Radical-polymerizable composition and civil engineering material

Abstract

To provide a radical-polymerizable composition from which a coating film that is excellent in storage stability, curability and tensile strength can be obtained.SOLUTION: A radical-polymerizable composition contains polyester (meth)acrylate (A) having an air dryness-imparting group and a (meth)acryloyl group, a (meth)acrylic monomer (B) and a wax (C), wherein the polyester (meth)acrylate (A) contains an unsaturated dibasic acid as an essential raw material, active hydrogen concentration in a resin component composed of the polyester (meth)acrylate (A) and the (meth)acrylic monomer (B) is 0.1 to 0.9 mol / kg, and a mass ratio (A / B) of the polyester (meth)acrylate (A) to the (meth)acrylic monomer (B) is 30 / 70 to 95 / 5.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a radically polymerizable composition and a civil engineering and construction material.

Background Art

[0002] Road bridges constructed during the period of high economic growth are aging rapidly after 50 years of construction. Therefore, measures for repairing and countermeasures against the aging of road bridges are urgent issues for the country. When repairing, a resin material for repair that has excellent curability and enables the long life of structures is desired.

[0003] Under such circumstances, as a resin material having excellent curability, a resin composition containing an air-drying unsaturated resin, a (meth)acryloyl group-containing monomer, cobalt soap, and an oxime compound has been proposed (see, for example, Patent Document 1). However, this resin composition has a problem in that its mechanical strength and storage stability are insufficient. Therefore, there has been a demand for a material that provides a coating film having excellent storage stability, curability, and mechanical strength.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The problem to be solved by the present invention is to provide a radically polymerizable composition that has excellent storage stability and curability and provides a coating film having excellent tensile strength.

Means for Solving the Problems

[0006] As a result of intensive research to solve the above problems, the present inventors have found that a radical polymerizable composition containing a specific polyester (meth)acrylate, a (meth)acrylic monomer, and a wax is excellent in storage stability and curability, and a coating film excellent in tensile strength can be obtained, thereby completing the present invention.

[0007] That is, the present invention provides a radical polymerizable composition containing a polyester (meth)acrylate (A) having an air-drying property-imparting group and a (meth)acryloyl group, a (meth)acrylic monomer (B), and a wax (C), wherein the polyester (meth)acrylate (A) uses an unsaturated dibasic acid as an essential raw material, the active hydrogen concentration in the resin component composed of the polyester (meth)acrylate (A) and the (meth)acrylic monomer (B) is 0.1 to 0.9 mol / kg, and the mass ratio (A / B) of the polyester (meth)acrylate (A) to the (meth)acrylic monomer (B) is 30 / 70 to 95 / 5.

Effects of the Invention

[0008] Since the radical polymerizable composition of the present invention is excellent in storage stability and curability, and a coating film excellent in tensile strength can be obtained, it can be suitably used for various civil engineering and construction material applications such as road repair materials.

Modes for Carrying Out the Invention

[0009] The radical polymerizable composition of the present invention is a radical polymerizable composition containing a polyester (meth) acrylate (A) having an air-drying property-imparting group and a (meth) acryloyl group, a (meth) acrylic monomer (B), and a wax (C), wherein the polyester (meth) acrylate (A) uses an unsaturated dibasic acid as an essential raw material, and the active hydrogen concentration in the resin component composed of the polyester (meth) acrylate (A) and the (meth) acrylic monomer (B) is 0.1 to 0.9 mol / kg, and the mass ratio (A / B) of the polyester (meth) acrylate (A) to the (meth) acrylic monomer (B) is 30 / 70 to 95 / 5.

[0010] In the present invention, the “(meth) acryloyl group” means one or both of an acryloyl group and a methacryloyl group, the “(meth) acrylate” means one or both of a methacrylate and an acrylate, the “(meth) acrylic monomer” means one or both of an acrylic monomer and a methacrylic monomer, and the “(meth) acrylic compound” means one or both of an acrylic compound and a methacrylic compound.

[0011] The polyester (meth) acrylate (A) has an air-drying property-imparting group. The air-drying property-imparting group can be easily introduced into the resin skeleton, for example, by subjecting a compound having an air-drying property-imparting group to an esterification reaction during the production of the polyester (meth) acrylate (A).

