Binder resin composition, cured product and pavement material

Abstract

To provide a binder resin composition having excellent workability and capable of obtaining a cured product having excellent tensile strength, tensile elongation and abrasion resistance.SOLUTION: There is provided a binder resin composition which comprises a resin component comprising a resin having polymerizable unsaturated groups at both terminals (A), an unsaturated polyester having a dicyclopentenyl group (B) and a (meth)acrylic monomer (C) and a wax (D), wherein the concentration of the dicyclopentenyl group in the resin component is 1 to 3 mol / kg.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a binder resin composition, a cured product, and a paving material.

Background Art

[0002] In the field of civil engineering and construction, radical curable unsaturated resins such as unsaturated polyester resins, vinyl ester resins, urethane methacrylate resins, and polyester methacrylate resins are used to shorten the construction period and cope with winter construction. However, when used outdoors, oxygen in the air inhibits radical polymerization, so there are drawbacks such as poor drying property on the surface of the coating film and easy adhesion of dirt.

[0003] In response to such problems, a resin composition in which a radical curable unsaturated resin and a dicyclopentadiene-based unsaturated polyester resin excellent in air drying property are used in combination has been proposed (see, for example, Patent Document 1). This resin composition is a combination of a urethane methacrylate resin, a polyester methacrylate resin, an ethylenically unsaturated monomer having a (meth)acryloyl group, and a dicyclopentadiene-based unsaturated polyester resin. Although it is excellent in coating film strength and elongation, there is a problem that the aggregate retention property (abrasion resistance) when used as a binder for anti-slip paving etc. is insufficient.

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 binder resin composition that is excellent in workability and can obtain a cured product excellent in tensile strength, tensile elongation, and abrasion resistance.

Means for Solving the Problems

[0006] As a result of intensive research to solve the above problems, the present inventors have found that a binder resin composition containing a resin having polymerizable unsaturated groups at both ends, a specific unsaturated polyester, a (meth)acrylic monomer, and wax can solve the above problems, and have completed the present invention.

[0007] That is, the present invention provides a binder resin composition containing a resin component comprising a resin (A) having polymerizable unsaturated groups at both ends, an unsaturated polyester (B) having a dicyclopentenyl group, and a (meth)acrylic monomer (C), and wax (D), wherein the concentration of the dicyclopentenyl group in the resin component is 1 to 3 mol / kg.

Advantages of the Invention

[0008] The binder resin composition of the present invention can be used for various applications. Since it has excellent workability and a cured product having excellent tensile strength, tensile elongation, and abrasion resistance can be obtained, it can be suitably used as a civil engineering and building material such as road paving.

Embodiments for Carrying Out the Invention

[0009] The binder resin composition of the present invention is a binder resin composition containing a resin component comprising a resin (A) having polymerizable unsaturated groups at both ends, an unsaturated polyester (B) having a dicyclopentenyl group, and a (meth)acrylic monomer (C), and wax (D), wherein the concentration of the dicyclopentenyl group in the resin component is 1 to 3 mol / kg.

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

[0011] Examples of the resin (A) having polymerizable unsaturated groups at both ends include polyester (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, and the like. These resins (A) having polymerizable unsaturated groups at both ends may be used alone or in combination of two or more.

[0012] As the polyester (meth)acrylate, for example, a saturated polyester or an unsaturated polyester having two or more (meth)acryloyl groups in one molecule can be used. The saturated polyester is obtained by subjecting a saturated dibasic acid and a polyhydric alcohol to a condensation reaction, and the unsaturated polyester is obtained by subjecting an α,β-unsaturated dibasic acid and a polyhydric alcohol to a condensation reaction, and both have a (meth)acryloyl group at the terminal.

[0013] As the saturated dibasic acid, α,β-unsaturated dibasic acid, and polyhydric alcohol, those similar to those used in the synthesis of the unsaturated polyester (B) described later can be used.

[0014] Examples of the method for producing the polyester (meth)acrylate include a method of reacting a saturated polyester or an unsaturated polyester with glycidyl (meth)acrylate by a known method.

[0015] As the urethane (meth)acrylate, for example, those obtained by reacting a polyol, a polyisocyanate, and a (meth)acrylic compound having a hydroxyl group or an isocyanate group by a conventionally known method can be used.

[0016] Examples of the polyol include polyester polyol, polycarbonate polyol, polyether polyol, acrylic polyol, caprolactone polyol, butadiene polyol, and the like. These polyols may be used alone or in combination of two or more.

