JPWO2011048970A1 - Radical curable resin composition, paving material using the same, and paving structure - Google Patents

Abstract

In the present invention, the radical curable resin (A) is one or more selected from an epoxy (meth) acrylate resin and a urethane (meth) acrylate resin, has a weight average molecular weight of 20,000 to 50,000, and butyl (meth) acrylate. 5% by mass to less than 70% by mass Copolymerization component (meth) acrylic copolymer (E) is included so that it is excellent in tire stain resistance after curing and tensile properties, and is a polymerizable unsaturated monomer (B). Is a mixture of a (meth) acrylic compound (B-1) having a flash point of 70 ° C. or higher and a (meth) acrylic compound (B-2) having a flash point lower than 21 ° C. The mixed mass ratio is (B-1) / (B-2) = 9/1 to 5/5 so that it passes the Fire Services Act No. 2 petroleum, and has low flammability, low odor, low viscosity, Radical curable resin composition with excellent compatibility It provides things.

Description

  The present invention provides a cured product excellent in tire stain resistance and tensile properties, and is a radical curable resin composition excellent in low flammability, low odor, low viscosity and compatibility, a paving material using the same, and The present invention relates to a pavement structure.

In the civil engineering industry, radical polymerization curable unsaturated resins such as unsaturated polyester resins, vinyl ester resins, and urethane acrylate resins are used for shortening the construction period and for winter construction. However, when used outdoors, since oxygen in the air inhibits radical polymerization, there are disadvantages that the surface of the coating film is poorly dried and that dirt easily adheres. Thus, air-drying unsaturated resins have been proposed. (Patent Document 1)
However, the unsaturated resin for paving materials gives followability to the ground such as asphalt that softens at high temperatures, so it is necessary to use an unsaturated resin that lowers the concentration of double bonds and lowers the reactivity. However, there was a drawback that the air drying property was further deteriorated. Therefore, in order to make up for these drawbacks, paraffin wax is added, or a normal unsaturated resin and an air-drying unsaturated resin are mixed and used. (Patent Document 2)

  However, when paraffin wax is added to such a resin composition, it has an action of blocking air on the surface of the coating film, which contributes to the improvement of air drying properties. Affects the appearance and appearance. In this case, even when an air-drying unsaturated resin is used in combination, the low molecular weight component of the radical-polymerizable air-drying component tends to remain at the time of curing. When the heavy bond concentration is lowered, the surface curability is remarkably lowered, and after construction on the asphalt road surface, there is a problem that the tire surface is inferior in resistance to dirt such as tire marks adhering to the road surface and is easily contaminated. .

JP 11-349855 A Japanese Patent Laid-Open No. 11-158805

  The object of the present invention is to provide a radical curable resin composition containing paraffin wax and a curing accelerator, which has excellent resistance to tire contamination after curing of the resin composition and excellent tensile physical properties, and has passed the Fire Services Act No. 2 Petroleum. An object of the present invention is to provide a radical curable resin composition that is flammable, low odor, low viscosity, and excellent in compatibility, a paving material using the same, and a paving structure.

  The inventors of the present invention have a radical curable resin composition containing paraffin wax and a curing accelerator that can pass the Fire Fighting Act No. 2 Petroleum and have low odor, and is resistant to tire contamination after the resin composition is cured. As a result of diligent research on a radical curable resin composition capable of improving tensile properties, when a (meth) acrylic copolymer having a specific weight average molecular weight is used and a mixture of specific polymerizable unsaturated monomers is used The present invention has been completed by passing the 2nd Petroleum Act of the Fire Service Act and finding that it has low odor, low viscosity, and can solve the problems of tire contamination resistance and tensile properties.

That is, the present invention is a radical polymerization comprising a radical curable resin (A) having both terminal (meth) acryloyl groups, a polymerizable unsaturated monomer (B), a paraffin wax (C), and a curing accelerator (D). In the functional resin composition,
The radical curable resin (A) is at least one selected from an epoxy (meth) acrylate resin and a urethane (meth) acrylate resin, and the polymerizable unsaturated monomer (B) is a (meth) acrylic compound. In a mixture of a (meth) acrylic compound (B-1) having a flash point of 70 ° C. or higher and a (meth) acrylic compound (B-2) having a flash point lower than 21 ° C., the mixing mass ratio thereof is ( B-1) / (B-2) = 9/1 to 5/5, the weight average molecular weight is 20000 to 50000, and butyl (meth) acrylate is copolymerized with 5% by mass to less than 70% by mass. The present invention relates to a radically polymerizable resin composition comprising a (meth) acrylic copolymer (E), a pavement material containing the same, and a pavement structure using the same.