[0012] Examples of the compound having an air-drying property-imparting group include compounds having active hydrogen. For example, as the polyvalent carboxylic acid, a compound (a1) containing a cyclic unsaturated aliphatic polybasic acid and its derivatives; as the polyhydric alcohol, a compound (a2) containing an allyl ether group having active hydrogen; as the polyhydric alcohol, an alcoholysis compound (a3) obtained by transesterification of a polyhydric alcohol and a fatty oil such as a drying oil having active hydrogen; as the polyhydric alcohol, a compound (a4) containing a dicyclopentadienyl group having active hydrogen, etc. These compounds may be used alone or in combination of two or more.

[0013] The active hydrogen of the compound having the air-drying property-imparting group is an active hydrogen composed of a bond with a carbon-hydrogen bond dissociation energy of 80 kcal / mol or less calculated based on the density functional method. In the present invention, this carbon-hydrogen bond is referred to as a C-H bond, and this hydrogen is referred to as active hydrogen.

[0014] As a method for calculating the amount of active hydrogen of a C-H bond having a dissociation energy of 80 kcal / mol or less in the unsaturated resin composition, an example using the air-drying polyester (meth)acrylate resin obtained in Synthesis Example 1 described later is shown. As described in the synthesis example, when the raw materials are condensed and dehydrated, 1050 (g) is produced. Among the raw materials, methyltetrahydrophthalic acid has 2 moles of active hydrogen per mole and a molecular weight of 166. Therefore, the active hydrogen in 1 Kg of the resin = 2×(50 / 166) / (1050 / 1000) = 0.6 moles.

[0015] Examples of the compound (a1) include tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, α-terpinene maleic anhydride adduct, trans-piperylene maleic anhydride adduct, and the like. These compounds may be used alone or in combination of two or more.

[0016] Examples of the compound (a2) include allyl ethers of polyhydric alcohols such as ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether, trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether, glycerin monoallyl ether, glycerin diallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, and pentaerythritol triallyl ether; and allyl ether compounds having an oxirane ring such as allyl glycidyl ether. These compounds may be used alone or in combination of two or more.

[0017] Examples of the polyhydric alcohol used as a raw material for the alcoholysis compound (a3) include trivalent alcohols such as glycerin, trimethylolethane, trimethylolpropane, and tris(hydroxymethyl)aminomethane, and tetravalent alcohols such as pentaerythritol. As the drying oil having active hydrogen, oils and fats having an iodine value of 130 or more are preferable, and examples thereof include linseed oil, soybean oil, cottonseed oil, peanut oil, and coconut oil. These compounds may be used alone or in combination of two or more.

[0018] Examples of the compound (a4) include dicyclopentenyl oxymethanol, dicyclopentenyl oxyethanol, and dicyclopentenyl oxypropanol. These compounds may be used alone or in combination of two or more.

[0019] The concentration of active hydrogen in the resin component composed of the polyester (meth)acrylate (A) and the (meth)acrylic monomer (B) is 0.1 to 0.9 mol / kg. However, since the balance between storage stability and curability is further improved, 0.2 to 0.8 mol / kg is preferable.

[0020] The polyester (meth)acrylate (A) is an unsaturated polyester having a (meth)acryloyl group, and is obtained, for example, by reacting an unsaturated polyester with glycidyl (meth)acrylate.

[0021] The unsaturated polyester is obtained by an esterification reaction of a compound having the air-drying property-imparting group, a polyvalent carboxylic acid having an α,β-unsaturated dibasic acid as an essential raw material, and a polyhydric alcohol.

[0022] As the α,β-unsaturated dibasic acid, for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, etc. can be used. These α,β-unsaturated dibasic acids may be used alone or in combination of two or more.

[0023] As the polyvalent carboxylic acid, a saturated dibasic acid can be used in combination. Examples of the saturated dibasic acid include phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, 4,4'-biphenyldicarboxylic acid, and dialkyl esters thereof. These saturated dibasic acids may be used alone or in combination of two or more.

[0024] Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3-butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, alkylene oxide adduct of bisphenol A, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, paraxylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalindiol, 2,7-decalindiol, and the like. These polyhydric alcohols may be used alone or in combination of two or more.

[0025] The (meth)acryloyl group concentration of the polyester (meth)acrylate (A) is preferably 0.1 to 2 mol / kg because the tensile strength is further improved.

