TWI889055B - Resin compositions, composite materials and hardened products thereof - Google Patents

Abstract

The resin composition of the present invention is a resin composition comprising an ethylenically unsaturated group-containing compound (A), an organic metal compound (B) and an alkyl group-containing compound (C), wherein the ethylenically unsaturated group-containing compound (A) contains a (meth)acryloyl group-containing compound (A1), wherein the content of the (meth)acryloyl group-containing compound (A1) is 40 parts by mass or more relative to 100 parts by mass of the ethylenically unsaturated group-containing compound (A), and the organic metal compound (B) contains at least one selected from the group consisting of metals belonging to Group 7, metals belonging to Group 8, metals belonging to Group 9 and metals belonging to Group 10, and does not contain an organic peroxide.

Description

Resin compositions, composite materials and hardened products thereof

The present invention relates to resin compositions, composite materials and hardened products thereof.

The cured resin composition containing a compound containing an ethylenically unsaturated group is a material with excellent mechanical strength and water resistance. Moreover, since the curing time of the resin composition containing a compound containing an ethylenically unsaturated group is set by adjusting the curing agent or accelerator without being affected by the temperature, it does not take a long time to cure like epoxy resin, and there is no curing failure especially when curing at low temperature. Therefore, the resin composition containing a compound containing an ethylenically unsaturated group has been widely used in coatings, adhesives, fiber reinforced plastic (hereinafter sometimes referred to as FRP) materials, concrete structure repair materials, and sheet molding compound (SMC) materials. For example, Patent Document 1 discloses a resin composition for repairing concrete structures, which contains: a free radical polymerizable composition (A), an organic metal salt (B), an organic compound having a nitrogen heterocyclic structure (C), and an organic peroxide (D). [Prior Art Document] [Patent Document]

Patent document 1: Japanese Patent Application Publication No. 2020-111947

[Problems to be solved by the invention]

Organic peroxides have been used as curing agents for curing resin compositions containing compounds containing ethylenically unsaturated groups, such as free radical polymerizable compositions. However, organic peroxides may become inactivated if they are not stored properly, causing the resin composition to be poorly cured, or organic peroxides may ignite due to contact with organic metal compounds used in curing accelerators, which is a problem that requires care in storage and handling.

The present invention was made in view of the above-mentioned prior art, and its purpose is to provide a resin composition that is hardened without using an organic peroxide, a composite material containing the above-mentioned resin composition, and the hardened product thereof. [Means for solving the problem]

That is, the present invention is as shown in the following [1] to [14]. [1] A resin composition comprising: a compound (A) containing an ethylenically unsaturated group, an organic metal compound (B) and a compound (C) containing an ethylenically unsaturated group, wherein the compound (A) containing an ethylenically unsaturated group contains a compound (A1) containing a (meth)acryloyl group, and the content of the compound (A1) containing a (meth)acryloyl group is 40 parts by mass or more relative to 100 parts by mass of the compound (A) containing an ethylenically unsaturated group, and the organic metal compound (B) contains at least one selected from a metal belonging to Group 7, a metal belonging to Group 8, a metal belonging to Group 9 and a metal belonging to Group 10, and does not contain an organic peroxide. [2] The resin composition of [1] above, wherein the metal conversion content of the above-mentioned organic metal compound (B) is 100 to 2,500 mass ppm relative to the total of the compound containing an ethylenically unsaturated group (A) and the organic metal compound (B). [3] The resin composition of [1] or [2] above, wherein the above-mentioned organic metal compound (B) contains at least one selected from manganese, iron, cobalt and nickel. [4] The resin composition of [1] or [2] above, wherein the above-mentioned organic metal compound (B) is at least one selected from manganese octylate, iron cycloalkanoate, cobalt octylate and nickel octylate. [5] The resin composition of any one of [1] to [4] above, wherein the content of the ethylenically unsaturated group-containing compound (C) is 0.01 to 15 parts by mass relative to 100 parts by mass of the ethylenically unsaturated group-containing compound (A). [6] The resin composition of any one of [1] to [5] above, wherein the (meth)acryl-containing compound (A1) is at least one selected from a (meth)acryl-containing urethane resin (A1a), a vinyl ester resin (A1b), a (meth)acryl-containing polyester resin (A1c), and a (meth)acrylate monomer (A1d). [7] The resin composition of any one of [1] to [6] above, further comprising a curing rate modifier (D). [8] The resin composition of [7], wherein the content of the curing rate modifier (D) is 0.01 to 5.0 parts by weight relative to 100 parts by weight of the compound (A) containing an ethylenically unsaturated group. [9] The resin composition of [7] or [8], wherein the curing rate modifier (D) is a curing accelerator (D1) having no hydroxyl group but having a carboxyl group. [10] The resin composition of [9], wherein the curing accelerator (D1) is an aliphatic carboxylic acid having 2 to 10 carbon atoms. [11] The resin composition of [7] or [8], wherein the curing rate modifier (D) is a curing retarder (D2) having a hydroxyl group. [12] A resin composition as described in [11] above, wherein the curing retarder (D2) is a hydroxyl-containing compound having 2 to 10 carbon atoms. [13] A composite material comprising a resin composition as described in any one of [1] to [12] above and at least one selected from a fiber substrate and a filler. [14] A cured product, which is a cured product of a resin composition as described in any one of [1] to [12] above or a cured product of a composite material as described in [13]. [Effect of the invention]

According to the present invention, a resin composition that is hardened without using peroxide, a composite material containing the resin composition, and a hardened product thereof can be provided.

First, the definitions and meanings of the terms and expressions in this specification are as follows. "(Meth) acrylic acid" is a general term for acrylic acid and methacrylic acid. Similarly, "(Meth) acrylate" is a general term for acrylate and methacrylate, and "(Meth) acryl" is a general term for acryl and methacrylic. "Weight average molecular weight Mw" (hereinafter also referred to as "Mw") and "number average molecular weight Mn" (hereinafter also referred to as "Mn") are standard polystyrene-converted molecular weights obtained by gel permeation chromatography (GPC). Specifically, they are measured by the method described in the examples described below. The "acid value" of the vinyl ester resin is measured in accordance with JIS K6901:2008 using a mixed solution of bromothymol blue and phenol red as an indicator, and is the number of mg of potassium hydroxide required to neutralize 1g of the vinyl ester resin. Specifically, it is measured by the method described in the examples described below.

[Resin composition] The resin composition of the present embodiment is a resin composition containing an ethylenically unsaturated group-containing compound (A), an organic metal compound (B) and an alkyl group-containing compound (C), wherein the aforementioned ethylenically unsaturated group-containing compound (A) contains a (meth)acryloyl group-containing compound (A1), the content of the aforementioned (meth)acryloyl group-containing compound (A1) is 40 parts by mass or more relative to 100 parts by mass of the aforementioned ethylenically unsaturated group-containing compound (A), and the aforementioned organic metal compound (B) contains at least one selected from metals belonging to Group 7 elements, metals belonging to Group 8 elements, metals belonging to Group 9 elements and metals belonging to Group 10 elements. Furthermore, the resin composition of the present embodiment does not contain an organic peroxide. Due to this structure, the resin composition can still be hardened even without the use of organic peroxides.

The resin composition of the present embodiment contains an ethylenically unsaturated group-containing compound (A), an organic metal compound (B) and a hydroxyl group-containing compound (C), and may contain other components described below. However, from the viewpoint of obtaining the effect of the present invention well, the total content of the ethylenically unsaturated group-containing compound (A), the organic metal compound (B) and the hydroxyl group-containing compound (C) in the resin composition is preferably 50-100% by mass, more preferably 60-100% by mass, and even more preferably 70-100% by mass.

<Compound containing ethylenically unsaturated groups (A)> The compound containing ethylenically unsaturated groups (A) of this embodiment contains a compound containing (meth)acryloyl groups (A1). The compound containing (meth)acryloyl groups (A1) may be a single type or two or more types may be used in combination. In addition, the compound containing ethylenically unsaturated groups (A) may also contain the monomer containing ethylenically unsaturated groups (A2) described later, as needed.

The content of the ethylenically unsaturated group-containing compound (A) in the resin composition is preferably 50 to 99.94 mass %, more preferably 60 to 99.84 mass %, and even more preferably 70 to 99.60 mass %.

[(Meth)acryloyl-containing compound (A1)] The (meth)acryloyl-containing compound (A1) is not particularly limited as long as it has a (meth)acryloyl group in the molecule, but from the viewpoint of exhibiting good curability, it is preferably at least one selected from the urethane resin (A1a), vinyl ester resin (A1b), polyester resin (A1c) and (meth)acrylate monomer (A1d) described below. The (meth)acryloyl-containing compound (A1) may be a single type or two or more types may be used in combination.

The content of the (meth)acryloyl group-containing compound (A1) in the resin composition is 40 mass % or more, preferably 42 to 100 mass %, more preferably 45 to 100 mass %, and even more preferably 50 to 100 mass % based on 100 mass parts of the ethylenically unsaturated group-containing compound (A) in order to exhibit good curability.

The content of the (meth)acryloyl group-containing compound (A1) in the resin composition is preferably 35 to 99 mass %, more preferably 39 to 99 mass %, and even more preferably 49 to 99 mass % from the viewpoint of exhibiting good curability.

(Urethane resin containing (meth)acryloyl group (A1a)) The urethane resin containing (meth)acryloyl group (A1a) (hereinafter referred to as urethane resin (A1a)) in this embodiment is a reaction product of polyol (1a-1), a compound containing isocyanate group (1a-2) and a compound containing hydroxyl group and (meth)acryloyl group (1a-3). The urethane resin (A1a) may be used alone or in combination of two or more.

From the viewpoint of the softness of the cured product, the weight average molecular weight Mw of the urethane resin (A1a) is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more. From the viewpoint of reducing the viscosity of the resin composition and improving the workability during the manufacture of the composite material, it is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less. That is, the weight average molecular weight Mw of the urethane resin (A1a) is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, and even more preferably 5,000 to 30,000.

From the viewpoint of the softness of the cured product, the number average molecular weight Mn of the urethane resin (A1a) is preferably 500 or more, more preferably 1,000 or more, and even more preferably 1,500 or more. From the viewpoint of lowering the viscosity of the resin composition and improving the workability during the manufacture of the composite material, it is preferably 10,000 or less, more preferably 7,000 or less, and even more preferably 5,000 or less. That is, the number average molecular weight Mn of the urethane resin (A1a) is preferably 500-10,000, more preferably 1,000-7,000, and even more preferably 1,500-5,000.