  The present invention includes a (meth) acrylic copolymer (E) having a specific weight average molecular weight of 5% by mass to 70% by mass of butyl (meth) acrylate as a copolymerization component in a radical polymerizable resin composition. Excellent resistance to tire contamination after curing of the composition and excellent tensile properties, low flammability and low odor, low passing by the Fire Services Act No. 2 petroleum with a specific amount of a mixture of specific (meth) acrylic compounds It is possible to provide a radical polymerizable resin composition excellent in compatibility with viscosity, a paving material containing the same, and a paving structure using the same.

  The radical curable resin (A) used in the present invention is an epoxy (meth) acrylate resin having a room temperature liquid viscosity of 100 to 2000 mPa · s (25 ° C.) dissolved in the polymerizable unsaturated monomer (B). , One or more selected from urethane (meth) acrylate resins, and may be used in combination with polyester (meth) acrylate resins. Specifically, the resin (A) is an epoxy (meth) acrylate resin derived from an addition reaction product of an epoxy resin and an unsaturated monobasic acid, and further contains a terminal isocyanate group containing a polyisocyanate and a polyol having a terminal hydroxyl group. It is one kind selected from urethane (meth) acrylate resins obtained by reacting a product with a hydroxyl group-containing (meth) acrylate. The polyester (meth) acrylate resin is derived from a polyester resin at both acid ends and glycidyl (meth) acrylate. Preferably it is a mixture of an epoxy (meth) acrylate resin and a urethane (meth) acrylate resin, and the mixing mass ratio is preferably 7/3 to 3/7.

  The epoxy (meth) acrylate resin is a resin obtained by mixing a bisphenol type epoxy resin alone or a bisphenol type epoxy resin and a novolac type epoxy resin, and its average epoxy equivalent is preferably in the range of 150 to 450. An epoxy vinyl ester resin obtained by reacting an epoxy resin in the above with an unsaturated monobasic acid in the presence of an esterification catalyst. Epoxy resins used include bisphenol A, bisphenol S, bisphenol F, novolac glycidyl ether, halogenated glycidyl ether, tetraphenylethane, isocyanurate, anhydrous phthalate, hydrogenated bisphenol, and glycol. Examples include glycidyl ether type and peracetic acid oxidation type, which can be used alone or in combination. Further, examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and sorbic acid, and they can be used alone or in combination. Methacrylic acid is preferred.

  The epoxy (meth) acrylate resin can be produced by reacting a low molecular weight bisphenol type epoxy and bisphenol A to synthesize an epoxy oligomer, and then reacting with an unsaturated monobasic acid. A part can be reacted with a dicarboxylic acid compound (adipic acid, sebacic acid, dimer acid, etc.) or a corresponding terminal carboxyl liquid rubber (liquid nitrile rubber, etc.). Moreover, the hydroxyl group of epoxy (meth) acrylate resin and an isocyanate compound or a terminal isocyanate group containing urethane prepolymer can also be made to react. These modified vinyl ether ester resins have the effect of improving adhesion, toughness, and chemical resistance.

  The reaction between the epoxy resin and the unsaturated monobasic acid is performed using an esterification catalyst at a temperature of 60 to 160 ° C, preferably 80 to 120 ° C. As the esterification catalyst, a known catalyst such as a tertiary amine such as triethylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline or diazabicyclooctane, or diethylamine hydrochloride can be used as it is. .

  The urethane (meth) acrylate resin is obtained by reacting, for example, a polyisocyanate and a polyol such as polyether polyol, polyester polyol, and acrylic polyol to form a terminal isocyanate group prepolymer, and further reacting with hydroxyalkyl (meth) acrylate. It is what An ether bond-containing urethane methacrylate resin is preferred.