[0017] Examples of the polyisocyanate include aromatic diisocyanates such as phenylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate; and aromatic polyisocyanates such as xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, polyphenylene polymethylene polyisocyanate, a formalin condensate of methylene diphenyl diisocyanate, and a carbodiimide-modified product of 4,4'-diphenylmethane diisocyanate. These polyisocyanates may be used alone or in combination of two or more.

[0018] Examples of the (meth)acrylic compound having a hydroxyl group include (meth)acrylic acid alkyl esters having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; and polyethylene glycol monoacrylate and polypropylene glycol monoacrylate. These compounds may be used alone or in combination of two or more.

[0019] Examples of the (meth)acrylic compound having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, and 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate. These compounds may be used alone or in combination of two or more.

[0020] As the epoxy (meth) acrylate, for example, those obtained by reacting an epoxy compound obtained by mixing a bisphenol type epoxy compound or a bisphenol type epoxy compound and a novolak type epoxy compound with an unsaturated monobasic acid by a conventionally known method can be used.

[0021] As the bisphenol type epoxy compound, for example, glycidyl ether type epoxy compounds having two or more epoxy groups in one molecule obtained by reacting epichlorohydrin with bisphenol A or bisphenol F, dimethyl glycidyl ether type epoxy compounds obtained by reacting methyl epichlorohydrin with bisphenol A or bisphenol F, epoxy compounds obtained by reacting an alkylene oxide adduct of bisphenol A with epichlorohydrin or methyl epichlorohydrin, etc. can be used. These epoxy compounds may be used alone or in combination of two or more.

[0022] As the novolak type epoxy compound, for example, epoxy compounds obtained by reacting phenol novolak or cresol novolak with epichlorohydrin or methyl epichlorohydrin, etc. can be used. These epoxy compounds may be used alone or in combination of two or more.

[0023] As the unsaturated monobasic acid, for example, (meth) acrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, monopropyl maleate, monobutene maleate, sorbic acid, mono(2-ethylhexyl) maleate, etc. can be used. These unsaturated monobasic acids may be used alone or in combination of two or more.

[0024] The number average molecular weight of the resin (A) is preferably 500 to 10,000, more preferably 1,000 to 6,000, since workability and curability can be further improved.

[0025] The average molecular weight in the present invention indicates a value measured by the gel permeation chromatography (GPC) method.

[0026] The unsaturated polyester (B) is obtained by reacting a polybasic acid containing an α,β-unsaturated dibasic acid, a polyhydric alcohol, and a dicyclopentadiene-based compound. By using the dicyclopentadiene-based compound, a cured product excellent in abrasion resistance can be obtained.

[0027] As the α,β-unsaturated dibasic acid, for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, etc. can be used. These dibasic acids may be used alone or in combination of two or more.

[0028] As the dibasic acid that can be used in addition to the α,β-unsaturated dibasic acid, a saturated dibasic acid can be used. For example, 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 their dialkyl esters, etc. can be used. These dibasic acids may be used alone or in combination of two or more.

[0029] 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, etc. These polyhydric alcohols may be used alone or in combination of two or more.

[0030] Examples of the dicyclopentadiene-based compound include dicyclopentadiene, hydroxydicyclopentadiene, dicyclopentadiene maleate (monoester of dicyclopentadiene and maleic acid), etc. These dicyclopentadiene-based compounds may be used alone or in combination of two or more.

[0031] The dicyclopentenyl group concentration of the unsaturated polyester (B) is preferably 2.5 to 7.5 mol / kg, more preferably 2.5 to 4.3 mol / kg, since the balance between the abrasion resistance and tensile elongation of the resulting cured product is further improved.

[0032] The number average molecular weight of the unsaturated polyester resin (B) is preferably 500 to 10,000, more preferably 500 to 5,000, since the balance between the abrasion resistance and workability is further improved.

[0033] The (meth)acrylic monomer (C) 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 (C) may be used alone or in combination of two or more.;

[0034] The dicyclopentenyl group concentration in the resin component composed of the resin (A) having polymerizable unsaturated groups at both ends, the unsaturated polyester (B) having the dicyclopentenyl group, and the (meth)acrylic monomer (C) is 1 to 3 mol / kg. However, 1.2 to 2.5 mol / kg is preferred because the balance between the abrasion resistance and tensile elongation of the resulting cured product is further improved.

[0035] In addition, the mass ratio ((A + B) / (C)) of the resin (A) and the unsaturated polyester (B) to the (meth)acrylic monomer (C) is preferably 50 / 50 to 80 / 20 because the balance between the abrasion resistance and workability of the resulting cured product is further improved.