From the viewpoint of balancing the tensile strength and elongation of the cured product, the content of the structural units derived from the polyol (1a-1) in the urethane resin (A1a) is preferably 5 to 50 mol %, more preferably 15 to 40 mol %, and even more preferably 18 to 35 mol %.

From the viewpoint of balancing the tensile strength and elongation of the cured product, the content of the structural unit derived from the isocyanate group-containing compound (1a-2) in the urethane resin (A1a) is preferably 10 to 80 mol %, more preferably 20 to 60 mol %, and even more preferably 30 to 50 mol %.

From the viewpoint of balancing the tensile strength and elongation of the cured product, the content of the structural unit derived from the compound (1a-3) containing a hydroxyl group and a (meth)acryloyl group in the urethane resin (A1a) is preferably 10 to 80 mol %, more preferably 20 to 60 mol %, and even more preferably 30 to 50 mol %.

≪Polyol (1a-1)≫ Polyol (1a-1) is a compound having at least two hydroxyl groups in one molecule. It can be used as a monomer, oligomer, or polymer. Its molecular weight and molecular structure are not particularly limited. Polyol (1a-1) may be used alone or in combination of two or more. Examples of the polyol (1a-1) include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, Diols such as polypropylene glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, p-xylene glycol, dicyclohexyl-4,4'-diol, 2,6-decahydronaphthalene glycol, 2,7-decahydronaphthalene glycol; diols such as adducts of dihydric phenols represented by hydrogenated bisphenol A, cyclohexanedimethanol, bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, etc. and oxirane represented by propylene oxide or ethylene oxide; trihydric or higher alcohols such as 1,2,3,4-tetrahydroxybutane, glycerol, trihydroxymethylpropane, pentaerythritol, etc. Among them, diols are preferred from the viewpoints of reactivity, cost and low elastic modulus of the cured product. Polyether polyols and polyester polyols are more preferred from the viewpoint of ease of reaction. Polyether polyols are more preferred from the viewpoint of availability and softness of the cured product. At least one selected from polyethylene glycol and polypropylene glycol is more preferred.

≪Isocyanate group-containing compound (1a-2)≫ The isocyanate group-containing compound (1a-2) is not particularly limited as long as it has an isocyanate group in one molecule. The isocyanate group-containing compound (1a-2) may be used alone or in combination of two or more. Examples of the isocyanate group-containing compound (1a-2) include 2,4-toluene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, hydrogenated xylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, xylene diisocyanate, cyclohexane-1,4-diisocyanate, cyclohexane-1,4-diylbis(methylene)diisocyanate, 4,4'-dicyclohexylmethane diisocyanate (H12MDI), 1,3-bis(isocyanatemethyl)hexane, TDI hydrogenate, and the like. Furthermore, the above-mentioned isocyanates modified with carbodiimide or isocyanurate can also be used. Among them, based on the viewpoints of versatility and ease of handling, at least one of isophorone diisocyanate and diphenylmethane diisocyanate is preferably selected, and based on the viewpoint of availability, diphenylmethane diisocyanate is more preferably selected.

≪Hydroxyl- and (meth)acryloyl-containing compounds (1a-3)≫ Hydroxyl- and (meth)acryloyl-containing compounds (1a-3) are compounds having at least one hydroxyl group and one acryl group in one molecule. The hydroxyl- and (meth)acryloyl-containing compounds (1a-3) may be used alone or in combination of two or more. Examples of the compound (1a-3) containing a hydroxyl group and a (meth)acryloyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, glycerol di(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, acrylic acid-modified products of diglycidyl hexahydrophthalate, acrylic acid-modified products of ethylene glycol diglycidyl ether, methacrylic acid-modified products of polyethylene glycol diglycidyl ether, methacrylic acid-modified products of diethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether diacrylate, etc. Among them, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are preferred from the viewpoints of good reactivity with isocyanate and reactivity during the production of cured products. 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate are more preferred from the viewpoints of versatility, availability and cost. 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate are even more preferred from the viewpoints of chemical resistance and imparting a certain elastic modulus to the cured product. 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate are even more preferred.

(Vinyl ester resin (A1b)) The vinyl ester resin (A1b) of this embodiment is an addition reaction product of raw materials containing an epoxy resin (1b-1) and an unsaturated monobasic acid (1b-2). In addition, for the purpose of increasing molecular weight and improving toughness, the vinyl ester resin (A1b) of this embodiment may also contain a compound obtained by addition reaction of the epoxy resin (1b-1) with a bisphenol compound, an unsaturated polybasic acid, and a saturated polybasic acid, and a product of addition reaction of an unsaturated monobasic acid (1b-2). The vinyl ester resin (A1b) may be a single type or two or more types may be used in combination.

The weight average molecular weight Mw of the vinyl ester resin (A1b) is preferably 400 or more, more preferably 500 or more, and even more preferably 600 or more from the viewpoint of toughness of the cured product, and is preferably 6,000 or less, more preferably 5,000 or less, and even more preferably 4,500 or less from the viewpoint of viscosity, workability, and compatibility with other components of the resin. That is, the weight average molecular weight Mw of the vinyl ester resin (A1b) is preferably 400 to 6,000, more preferably 500 to 5,000, and even more preferably 600 to 4,500.

The number average molecular weight Mn of the vinyl ester resin (A1b) is preferably 300 or more, more preferably 400 or more, and even more preferably 500 or more, from the viewpoint of the physical toughness of the cured product, and is preferably 3,000 or less, more preferably 2,500 or less, and even more preferably 2,000 or less, from the viewpoint of the viscosity, workability, and compatibility with other components of the resin. That is, the number average molecular weight Mn of the vinyl ester resin (A1b) is preferably 300 to 3,000, more preferably 400 to 2,500, and even more preferably 500 to 2,000.

The acid value of the vinyl ester resin (A1b) is preferably 0 KOHmg/g or more, more preferably 0.1 KOHmg/g or more, and more preferably 1.0 KOHmg/g or more, from the viewpoint of the storage stability of the resin composition, and is preferably 25 KOHmg/g or less, more preferably 20 KOHmg/g or less, and more preferably 16 KOHmg/g or less, from the viewpoint of the reactivity during curing of the resin composition and the color stability of the cured product. That is, the acid value of the vinyl ester resin (A1b) is preferably 0-25 KOHmg/g, more preferably 0.1-20 KOHmg/g, and more preferably 1.0-16 KOHmg/g.

In the vinyl ester resin (A1b), the amount of the unsaturated monoacid (1b-2) is preferably 50 mol or more, more preferably 60 mol or more, and even more preferably 70 mol or more, based on the viewpoint of exhibiting good curability, relative to 100 mol of the total amount of epoxy groups in the epoxy compound (1b-1). From the viewpoint of production stability, it is preferably 120 mol or less, more preferably 110 mol or less, and even more preferably 105 mol or less. That is, the amount of the unsaturated monoacid (1b-2) in the vinyl ester resin (A1b) is preferably 50 to 120 mol, more preferably 60 to 110 mol, and even more preferably 70 to 105 mol, relative to 100 mol of the total amount of epoxy groups in the epoxy compound (1b-1).

≪Epoxy compound (1b-1)≫ Epoxy compound (2b-1) is a compound having two epoxy groups in one molecule, and can be used as a monomer, oligomer, or polymer, and its molecular weight and molecular structure are not particularly limited. Epoxy compound (2b-1) may be a single species or two or more species may be used in combination. Examples of the aforementioned epoxy compound (2b-1) include bisphenol-type epoxy resins such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, and bisphenol AF-type epoxy resin; tert-butylcatechol-type epoxy resin, naphthalene-type epoxy resin, naphthol-type epoxy resin, anthracene-type epoxy resin; Epoxy resins, glycidyl ester epoxy resins, biphenyl epoxy resins, linear aliphatic epoxy resins, epoxy resins with butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, epoxy resins containing spiro rings, cyclohexanedimethanol epoxy resins, naphthyl ether epoxy resins, novolac phenol epoxy resins, etc. Among them, based on the viewpoint of mechanical strength and corrosion resistance of the cured product, at least one selected from bisphenol epoxy resins and novolac phenol type epoxy resins is preferred, at least one selected from bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins and novolac phenol type epoxy resins is more preferred, and at least one selected from bisphenol A type epoxy resins and novolac phenol type epoxy resins is even more preferred.

The epoxy equivalent of the epoxy compound (2b-1) is preferably 170 to 1,000, more preferably 170 to 500, and even more preferably 170 to 400 from the viewpoint of workability during curing of the resin composition, and even more preferably 170 to 300 from the viewpoint of workability during synthesis of the vinyl ester resin (A1b).

≪Unsaturated monoacid (1b-2)≫ The unsaturated monoacid (1b-2) is preferably a monocarboxylic acid having an ethylenically unsaturated group, and is preferably a compound having an acryloyl group from the viewpoint of introducing a (meth)acryloyl group into the vinyl ester resin (A1b). The unsaturated monoacid (1b-2) may be a single type or two or more types may be used in combination. Examples of the unsaturated monoacid include (meth)acrylic acid, crotonic acid, cinnamic acid, and the like. Among them, based on the versatility, reactivity during synthesis of the vinyl ester resin (A1b), and the viewpoint of obtaining a resin composition with good curability, at least one selected from (meth)acrylic acid and crotonic acid is preferred, and based on the viewpoint of ease of handling and chemical resistance, acrylic acid and methacrylic acid are more preferred.

(Polyester resin (A1c) containing (meth)acryl groups) The polyester resin (A1c) containing (meth)acryl groups of this embodiment (hereinafter referred to as polyester resin (A1c)) is a reaction product of polyol (1c-1), dibasic acid (1c-2) and glycidyl (meth)acrylate (1c-3). The polyester resin (A1c) may be used alone or in combination of two or more.

The weight average molecular weight Mw of the polyester resin (A1c) is preferably 1,000 or more, more preferably 1,500 or more, and even more preferably 2,000 or more from the viewpoint of toughness of the cured product, and is preferably 10,000 or less, more preferably 6,000 or less, and even more preferably 4,000 or less from the viewpoint of lowering the viscosity of the resin composition and improving workability during composite material production. That is, the weight average molecular weight Mw of the polyester resin (A1c) is preferably 1,000 to 10,000, more preferably 1,500 to 6,000, and even more preferably 2,000 to 4,000.

The number average molecular weight Mn of the polyester resin (A1c) is preferably 500 or more, more preferably 800 or more, and more preferably 1,000 or more from the viewpoint of toughness of the cured product, and is preferably 5,000 or less, more preferably 3,000 or less, and more preferably 2,000 or less from the viewpoint of lowering the viscosity of the resin composition and improving workability during composite material production. That is, the number average molecular weight Mn of the polyester resin (A1c) is preferably 1,000-10,000, more preferably 1,500-6,000, and more preferably 2,000-4,000.