  The polyether polyol, polyester polyol, and acrylic polyol here are preferably those having a number average molecular weight of 200 or more, particularly preferably from 300 to 2,000. Examples of the polyether polyol include polyoxypropylene diol (hereinafter abbreviated as PPG), polytetramethylene glycol ether (hereinafter abbreviated as PTMG), polyoxyethylene diol, and the like. Similarly, a polyester polyol is produced by polycondensation of a saturated dibasic acid or an acid anhydride thereof with glycols. In some cases, aromatic and aliphatic or alicyclic saturated dibasic acids are used in combination as an acid component. Saturated polyester produced in the above manner. The acrylic polyol is an acrylic monomer containing a polymerizable monomer having an acryloyl group (for example, methyl acrylate) and a copolymerizable ethylene compound (for example, styrene, vinyl acetate), or a conjugated diene compound (for example, butadiene) and a hydroxyl group. It is an acrylic polymer having hydroxyl groups at both ends or side chains obtained by reacting a polymerizable monomer [for example, 2-hydroxyalkyl (meth) acrylate] and another acrylic polymerizable monomer. Such a reaction can be obtained using a normal method for producing an acrylic polymer in the presence of a radical polymerization initiator.

  Examples of the aromatic saturated dibasic acid or acid anhydride thereof include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride, and the like. Examples of aliphatic or cycloaliphatic saturated dibasic acids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof. Etc., and each is used alone or in combination.

  Examples of the glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, and triethylene. Glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di- (4-hydroxypropoxydiphenyl) propane and the like. These can be used alone or in combination, but other adducts such as ethylene oxide and propylene oxide can also be used. Polycondensates such as polyethylene terephthalate can also be used as part of the glycols and acid component.

  Examples of the polyisocyanate include 2,4-tolylene diisocyanate and its isomer or a mixture of isomers (hereinafter abbreviated as TDI), diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and hydrogenated xylylene diisocyanate. , Dicyclohexylmethane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, Vernock D-750 (DIC Corporation product), Chris Bon NX (DIC Corporation product), Desmodur L (Sumitomo Bayer product), Coronate L (product of Nippon Polyurethane Co., Ltd.) and the like can be mentioned, and TDI is particularly preferably used.

  Examples of the hydroxyalkyl (meth) acrylate include HEMA (hydroxyethyl methacrylate), HEA (hydroxyethyl acrylate), HPMA (hydroxypropyl methacrylate), HPA (hydroxypropyl acrylate), DCPD (dicyclopentadiene), and maleic anhydride. And 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and the like are preferable.

  The polyester (meth) acrylate resin is preferably a saturated or unsaturated polyester containing at least one (meth) acrylic acid ester group in one molecule.

  As a method for producing the above polyester (meth) acrylate resin, α, β-unsaturated dibasic acid or its acid anhydride or aromatic saturated dibasic acid or its acid anhydride, and polycondensation of glycols, and in some cases Unsaturation after reaction according to a conventional method using an acid component in excess of an acid / glycol molar ratio of 1/1 to 1.1 / 1 in combination with an aliphatic or aliphatic saturated dibasic acid as the acid component It can be produced by reacting a glycidyl compound having a double bond.

  Examples of the α, β-unsaturated dibasic acid or acid anhydrides thereof include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof. Examples of the dibasic acid or its acid anhydride include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride, and esters thereof. And aliphatic or cycloaliphatic saturated dibasic acids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof. Each is used alone or in combination.

  Examples of the glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, and triethylene. Glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di- (4-hydroxypropoxydiphenyl) propane and the like. . These are used alone or in combination, but besides these, polyether glycols of addition products such as ethylene oxide and propylene oxide can also be preferably used. Polycondensates such as polyethylene terephthalate can also be used as part of the glycols and acid component.

  Examples of the unsaturated glycidyl compound include glycidyl acrylate and glycidyl methacrylate. Glycidyl methacrylate is preferred.

  The polymerizable unsaturated monomer (B) is a (meth) acrylic compound having one (meth) acryloyl group, and is flammable with a (meth) acrylic compound (B-1) having a flash point of 70 ° C. or higher. A point is a mixture with the (meth) acrylic compound (B-2) smaller than 21 degreeC. The mixing mass ratio is (B-1) / (B-2) = 9/1 to 5/5. Outside this range, it is not preferable because it does not become low flammability that passes the second petroleum of the Fire Service Act.