[0036] The resin (A) in the resin component composed of the resin (A), the unsaturated polyester (B), and the (meth)acrylic monomer (C) is preferably 10 to 40% by mass because the balance between the abrasion resistance and tensile elongation of the resulting cured product is further improved.

[0037] The unsaturated polyester (B) in the resin component is preferably 40 to 70% by mass because the balance between the abrasion resistance and tensile elongation of the resulting cured product is further improved.

[0038] The (meth)acrylic monomer (C) in the resin component is preferably 20 to 50% by mass because the balance between the abrasion resistance and tensile elongation of the resulting cured product is further improved.

[0039] The wax (D) prevents inhibition of curing by oxygen, and examples thereof include paraffin wax, microcrystalline wax, petrolactam, etc. From the viewpoints of compatibility and curability with the resin (A), the unsaturated polyester (B), and the (meth)acrylic monomer (C), it is preferable to use paraffin wax.

[0040] As the melting point of the wax (D), from the viewpoints of compatibility and curability with the resin (A), the unsaturated polyester (B), and the (meth)acrylic monomer (C), 40 to 75°C is preferable, and 45 to 60°C is more preferable. The melting point of the wax (D) indicates the melting point measured based on JIS K2235.

[0041] The amount of the wax (D) used is preferably 0.01 to 3 parts by mass, and more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the resin component, from the viewpoints of curability and recoatability.

[0042] The binder resin composition of the present invention contains the resin (A), the unsaturated polyester (B), the (meth)acrylic monomer (C), and the wax (D), but may contain other additives, etc. as necessary.

[0043] Examples of the other additives that can be used include organic peroxides, curing accelerators, polymerization inhibitors, pigments, thixotropy-imparting agents, antioxidants, solvents, fillers, reinforcing materials, aggregates, flame retardants, etc. From the viewpoint of more excellent curability, it is preferable to use organic peroxides and curing accelerators. These additives may be used alone or in combination of two or more.

[0044] 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 can be used alone or in combination of two or more.

[0045] As the diacyl peroxide compound, for example, benzoyl peroxide, toluoyl peroxide, acetyl peroxide, lauroyl peroxide, etc. can be used. Among these, it is preferable to use benzoyl peroxide. These compounds can be used alone or in combination of two or more.

[0046] As the hydroperoxide compound, for example, cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, etc. can be used. Among these, due to the superiority of the coating film curability, it is preferable to use cumene hydroperoxide and diisopropylbenzene hydroperoxide, and it is more preferable to use cumene hydroperoxide. These compounds can be used alone or in combination of two or more.

[0047] As the usage amount of the organic peroxide, since the balance between curability and storage stability is further improved, 0.5 to 10 parts by mass is preferable, and 1 to 6 parts by mass is more preferable with respect to 100 parts by mass of the resin component.

[0048] 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; organic acid salts such as zinc octylate, vanadium octylate, copper naphthenate, and barium naphthenate; metal chelate compounds such as vanadium acetylacetate, cobalt acetylacetate, 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 N,N-dimethyl-p-toluidine, the ethylene oxide adduct 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; amine compounds such as p-toluidine, etc. These compounds can be used alone or in combination of two or more. From the viewpoint of excellent coating film curability, 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, the toluidine compound is preferable.

[0049] Regarding the amount of the curing accelerator used, since the balance between curability and storage stability is further improved, 0.1 to 5 parts by mass is preferable, and 0.2 to 2 parts by mass is more preferable with respect to 100 parts by mass of the resin component.

[0050] The binder resin composition of the present invention is excellent in workability and can provide a cured product excellent in tensile strength, tensile elongation, and wear resistance. Therefore, it can be suitably used as a civil engineering and construction material such as road paving.

Examples

[0051] The present invention will be described in more detail below with specific examples. The acid value was measured in accordance with JIS-K-6901, and the average molecular weight was measured under the following GPC measurement conditions.

[0052] [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 piece "TSKgel G4000" (7.8 mm I.D. × 30 cm) × 1 piece "TSKgel G3000" (7.8 mm I.D. × 30 cm) × 1 piece "TSKgel G2000" (7.8 mm I.D. × 30 cm) × 1 piece 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.

[0053] (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

[0054] (Synthesis Example 1: Synthesis of Resin (A-1) Having Polymerizable Unsaturated Groups at Both Ends) Into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 260 parts of neopentyl glycol, 100 parts of propylene glycol, 400 parts of adipic acid, and 110 parts of maleic anhydride were charged. 0.5 part of monobutyltin oxide and 0.5 part of methylhydroquinone were added as an esterification catalyst, and the reaction was carried out at 220°C for 10 hours. Then, it was cooled to 130°C, and then 20 parts of glycidyl methacrylate was added and reacted for 5 hours to obtain a polyester methacrylate having a number average molecular weight of 2150 as a resin (A-1) having polymerizable unsaturated groups at both ends.