The acid value of the polyester resin (A1c) is preferably 0KOHmg/g or more, more preferably 1KOHmg/g or more, and more preferably 2KOHmg/g or more, based on the viewpoint of the storage stability of the resin composition, and is preferably 25KOHmg/g or less, more preferably 20KOHmg/g or less, and more preferably 15KOHmg/g or less, based on the viewpoint of the reactivity during curing of the resin composition and the color stability of the cured product. That is, the acid value of the polyester resin (A1c) is preferably 0-25KOHmg/g, more preferably 1-20KOHmg/g, and more preferably 2-15KOHmg/g.

In the polyester resin (A1c), from the viewpoint of the reactivity of the cured product, the structural unit derived from the polyol (1c-1) is preferably 10 to 70 mol %, more preferably 20 to 60 mol %, and even more preferably 30 to 50 mol % based on 100 mol % of the total of the polyol (1c-1) and the dibasic acid (1c-2).

In the polyester resin (A1c), based on the physical properties of the cured product, the structural unit derived from the dibasic acid (1c-2) is preferably 30 to 90 mol %, more preferably 40 to 80 mol %, and even more preferably 50 to 70 mol % based on 100 mol % of the total of the polyol (1c-1) and the dibasic acid (1c-2).

In the polyester resin (A1c), the amount of glycidyl (meth)acrylate (1c-3) is preferably 10 to 60 parts by mass, more preferably 20 to 55 parts by mass, and even more preferably 25 to 50 parts by mass based on the reactivity during curing of the resin composition, relative to 100 parts by mass of the total of the polyol (1c-1) and the dibasic acid (1c-2).

≪Polyol (1c-1)≫ Polyol (1c-1) is a compound having at least two hydroxyl groups in one molecule, and can be used as a monomer, oligomer, or polymer, and its molecular weight and molecular structure are not particularly limited. Polyol (1c-1) may be a single type, or two or more types may be used in combination. Examples of polyol (1c-1) include, for example, the same polyol (1c-1) as in the above-mentioned urethane resin (A1a). Among them, from the viewpoint of the flexibility of the cured product and the cost, at least one selected from ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol is preferred, ethylene glycol and diethylene glycol are more preferred, and dipropylene glycol is even more preferred.

≪Dibasic acid (1c-2)≫ Dibasic acid (1c-2) is a compound having two carboxyl groups in one molecule. Dibasic acid (1c-2) may be used alone or in combination of two or more. Examples of the dibasic acid (1c-2) include isophthalic acid, terephthalic acid, phthalic anhydride, maleic anhydride, maleic acid, fumaric acid, itaconic acid, succinic acid, adipic acid, sebacic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, hexahydrophthalic acid (1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid), phthalic acid, naphthalene dicarboxylic acid, trimellitic acid, pyromellitic acid, chlorendic acid, Acid (Het acid), tetrabromophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, succinic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, etc. Among them, based on the durability, flexibility and cost of the cured product, isophthalic acid, terephthalic acid, phthalic anhydride, maleic anhydride and fumaric acid are preferred, and isophthalic acid, terephthalic acid, phthalic anhydride and maleic anhydride are more preferred. Based on the ease of reaction, versatility and cost when synthesizing polyester resin (A1c), phthalic anhydride is more preferred.

≪(Meth) Glycidyl Acrylate (1c-3)≫ (Meth) Glycidyl Acrylate (1c-3) is a compound having at least one epoxy group and at least one (meth)acryloyl group in one molecule. By adding the carboxyl group of the polyester resin to the epoxy group of (meth) glycidyl acrylate (1c-3), the (meth)acryloyl group can be introduced into the polyester resin. (Meth) Glycidyl Acrylate (1c-3) may be used alone or in combination of two or more. Examples of the glycidyl (meth)acrylate (1c-3) include glycidyl (meth)acrylate, α-ethyl glycidyl (meth)acrylate, α-n-propyl glycidyl (meth)acrylate, α-n-butyl glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 4,5-epoxypentyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, α-ethyl (meth)acrylate-6,7-epoxyheptyl, (meth)acrylate-3-methyl-3,4-epoxybutyl, (meth)acrylate-4-methyl-4,5-epoxypentyl, (meth)acrylate-5-methyl-5,6-epoxyhexyl, (meth)acrylate-β-methylglycidyl (meth)acrylate, α-ethyl (meth)acrylate-β-methylglycidyl, etc. Among them, based on the workability, versatility and cost when synthesizing the polyester resin (A1c), glycidyl (meth)acrylate is preferred, and based on the chemical resistance, glycidyl methacrylate is more preferred.

(Monomer (A1d) containing a (meth)acryloyl group) The (meth)acrylate monomer (A1d) of this embodiment is not particularly limited as long as it is at least one monomer having a (meth)acryloyl group in one molecule. The (meth)acryloyl group-containing monomer (A1d) may be a single monomer or two or more monomers may be used in combination.

Examples of the (meth)acryl group-containing monomer (A1d) include monofunctional (meth)acrylate monomers, polyfunctional (meth)acrylate monomers, 4-acryloylmorpholine, 2-hydroxyethyl (meth)acrylamide, 3-hydroxypropyl (meth)acrylamide, and N-(2,3-dihydroxypropyl) (meth)acrylamide.

Examples of the monofunctional (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, stearyl (meth)acrylate, tridecyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monobutyl ether (meth)acrylate, ethylene Glycol monohexyl ether (meth)acrylate, ethylene glycol mono-2-ethylhexyl ether (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol monobutyl ether (meth)acrylate, diethylene glycol monohexyl ether (meth)acrylate, diethylene glycol mono-2-ethylhexyl ether (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tricyclodecyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, caprolactone-modified hydroxyalkyl (meth)acrylate, allyl (meth)acrylate, and the like.

Examples of the multifunctional (meth)acrylate include ethylene glycol di(meth)acrylate, 1,2-propylene glycol (meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate. Examples of the present invention include polyoxyalkylene glycol di(meth)acrylates such as trihydroxymethylpropane di(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol diacrylate monostearate, 1,3-bis((meth)acryloyloxy)-2-hydroxypropane, ethoxylated bisphenol A di(meth)acrylate, and tris-(2-(meth)acryloyloxyethyl) isocyanurate.

Among them, from the viewpoint of strength, toughness, heat resistance, chemical resistance, etc. of the cured product and cost, at least one selected from methyl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate and neopentyl glycol di(meth)acrylate is preferred, at least one selected from methyl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, diethylene glycol di(meth)acrylate and neopentyl glycol (meth)acrylate is more preferred, and at least one selected from methyl (meth)acrylate and phenoxyethyl (meth)acrylate is even more preferred.

[Ethylenically unsaturated group-containing monomer (A2)] The ethylenically unsaturated group-containing compound (A) of the present embodiment may include an ethylenically unsaturated group-containing monomer (A2) as needed. The ethylenically unsaturated group-containing monomer (A2) is not particularly limited as long as it is a monomer having an ethylenically unsaturated group in one molecule other than the above-mentioned ethylenically unsaturated group-containing compound (A1). Examples of the ethylenically unsaturated group-containing monomer (A2) include styrene, p-chlorostyrene, vinyltoluene, α-methylstyrene, dichlorostyrene, divinylbenzene, tert-butylstyrene, vinyl acetate, diallyl fumarate, triallyl isocyanurate, and further examples include vinylbenzyl compounds such as vinylbenzyl butyl ether, vinylbenzyl hexyl ether, vinylbenzyl octyl ether, and divinylbenzyl ether. Among them, based on the viewpoint of dilution efficiency and cost, at least one selected from styrene, p-chlorostyrene, vinyltoluene, α-methylstyrene, dichlorostyrene, divinylbenzene and tert-butylstyrene is preferred, at least one selected from styrene, p-chlorostyrene and vinyltoluene is more preferred, and styrene is even more preferred.

The content of the ethylenically unsaturated group-containing monomer (A2) is preferably 0 to 60 parts by mass, more preferably 0 to 55 parts by mass, and even more preferably 0 to 50 parts by mass, based on 100 parts by mass of the ethylenically unsaturated group-containing compound (A), from the viewpoint of exhibiting good curability.

The content of the ethylenically unsaturated group-containing monomer (A2) in the resin composition is preferably 0 to 60% by mass, more preferably 0 to 55% by mass, and even more preferably 0 to 50% by mass, from the viewpoint of exhibiting good curability.

<Organometallic compound (B)> The organic metal compound (B) contains at least one selected from metals belonging to Group 7 elements, Group 8 elements, Group 9 elements, and Group 10 elements. The organic metal compound (B) may be used alone or in combination of two or more.

Examples of metals belonging to Group 7, Group 8, Group 9, and Group 10 include manganese, technetium, rhodium, thorium, iron, ruthenium, nirconium, thorium, cobalt, rhodium, iridium, ytterbium, nickel, palladium, platinum, and darwinium.

From the viewpoint of promoting the hardening effect and hardening in a short time at a low temperature, the organometallic compound (B) preferably contains at least one selected from manganese, iron, cobalt, and nickel, more preferably manganese, iron, nibronium, cobalt, rhodium, nickel, palladium, and platinum, and even more preferably manganese, iron, cobalt, and nickel.

From the viewpoint of accelerating the hardening effect and hardening in a short time at a low temperature, the organic metal compound (B) is preferably a salt of an acidic compound. Examples of the aforementioned acidic compound include carboxylic acids, diketones, etc. Examples of the carboxylic acid include heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, hexacosanoic acid, octacosanoic acid, triacontanoic acid, behenic acid, cycloalkane acid, oleic acid, linoleic acid, linolenic acid, abietic acid, linseed oil fatty acid, soybean oil acid, tall oil acid, formic acid, acetic acid, citric acid, oxalic acid, benzoic acid, amino acid, bile acid, sugar acid, hydroxycinnamic acid, hydroxy acid, aromatic acid, folic acid, ascorbic acid, alpha acid, imine acid, isoascorbic acid, croconic acid, kojic acid, squaric acid, sulfinic acid, sulfonic acid, teichoic acid, acid), thioacetic acid, dehydroacetic acid, delta acid, uric acid, hydroxyl oxime acid, humic acid, fulvic acid, phosphonic acid, Meldrum's acid, etc.

Examples of the diketones include 2,4-pentanedione, 2-acetylcyclopentanone, 2-isobutyryl-1-cyclohexanone, 6-methyl-2,4-heptanedione, hexafluoroacetylacetone, and 3-methylnonane-2,4-dione.