Examples of the (meth) acrylic compound (B-2) having a flash point lower than 21 ° C. include methyl (meth) acrylate and ethyl (meth) acrylate, and the (flash) having a flash point of 70 ° C. or higher. The acrylic compound (B-1) is, for example, 2-ethylhexyl acrylate, n-octyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, polycaprolactone acrylate, diethylene glycol monomethyl ether monoacrylate, dipropylene glycol monomethyl ether Monoacrylate, 2-ethylhexyl carbitol acrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, styrene methacrylate Rohexyl, tetrahydrofurfuryl methacrylate, polycaprolactone methacrylate, diethylene glycol monomethyl ether monomethacrylate, dipropylene glycol monomethyl ether monomethacrylate, 2-ethylhexyl carbitol methacrylate, phenoxyethyl acrylate, phenol ethylene oxide (EO) modified acrylate, nonylphenyl carbitol Acrylate, nonylphenol EO modified acrylate, phenoxypropyl acrylate, phenol propylene oxide (PO) modified acrylate, nonylphenoxypropyl acrylate, nonylphenol PO modified acrylate, acryloyloxyethyl phthalate, phenoxyethyl methacrylate, phenol EO modified methacrylate Rate, nonylphenyl carbitol methacrylate, nonylphenol EO modified methacrylate, phenoxypropyl methacrylate, phenol PO modified methacrylate, nonylphenoxypropyl methacrylate, nonylphenol PO modified methacrylate, methacryloyloxyethyl phthalate, dicyclopentenyloxyethyl (meth) acrylate, 2-hydroxy Examples include ethyl (meth) acrylate. Of these, phenoxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, which has a molecular weight of 180 or more and hardly volatilizes, 2-hydroxyethyl (meth) which has a hydrogen bond and hardly volatilizes Even if the acrylate is left unreacted in a small amount in the coating film, it is preferable in that it does not easily become TVOC.
Moreover, the reactive monomer which has unsaturated groups, such as styrene, vinyl acetate, vinyl toluene, (alpha) -methyltoluene, can also be used in the range which does not impair the effect of invention.

In combination with the polymerizable unsaturated monomer (B), a monomer having at least two ethylenically unsaturated groups, preferably a (meth) acryloyl group in one molecule, as long as the effects of the present invention are not impaired. You may do it. By using this monomer in combination, it is possible to improve the wear resistance, scratch resistance, peristaltic resistance, chemical resistance and the like of the cured product surface. Examples of the compound having at least two ethylenically unsaturated groups in one molecule include ethylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, and 1,3-butylene glycol di (meth). ) Acrylate, 1,6-hexanediol di (meth) acrylate alkanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate polyethylene Examples include polyoxyalkylene-glycol di (meth) acrylates such as glycol di (meth) acrylate, and these are used alone or in combination of two or more.
In addition, divinylbenzene, diallyl phthalate, diallyl isophthalate, diallyl tetrabromophthalate, triallyl phthalate, and the like can be used as long as the effects of the invention are not impaired.

  The mass mixing ratio (%) of the radical curable resin (A) and the polymerizable unsaturated monomer (B) is preferably (A) / (B) = 30/70 to 70/30 (mass%). More preferably, it is 50 / 50-70 / 30 (mass%). When the amount (A) is less than 30% by mass, the curability of the resin composition is deteriorated. When the amount is more than 70% by mass, the viscosity of the resin composition is increased and the workability is deteriorated. When the amount of the monomer (B) exceeds 70% by mass, elution of the asphalt solidifying the aggregate of the asphalt pavement into the polymerizable unsaturated monomer (B) component and asphalt cutback are performed. This is not preferable because it promotes damage to the asphalt pavement itself.

  The paraffin wax (C) is added as a component for assisting in drying the coating film, and petroleum wax, synthetic wax, that is, polyethylene wax, oxidized paraffin, alcohol type wax and the like can be used. Paraffin wax having a melting point of 115 ° F. to 155 ° F. is preferred. The melting point here is a melting point measured based on JIS K 2235. The amount of (C) added is preferably 500 ppm to 10,000 ppm with respect to the resin composition comprising (A) and (B). Furthermore, it is more preferable that it is 2000 ppm-8000 ppm from the point of drying property and a viscosity.

  The curing accelerator (D) is preferably an amine compound, such as aniline, N, N-dimethylaniline, N, N-diethylaniline, p-toluidine, N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p-toluidine (abbreviated as PTD-2EO), N-methyl-N- (2-hydroxyethyl) -p-toluidine, N-ethyl-N- (2-hydroxyethyl) -P-toluidine, N-methyl-N- (2-hydroxyethyl) -m-toluidine, N-ethyl-N- (2-hydroxyethyl) -m-toluidine, 4- (N, N-dimethylamino) benzaldehyde 4- [N, N-bis (2-hydroxyethyl) amino] benzaldehyde, 4- (N-methyl-N-hydroxyethylamino) benzaldehyde, N, N- Bis (2-hydroxypropyl) -p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N, N-bis (hydroxyethyl) aniline, diethanol Examples include amines such as N, N-substituted anilines such as aniline, N, N-substituted-p-toluidine, and 4- (N, N-substituted amino) benzaldehyde. More preferred is N, N-substituted-p-toluidine, especially PTD-2EO. The addition amount is preferably 0.1 to 3 parts by mass, more preferably 0.1 to 1 part by mass with respect to 100 parts by mass in total of the components (A) and (B).

