxy compounds may be used alone or in combination of two or more.

As the (meth) acrylic acid used as a raw material for the vinyl ester compound, only one of acrylic acid and methacrylic acid may be used.
You may mix and use a kind. In addition, unsaturated (meth) acrylic acid and unsaturated monobasic acids other than (meth) actalic acid such as crotonic acid, half-esters such as maleic acid and itaconic acid, and polyvalent compounds such as fumaric acid, itaconic acid and citraconic acid. Carboxylic acids, saturated monovalent carboxylic acids such as acetic acid, propionic acid, lauric acid, and palmitic acid; saturated polyvalent carboxylic acids such as phthalic acid or their anhydrides; saturated or unsaturated alkyds having terminal carboxyl groups. You may use together with such compounds.

Specific examples of the esterification catalyst used in the production of the vinyl ester compound include tertiary amines such as dimethylbenzylamine and tributylamine; trimethylbenzylammonium chloride, tetrabutylammonium chloride and the like. Quaternary ammonium salts; inorganic salts such as lithium chloride and chromium chloride; imidazole compounds such as 2-ethyl-4-methylimidazole;
Tetramethylphosphonium chloride, diethylphenylpropylphosphonium chloride, triethylphenylphosphonium chloride, benzyltriethylphenylphosphonium chloride, dibenzylethylmethylphosphonium chloride, benzylmethyldiphenylphosphonium chloride, tetraphenylphosphine Phosphonium salts such as phonium bromide; secondary amines; tetrabutylurea; triphenylphosphine;
Examples thereof include, but are not limited to, tritolylphosphine and triphenylstibine. These esterification catalysts may be used alone or in combination of two or more.

What is a urethane (meth) acrylate resin?
For example, as a compound (A), it is obtained by reacting a polyisocyanate with a polyhydroxy compound or a polyhydric alcohol, and then further reacting with a hydroxyl group-containing (meth) acrylic compound and optionally a hydroxyl group-containing allyl ether compound. Urethane (meta) that can
This is a mixture of an acrylate compound and the compound (B). In this case, the urethane (meth) acrylate compound may be a compound obtained by reacting a hydroxyl group-containing (meth) acrylic compound with a polyhydroxy compound or a polyhydric alcohol and then further reacting with a polyisocyanate.

The above polyisocyanate used as a raw material for the urethane (meth) acrylate compound is
Specifically, 2,4-tolylene diisocyanate and its isomers, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, hexamethylene diisocyanate, isophorone diisocyanate,
Xylylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate,
Trisine diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, Vernock D-750, Crisbon NX (trade name; manufactured by Dainippon Ink and Chemicals, Inc.), Tess Module L (trade name; manufactured by Sumitomo Bayer Co., Ltd.), Coronate L (trade name) Examples thereof include Nippon Polyurethane Co., Ltd., Takenate D102 (trade name; Takeda Pharmaceutical Co., Ltd.), ISONATE 143L (trade name; Mitsubishi Chemical Co., Ltd.) and the like, but are not particularly limited. Only one of these polyisocyanates may be used, or 2
You may use it in mixture of 2 or more types.

Examples of the polyhydroxy compound used as a raw material for the urethane (meth) acrylate compound include polyester polyols and polyether polyols. Specific examples thereof include glycerin-ethylene oxide adducts and glycerin-propylene oxide adducts. , Glycerin-tetrahydrofuran adduct, glycerin-ethylene oxide-propylene oxide adduct, trimethylolpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide adduct, trimethylolpropane-tetrahydrofuran adduct, trimethylolpropane-ethyleneoxide-propyleneoxide Adduct, pentaerythritol-ethylene oxide adduct, pentaerythritol-propylene oxide adduct, penta Lithritol-tetrahydrofuran adduct, pentaerythritol-ethylene oxide-propylene oxide adduct, dipentaerythritol-ethylene oxide adduct, dipentaerythritol-propylene oxide adduct, dipentaerythritol-tetrahydrofuran adduct, dipentaerythritol-ethylene oxide-propylene oxide adduct. Examples thereof include, but are not particularly limited to. Only one kind of these polyhydroxy compounds may be used, or 2
You may use it in mixture of 2 or more types.