From the viewpoint of accelerating the curing effect and curing in a short time at a low temperature, the acidic compound is preferably at least one selected from cycloalkanoic acid, octanoic acid, octenoic acid, 2,4-pentanedione, 2-acetylcyclopentanone, 2-isobutyryl-1-cyclohexanone, 6-methyl-2,4-heptanedione, and neodecanoic acid, more preferably cycloalkanoic acid, octanoic acid, octenoic acid, 2,4-pentanedione, and neodecanoic acid, and even more preferably cycloalkanoic acid and octanoic acid.

From the viewpoint of promoting the curing effect and curing in a short time at a low temperature, the organometallic compound (B) is preferably selected from manganese cycloalkanoate, iron cycloalkanoate, cobalt cycloalkanoate, nickel cycloalkanoate, manganese octoate, iron octoate, cobalt octoate, nickel octoate, manganese octenoate, iron octenoate, cobalt octenoate, nickel octenoate, manganese neodecanoate, iron neodecanoate, cobalt neodecanoate, nickel neodecanoate, acetyl At least one of manganese (III) pyruvate, manganese (II) acetylaceruvate, iron (III) acetylaceruvate, cobalt (II) acetylaceruvate, cobalt (III) acetylaceruvate, and nickel (II) acetylaceruvate is more preferably selected from iron cycloalkanoate, manganese octoate, cobalt octoate, and nickel octoate. From the viewpoint of reactivity, iron cycloalkanoate and manganese octoate are more preferably used.

From the viewpoint of the curing acceleration effect, the content of the organic metal compound (B) in the resin composition is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5.0 parts by mass, and even more preferably 0.3 to 2.5 parts by mass, relative to 100 parts by mass of the total of the compound (A) containing an ethylenic unsaturated group and the organic metal compound (B). From the viewpoint of the curing acceleration effect, the content of the organic metal compound (B) in the resin composition in terms of metal component conversion is preferably 100 to 2,500 ppm by mass, more preferably 200 to 2,000 ppm by mass, and even more preferably 300 to 1,500 ppm by mass, relative to the total of the compound (A) containing an ethylenic unsaturated group and the organic metal compound (B).

From the viewpoint of accelerating hardening, the content of the organometallic compound (B) in the resin composition is preferably 0.05-10% by mass, more preferably 0.1-5.0% by mass, and even more preferably 0.3-2.5% by mass.

<Hydryl-containing compound (C)> The hydryl-containing compound (C) is not particularly limited as long as it has one or more hydryl groups in the molecule. The hydryl-containing compound (C) may be used alone or in combination of two or more.

From the viewpoint of controlling the stability and curability of the resin composition, the butylene-containing compound (C) preferably has at least one structure represented by the following formula (Q), and preferably has one or more butylene groups in the molecule including the butylene group in the structure represented by the following formula (Q).

In formula (Q), ^R1 and ^R2 are independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms, and * indicates linkage with any organic group. a is an integer of 0 to 2.

From the viewpoint of controlling the storage stability and curability of the resin composition, it is preferred that ^R1 in formula (Q) is a hydrogen atom and that the compound has two or more secondary alkyl groups in the molecule. That is, the alkyl group-containing compound (C) is preferably a secondary thiol compound (C1) in which the carbon atom to which the alkyl group in formula (Q) is bonded is a secondary carbon atom.

Furthermore, from the viewpoint of controlling the storage stability and curability of the resin composition, the alkyl group with 1 to 10 carbon atoms in R ¹ and R ² of formula (Q) may be a straight chain or a branched one. Specific examples include methyl, ethyl, various propyl groups, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, etc. The so-called "various" refers to various isomers including normal-, second-, third-, and iso-. Among the alkyl groups, methyl and ethyl groups are preferred. Furthermore, from the viewpoint of controlling the storage stability and curability of the resin composition, the aromatic group with 6 to 18 carbon atoms in R ¹ and R ² of formula (Q) may include, for example, phenyl, benzyl, naphthyl, anthracenyl, phenanthryl, etc. Furthermore, the aromatic groups may be substituted by halogen atoms, amine groups, nitro groups, cyano groups, etc. In formula (Q), a is an integer of 0 to 2, preferably 1, from the viewpoint of controlling the stability and curability of the resin composition. In addition, the aforementioned hydroxyl-containing compound (C) preferably has at least one ester structure represented by the following formula (Q-1).

In formula (Q-1), R ¹ , R ² , * and a have the same meanings as R ¹ , R ² , * and a in the aforementioned formula (Q).

From the viewpoint of controlling the storage stability and curability of the resin composition, a in formula (Q-1) is preferably 1. In particular, when ^R1 is a hydrogen atom (the compound represented by (Q-1) is a secondary thiol compound (C1)), from the viewpoint of controlling the storage stability and curability of the resin composition, a in formula (Q-1) is preferably 1.

The ester structure represented by formula (Q-1) is preferably derived from a hydroxyl-containing carboxylic acid represented by the following formula (S) and a polyol (c-1) from the viewpoint of controlling the storage stability and curability of the resin composition. This compound is obtained by esterifying a hydroxyl-containing carboxylic acid with a polyol (c-1) by a known method.

In formula (S), R ¹ , R ² and a have the same meanings as R ¹ , R ² and a in the aforementioned formula (Q).

When the alkyl-containing carboxylic acid represented by the above general formula (S) is a compound derived from the secondary thiol compound (C1), specific examples include 2-alkylpropionic acid, 3-alkylbutyric acid, 3-alkyl-3-phenylpropionic acid, etc. In addition, when it is a compound derived from the tertiary thiol compound (C2), specific examples include 2-alkylisobutylic acid, 3-alkyl-3-methylbutyric acid, etc.

Examples of the polyol (c-1) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, neopentyl glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, tricyclodecanedimethanol, 2,2-bis(2-hydroxyethoxyphenyl)propane, bisphenol A epoxide adduct, bisphenol F epoxide adduct, bisphenol S epoxide adduct, 1,4-cyclohexanediol, 1,4- Divalent alcohols such as cyclohexanedimethanol, 1,2-hexanediol, 1,3-hexanediol, 2,3-hexanediol, 1,4-hexanediol, 2,4-hexanediol, 3,4-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, and 9,9-bis[4-(2-hydroxyethyl)phenyl]fluorene; trivalent or higher alcohols such as glycerol, diglycerol, trihydroxymethylethane, trihydroxymethylpropane, dihydroxymethylpropane, tris(2-hydroxyethyl)isocyanurate, hexanetriol, sorbitol, pentaerythritol, dipentaerythritol, sucrose, and 2,2-bis(2,3-dihydroxypropoxyphenyl)propane; and polycarbonate diols, dimer acid polyester polyols, and the like.

Among them, preferred are dihydric alcohols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, and 1,4-butylene glycol, from the viewpoint of easy availability and the ability to accelerate hardening even under wet conditions; trihydric or higher alcohols such as glycerol, trihydroxymethyl ethane, trihydroxymethyl propane, tris(2-hydroxyethyl) isocyanurate, pentaerythritol, dipentaerythritol, and 2,2-bis(2,3-dihydroxypropoxyphenyl) propane, from the viewpoint of easy availability and the ability to accelerate hardening even under wet conditions; and polycarbonate diols and dimer acid polyester polyols, and more preferred are 1,4-butylene glycol, trihydroxymethyl ethane, trihydroxymethyl propane, tris(2-hydroxyethyl) isocyanurate, pentaerythritol, polycarbonate diols, and dimer acid polyester polyols from the viewpoint of the number of functional groups and vapor pressure.

Examples of the alkyl group-containing compound (C) include 1-hexanethiol, 1-octanethiol, 1-dodecanethiol, t-dodecanethiol, 2-naphthalenethiol, 3-alkylpropionic acid, 4-alkylbutyric acid, 2-alkylpropionic acid, 3-alkylbutyric acid, 3-alkyl-3-phenylpropionic acid, 3-alkylbutyric acid, 1,4-bis(3-alkylbutyryloxy)butane, pentaerythritol tetrakis(3-alkylpropionate), pentaerythritol tetrakis(3-alkylbutyrate), 1,3,5-tris(3-alkylbutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H, 5H)-trione, trihydroxymethylethane tris(3-butyl butyrate), trihydroxymethylpropane tris(3-butyl butyrate), di(2-butyl isobutyl) phthalate, ethylene glycol bis(2-butyl isobutyrate), propylene glycol bis(2-butyl isobutyrate), diethylene glycol bis(2-butyl isobutyrate), butanediol bis(2-butyl isobutyrate), octanediol bis(2-butyl isobutyrate), trihydroxymethylethane tris(2-butyl isobutyrate), trihydroxymethylpropane tris(2-butyl isobutyrate), pentaerythritol tetra(2-butyl isobutyrate), dipentaerythritol hexa(2-butyl isobutyrate), Phthalic acid di(3-butyl-3-methylbutyl) ester, ethylene glycol bis(3-butyl-3-methylbutyrate), propylene glycol bis(3-butyl-3-methylbutyrate), diethylene glycol bis(3-butyl-3-methylbutyrate), butanediol bis(3-butyl-3-methylbutyrate), octanediol bis(3-butyl-3-methylbutyrate), trihydroxymethylethane di(3-butyl-3-methylbutyrate), trihydroxymethylpropane tri(3-butyl-3-methylbutyrate), pentaerythritol tetra(3-butyl-3-methylbutyrate), dipentaerythritol hexa(3-butyl-3-methylbutyrate), etc.

From the viewpoint of effectively hardening the resin composition, the alkyl group-containing compound (C) is preferably at least one selected from pentaerythritol tetrakis(3-alkylbutyrate), pentaerythritol tetrakis(3-alkylpropionate), 1,4-bis(3-alkylbutyryloxy)butane and 1-dodecanethiol, more preferably at least one selected from pentaerythritol tetrakis(3-alkylbutyrate), pentaerythritol tetrakis(3-alkylpropionate), 1,4-bis(3-alkylbutyryloxy)butane and 1-dodecanethiol, and even more preferably at least one selected from pentaerythritol tetrakis(3-alkylbutyrate), pentaerythritol tetrakis(3-alkylpropionate), 1,4-bis(3-alkylbutyryloxy)butane and 1-dodecanethiol.

From the viewpoint of odor suppression, the molecular weight of the hydroxyl group-containing compound (C) is preferably 150 or more, more preferably 160 or more, and even more preferably 170 or more.

From the viewpoint of exhibiting good curability, the content of the ethylenically unsaturated group-containing compound (C) in the resin composition is preferably 0.01 to 15 parts by mass, more preferably 0.05 to 12 parts by mass, and even more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the ethylenically unsaturated group-containing compound (A).