  The (meth) acrylic copolymer (E) is a (meth) acrylic acid copolymer using alkyl acrylate or alkyl methacrylate as a polymerization component, and butyl (meth) acrylate is contained in an amount of 5% by mass to less than 70% by mass. , Preferably 5 to 60% by mass, and other alkyl (meth) acrylates 95% to 30% by mass or more, preferably 95 to 40% by mass. The copolymer (E) has a weight average molecular weight of 20,000 to 50,000, preferably 30,000 to 40,000. If it is out of this range, the compatibility with the radical polymerizable resin (A) will be poor, and it will be separated during storage, resulting in poor storage stability. Further, if the weight average molecular weight is smaller than the above range, the tire contamination resistance is inferior, and if the molecular weight is high, the workability is inferior due to thickening. The butyl (meth) acrylate is selected from, for example, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, and the like. is there.

Examples of the other alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, i-propyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) ) acrylate, lauryl (meth) acrylate, "acrylic ester SL" [Mitsubishi rayon Co., Ltd., C ₁₂ - / C ₁₃ methacrylate mixture, stearyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, isobornyl (Meth) acrylate, adamantyl (meth) acrylate, acrylamide, and the like. Methyl (meth) acrylate is preferred. Preferably, the other alkyl (meth) acrylate is used in an amount of 95 to 30% by mass and 95 to 40% by mass in the copolymer. Outside this range, the compatibility and storage stability will be poor.

  In the present invention, a known air-drying unsaturated resin may be used in combination. In that case, it is preferable that a non volatile matter (resin solid content) is 30-70 mass%. If it deviates from this, the reinforcing effect of the pavement layer is not sufficient.

  The air-drying unsaturated resin that can be used in combination is a resin in which an air-drying imparting group is introduced using a compound having an air-drying imparting group as an essential component in unsaturated polyester, vinyl ester resin, and the like. Examples thereof include a water-soluble polyester (meth) acrylate resin, an air-drying epoxy (meth) acrylate, an air-drying urethane (meth) acrylate, and an air-drying unsaturated polyester. Among these, air-drying polyester (meth) acrylate is preferably mentioned in terms of easy physical property adjustment and yellowing resistance.

  In the present invention, it is desirable to add a drying aid in addition to the curing accelerator (D) as long as the effects of the present invention are not impaired. The drying aid is a component that assists in drying the coating film, and is preferably a cobalt-based organic acid salt. Examples of the cobalt-based organic acid salt include metal soaps such as cobalt naphthenate and cobalt octylate. The addition amount is preferably 0.1 to 3 parts by mass, more preferably 0.3 to 1 part by mass with respect to 100 parts by mass in total of the components (A) and (B). Examples of other drying aids include metal soaps such as zinc octylate, vanadium octylate, copper naphthenate, and barium naphthenate, and metal chelates such as vanadium acetyl acetate, cobalt acetyl acetate, and iron acetylacetonate. . These drying aids may be added to the resin composition in advance, or may be added at the time of use. The usage-amount of a hardening accelerator is 0.1-5 mass parts.

  In the resin composition of the present invention, a radical curing agent, a photo radical initiator, and a polymerization inhibitor can be used to adjust the curing rate.

  Examples of the radical curing agent include organic peroxides, specifically, diacyl peroxides, peroxyesters, hydroperoxides, dialkyl peroxides, ketone peroxides, peroxyketals, alkyls. Publicly known ones such as peresters and percarbonates may be mentioned. It is preferable that the usage-amount of a radical hardening agent is 0.1-6 mass parts with respect to 100 mass parts of total amounts of the resin composition which consists of said (A) (B).

  Examples of photo radical initiators, that is, photosensitizers, include benzoin ethers such as benzoin alkyl ether, benzophenones such as benzophenone, benzyl and methyl orthobenzoylbenzoate, benzyl dimethyl ketal, 2,2-diethoxyacetophenone, 2 Acetophenones such as -hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 1,1-dichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone And thioxanthone series.