[0055] (Synthesis Example 2: Synthesis of Resin (A-2) Having Polymerizable Unsaturated Groups at Both Ends) A reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet, and a reflux condenser was charged with 500 parts by mass of polypropylene glycol (abbreviated as PPG) having a number average molecular weight of 3000, 140 parts by mass of tolylene diisocyanate (abbreviated as TDI), and 30 parts by mass of isophorone diisocyanate (abbreviated as IPDI), and reacted at 80 °C for 2 hours under a nitrogen stream. After confirming that the NCO% had reached 6% or less, it was cooled to 50 °C. Under an air stream, 0.07 part by mass of hydroquinone was added, 140 parts by mass of 2-hydroxyethyl methacrylate (abbreviated as HEMA) was added, and the mixture was reacted at 90 °C for 4 hours. When the NCO% reached 0.1% or less, 0.5 part by mass of methylhydroquinone was added to obtain a urethane methacrylate having a number average molecular weight of 3652 as a resin (A-2) having polymerizable unsaturated groups at both ends.

[0056] (Synthesis Example 3: Synthesis of resin (A-3) having polymerizable unsaturated groups at both ends) A reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet, and a reflux condenser was charged with 500 parts by mass of polytetramethylene ether glycol (abbreviated as PTMG) having a number average molecular weight of 1000, 140 parts by mass of TDI, and 30 parts by mass of IPDI, and reacted at 80 °C for 2 hours under a nitrogen stream. After confirming that the NCO% had reached 6% or less, it was cooled to 50 °C. Under an air stream, 0.07 part by mass of hydroquinone was added, 140 parts by mass of HEMA was added, and the mixture was reacted at 90 °C for 4 hours. When the NCO% reached 0.1% or less, 0.3 part by mass of methylhydroquinone was added to obtain a urethane methacrylate having a number average molecular weight of 1700 as a resin (A-3) having polymerizable unsaturated groups at both ends.

[0057] (Synthesis Example 4: Synthesis of unsaturated polyester (B-1)) A four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser was charged with 70 parts by mass of water, 500 parts by mass of dicyclopentadiene, 0.1 part by mass of hydroquinone, and 340 parts by mass of maleic anhydride, and reacted at 80 °C for 4 hours under a nitrogen stream. When the acid value reached 215, 115 parts by mass of ethylene glycol was charged and reacted at 200 °C for 6 hours to obtain an unsaturated polyester (B-1) having an acid value of 15 and a number average molecular weight of 624.

[0058] (Synthesis Example 5: Synthesis of Unsaturated Polyester (B-2)) 60 parts by mass of water, 460 parts by mass of dicyclopentadiene, 0.1 part by mass of hydroquinone, and 320 parts by mass of maleic anhydride were charged into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, and reacted at 80 °C for 4 hours under a nitrogen stream. When the acid value reached 215, 180 parts by mass of diethylene glycol was charged and reacted at 200 °C for 6 hours to obtain an unsaturated polyester (B-2) having an acid value of 15 and a number average molecular weight of 712.

[0059] (Synthesis Example 6: Synthesis of Unsaturated Polyester (B-3)) 60 parts by mass of water, 460 parts by mass of dicyclopentadiene, 0.1 part by mass of hydroquinone, and 320 parts by mass of maleic anhydride were charged into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, and reacted at 80 °C for 4 hours under a nitrogen stream. When the acid value reached 215, 260 parts by mass of triethylene glycol was charged and reacted at 200 °C for 6 hours to obtain an unsaturated polyester (B-3) having an acid value of 15 and a number average molecular weight of 800.

[0060] (Example 1: Preparation and Evaluation of Binder Resin Composition (1)) 220 parts by mass of resin (A-3) having polymerizable unsaturated groups at both ends, 480 parts by mass of unsaturated polyester (B-2), 240 parts by mass of methyl methacrylate, and 5 parts by mass of 125°F paraffin wax were added to a light-shielding container equipped with a stirrer, a reflux condenser tube, and a thermometer, and heated and dissolved at 60 °C to obtain a binder resin composition (1).