From the viewpoint of exhibiting good curability, the content of the hydroxyl-containing compound (C) in the resin composition is preferably 0.01-15% by mass, more preferably 0.05-12% by mass, and even more preferably 0.1-10% by mass.

<Hardening rate adjuster (D)> The resin composition of this embodiment may also contain a hardening rate adjuster (D). Examples of the hardening rate adjuster (D) include a hardening accelerator (D1) and a hardening retarder (D2).

[Hardening accelerator (D1)] The hardening accelerator (D1) is a compound having no hydroxyl group but having a carboxyl group. Since the resin composition of this embodiment contains the hardening accelerator (D1), the hardening of the resin composition can be accelerated and the hardening time can be shortened. The hardening accelerator (D1) may be a single type or two or more types may be used in combination.

From the viewpoint of workability when mixing the resin composition components, the curing accelerator (D1) is preferably an aliphatic carboxylic acid having 2 to 10 carbon atoms. Examples of the curing accelerator (D1) include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, octanoic acid, nonanoic acid, decanoic acid, acrylic acid, methacrylic acid, etc. Among them, from the viewpoint of curing acceleration, at least one selected from formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, octanoic acid, nonanoic acid, decanoic acid, acrylic acid and methacrylic acid is preferred, and propionic acid, methacrylic acid and octanoic acid are more preferred.

[Hardening retarder (D2)] The hardening retarder (D2) is a compound having a hydroxyl group. Since the resin composition of this embodiment contains the hardening retarder (D2), the hardening of the resin composition can be inhibited and the hardening time can be extended. The aforementioned hardening retarder (D2) can be used alone or in combination of two or more.

From the viewpoint of workability when mixing the components of the resin composition, the curing retarder (D2) is preferably a hydroxyl-containing compound having 2 to 10 carbon atoms. Examples of the curing retarder (D2) include divalent or higher polyols such as ethylene glycol, propylene glycol and glycerol; compounds containing hydroxyl and carboxyl groups such as glycolic acid, glyceric acid, hydroxybutyric acid, malic acid, tartaric acid, citric acid glyceride and lactic acid. From the viewpoint of appropriately inhibiting curing, at least one selected from glycerol, ethylene glycol, propylene glycol and lactic acid is preferred, and glycerol, ethylene glycol and lactic acid are more preferred.

From the viewpoint of appropriately promoting hardening or appropriately inhibiting hardening, the content of the hardening rate modifier (D) in the resin composition is preferably 0.01 to 5.0 parts by mass, more preferably 0.03 to 3.0 parts by mass, and even more preferably 0.05 to 2.0 parts by mass, relative to 100 parts by mass of the compound (A) containing an ethylenically unsaturated group.

From the viewpoint of appropriately promoting hardening or appropriately inhibiting hardening, the content of the hardening rate modifier (D) in the resin composition is preferably 0.01-5.0 mass %, more preferably 0.03-3.0 mass %, and even more preferably 0.05-2.0 mass %.

<Other ingredients> The resin composition of this embodiment may contain ingredients other than the aforementioned ingredients as long as they do not particularly affect the effects of the present invention. Examples of ingredients that may be contained include mixtures that can impart properties such as coagulation adjustment, viscosity enhancement, water retention, defoaming, water repellency, waterproofing, flame retardancy, and shrinkage retardation, fibers made of materials such as metals, polymers, or carbon, pigments, fillers (inorganic fillers, organic fillers), foaming materials, and mixtures of clay minerals such as zeolite. In addition, examples of ingredients that may be contained include coupling agents, plasticizers, anion fixing components, solvents, polyisocyanate compounds, surfactants, wetting dispersants, waxes, mutagenic agents, polymerization inhibitors, etc.

[Polymerization inhibitor] The resin composition of the present embodiment may contain a polymerization inhibitor from the viewpoint of inhibiting excessive polymerization of the compound (A) containing an ethylenically unsaturated group and controlling the curing speed. Examples of polymerization inhibitors include hydroquinone, methylhydroquinone, phenothiazine, catechol, 4-tert-butylcatechol, and the like. When the resin composition of the present embodiment contains a polymerization inhibitor, the amount thereof is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 3 parts by mass, and even more preferably 0.001 to 0.1 parts by mass, relative to 100 parts by mass of the compound (A) containing an ethylenically unsaturated group. When the resin composition of this embodiment contains a polymerization inhibitor, the amount is preferably 0.0001 to 10% by mass, more preferably 0.001 to 3% by mass, and even more preferably 0.001 to 0.1% by mass.

[Manufacturing method of resin composition] The manufacturing method of the resin composition of this embodiment is not particularly limited, and a method known in the art can be used. For example, it can be manufactured by mixing a compound (A) containing an ethylenically unsaturated group, an organic metal compound (B) and a compound (C) containing an ethylene group. In addition, a curing speed regulator (D) or a polymerization inhibitor can also be added as needed.

[Composite material] The composite material of this embodiment contains the above-mentioned resin composition and at least one selected from a fiber substrate and a filler. As a composite material, it is preferred that the resin composition is impregnated in a fiber substrate (also referred to as a substrate impregnated with the resin composition). Such composite materials can obtain a hardened product (molded product) with excellent mechanical strength. As a composite material, specifically, it is used as residential facilities, parts related to transportation machinery, shapes and infrastructure, for example, the construction (repair) of structures such as concrete, etc., and can be preferably used in the manufacture of various molded products and the construction of structures.

Based on the viewpoints of the formability, ease of obtaining and mechanical strength of the composite material, the content of the resin component in the composite material is preferably 20-90 mass%, more preferably 23-85 mass%, and even more preferably 25-80 mass%, relative to 100 mass% of the composite material. If the content of the resin component is 20 mass% or more, the formability of the composite material is excellent. If the content of the resin component is 90 mass% or less, sufficient strength can be given to the composite material.

<Fiber substrate> Based on the viewpoint of mechanical strength, fiber materials used as fiber substrates include synthetic fibers such as amide, nylon, aramid, vinylon, zylon, polyethylene, polyester, and phenolic resins, boron, carbon fiber, glass fiber, metal fiber, ceramic fiber, plant-based and animal-based natural fibers, and all reinforced fibers, or composite fibers thereof. These may be a single type or two or more types may be used in combination. Among these, polyester fiber, aramid fiber, carbon fiber, and glass fiber are preferred, and glass fiber is more preferred based on the viewpoints of strength, hardness, availability, price, and the like. For example, in the case of glass fiber, the generally used fiber diameter is preferably 1~15μm, and more preferably 3~10μm.

Examples of the form of the fiber substrate include sheets, chopped strands, chopped fibers, wrought fibers, etc. Examples of sheets include those formed by aligning multiple reinforcing fibers in one direction, bidirectional fibers such as plain weave or twill weave, multi-axial fabrics, non-wrinkled fabrics, nonwoven fabrics, pads, knitting, braiding, and paper made from reinforcing fibers. The fiber substrate may be a single type or a combination of two or more types, and may be a single layer or multiple layers. Based on the impregnation property of the resin composition, the thickness of the sheet is preferably 0.01-5 mm in the case of a single layer, and when multiple layers are laminated, the total thickness is preferably 1-20 mm, and more preferably 1-15 mm. In addition, when the composite material is a substrate impregnated with a resin composition, the fiber substrate content in the substrate impregnated with the resin composition is preferably 10-80% by mass, more preferably 15-77% by mass, and more preferably 20-75% by mass.

<Filler> The resin composition of the present embodiment may also contain fillers within the scope of not impairing the effect of the present invention. These may be used alone or in combination of two or more. Examples of fillers include silicon oxide, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, etc. The content of the filler in the composite material is preferably 5-90% by mass, more preferably 15-80% by mass, and more preferably 25-70% by mass.

[Hardened Product] The cured product of this embodiment is a cured product of the above-mentioned resin composition or composite material. For example, when the composite material is a substrate impregnated with a resin composition and glass fiber is used as a fiber substrate, the flexural strength of the cured product (FRP) of the substrate impregnated with a resin composition is preferably 100-750 MPa, more preferably 110-550 MPa, and more preferably 120-350 MPa. And the flexural modulus of FRP is preferably 3-30 GPa, more preferably 4-20 GPa, and more preferably 5-15 GPa. In addition, the values of the aforementioned flexural strength and flexural modulus are values measured according to JIS K7171:2016. [Example]

The present invention is described in more detail below by way of examples, but the present invention is not limited by the examples.

[Synthesis of compounds containing ethylenically unsaturated groups] First, as compounds containing ethylenically unsaturated groups for preparing resin compositions, urethane resins containing (meth)acrylic groups (A1a-1), vinyl ester resins (A1b-1), vinyl ester resins (A1b-2), polyester resins containing (meth)acrylic groups (A1c-1), and compounds containing ethylenically unsaturated groups (A') were synthesized by the following synthesis examples and comparative synthesis examples.

<Synthesis Example 1> In a 1L four-necked flask equipped with a stirrer, a reflux cooling tube, a gas inlet tube and a thermometer, 540 g (0.27 mol) of polypropylene glycol (1) ("Actocol D-2000", manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd., weight average molecular weight 2000) and 24 g (0.06 mol) of polypropylene glycol (2) ("Adeka Polyether P-400", manufactured by ADEKA Co., Ltd., weight average molecular weight 400) as the polyol (1a-1), diphenylmethane diisocyanate ("Milinate MT, manufactured by TOSOH Co., Ltd.) 135 g (0.54 mol) and dibutyltin dilaurate ("KS-1260", manufactured by Sakai Chemical Industry Co., Ltd.) as a catalyst 0.01 g (0.001 parts by mass relative to 100 parts by mass of the total of polypropylene glycol, diphenylmethane diisocyanate and 2-hydroxypropyl methacrylate) were added, the temperature was raised to 70°C, and the reaction was carried out for about 2 hours. Furthermore, 78 g (0.54 mol) of 2-hydroxypropyl methacrylate ("Light Ester HOP(N)"), manufactured by Kyoeisha Chemical Co., Ltd., which is a compound (1a-3) containing a hydroxyl group and a (meth)acryloyl group, was added dropwise over a period of about 1 hour, and then reacted for another 3 hours to produce a urethane resin (A1a-1) containing a (meth)acryloyl group. The obtained urethane resin (A1a-1) had an Mw of 13,900 and an Mn of 2,650.