  Examples of the polymerization inhibitor include trihydrobenzene, toluhydroquinone, 14-naphthoquinone, parabenzoquinone, hydroquinone, benzoquinone, hydroquinone monomethyl ether, p-tert-butylcatechol, 2,6-di-tert-butyl-4-methyl. Phenol and the like can be mentioned. Preferably, 10 to 1000 ppm can be added to the resin composition.

  In addition to the above, the resin composition of the present invention includes various additives such as fillers, ultraviolet absorbers, pigments, thickeners, low shrinkage agents, anti-aging agents, plasticizers, aggregates, flame retardants, electrification. Inhibitors, stabilizers, fiber reinforcements and the like can be used.

  Examples of fillers include hydraulic silicate materials, calcium carbonate powder, clay, alumina powder, meteorite powder, talc, barium sulfate, silica powder, glass powder, glass beads, mica, aluminum hydroxide, cellulose, silica sand, quartz Examples thereof include sand, river sand, cold water stone, marble waste, crushed stone, colored porcelain, and baked and hardened ceramic body.

  In addition, as a filler for imparting thixotropy, silica powder such as asbestos, ceviolite, and aerosil can be added. In addition to the above, coloring pigments and dyes can be used as the filler. For example, titanium oxide, barium sulfate, carbon black, crimver million, bengara, ultramarine blue, cobalt blue, phthalocyanine blue, phthalocyanine green and the like are used. The amount added is 1 to 500 parts by mass of these fillers per 100 parts by mass of the resin composition of the present invention, and is used for coating.

The composition of the present invention can be cured within 2 hours in a temperature range of −30 ° C. to 50 ° C. using a known redox catalyst comprising a combination of a curing agent and a curing accelerator.
For example, an ultraviolet absorber can be added to the resin composition of the present invention in order to further improve the weather resistance. Examples of such an ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-decyloxybenzophenone, 2-hydroxy-4,4′-dimethoxybenzophenone. Derivatives of 2-hydroxybephenone such as 2-hydroxy-4,4′dibutoxybenzophenone, or 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′) , 5-ditertiarybutylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (2,2′-dimethylpropyl) phenyl] benzotriazole, or a halogen thereof, or phenyl salicylate, p. -Tertiary butyl phenyl salicylate, etc. And the like esters of salicylic acid. The ultraviolet absorber is preferably added in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the resin composition of the present invention.

  The resin composition of the present invention is composed of γ-methacrylopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, N for the purpose of improving the durability of the adhesive strength to the base and the adhesive strength with the filler. Silane coupling agents such as -β- (aminoethyl) -γ-aminopropyltrimethoxysilane and γ-methcaptopropyltrimethoxysilane can be added.

  Further, various antifoaming agents and leveling agents are added for the purpose of adjusting the surface appearance of the coating film, or hydroquinone, hydroquinone monomethyl ether, 2,4-dimethyl for the purpose of improving the storage stability of the resin composition before coating. A polymerization inhibitor such as -6-t-butylphenol can be added to the resin composition of the present invention.

The resin composition of the present invention has a solar reflectance of 15% or more in a wavelength range of 350 to 2100 nm as defined in JIS A 5759 for the purpose of heat shielding, and L in the CIE 1976 L ^* a ^* b ^* color space. ^* A pigment with a value of 30 or less, more preferably a L ^* value of 24 or less may be added. Furthermore, it is also preferable to use a color pigment having a solar reflectance of 12% or more in a wavelength range of 350 to 2100 nm as defined in JIS A 5759 and a white pigment as necessary. Examples of coloring pigments that satisfy this condition include yellow pigments such as monoazo yellow (trade name Hoster Palm Yellow H3G: manufactured by Hoechst), iron oxide (trade name Toda Color 120ED: manufactured by Toda Kogyo Co., Ltd.), Red pigments such as quinacridone red (trade name Hostaperm Red E2B70: manufactured by Hoechst), blue pigments such as phthalocyanine blue (trade name cyanine blue SPG-8: manufactured by DIC Corporation), phthalocyanine green (trade name cyanine) Green 5310: manufactured by Dainichi Seika Kogyo Co., Ltd.) and the like.

  The paving material of the present invention is obtained by adding various additives such as the pigment to the resin composition of the present invention as required, and is applied to an asphalt paving layer. Asphalt pavement is an asphalt composition in which aggregate selected in asphalt is mixed at a heating temperature of 150 to 260 ° C, laid on a base such as a roadbed, and compacted with a power roller to form a pavement layer. . Examples of the asphalt include natural asphalt such as lake asphalt, rock asphalt, and asphaltite, petroleum asphalt such as straight asphalt and blown asphalt, semi-blown asphalt, hard asphalt, thermosetting resin, thermoplastic resin, rubber, etc. It also contains asphalt that has been modified.