Specific examples of the polyhydric alcohols used as a raw material for the urethane (meth) acrylate compound include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
Polypropylene glycol, 2-methyl-1,3-propanediol, 1,3-butanediol, neopentyl glycol, adduct of bisphenol A with propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin Trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, paraxylene glycol, bicyclohexyl-4,4'-diol,
Examples thereof include 2,6-decalin glycol and 2,7-decalin glycol, but are not particularly limited.
These polyhydric alcohols may be used alone or in combination of two or more.

The hydroxyl group-containing (meth) acrylic compound used as a raw material for the urethane (meth) acrylate compound is not particularly limited, but a hydroxyl group-containing (meth) acrylic acid ester is preferable, and specifically, For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3
-Hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, di (meth) acrylate of tris (hydroxyethyl) isocyanuric acid, pentaerythritol tri (meth) acrylate and the like can be mentioned. These hydroxyl group-containing (meth) acrylic compounds may be used alone or in combination of two or more.

Specific examples of the hydroxyl group-containing allyl ether compound used as a raw material of the urethane (meth) acrylate compound include, for example, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, and triethylene glycol monoallyl ether. Ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol Monoallyl ether, hexylene glycol monoallyl ether, octylene glycol monoallyl ether, trimethylol pro Nji allyl ether, glycerol diallyl ether, although pentaerythritol triallyl ether, and the like, but is not particularly limited.
These hydroxyl group-containing allyl ether compounds may be used alone or in combination of two or more.

The ester (meth) acrylate resin is
For example, a mixture obtained by using, as the compound (A), an ester (meth) acrylate compound which can be obtained by reacting an (meth) acrylic compound with an end of an unsaturated or saturated polyester, and compounding the compound (B) therein Is. Specific examples of the unsaturated or saturated polyester used as a raw material for the ester (meth) acrylate compound include polyesters that can be obtained by subjecting a dibasic acid and a polyhydric alcohol to a condensation reaction. You can use only types,
You may use it in mixture of 2 or more types.

Specific examples of the dibasic acid used as a raw material for unsaturated or saturated polyesters include α, β-unsaturated diacids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid and itaconic anhydride. Basic acid; phthalic acid,
Phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid , Glutaric acid, adipic acid, sebacic acid, 1,12-dodecane diacid, 2,
6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-
Examples thereof include naphthalenedicarboxylic acid anhydride, 4,4′-bisphenyldicarboxylic acid, and saturated dibasic acids such as dialkyl esters thereof, but are not particularly limited. These dibasic acids may be used alone or in combination of two or more.

Specific examples of the polyhydric alcohols used as a raw material for unsaturated or saturated polyesters include ethylene glycol, diethylene glycol,
Triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3-butanediol, an adduct of bisphenol A and propylene oxide or ethylene oxide,
1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, paraxylene glycol, Bicyclohexyl-
4,4'-diol, 2,6-decalin glycol,
Examples thereof include 2,7-decalin glycol, but are not particularly limited. 1 of these polyhydric alcohols
Only one kind may be used, or two or more kinds may be mixed and used. If necessary, a dicyclopentadiene compound may be incorporated in the resin skeleton.

Specific examples of the (meth) acrylic compound used as a raw material for the ester (meth) acrylate compound include unsaturated glycidyl compounds, unsaturated monobasic acids such as (meth) acrylic acid, and glycidyl esters thereof. However, it is not particularly limited. These (meth) acrylic compounds may be used alone or in combination of two or more.

The mixing conditions of the respective raw materials when the compound (A) such as the vinyl ester compound, the urethane (meth) acrylate compound, the ester (meth) acrylate compound and the like are prepared are determined by the physical properties required for the resin (a). It may be set appropriately in consideration of the above, and is not particularly limited. Further, the reaction temperature at the time of carrying out the reaction is not particularly limited, and may be appropriately set in consideration of, for example, that the reaction can be carried out efficiently. As an example, the reaction temperature when the epoxy compound and the unsaturated monobasic acid are reacted with each other using an esterification catalyst to obtain a vinyl ester compound is preferably in the range of 60 to 150 ° C. The reaction time is not particularly limited, and may be appropriately set depending on the type and combination of raw materials, the amount used, the reaction temperature, and the like.