<Synthesis Example 2> In a 5L four-necked flask equipped with a stirrer, a reflux cooling tube, a gas inlet tube and a thermometer, 3,760 g of bisphenol A type epoxy resin ("EOMIK (registered trademark) R140P", manufactured by Mitsui Chemicals Co., Ltd., epoxy equivalent 188) as the epoxy compound (1b-1) was added, and the temperature was raised to 110°C. Next, 2.0 g (0.04 parts by mass relative to 100 parts by mass of the total of the epoxy compound (1b-1) and the unsaturated monoacid (1b-2)) of p-methoxyphenol (MEHQ) ("METHOQUINONE", manufactured by Seiko Chemical Co., Ltd.) as a polymerization inhibitor and 15.3 g (0.04 parts by mass relative to 100 parts by mass of the total of the epoxy compound (1b-1) and the unsaturated monoacid (1b-2)) of triphenylphosphine ("TPP", manufactured by Hokko Chemical Industry Co., Ltd.) as an esterification catalyst were added. 1b-2) is 0.3 parts by mass in total), and then 1,339 g of acrylic acid (manufactured by Nippon Catalyst Co., Ltd.) as an unsaturated monoacid (1b-2) is added dropwise over a period of about 1 hour (93 moles of acid groups relative to 100 moles of the total amount of epoxy groups in the epoxy compound (1b-1)), and then the temperature is raised to 125°C, and the reaction is carried out for about 2 hours until the acid value is 5 KOHmg/g, thereby producing a vinyl ester resin (A1b-1) of a vinyl ester resin (A1b). The obtained vinyl ester resin (A1b-1) has an Mw of 762 and an Mn of 612.

<Synthesis Example 3> In a 3L four-necked flask equipped with a stirrer, a reflux cooling tube, a gas inlet tube and a thermometer, 1,316 g of bisphenol A type epoxy resin ("EOMIK (registered trademark) R140P", manufactured by Mitsui Chemicals, Inc., epoxy equivalent 188) as the epoxy compound (1b-1) and 345 g of 2-phenoxyethyl methacrylate ("Light Ester PO", manufactured by Kyoeisha Chemical Co., Ltd.) as the (meth)acrylate monomer (A1d) were added (10% by mass based on the total mass of the formulated components), and the temperature was raised to 110°C. Next, 0.8 g (0.04 parts by mass relative to 100 parts by mass of the total of the epoxy compound (1b-1) and the unsaturated monoacid (1b-2)) of methyl hydroquinone ("MH", manufactured by Seiko Chemical Industries, Ltd.) as a polymerization inhibitor and 5.8 g (0.04 parts by mass relative to 100 parts by mass of the total of the epoxy compound (1b-1) and the unsaturated monoacid (1b-2)) of tetradecyl dimethyl benzyl ammonium chloride ("CATION (registered trademark) M2-100R", manufactured by NOF Corporation) as an esterification catalyst were added. ) is 0.3 parts by mass to a total of 100 parts by mass of methacrylic acid ("methacrylic acid MAA", manufactured by Mitsubishi Chemical Co., Ltd.) as an unsaturated monoacid (1b-2) and then 602 g (100 moles of acid groups relative to 100 moles of the total amount of epoxy groups in the epoxy compound (1b-1)) is added dropwise over a period of about 1 hour, and then the temperature is raised to 125°C and the reaction is carried out for about 3 hours until the acid value reaches 12 KOHmg/g to produce a vinyl ester resin (A1b-2). The obtained vinyl ester resin (A1b-2) has an Mw of 798 and an Mn of 635.

<Synthesis Example 4> In a 5L four-necked flask equipped with a stirrer, a reflux cooling tube, a gas inlet tube and a thermometer, 771g (5.75 mol) of dipropylene glycol ("dipropylene glycol industrial grade", manufactured by Dow Chemical Japan Co., Ltd.) as a polyol (1c-12) and 1,309g (8.84 mol) of phthalic anhydride ("phthalic anhydride", manufactured by Kawasaki Chemical Industries, Ltd.) as a dibasic acid (1c-2) were added, and the temperature was raised to 210°C and a condensation reaction was carried out for 10 hours to obtain a reaction product. The acid value of the obtained mixture was 156KOHmg/g. Next, the reaction product was cooled to 120°C, and 0.8 g (0.04 parts by mass relative to 100 parts by mass of the total of polyol (1c-1) and dibasic acid (1c-2)) of methyl hydroquinone ("MH", manufactured by Seiko Chemical Co., Ltd.) was added as a polymerization inhibitor. Next, 850 g (5.98 mol) of glycidyl methacrylate ("GMA (glycidyl methacrylate)", manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added as glycidyl (meth)acrylate (1c-3), and the temperature was raised to 120°C for reaction. The reaction was carried out for about 4 hours until the acid value of the obtained polyester resin (A1c-1) was 8 KOHmg/g, thereby producing a polyester resin (A1c-1) containing a (meth)acryloyl group. The obtained (meth)acryl-containing polyester resin (A1c-1) has a Mw of 2,520 and a Mn of 1,250.

<Comparative Synthesis Example 1> In a 3L four-necked flask equipped with a thermometer, a stirrer and a reflux cooling tube, 680g (8.94 mol) of propylene glycol ("propylene glycol industrial grade", manufactured by Dow Chemical Japan Co., Ltd.), 144g (0.87 mol) of isophthalic acid ("high purity isophthalic acid (PIA)", manufactured by Mitsubishi Gas Chemical Co., Ltd.), 432g (2.60 mol) of terephthalic acid ("PTA", manufactured by Mitsui Chemicals Co., Ltd.), and 510g (5.20 mol) of maleic anhydride (manufactured by Mitsubishi Chemical Co., Ltd.) were added, and the temperature was raised to 215°C, and a condensation reaction was carried out for 10 hours until the acid value was 20KOHmg/g or less, to produce a polyester resin containing an ethylenically unsaturated group (A') without a (meth)acryloyl group. The obtained ethylenically unsaturated compound (A’) has a Mw of 12,200 and a Mn of 3,490.

[Evaluation of compounds containing ethylenically unsaturated groups] The weight average molecular weight Mw, number average molecular weight Mn and acid value of the resins obtained in the above synthesis examples and comparative synthesis examples were measured under the following conditions. The evaluation results are summarized in Table 1 below.

<Weight average molecular weight Mw and number average molecular weight Mn> Mw and Mn were measured by gel permeation chromatography (GPC) under the following conditions and calculated using standard polystyrene-converted molecular weight. • Apparatus: "Shodex (registered trademark) GPC-101" (manufactured by Showa Denko Co., Ltd.) • Column: "Shodex (registered trademark) LF-804" (manufactured by Showa Denko Co., Ltd.) • Detector: Differential refractometer "Shodex (registered trademark) RI-71S" (manufactured by Showa Denko Co., Ltd.) • Column temperature: 40°C • Sample: 0.2 mass% tetrahydrofuran solution of (meth)acryloyl-containing compound (A1) • Developing solvent: tetrahydrofuran • Flow rate: 1.0 mL/min • Sample injection volume: 20μL • Standard sample: Polystyrene

<Acid value> The acid value is determined by measuring the mass of potassium hydroxide required to neutralize the acid component contained in the vinyl ester resin (A1b) and the polyester resin (A1c) and the ethylenically unsaturated group-containing compound (A') in accordance with JIS K6901:2008 "Partial acid value (indicator titration method)". The "Automatic titrator UCB-2000" (manufactured by Hiranuma Sangyo Co., Ltd.) is used as the titration device, and a mixed indicator of bromothymol blue and phenol red is used as the indicator.

[Manufacturing of resin composition] In the following examples and comparative examples, the details of the (meth)acrylate monomer (A1d), the monomer containing an ethylenically unsaturated group (A2), the organic metal compound (B), the organic metal compound (B'), the butyl group-containing compound (C), the hardening accelerator (D1) and the hardening accelerator (D2) used to manufacture the resin composition are as follows.

<Monomers containing (meth)acryloyl groups (A1d)> •Monomer (A1d-1): Ethoxylated bisphenol A dimethacrylate; "NK Ester BPE-500", manufactured by Shin-Nakamura Chemical Co., Ltd. •Monomer (A1d-2): Methyl methacrylate; "MMA", manufactured by KURARAY Co., Ltd. •Monomer (A1d-3): Phenoxyethyl methacrylate; "Light Ester PO", manufactured by Kyoeisha Chemical Co., Ltd. •Monomer (A1d-4): Lauryl methacrylate; "Light Ester L", manufactured by Kyoeisha Chemical Co., Ltd. •Monomer (A1d-5): 2-ethylhexyl acrylate; manufactured by Toagosei Co., Ltd.

<Monomer containing ethylenically unsaturated groups (A2)> •Styrene; "Styrene", manufactured by Idemitsu Kosan Co., Ltd.

<Organometallic compounds (B)> •Iron cycloalkanoate; manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., iron content 5% by mass •Manganese octanoate; manufactured by Dongrong Chemical Industry Co., Ltd., manganese content 8% by mass •Cobalt octanoate; manufactured by Nippon Chemical Industry Co., Ltd., cobalt content 8% by mass •Nickel octanoate; manufactured by Nippon Chemical Industry Co., Ltd., nickel content 8% by mass

<Organometallic compounds (B’)> • Potassium octanoate; manufactured by Toei Chemical Co., Ltd., potassium content 10% by mass • Calcium octanoate; manufactured by Fuji Film & Wako Pure Chemical Co., Ltd., calcium content 3% by mass • Yttrium octanoate; manufactured by Fuji Film & Wako Pure Chemical Co., Ltd., ruthenium content 5% by mass • Zirconium octanoate; manufactured by Nippon Chemical Industry Co., Ltd., zirconium content 12% by mass • Chromium octanoate; manufactured by Yoshida Chemical Industry Co., Ltd., chromium content 3% by mass • Copper octanoate; manufactured by Toei Chemical Co., Ltd., copper content 5% by mass • Zinc octanoate; manufactured by Toei Chemical Co., Ltd., zinc content 15% by mass • Tin octanoate; manufactured by Nippon Chemical Industry Co., Ltd., tin content 8% by mass

＜Compounds containing hydroxyl groups (C)＞ •Compounds containing hydroxyl groups (C-1): Pentaerythritol tetra(3-hydroxybutyrate); "Karenz MT (registered trademark) PE1", manufactured by Showa Denko Co., Ltd., Class 2 tetrafunctional thiol •Compounds containing hydroxyl groups (C-2): 1-dodecanethiol; manufactured by Kanto Chemical Co., Ltd., Class 1 monofunctional thiol •Compounds containing hydroxyl groups (C-3): 2,2-bis([(3-hydroxypropionyl)oxy]methyl)trimethylenebis[3-hydroxypropionate]; "PEMP", manufactured by SC Organic Chemicals Co., Ltd., Class 1 tetrafunctional thiol •Compounds containing hydroxyl groups (C-4): 1,4-bis(3-hydroxybutyryloxy)butane; "Karenz MT (registered trademark) BD1", manufactured by Showa Denko Co., Ltd., secondary bifunctional thiol

＜Hardening accelerator (D1)＞ •Propionic acid; manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. •Caprylic acid; "2-ethylhexanoic acid (deer special grade)", manufactured by Kanto Chemical Co., Ltd.