  The pavement structure of the present invention is a structure such as a road having an asphalt pavement layer such as a bridge, a viaduct or a general road, and is obtained by applying the resin composition of the present invention or the pavement material to the asphalt pavement layer. It is done.

  The resin composition of the present invention is particularly useful as an asphalt pavement material and road marking material because it passes the Fire Services Act No. 2 petroleum, is excellent in low odor, and is excellent in tire contamination resistance and tensile properties during use. However, it is also useful when used for various purposes such as putty, paint, flooring, wall coating material, lining material.

  Hereinafter, the present invention will be described in more detail with reference to examples. Also, “parts” and “%” in the text indicate parts by mass and mass%.

Synthesis Example 1 <Epoxy (meth) acrylate resin>
Epichlorone 850 (made by DIC Corporation) having an epoxy equivalent of 185 obtained by reaction of bisphenol A and epichlorohydrin in a three-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 1850 g of methacrylic acid, 860 g Then, 1.36 g of hydroquinone and 10.8 g of triethylamine were charged, the temperature was raised to 120 ° C., and the mixture was reacted at the same temperature for 10 hours to obtain an epoxy methacrylate resin (A-1) having an acid value of 3.5.

Synthesis Example 2 <Urethane (meth) acrylate resin>
In a 5 liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser, 2461 parts of polypropylene glycol (number average molecular weight 984.2), 739.5 parts of tolylene diisocyanate, isophorone diisocyanate 166.8 parts were charged, heated to 80 ° C. in a nitrogen atmosphere, reacted for 3 hours, and when NCO equivalent 697 was reached, after cooling to 50 ° C., in a nitrogen / air (flow rate ratio 1/1) mixed gas stream Then, 0.337 parts of toluhydroquinone and 657.7 parts of hydroxyethyl methacrylate are added, and the temperature is raised again to 90 ° C. The reaction was performed for 3 hours to obtain a urethane methacrylate resin (A-2) having a residual NCO amount of 0.0343%.

Synthesis Example 3 <(Meth) acrylic copolymer> Polymer (1)
450 parts of xylene was added to a reaction vessel equipped with a stirrer, a thermometer, a cooler, and a nitrogen introduction tube, and the temperature was raised to 115 ° C. and maintained at this temperature. Next, 240 parts of methyl methacrylate (MMA), 160 parts of n-butyl methacrylate (nBMA), 3 parts of di-tert-butyl peroxide, and 150 parts of xylene were added dropwise over 4 hours.
Even after completion of dropping, the solution was kept at 120 ° C. for 8 hours to obtain a solution of polymer (1) having a nonvolatile content of 40%. Thereafter, the temperature was raised to 170 ° C. and the pressure was reduced to obtain a polymer (1) having a weight average molecular weight of 35,000.
Synthesis Example 4 <(Meth) acrylic copolymer> Polymers (2), (3), (4), (5)
In the same reaction vessel and reaction conditions as in Synthesis Example 3, the weight-average molecular weight was mixed with di-tert-butyl peroxide in the mixing ratio of methyl methacrylate (MMA) and n-butyl methacrylate (nBA) as shown in Table 1. The amount was adjusted to 15 parts for 10,000 to 15,000 and 1.0 part for 100,000 or more. Other (meth) acrylic copolymer polymers ((2), (3), (4), (5)) having the weight average molecular weight and composition ratio shown in Table 1 below were obtained. Polymers (2), (3) The weight average molecular weights of (4) and (5) were (2) 34,000, (3) 11,000, (4) 100,500, (5) 36,000.

Example 1-6, Comparative Example 1-11
Using the resin compositions shown in Tables 2, 3, and 4, the following evaluation methods were tested with the formulation of Example 1-6 shown in Table 2 and Comparative Example 1-11 shown in Table 3-4.

(Evaluation method)
<Pass / fail of the Fire Services Act 2nd Petroleum>
The flash point of the compounded resin compositions of Examples and Comparative Examples in each table was measured according to JIS K2265-2 using a Seta hermetic flash point measuring instrument (manufactured by Kitahama Measurement Co., Ltd.). Whether the flash point was 21 ° C. or higher or lower than 21 ° C. was judged as acceptable or rejected.