[0026] The polymerizable double bond concentration of the polyester (meth)acrylate (A) is preferably 0.3 to 3 mol / kg because the balance between curability and tensile strength is further improved. Here, the polymerizable double bond concentration is a value obtained by the following formula. Polymerizable double bond concentration = (「Number of moles of polymerizable double bonds derived from unsaturated dibasic acid」 + 「Number of moles of polymerizable double bonds derived from glycidyl (meth)acrylate」) / Mass of polyester (meth)acrylate

[0027] The number average molecular weight of the polyester (meth)acrylate (A) is preferably 500 to 10,000, more preferably 1,000 to 6,000.

[0028] The average molecular weight in the present invention indicates a value measured by gel permeation chromatography (GPC) method.

[0029] The (meth)acrylic monomer (B) is not particularly limited as long as it can dilute the resin viscosity. For example, (meth)acrylic monomers having an alicyclic structure such as isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate; aliphatic (meth)acrylic monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, sec-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, n-octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, 3-methylbutyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, neopentyl (meth)acrylate, hexadecyl (meth)acrylate, isoamyl (meth)acrylate; (meth)acrylic monomers having an ether group such as 3-methoxybutyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 2-methoxybutyl (meth)acrylate, methoxypolyethylene glycol acrylate with the added mole number of oxyethylene in the range of 1 to 15, ethoxy-diethylene glycol (meth)acrylate, ethyl carbitol (meth)acrylate; (meth)acrylic monomers having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; aromatic (meth)acrylic monomers such as benzyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol acrylate, phenyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate;(Meth)acrylic monomers having a nitrogen atom such as (meth)acrylamide, dimethyl(meth)acrylamide, acryloylmorpholine, dimethylaminopropyl(meth)acrylamide, isopropyl(meth)acrylamide, diethyl(meth)acrylamide, diacetone(meth)acrylamide, hydroxyethylacrylamide, etc. can be used. Among these, (meth)acrylate compounds having a molecular weight of 300 or less are preferred because of their excellent curability. These (meth)acrylic monomers (B) may be used alone or in combination of two or more.;

[0030] The mass ratio (A / B) of the polyester (meth)acrylate (A) to the (meth)acrylic monomer (B) is 30 / 70 to 95 / 5, but 40 / 60 to 70 / 30 is preferred because workability is improved.;

[0031] The wax (C) prevents curing inhibition by oxygen. Examples include paraffin wax, microcrystalline wax, petrolactam, etc. From the viewpoints of compatibility and curability with the polyester (meth)acrylate (A) and the (meth)acrylic monomer (B), it is preferable to use paraffin wax.;

[0032] The melting point of the wax (C) is preferably 40 to 75°C, more preferably 45 to 60°C, from the viewpoints of compatibility and curability with the polyester (meth)acrylate (A) and the (meth)acrylic monomer (B). The melting point of the wax (C) indicates the melting point measured based on JIS K2235.;

[0033] The amount of the wax (C) used is preferably 0.01 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass in total of the polyester (meth)acrylate A) and the (meth)acrylic monomer (B), from the viewpoints of curability and recoatability.;

[0034] The radical polymerizable composition of the present invention contains polyester (meth)acrylate (A), (meth)acrylic monomer (B), and wax (C), and may contain other additives and the like as necessary.

[0035] As the other additives, for example, organic peroxides, curing accelerators, polymerization inhibitors, pigments, thixotropy imparting agents, antioxidants, solvents, fillers, reinforcing materials, aggregates, flame retardants, etc. can be used. However, since the curability is more excellent, it is preferable to use organic peroxides and curing accelerators. These additives may be used alone or in combination of two or more.

[0036] As the organic peroxide, for example, diacyl peroxide compounds, peroxyester compounds, hydroperoxide compounds, dialkyl peroxide compounds, ketone peroxide compounds, peroxyketal compounds, alkyl perester compounds, percarbonate compounds, etc. can be used. Among these, due to the superiority of the coating film curability, it is preferable to use diacyl peroxide compounds, hydroperoxide compounds, and ketone peroxide compounds, and it is more preferable to use diacyl peroxide compounds and hydroperoxide compounds. These compounds may be used alone or in combination of two or more.

[0037] As the diacyl peroxide compound, for example, benzoyl peroxide, toluyl peroxide, acetyl peroxide, lauroyl peroxide, etc. can be used. Among these, it is preferable to use benzoyl peroxide. These compounds may be used alone or in combination of two or more.