＜Hardening delay agent (D2)＞ • Lactic acid; "Musashino lactic acid (registered trademark) 90", manufactured by Musashino Chemical Research Institute Co., Ltd. • Glycerin; "Purified glycerin", manufactured by Sakamoto Pharmaceutical Co., Ltd. • Ethylene glycol; "Ethylene glycol", manufactured by Mitsubishi Chemical Co., Ltd.

<Example 1> A mixture of 35 g of a urethane resin (A1a-1) containing a (meth)acryl group-containing urethane resin (A1a) and 15 g of a monomer (A1d-2) containing a (meth)acryl group-containing monomer (A1d) (50 g of the ethylenically unsaturated group-containing compound (A) component) is placed in a 150 ^cm3 beaker, and the mixture is heated and dissolved at 80°C for 30 minutes, and then the mixture is adjusted to 25±0.2°C. When the temperature of the mixture reaches 25±0.2°C, 0.8 g of iron cycloalkanoate (iron content 5 mass %) as the organometallic compound (B) (metal conversion content is 787 mass ppm relative to the total of the ethylenically unsaturated group-containing compound (A) and the organometallic compound (B)) and 0.5 g of the hydroxyl group-containing compound (C-1) are added thereto in sequence, and the mixture is uniformly mixed with a glass rod to obtain a resin composition (X-1).

<Examples 2 to 19, 24 to 36, 44 to 45 and Comparative Examples 1 to 9> In Example 1, except that the raw materials and blending ratios described in Tables 2 to 8 and 10 were used, the resin compositions (X-2) to (X-19), (X-24) to (X-36), (X-44) to (X-45) and (X'-1) to (X'-9) were obtained in the same manner.

<Example 20> 50 g of the monomer (A1d-1) of the (meth)acryloyl group-containing monomer (A1d) was placed in a 150 ^cm3 beaker and the monomer was adjusted to 25±0.2°C. When the temperature of the monomer reached 25±0.2°C, 0.8 g of iron cycloalkanoate (iron content 5 mass%) as an organic metal compound (B) (metal conversion content was 787 mass ppm relative to the total of the ethylenically unsaturated group-containing compound (A) and the organic metal compound (B)) and 0.5 g of the butyl group-containing compound (C-1) were added thereto in sequence, and the mixture was uniformly mixed with a glass rod to obtain a resin composition (X'-20).

<Examples 21 to 23> In Example 21, except that the raw materials and blending ratios are set as those in Table 4, the resin compositions (X-21) to (X-23) are obtained in the same manner.

<Comparative Example 10> 21 g of the ethylenically unsaturated group-containing compound (A') (42 mass % relative to 100 mass % of the total of the (meth)acryloyl group-containing compound (A1), the ethylenically unsaturated group-containing compound (A') and the ethylenically unsaturated group-containing monomer (A2)) and 0.0035 g of hydroquinone as a polymerization inhibitor (0.0035 g relative to 100 mass % of the total of the (meth)acryloyl group-containing compound (A1), the ethylenically unsaturated group-containing compound (A') and the ethylenically unsaturated group-containing monomer (A2)) were added to the mixture. 0.01 parts by mass based on the total 100 parts by mass of the monomer (A2) containing an ethylenic unsaturated group) and 14 g of styrene as the monomer (A2) containing an ethylenic unsaturated group (28 parts by mass relative to the total 100 parts by mass of the (meth)acryloyl group-containing compound (A1), the compound (A') containing an ethylenic unsaturated group and the monomer (A2) containing an ethylenic unsaturated group) were placed in a 150 ^cm3 beaker, and the mixture was heated and dissolved at 100°C for 30 minutes, and then the mixture was adjusted to 25±0.2°C to prepare a mixture (1). Then, 15 g of the monomer (A1d-2) of the (meth)acryloyl group-containing monomer (A1d) (30% by mass relative to 100% by mass of the total of the (meth)acryloyl group-containing compound (A1), the ethylenically unsaturated group-containing compound (A') and the ethylenically unsaturated group-containing monomer (A2)) was added, and when the temperature of the above mixture reached 25±0.2°C, 0.8 g of iron cycloalkanoate (iron content 5 mass %) as an organic metal compound (B) (metal conversion content is 787 mass ppm relative to the total of the compound (A) containing an ethylenically unsaturated group and the organic metal compound (B)) and 0.5 g of the butyl group-containing compound (C-1) were added in sequence and uniformly mixed with a glass rod to obtain a resin composition (X'-10).

<Comparative Example 11> 30 g of the ethylenically unsaturated group-containing compound (A') (60 mass % relative to 100 mass % of the total of the ethylenically unsaturated group-containing compound (A') and the ethylenically unsaturated group-containing monomer (A2)), 0.005 g of hydroquinone as a polymerization inhibitor (0.01 mass part relative to 100 mass % of the total of the ethylenically unsaturated group-containing compound (A') and the ethylenically unsaturated group-containing monomer (A2)), and 20 g of styrene as the ethylenically unsaturated group-containing monomer (A2) (40 mass % relative to 100 mass % of the total of the ethylenically unsaturated group-containing compound (A') and the ethylenically unsaturated group-containing monomer (A2)) were placed in a 150 cm ³ , the mixture was heated and dissolved at 100°C for 30 minutes, and then the mixture was adjusted to 25±0.2°C. When the temperature of the mixture reached 25±0.2°C, 0.8 g of iron cycloalkanoate (iron content 5 mass%) as the organometallic compound (B) (metal conversion content was 787 mass ppm relative to the total of the ethylenically unsaturated group-containing compound (A) and the organometallic compound (B)) and 0.5 g of the hydroxyl group-containing compound (C-1) were added thereto in sequence, and the mixture was uniformly mixed with a glass rod to obtain a resin composition (X'-11).

<Comparative Example 12> 50 g of styrene was placed in a 150 ^cm3 beaker and the styrene was adjusted to 25±0.2°C. When the temperature of the styrene reached 25±0.2°C, 0.8 g of iron cycloalkanoate (iron content 5 mass%) as an organometallic compound (B) (metal conversion content was 787 mass ppm relative to the total of the ethylenically unsaturated group-containing compound (A) and the organometallic compound (B)) and 0.5 g of the hydroxyl group-containing compound (C-1) were added thereto in sequence and mixed uniformly with a glass rod to obtain a resin composition (X'-12).

<Example 37> A mixture of 35 g of a vinyl ester resin (A1b-1) of a vinyl ester resin (A1b) and 15 g of a monomer (A1d-2) of a (meth)acryloyl group-containing monomer (A1d) (50 g of the compound (A) containing an ethylenically unsaturated group) is placed in a 150 ^cm3 beaker, and the mixture is heated and dissolved at 80°C for 30 minutes, and then the mixture is adjusted to 25±0.2°C. When the temperature of the above mixture reached 25±0.2°C, 0.75 g (metal-converted content: 1,182 ppm) of manganese octylate (manganese content: 8 mass%) as an organic metal compound (B), 0.5 g of a hydroxyl-containing compound (C-1), and 0.1 g of propionic acid as a curing speed regulator (D) were added thereto in sequence, and the mixture was uniformly mixed with a glass rod to obtain a resin composition (X-37).

<Examples 38 to 43> Example 37 was prepared in the same manner except that the raw materials and blending ratios were set to those listed in Table 9, and resin compositions (X-38) to (X-43) were obtained.

[Evaluation of Resin Compositions] For the resin compositions (X-1) to (X-23) and (X'-1) to (X'-14) obtained in the above-mentioned embodiments and comparative examples, the following 25°C curing properties were evaluated. In addition, for the resin compositions (X-24) to (X-43), the following gel curing time, curing time and maximum heating temperature were evaluated. In addition, for the resin compositions (X-37) to (X-43), the following curing time shortening effect and curing time extension effect were evaluated. The evaluation results are summarized in Tables 2 to 9 below.

<25℃ Curing property> 30g of the resin composition obtained in the embodiment and the comparative example was poured into a 100mL polypropylene cup and left in an open state at 25℃ for 24 hours. After leaving for 24 hours, the fluidity of the resin composition was visually confirmed. In the 25℃ curing property column of Tables 2 to 6, "○" indicates no fluidity, "△" indicates gel state, and "×" indicates fluidity. In the above evaluation, the resin composition was judged to be cured when its fluidity was in a gel state.

<Gel curing time> According to the room temperature curing characteristics (thermal method) of JIS K6901:2021, the time required for the temperature of the resin composition to reach 30°C from the components of the mixed resin composition is measured, and this time is set as the gel curing time. Specifically, a test tube with an outer diameter of 18mm and a length of 165mm specified in JIS R3503:2007 is placed in a constant temperature water bath at 25±0.2°C, and the resin composition obtained in the embodiment and the comparative example is injected to a height of 100mm from the bottom of the test tube. The time required for the temperature of the resin composition to reach 30°C from the components of the mixed resin composition in the embodiment and the comparative example is measured, and this time is set as the gel curing time.

<Curing time> According to the room temperature curing characteristics (thermal method) of JIS K6901:2021, the time from the components of the mixed resin composition to the maximum temperature is measured, and this time is set as the curing time. Specifically, a test tube with an outer diameter of 18mm and a length of 165mm specified in JIS R3503:2007 is placed in a constant temperature water tank at 25±0.2℃, and the resin composition obtained in the embodiment and the comparative example is injected to a height of 100mm from the bottom of the test tube. The time from the components of the mixed resin composition to the resin composition temperature reaching the maximum temperature in the embodiment and the comparative example is measured, and this time is set as the curing time.

<Maximum heating temperature> According to the room temperature curing characteristics (heating method) of JIS K6901:2021, after mixing the components of the resin composition, the temperature of the resin composition is measured, and the maximum temperature reached by the resin composition at this time is set as the maximum heating temperature. Specifically, a test tube with an outer diameter of 18mm and a length of 165mm specified in JIS R3503:2007 is placed in a constant temperature water bath at 25±0.2℃, and the resin composition obtained in the embodiment and the comparative example is injected to a height of 100mm from the bottom of the test tube, and the temperature of the resin composition is measured, and the maximum temperature reached by the resin composition at this time is set as the maximum heating temperature.