In carrying out the above reaction, a polymerization inhibitor is used if necessary. Examples of the polymerization inhibitor include hydroquinones such as hydroquinone, methylhydroquinone, methoxyhydroquinone, and tert-butylhydroquinone; quinones such as benzoquinone; catechol; copper naphthenate; copper powder; 1-oxyl-2, 2, 6, Examples thereof include N-oxyl compounds such as 6-tetramethylpiperidine, but are not particularly limited. The amount used is also not particularly limited.

The above reaction can be carried out without a solvent, but a solvent may be used. The type and amount of the solvent used are not particularly limited. The vinyl ester compound, urethane (meth) acrylate compound, ester (meth)
The compound (B) to be combined with the compound (A) such as an acrylate compound may be appropriately selected according to the purpose of use or application and is not particularly limited, and examples thereof include styrene, divinylbenzene, chlorostyrene, ( (Meth) acrylic acid ester, diallyl phthalate, vinyl acetate,
Examples include trimethylolpropane triacrylate. These compounds (B) may be used alone or in combination of two or more. Compound (B)
May be used as a solvent when synthesizing the compound (A), or may be a solvent used for viscosity adjustment when the compound (A) has a high viscosity.

The mutual weight ratio of the compound (A) and the compound (B) contained in the resin (a) (compound (A) / compound (B)) is 10/90 to 90/10, preferably 30. / 70 to 75/25. If the amount of the compound (A) is less than the above-mentioned essential range, the viscosity becomes extremely low and it becomes difficult to use it for applications such as paints and molding materials. On the other hand, when the amount is more than the above essential range, the fluidity is lowered, and it becomes difficult to use it for applications such as paints and molding materials.

The (meth) acryloyl group of the compound (A), the number of radically polymerizable groups of the compound (B) and the structure other than the radically polymerizable groups of the compound (B) are not particularly limited, and the resin composition is not limited. It is adjusted as needed according to the physical properties required for each use of the product. [Redox-active organic cobalt compound (b)] Redox-active organic cobalt compound (b) used in the present invention
Is capable of decomposing a curing agent such as peroxide at room temperature to generate radicals, is indispensable for performing room temperature curing, and also has an effect of improving hot water resistance after curing.

Redox-active organic cobalt compound (b)
The specific examples thereof include, but are not limited to, cobalt salts of organic acids, organic cobalt complexes, and the like.
One kind or two or more kinds can be used. Examples of the cobalt salt of the organic acid include cobalt naphthenate and cobalt octenoate. These cobalt salts of organic acids may be used alone or in combination of two or more.

Examples of the above organic cobalt complex include:
Examples include cobalt acetylacetonate. [Hydroquinones having two or more alkyl substituents (c)] Hydroquinones used in the present invention (c)
Is a hydroquinone having two or more alkyl substituents, and has an action of preventing the resin (a) from gelling during the storage of the resin composition and improving the storage stability of the resin composition. The effect of improving the storage stability is synergized by the combined use with the N-oxyl compound (d).

Specific examples of the hydroquinones (c) are not particularly limited, but 2,5-di-tert-butylhydroquinone, 2,3-dimethylhydroquinone, 2,5-di-tert-amylhydroquinone, trimethyl Hydroquinone etc. are mentioned. Only one kind of these hydroquinones (c) may be used, or 2
You may use it in mixture of 2 or more types. [N-oxyl compound (d)] N- used in the present invention
The oxyl compound (d) is, for example, a compound having a structure represented by the following formula (1) in the molecule.

[0030]

[Chemical 1]

(In the formula, R ¹ and R ² represent a substituted or unsubstituted alkyl group having 1 or more carbon atoms. Each of these alkyl groups may be a single alkyl group,
Alternatively, both may be combined to form a ring structure.
Further, when R ¹ and R ² are each a single alkyl group,
They may be the same or different from each other. ) The N-oxyl compound (d) has an action of preventing the resin (a) from gelling during the storage of the resin composition and improving the storage stability of the resin composition. The effect of improving the storage stability is synergized by the combined use with the hydroquinone (c).