[0061] [Evaluation of Workability (Viscosity)] The viscosity of the binder resin composition (1) obtained above was measured at 25 °C using a Type i, BM viscometer in accordance with "5.5.1 Brookfield Viscometer Method" of JIS K6901:2008, and the workability was evaluated according to the following criteria. ○: 1300 mPa·s or more and less than 1900 mPa·s ×: Less than 1300 mPa·s or 1900 mPa·s or more

[0062] [Preparation of test samples for evaluation] To 100 parts by mass of the binder resin composition (1) obtained above, 4 parts by mass of 6% cobalt octylate ("DICNATE 208V" manufactured by DIC Corporation), 4 parts by mass of p-toluidine-2-hydroxyethyl, and 2 parts by mass of an organic peroxide ("NYPER NS", benzoyl peroxide manufactured by NOF Corporation) were added and blended to obtain an evaluation resin composition (1).

[0063] [Evaluation of tensile strength and elongation at break] In an environmental test chamber at an indoor temperature of 23°C and a humidity of 50%, the evaluation resin composition (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 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

[0064] [Evaluation of abrasion resistance] [Preparation of test specimens] In an environmental test chamber at an indoor temperature of 23°C and a humidity of 50%, after recording the weight of a concrete slab (30 cm × 30 cm × 6 cm), 135 g of the evaluation resin composition (1) was applied (resin coating amount 1.5 kg / m 2 ), and the weight was measured again. Before the resin hardened, 540 g of aggregate was scattered (aggregate scattering amount 6 kg / m 2 ), and the weight was measured. After the resin hardened, the unbonded aggregate was collected and the weight was measured. [Cutting-in test] The test specimens obtained above were tested using a urethane rubber tire on a fixed-displacement testing machine (Nikken Co., Ltd. "NKA-183D") under the conditions of a load of 75 kg and 1,000 rotations. The weight of the test specimens after the test was measured, the aggregate retention rate was calculated, and the abrasion resistance was evaluated according to the following criteria. ○: Aggregate retention rate is 90% or more ×: Aggregate retention rate is less than 90%

[0065] (Examples 2 to 5: Preparation and evaluation of binder resin compositions (2) to (4)) Binder resin compositions (2) to (4) were prepared and each physical property was evaluated in the same manner as in Example 1, except that the formulation of Example 1 was as described in Table 1.

[0066] (Comparative Examples 1 and 2: Preparation and evaluation of binder resin compositions (R1) and (R2)) Binder resin compositions (R1) and (R2) were prepared and each physical property was evaluated in the same manner as in Example 1, except that the formulation of Example 1 was as described in Table 2.

[0067] The compositions and evaluation results of the binder resin compositions (1) to (4) and (R1) to (R2) obtained above are shown in Tables 1 and 2.

[0068]

Table 1

[0069]

Table 2

[0070] The abbreviations in the tables are as follows. MMA: Methyl methacrylate n-BA: n-Butyl acrylate PhOEMA: 2-Phenoxyethyl methacrylate HEMA: 2-Hydroxyethyl methacrylate ACMO: Acryloyl morpholine

[0071] It was confirmed that the binder resin compositions of the present invention in Examples 1 to 4 are excellent in workability and can obtain cured products excellent in tensile strength, tensile elongation, and abrasion resistance.

[0072] Comparative Example 1 is an example in which the dicyclopentenyl group concentration in the resin component is lower than the lower limit of the present invention, and it was confirmed that the abrasion resistance of the cured product is insufficient.

[0073] Comparative Example 2 is an example in which the dicyclopentadiene concentration in the resin component is higher than the upper limit of the present invention. It was confirmed that the viscosity is high, the workability is poor, and the tensile elongation of the cured product is insufficient.

Claims

1. A binder resin composition containing a resin component comprising a resin (A) having polymerizable unsaturated groups at both ends, an unsaturated polyester (B) having dicyclopentenyl groups, and a (meth)acrylic monomer (C), and a wax (D), wherein the dicyclopentenyl group concentration in the resin component is 1 to 3 mol / kg.

2. The binder resin composition according to Claim 1, wherein the mass ratio ((A + B) / (C)) of the resin (A) and the unsaturated polyester (B) to the (meth)acrylic monomer (C) is 50 / 50 to 80 / 20.

3. The binder resin composition according to Claim 1, wherein the wax (D) is 0.01 to 3 parts by mass with respect to 100 parts by mass of the resin component.

4. The binder resin composition according to Claim 1, wherein the resin (A) is urethane (meth)acrylate and / or polyester (meth)acrylate.

5. A cured product of the binder resin composition according to any one of Claims 1 to 4.

6. A paving material having the cured product according to Claim 5 and an aggregate.

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