[0038] Examples of the hydroperoxide compound include cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, etc. Among these, cumene hydroperoxide and diisopropylbenzene hydroperoxide are preferably used from the superiority of the coating film curability, and cumene hydroperoxide is more preferably used. These compounds may be used alone or in combination of two or more.

[0039] Regarding the usage amount of the organic peroxide, since the balance between curability and workability is further improved, it is preferably 0.5 to 10 parts by mass, more preferably 1 to 6 parts by mass, based on 100 parts by mass in total of the polyester (meth) acrylate resin (A) and the (meth) acrylic monomer (B).

[0040] The curing accelerator is preferably a substance that decomposes the organic peroxide by a redox reaction and facilitates the generation of active radicals. For example, cobalt salts of organic acids such as cobalt naphthenate and cobalt octylate; metal chelate compounds such as zinc octylate, vanadium octylate, copper naphthenate, and barium naphthenate; metal acetylacetonate compounds such as vanadium acetylacetonate, cobalt acetylacetonate, and iron acetylacetonate; N,N-substituted anilines such as aniline, N,N-dimethylaniline, N,N-diethylaniline, 4-(N,N-dimethylamino)benzaldehyde, 4-[N,N-bis(2-hydroxyethyl)amino]benzaldehyde, 4-(N-methyl-N-hydroxyethylamino)benzaldehyde, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N,N-bis(hydroxyethyl)aniline, and diethanolaniline; N,N-substituted-p-toluidines such as p-toluidine, N,N-dimethyl-p-toluidine, ethylene oxide adducts of N,N-dimethyl-p-toluidine, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxypropyl)-p-toluidine, and N-ethyl-m-toluidine; and amine compounds such as 4-(N,N-substituted amino)benzaldehyde. These compounds may be used alone or in combination of two or more. From the viewpoint of excellent film curing properties, it is preferable to use cobalt salts of organic acids and amine compounds, and it is more preferable to use them in combination. As the cobalt salt of the organic acid, cobalt naphthenate and cobalt octylate are preferable, and as the amine compound, a toluidine compound is preferable.

[0041] Regarding the amount of the curing accelerator used, from the viewpoint of better balance between curability and workability, it is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 2 parts by mass, based on 100 parts by mass in total of the polyester (meth)acrylate resin (A) and the (meth)acrylic monomer (B).

[0042] The radical polymerizable composition of the present invention is excellent in storage stability and curability, and a coating film excellent in tensile strength can be obtained. Therefore, it can be suitably used for various civil engineering and construction material applications such as road repair materials.

Examples

[0043] The present invention will be described in more detail below with specific examples. The average molecular weight was measured under the following GPC measurement conditions.

[0044] [GPC Measurement Conditions] Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation) Columns: The following columns manufactured by Tosoh Corporation were connected in series and used. "TSKgel G5000" (7.8 mm I.D. × 30 cm) × 1 "TSKgel G4000" (7.8 mm I.D. × 30 cm) × 1 "TSKgel G3000" (7.8 mm I.D. × 30 cm) × 1 "TSKgel G2000" (7.8 mm I.D. × 30 cm) × 1 Detector: RI (differential refractometer) Column temperature: 40 °C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 4 mg / mL) Standard sample: A calibration curve was created using the following monodisperse polystyrene.

[0045] (Monodisperse polystyrene) "TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

[0046] (Synthesis Example 1: Synthesis of Polyester (Meth) Acrylate (A-1)) Into a four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser, 140 parts of diethylene glycol, 370 parts of triethylene glycol, 540 parts of phthalic anhydride, 50 parts of methyltetrahydrophthalic anhydride, and 20 parts of maleic anhydride were charged. 0.5 part of dibutyltin oxide and 0.2 part of methylhydroquinone were added as esterification catalysts, and the reaction was carried out at 220 °C for 10 hours. Then, it was cooled to 130 °C, and then 60 parts of glycidyl methacrylate were added and reacted for 5 hours to obtain polyester (meth) acrylate (A-1) with a number average molecular weight of 5400.