Specific examples of the N-oxyl compound (d) are not particularly limited, but 1-oxyl-2,2,2
6,6-tetramethylpiperidine, 1-oxyl-2,
2,6,6-tetramethylpiperidin-4-ol, 4
-Methoxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-acetate, 1-oxyl-2,2,6 , 6-Tetramethylpiperidine-4-
Yl-2-ethylhexanoate, 1-oxyl-2,
2,6,6-Tetramethylpiperidin-4-yl-stearate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-4-tert-butylbenzoate, 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-tetramethylpiperidine-4-
Yl) sebacate ester, bis (1-oxyl-2,
2,6,6-Tetramethylpiperidin-4-yl) n-
Butyl malonate, bis (1-oxyl-2,
2,6,6-Tetramethylpiperidin-4-yl) phthalic acid ester, bis (1-oxyl-2,2,6,6-
Tetramethylpiperidin-4-yl) isophthalic acid ester, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) terephthalic acid ester, bis (1-oxyl-2,2,6,6) 6-Tetramethylpiperidin-4-yl) hexahydroterephthalic acid ester, 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-tetramethylpiperidin-4-yl)]-s-triazine,
1-oxyl-2,2,6,6-tetramethylpiperidin-4-one and the like can be mentioned. These N-oxyl compounds (d) may be used alone or in combination of two or more. [Resin composition] In the resin composition of the present invention, the mixing ratio of the hydroquinones (c) is 0.005 with respect to the resin (a).
~ 0.5 wt% is preferred, 0.01-0.05 wt%
Is more preferable. When the blending ratio of the hydroquinone (c) is less than 0.005% by weight, the storage stability of the resin composition tends to deteriorate. On the other hand, if the mixing ratio of the hydroquinones (c) exceeds 0.5% by weight, the curing time of the resin composition tends to be extremely long, which is not preferable.

In the resin composition of the present invention, the compounding ratio of the N-oxyl compound (d) is 0.005 with respect to the resin (a).
~ 0.5 wt% is preferred, 0.01-0.05 wt%
Is more preferable. When the blending ratio of the N-oxyl compound (d) is less than 0.005% by weight, the storage stability of the resin composition tends to deteriorate. On the other hand, when the blending ratio of the N-oxyl compound (d) exceeds 0.5% by weight, the curing time of the resin composition tends to be extremely long, which is not preferable.

In the resin composition of the present invention, the mixing ratio of the redox active organic cobalt compound (b) is preferably 0.05 to 1.0% by weight, and 0.1 to 0.
5% by weight is more preferred. If the compounding ratio of the redox-active organic cobalt compound (b) is less than 0.05% by weight, room temperature curing may not be possible. On the other hand, if the compounding ratio of the redox-active organic cobalt compound (b) exceeds 1.0% by weight, the curing time becomes extremely high and the pot life tends to be shortened, which is not preferable.

The resin composition of the present invention contains the above four essential components, that is, the resin (a), the redox active organic cobalt compound (b), the hydroquinones (c) and the N-oxyl compound (d). , And, if necessary, may contain other components. Other components are not particularly limited, but include, for example, unsaturated polymers having a functional group other than (meth) acryloyl group such as unsaturated polyester, and polymerization inhibitors (other than the above-mentioned (c) and (d)). ), Fillers, ultraviolet absorbers, pigments, thickeners, antioxidants, plasticizers, flame retardants, stabilizers, reinforcing agents, defoamers,
A thixotropic agent, a leveling agent, etc. can be mentioned. Only one type of these other components may be used, or two or more types may be mixed and used. The blending amount is not particularly limited.

The resin composition of the present invention comprises a resin (a), a redox-active organic cobalt compound (b), a hydroquinone (c) and an N-oxyl compound (d) together with other components used as necessary. It is manufactured by mixing. The resin composition of the present invention can be suitably used for applications such as paints and molding materials.

[0037]