<Effect of shortening curing time> Under the above-mentioned evaluation conditions of curing property at 25°C, a resin composition containing only a curing accelerator (D1) without a curing speed regulator (D) was produced, and the above-mentioned gel curing time was measured in the same manner. When the gel curing time of the resin composition containing the curing accelerator (D1) was shortened by 1 minute or more relative to the gel curing time of the resin composition not containing the curing accelerator (D1), it was recorded as "○" (curing time shortening effect), and when the shortening time was less than 1 minute or the gel curing time was prolonged, it was recorded as "×" (no curing time shortening effect).

<Effect of prolonging curing time> Under the above-mentioned evaluation conditions of curing property at 25°C, a resin composition containing only a curing retarder (D2) without a curing speed adjuster (D) was produced, and the above-mentioned gel curing time was measured in the same manner. When the gel curing time of the resin composition containing the curing retarder (D2) was prolonged by more than 1 minute relative to the gel curing time of the resin composition not containing the curing retarder (D2), it was recorded as "○" (curing time prolonging effect), and when the extended time was less than 1 minute or the gel curing time was shortened, it was recorded as "×" (no curing time prolonging effect).

As shown in Tables 2 to 9, the resin compositions of Examples 1 to 43 can be cured even without using an organic peroxide. On the other hand, the resin compositions of Comparative Examples 1 to 12 are all uncured.

[Manufacturing of cured products (injection molded products, FRP)] <Example 44> 70 parts by mass of a vinyl ester resin (A1b-1) heated to 80°C as a (meth)acryloyl group-containing compound (A1) and 30 parts by mass of a monomer (A1d-2) were mixed at 1000-2000 rpm for 20 minutes using a disperser (high-speed disperser "Homo Disperser 2.5" manufactured by Primix Co., Ltd.), and the mixture was adjusted to 25±0.2°C. Then, 1.5 parts by mass of manganese octylate (manganese content 8% by mass) as an organic metal compound (B) (metal conversion content 1182 ppm relative to the total of the compound (A) containing ethylenically unsaturated groups and the organic metal compound (B)) and 0.1 parts by mass of a hydroxyl group-containing compound (C-2) were added, and a disperser (high-speed disperser "Homo Disperser 2.5 type" manufactured by Primix Co., Ltd.) was used to mix at 1000-2000 rpm for 1 minute at each addition step to obtain a resin composition (X-44). As shown in FIG1, a U-shaped spacer with a thickness of 4 mm was sandwiched between two glass plates (150 mm×150 mm) that had been subjected to a demolding treatment to prepare a mold for manufacturing a cured product (injection molded product). The resin composition (X-44) was poured into the mold for manufacturing the hardened product (injection molded product), and left at 25°C for 24 hours with the upper part open. After visually confirming that the resin composition had hardened, it was left open at 25°C for 3 days (72 hours) to obtain a hardened product (injection molded product) of 150mm×150mm and 4mm thickness. Furthermore, on a 5mm thick, 300mm×300mm glass plate that had been demolded, 3 sheets of chopped felt ("MC 450A", manufactured by Nitto Boshin Co., Ltd., 150mm×150mm) of glass fiber impregnated with about 24g of the resin composition (X-44) were stacked, the 3 sheets of chopped felt impregnated with the resin composition (X-44) were clamped and fixed with a 3mm thick spacer, a 5mm thick, 300mm×300mm glass plate that had been demolded was placed on it, and then a 5kg weight was placed, to obtain a substrate impregnated with the resin composition (see Figure 2). The substrate impregnated with the resin composition was left at 25°C for 24 hours. After visually confirming that the resin composition has hardened, it is then left at 25°C for 3 days (72 hours) to obtain a hardened material (FRP: glass fiber content 30% by mass) with a size of 150mm×150mm and a thickness of 3mm.

<Example 45> The resin composition (X-44) produced in Example 44 was poured between two glass plates fixed with a spacer of 4 mm thickness on three sides other than the upper part, and left open at 25°C for 24 hours. After visually confirming that the resin composition was hardened, it was heated at 120°C for 2 hours to obtain a hardened product (injection molded product) of 150 mm × 150 mm and 4 mm thickness. Furthermore, on a glass plate with a thickness of 5 mm and a size of 300 mm × 300 mm that had been subjected to demolding, 3 sheets of chopped felt ("MC 450A", manufactured by Nitto Boshin Co., Ltd., 150 mm × 150 mm) impregnated with about 24 g of a resin composition (X-44) were stacked, and the 3 stacked chopped felt sheets of glass fiber impregnated with a resin composition (X-44) were fixed by a spacer with a thickness of 3 mm, and a glass plate with a thickness of 5 mm and a size of 300 mm × 300 mm that had been subjected to demolding was placed thereon, and then a weight of 5 kg was placed, thereby obtaining a substrate impregnated with a resin composition. The substrate impregnated with a resin composition was left to stand at 25° C. for 24 hours. After visually confirming that the resin composition has hardened, it is heated at 120°C for 2 hours to obtain a hardened material of 150mm×150mm and 3mm thickness (FRP: glass fiber content 30% by mass).

[Evaluation of hardened products (injection molded products, FRP)] The hardened products obtained in the above-mentioned Examples 35 and 36 were evaluated for flexural strength, flexural modulus and thermal deformation temperature. The evaluation results are shown in Table 10 below. In addition, for the flexural strength and flexural modulus of the injection molded products, the test pieces were cut into 80 mm long and 10 mm wide, for the thermal deformation temperature of the injection molded products, the test pieces were cut into 100 mm long and 10 mm wide, and for the FRP, the test pieces were cut into 100 mm long and 15 mm wide, and the test pieces for evaluation were made.

<Bending Strength> Based on JIS K7171:2016, the test specimens for evaluation were measured using a universal material testing machine ("Tensilon UCT-1T", manufactured by Orientec Co., Ltd.) at a temperature of 23°C and a humidity of 50%, and the average value was set as the bending strength of the cured product of the resin composition. For the cured product (injection molded product), the support distance was set to 64 mm, the test speed was 2.0 mm/min, and 3 test specimens were tested (N=3); for the cured product (FRP), the support distance was set to 80 mm, the test speed was 1.5 mm/min, and 5 test specimens were tested (N=5).

<Flexural modulus> Based on JIS K7171:2016, the test specimens for evaluation were measured using a universal material testing machine ("Tensilon UCT-1T", manufactured by Orientec Co., Ltd.) at a temperature of 23°C and a humidity of 50%, and the average value was set as the flexural strength of the cured product of the resin composition. For the cured product (injection molded product), the support distance was set to 64 mm, the test speed was 2.0 mm/min, and 3 test specimens were tested (N=3). For the cured product (FRP), the support distance was set to 80 mm, the test speed was 1.5 mm/min, and 5 test specimens were tested (N=5).

<Heat deformation temperature> For the hardened products (injection molded products) obtained in Examples 35 and 36, according to JIS K7191-1:2015, a load strain temperature (HDT) measuring device ("HDT tester S-3M", manufactured by Toyo Seiki Seisaku-sho Co., Ltd.) was used to measure three test pieces for measurement and evaluation, and the average value was set as the heat deformation temperature of the hardened product of the resin composition.

The cured products of the resin compositions of Examples 44 and 45 can be said to have sufficient mechanical strength.

[Figure 1] is an illustration of a mold used to manufacture a hardened product (injection molded product). [Figure 2] is an illustration related to the manufacture of a hardened product (FRP).

Claims (11)

A resin composition comprising a compound (A) containing an ethylenically unsaturated group, an organic metal compound (B), a compound (C) containing an acetyl group, and a curing rate modifier (D), wherein the compound (A) containing an ethylenically unsaturated group contains a compound (A1) containing a (meth)acryloyl group, wherein the content of the compound (A1) containing a (meth)acryloyl group is 40 parts by mass or more relative to 100 parts by mass of the compound (A) containing an ethylenically unsaturated group, and wherein the organic metal compound (B) contains at least one selected from a metal belonging to Group 7, a metal belonging to Group 8, a metal belonging to Group 9, and a metal belonging to Group 10, The aforementioned curing speed adjuster (D) is a curing accelerator (D1) having a carboxyl group instead of a hydroxyl group, and does not contain an organic peroxide. A resin composition comprising a compound (A) containing an ethylenically unsaturated group, an organic metal compound (B), a compound (C) containing an acetyl group, and a curing rate modifier (D), wherein the compound (A) containing an ethylenically unsaturated group contains a compound (A1) containing a (meth)acryloyl group, wherein the content of the compound (A1) containing a (meth)acryloyl group is 40 parts by mass or more relative to 100 parts by mass of the compound (A) containing an ethylenically unsaturated group, and wherein the organic metal compound (B) contains at least one selected from a metal belonging to Group 7, a metal belonging to Group 8, a metal belonging to Group 9, and a metal belonging to Group 10, The aforementioned curing speed regulator (D) is a polyol with a valence of 2 or more and a compound containing a hydroxyl group and a carboxyl group, and does not contain an organic peroxide. The resin composition of claim 1 or 2, wherein the metal conversion content of the aforementioned organic metal compound (B) is 100 to 2,500 mass ppm relative to the total of the compound containing an ethylenically unsaturated group (A) and the organic metal compound (B). The resin composition of claim 1 or 2, wherein the organometallic compound (B) contains at least one selected from manganese, iron, cobalt and nickel. The resin composition of claim 1 or 2, wherein the aforementioned organic metal compound (B) is at least one selected from manganese octoate, iron cycloalkanoate, cobalt octoate and nickel octoate. The resin composition of claim 1 or 2, wherein the content of the aforementioned ethylene-containing compound (C) is 0.01 to 15 parts by mass relative to 100 parts by mass of the aforementioned ethylenically unsaturated compound (A). The resin composition of claim 1 or 2, wherein the aforementioned (meth)acryl-containing compound (A1) is at least one selected from a (meth)acryl-containing urethane resin (A1a), a vinyl ester resin (A1b), a (meth)acryl-containing polyester resin (A1c), and a (meth)acrylate monomer (A1d). The resin composition of claim 1 or 2, wherein the content of the aforementioned curing rate modifier (D) is 0.01 to 5.0 parts by mass relative to 100 parts by mass of the aforementioned ethylenically unsaturated group-containing compound (A). The resin composition of claim 1, wherein the aforementioned hardening accelerator (D1) is an aliphatic carboxylic acid having 2 to 10 carbon atoms. A composite material comprising the resin composition of claim 1 or 2 and at least one selected from a fiber base material and a filler. A hardened product, which is a hardened product of the resin composition of claim 1 or 2 or a hardened product of the composite material of claim 10.