[0047] (Synthesis Example 2: Synthesis of Polyester (Meth) Acrylate (A-2)) 140 parts of diethylene glycol, 370 parts of triethylene glycol, 250 parts of phthalic anhydride, 60 parts of methyltetrahydrophthalic anhydride, and 200 parts of itaconic acid were charged into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. 0.5 part of dibutyltin oxide was added as an esterification catalyst, and the mixture was reacted at 220 °C for 10 hours. Then, it was cooled to 130 °C, and then 60 parts of glycidyl methacrylate was added and reacted for 5 hours to obtain a polyester (meth)acrylate (A-2) having a number average molecular weight of 4980.

[0048] (Synthesis Example 3: Synthesis of polyester (meth)acrylate (A-3)) 140 parts of diethylene glycol, 370 parts of triethylene glycol, 100 parts of phthalic anhydride, 60 parts of methyltetrahydrophthalic anhydride, and 300 parts of fumaric acid were charged into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. 0.5 part of dibutyltin oxide was added as an esterification catalyst, and the mixture was reacted at 220 °C for 10 hours. Then, it was cooled to 130 °C, and then 60 parts of glycidyl methacrylate was added and reacted for 5 hours to obtain a polyester (meth)acrylate (A-3) having a number average molecular weight of 4700.

[0049] (Synthesis Example 4: Synthesis of polyester (meth)acrylate (RA-1)) 140 parts of diethylene glycol, 370 parts of triethylene glycol, 300 parts of phthalic anhydride, and 330 parts of methyltetrahydrophthalic anhydride were charged into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. 0.5 part of dibutyltin oxide was added as an esterification catalyst, and the mixture was reacted at 220 °C for 10 hours. Then, it was cooled to 130 °C, and then 60 parts of glycidyl methacrylate was added and reacted for 5 hours to obtain a polyester (meth)acrylate (A-4) having a number average molecular weight of 5400.

[0050] (Synthesis Example 5: Synthesis of unsaturated polyester (1)) Into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 180 parts of diethylene glycol, 500 parts of triethylene glycol, and 260 parts of phthalic anhydride were charged. 0.5 part of dibutyltin oxide and 0.2 part of methylhydroquinone were added as an esterification catalyst, and the mixture was reacted at 220 °C for 10 hours. Then, 60 parts of maleic anhydride was added and reacted for 5 hours to obtain an unsaturated polyester (1) having a number average molecular weight of 3800.

[0051] (Synthesis Example 6: Synthesis of polyester (meth)acrylate (RA-2)) Into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 140 parts of diethylene glycol, 400 parts of triethylene glycol, and 550 parts by mass of phthalic anhydride were charged. 0.5 part of dibutyltin oxide and 0.2 part of methylhydroquinone were added as an esterification catalyst, and the mixture was reacted at 220 °C for 10 hours. Then, it was cooled to 130 °C, and then 30 parts of glycidyl methacrylate was added and reacted for 5 hours to obtain a polyester (meth)acrylate (RA-2) having a number average molecular weight of 5400.

[0052] (Example 1: Preparation and evaluation of radical polymerizable resin composition (1)) Into a light-shielding container equipped with a stirrer, a reflux condenser tube, and a thermometer, 650 parts by mass of the polyester (meth)acrylate (A-1) obtained in Synthesis Example 1, 230 parts by mass of methyl methacrylate, 120 parts by mass of 2-phenoxyethyl methacrylate, and 1 part by mass of paraffin wax 120°F were added, and the mixture was heated and dissolved at 60 °C to obtain a radical polymerizable resin composition (1). Next, to 100 parts by mass of this radical polymerizable resin composition (1), 0.5 part by mass of 6% cobalt octylate ("DICNATE208V" manufactured by DIC Corporation) as a curing accelerator, 0.2 part by mass of p-toluidine-2-hydroxyethyl (PTD-2EO), 0.2 part by mass of p-toluidine-2-hydroxyphenyl (PTD-2PO), and 2 parts by mass of an organic peroxide ("Niper NS", benzoyl peroxide manufactured by NOF Corporation) were added and formulated to obtain an evaluation resin composition (1).