EXAMPLES Hereinafter, examples of the present invention will be described together with comparative examples. Prior to the examples, synthetic examples of a resin (a) containing a redox active organic cobalt compound (b) as a curing accelerator. Will be explained. -Synthesis Example 1- [Synthesis of Vinyl Ester Resin VE Containing Curing Accelerator] A four-necked flask having a capacity of 5 liters equipped with a stirrer, a reflux cooling tube, a gas introduction tube and a thermometer, and a bisphenol A type epoxy having an epoxy equivalent of 465. Resin (Brand name "Epototo YD-901", manufactured by Tohto Kasei Co., Ltd.) 1836 g, bisphenol A type epoxy resin having a epoxy equivalent of 185 (Brand name "Araldite GY-250", manufactured by Ciba Geigy) 4
18 g, 545 g of methacrylic acid, 15 g of tetrabutylammonium chloride as an esterification catalyst and 0.75 g of hydroquinone were charged and stirred. Next, dry air of 120 ml / in the four-necked flask described above.
The vinyl ester compound (compound (A)) was obtained by stirring and reacting the above-mentioned charge at 110 ° C. for 6 hours while flowing at a flow rate of min. Then, by adding 2200 g of styrene monomer (compound (B)), a vinyl ester resin having an acid value of 5.0 mgKOH / g was obtained. The mutual weight ratio (compound (A) / compound (B)) of the compound (A) and the compound (B) contained in this resin was 56/44. The compound (A) was solid at 25 ° C, and the viscosity (25 ° C) of the compound (B) was 1 centipoise or less.

Then, the obtained vinyl ester resin 10
A vinyl ester resin VE containing a curing accelerator was obtained by adding 0.3 parts by weight of cobalt octenoate, which is a redox active organic cobalt compound, as a curing accelerator to 0 part by weight. -Synthesis Example 2- [Curing accelerator-containing urethane (meth) acrylate resin U]
Synthesis of A] A four-necked flask having a capacity of 5 liters equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer was charged with polyisocyanate Polymeric MDI (4,4′-diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate). Of styrene, a styrene monomer (compound (B)) of 1626 g, benzoquinone of 1.0 g, and dibutyltin dilaurate of 6.1 g as a catalyst were charged and stirred. Next, while the dry air was allowed to flow in the above four-necked flask at a flow rate of 120 ml / min, the above charge was heated to 70 ° C., and then a propylene oxide adduct of bisphenol A as polyhydric alcohol was added thereto. 1033 g (commercial name "BPX-11", manufactured by Asahi Denka Co., Ltd.) was added, and the charged material after the addition was reacted for 4 hours while being kept at 90 ° C. After that, the temperature was adjusted again to 70 ° C., and then 491 g of 2-hydroxyethyl methacrylate, which is a hydroxyl group-containing methacrylic compound, was added dropwise to this reaction liquid over 1 hour, and after the addition was completed, the reaction was carried out at 90 ° C. for 4 hours. A urethane (meth) acrylate resin containing a urethane (meth) acrylate compound (compound (A)) and a styrene monomer (compound (B)) was obtained.
The mutual weight ratio (compound (A) / compound (B)) of the compound (A) and the compound (B) contained in this resin was 60/40. Further, the compound (A) is solid at 25 ° C.,
The viscosity (25 ° C.) of the compound (B) was 1 centipoise or less.

Next, to 100 parts by weight of the obtained urethane (meth) acrylate resin, 0.3 part by weight of cobalt octenoate, which is a redox active organic cobalt compound, is added as a curing accelerator to obtain a urethane containing a curing accelerator ( A (meth) acrylate resin UA was obtained. -Synthesis Example 3- [Curing accelerator-containing ester (meth) acrylate resin E]
Synthesis of A] In a four-necked flask having a capacity of 5 liters equipped with a stirrer, a reflux condenser, a gas inlet tube and a thermometer, 1650 g of propylene glycol which is a polyhydric alcohol, 1800 g of isophthalic acid which is a dibasic acid and maleic anhydride. 1720 g was charged and stirred. Next, while flowing nitrogen at a flow rate of 50 ml / min into the above four-necked flask, the above-mentioned charge was reacted under stirring at 200 ° C. for 8 hours to give an unsaturated polyester oligomer having an acid value of 60 mgKOH / g. Obtained. 1040 g of this unsaturated polyester oligomer and styrene monomer (compound (B))
800g and then hydroquinone 0.6
g, 2 g of zinc octenoate, and 158 g of glycidyl methacrylate which is a (meth) acrylic compound,
By allowing dry air to flow in the reaction system at a flow rate of 30 ml / min while stirring at 100 ° C. for 3 hours to cause reaction,
Ester (meth) acrylate compound (compound (A))
An ester (meth) acrylate resin containing styrene and a styrene monomer (compound (B)) was obtained. The mutual weight ratio (compound (A) / compound (B)) of the compound (A) and the compound (B) contained in this resin was 60/40. The compound (A) was solid at 25 ° C, and the viscosity (25 ° C) of the compound (B) was 1 centipoise or less.

Then, to 100 parts by weight of the obtained ester (meth) acrylate resin, 0.3 part by weight of cobalt octenoate, which is a redox active organic cobalt compound, is added as a curing accelerator to obtain a curing accelerator-containing ester ( A (meth) acrylate resin EA was obtained. -Examples 1 to 6 and Comparative Examples 1 to 7- [Preparation of Resin Composition] Hydroquinones (c) and / or N were added to the resin containing the curing accelerator obtained in the above Synthesis Example.
-The resin composition was obtained by adding and mixing the oxyl compound (d) in the compounding amounts shown in Tables 1 and 2. In Comparative Example 7, the resin composition was used as it was without adding any additive to the vinyl ester resin VE containing the curing accelerator obtained in Synthesis Example 1 above. [Evaluation of Storage Stability of Resin Composition] The storage stability of the obtained resin composition was evaluated by determining the storable days of the resin composition by the following method.

A 500 g square can was filled with 500 g of the resin composition and stored in an atmosphere at 60 ° C. After a certain number of days,
The resin composition was taken out. After the removal, all the resin composition in the can was scraped out, and if gel was found in the composition, it was considered that gelation had occurred, and the number of days elapsed in the preceding day was defined as the storable number of days. The results are shown in Tables 1-2.

[0042]

[Table 1]

[0043]

[Table 2]

In Tables 1 and 2, ppm is the ratio (weight basis) of each additive to only the resin (a) obtained by removing the curing accelerator from the curing accelerator-containing resin. The specific name of each additive is as follows. N-oxyl compound (d): 1-oxyl-2,2
6,6-Tetramethylpiperidin-4-ol hydroquinone (c1): 2,5-di-tert-butylhydroquinone hydroquinone (c2): 2,3-dimethylhydroquinone hydroquinone (c3): 2,5-di -Tert-amylhydroquinone hydroquinones (c4): trimethylhydroquinone

[0045]

Since the resin composition of the present invention contains the specific hydroquinone (c) and the N-oxyl compound (d), the redox-active organic cobalt compound is stored during storage of the resin composition. Since the components (c) and (d) prevent the resin (a) from gelling due to (b), the redox-active organic cobalt compound can be stored for a long period of time while being blended with the resin (a). This storage stability improving effect does not impair the room temperature curing property of the resin composition brought about by the redox-active organic cobalt compound (b), and also has the excellent corrosion resistance, chemical resistance, water resistance, and heat resistance of the resin (a). It is possible to obtain properties such as properties and mechanical properties without inhibiting the development of the cured product of the resin composition.

Continuation of front page (56) Reference JP-A-10-175912 (JP, A) JP-A-6-345681 (JP, A) JP-A-10-7918 (JP, A) JP-A-4-146951 (JP , A) JP 58-208315 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 290/00-290/14 C08F 299/00-299/08 C08F 4/40 C08K 5/16

Claims (5)

(57) [Claims] 1. A compound comprising (a) a compound (A) having a (meth) acryloyl group at the terminal and / or side chain of a molecular chain and a radically polymerizable compound (B), wherein the compound (A) is 25 The compound (B) has a solid state or a viscosity of 100 poise or more at 25 ° C., the compound (B) has a viscosity of 10 poise or less at 25 ° C., and the mutual weight ratio of the compound (A) and the compound (B) (compound ( A) / compound (B)) is 10/90 to 90/10, (b) a redox active organic cobalt compound, (c) a hydroquinone having two or more alkyl substituents, and (d) A resin composition containing an N-oxyl compound. 2. The resin (a) is a vinyl ester resin,
The resin composition according to claim 1, which is at least one selected from the group consisting of a urethane (meth) acrylate resin and an ester (meth) acrylate resin. 3. The resin composition according to claim 1 or 2, wherein the blending ratio of the hydroquinones (c) to the resin (a) is 0.005 to 0.5% by weight. 4. The resin composition according to claim 1, wherein the compounding ratio of the N-oxyl compound (d) to the resin (a) is 0.005 to 0.5% by weight. . 5. The compounding ratio of the redox-active organic cobalt compound (b) to the resin (a) is 0.05 to.
The resin composition according to any one of claims 1 to 4, which is 1.0% by weight.