[0053] [Evaluation of storage stability] 400 g of the radically polymerizable resin composition (1) was weighed into a metal can with a capacity of 500 mL and covered. It was left standing in a dryer at 60°C, and after 3 weeks, the occurrence of gelation and skin burrs was visually confirmed, and the storage stability was evaluated according to the following criteria. ○: No change ×: Gelation or skin burrs present

[0054] [Evaluation of curability] A coating film with a thickness of 0.2 mm was prepared on a slate plate under the condition of 25°C using the resin composition for evaluation (1) obtained above. The time (minutes) until it became tack-free by finger touch was measured from the time of coating film preparation, and it was evaluated according to the following criteria. 〇: Less than 30 minutes ×: 30 minutes or more

[0055] [Evaluation of tensile strength] In an environmental test chamber at an indoor temperature of 23°C and a humidity of 50%, the resin composition for evaluation (1) was poured into a mold, cured for 24 hours, and then demolded. Thereafter, a No. 2 dumbbell-shaped test piece with a thickness of 3 mm was obtained. This test piece was subjected to a tensile test at 23°C according to JIS-K6251:2010, and the tensile fracture strength and tensile elongation at break at the time of fracture were measured. ○: 5 MPa or more ×: Less than 5 MPa Testing equipment: "Autograph AG-I" manufactured by Shimadzu Corporation Test speed (H, S): 50 mm / min Between gauge marks: 20 mm Measurement temperature: 23°C

[0056] (Examples 2 to 5: Preparation and evaluation of radically polymerizable compositions (2) to (5)) Except for changing the formulation in Table 1, in the same manner as in Example 1, after adjusting the radically polymerizable compositions (2) to (5), the resin compositions for evaluation (2) to (5) were prepared, and each physical property was evaluated.

[0057] (Comparative Examples 1 to 3: Preparation and evaluation of radically polymerizable compositions (R1) to (R3)) Except for changing the formulation in Table 2, radical polymerizable compositions (R1) to (R3) were prepared in the same manner as in Example 1. Then, resin compositions (R1) to (R3) for evaluation were prepared, and each physical property was evaluated.

[0058] The compositions and evaluation results of the radical polymerizable compositions (1) to (5) and (R1) to (R3) obtained above are shown in Tables 1 and 2.

[0059]

Table 1

[0060]

Table 2

[0061] The abbreviations in the table are as follows. MMA: Methyl methacrylate 2-EHA: 2-Ethylhexyl acrylate PhOEMA: 2-Phenoxyethyl methacrylate ACMO: Acryloylmorpholine n-BA: n-Butyl acrylate DCPDOEMA: Dicyclopentenyl oxyethyl methacrylate Bis-AEODMA: EO-modified bisphenol A dimethacrylate

[0062] It was confirmed that the radical polymerizable compositions of the present invention in Examples 1 to 5 are excellent in storage stability and curability, and a coating film excellent in tensile strength can be obtained.

[0063] Comparative Example 1 is an example in which an unsaturated dibasic acid was not used as a raw material for polyester (meth) acrylate (A), but it was confirmed that the tensile strength of the obtained coating film was insufficient.

[0064] Comparative Example 2 is an example in which an unsaturated polyester was used instead of polyester (meth) acrylate (A), but it was confirmed that the tensile strength of the obtained coating film was insufficient.

[0065] Comparative Example 3 is an example in which the polyester (meth) acrylate (A) does not have an air-drying property-imparting group, but it was confirmed that the curability of the resulting coating film was insufficient.

Claims

1. A radical polymerizable composition containing a polyester (meth)acrylate (A) having an air-drying property-imparting group and a (meth)acryloyl group, a (meth)acrylic monomer (B), and a wax (C), wherein the polyester (meth)acrylate (A) is made using an unsaturated dibasic acid as an essential raw material, the active hydrogen concentration in the resin component composed of the polyester (meth)acrylate (A) and the (meth)acrylic monomer (B) is 0.1 to 0.9 mol / kg, and the mass ratio (A / B) of the polyester (meth)acrylate (A) to the (meth)acrylic monomer (B) is 30 / 70 to 95 / 5. A radical polymerizable resin composition characterized by this.

2. The radical polymerizable resin composition according to Claim 1, wherein the (meth)acryloyl group concentration of the polyester (meth)acrylate (A) is 0.1 to 2 mol / kg.

3. The radical polymerizable resin composition according to Claim 1, wherein the wax (C) is 0.01 to 3 parts by mass with respect to 100 parts by mass in total of the polyester (meth)acrylate (A) and the (meth)acrylic monomer (B).

4. A civil engineering and building material containing the radical polymerizable resin composition according to any one of Claims 1 to 3.

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