<Odor>
The smell of the blended resin composition in each table was directly sniffed and judged.

<Viscosity>
After adjusting the compounded resin composition of each table | surface to 5 degreeC, it measured with the rotary viscometer according to JISK6901-5.5.

<Compatibility>
It was visually confirmed that the blended resin compositions in each table were separated for 1 month or longer, and in particular, the separated portion was not solidified.

<Tensile properties>
Two parts by mass of 40% benzoyl peroxide (40% BPO) were mixed and added to the blended resin compositions in each table. After curing at 23 ° C. for 3 days, the tensile properties were measured according to JIS K6911-5.18. The test speed is 5 mm / min.

<Tire resistance>
Regarding tire stain resistance, 50 g of the blended resin composition shown in each table was weighed into a 100-ml capacity descup and the resin temperature was adjusted to 5 ° C., and then 5 parts of 40% benzoyl peroxide (40% BPO) was mixed and added. This was applied with an applicator so as to have a thickness of 0.07 mm on a slate plate in an environmental test chamber under predetermined conditions (5 ° C., 80%). After blending the curing agent, the black rubber plug was rubbed 120 minutes later, and the elapsed time until the rubbed material could be removed with an eraser was measured.

I-butyl methacrylate (flash point: 45 ° C)
Pentyl methacrylate (flash point: 65 ° C)
2-hydroxyethyl methacrylate (flash point: 108 ° C)
Cyclohexyl methacrylate (flash point: 91 ° C)
Dicyclopentenyloxyethyl methacrylate (flash point: 176 ° C)
Human lahydrofurfuryl methacrylate (flash point: 102 ° C)
Methyl methacrylate (flash point: 10 ° C)
Source: Chemical products of 15308 (Chemical Industry Daily)

<Pass / fail of 2nd petroleum>
○: 21 ℃ or higher Pass ×: less than 21 ℃ Fail

<Odor>
◎: Odorless ○: MMA odor ×: Odor

<Evaluation of compatibility>
○: No separation over 1 month
△: Separation within 1 day
×: separated immediately after compounding

<Evaluation of viscosity (5 ° C.)>
○: Less than 1000 mPa · s
Δ: 1000 or more to less than 2000 mPa · s ×: 2000 mPa · s or more

<Evaluation of tensile strength (25 ℃)>
○: 40 MPa or more
Δ: 30 to less than 40 MPa
×: Less than 30 MPa

<Tire contamination resistance evaluation>
○: No contamination within 2 hours.
Δ: No contamination after 2 hours and less than 4 hours.
×: Contaminated even after 4 hours or more.

<Pass / fail of 2nd petroleum>
○: 21 ℃ or higher Pass ×: less than 21 ℃ Fail

<Odor>
◎: Odorless ○: MMA odor ×: Odor

<Evaluation of compatibility>
○: No separation over 1 month
△: Separation within 1 day
×: separated immediately after compounding

<Evaluation of viscosity (5 ° C.)>
○: Less than 1000 mPa · s
Δ: 1000 or more to less than 2000 mPa · s ×: 2000 mPa · s or more

<Evaluation of tensile strength (25 ℃)>
○: 40 MPa or more
Δ: 30 to less than 40 MPa
×: Less than 30 MPa

<Tire contamination resistance evaluation>
○: No contamination within 2 hours.
Δ: No contamination after 2 hours and less than 4 hours.
×: Contaminated even after 4 hours or more.

(Abbreviation explanation)
PTD-2EO: paratoluidine ethylene oxide 2-mole adduct cobalt: cobalt octylate (DICnate 208V manufactured by DIC Corporation)

  The polymer (2) that does not use butyl methacrylate as the (E) as in Comparative Example 7 has insufficient compatibility, and the use of the polymer (3) having a small weight average molecular weight as in Comparative Example 8 prevents tire contamination. When the polymer (4) having a large weight average molecular weight as in Comparative Example 9 is used, the viscosity of the composition is deteriorated, and the polymer (5) having 70% by mass of butyl methacrylate as in Comparative Example 10 is used. Then, the tire contamination resistance is poor. If the radical curable resin (A) is not used as in Comparative Example 11, the viscosity, tensile strength, and elongation rate are inferior.

  The present invention includes a radically polymerizable resin composition containing an acrylic copolymer (E) having a specific weight average molecular weight in a specific amount of a mixture of a specific (meth) acrylic compound, thereby preventing tire contamination after curing the resin composition. A radically polymerizable resin composition that is superior in property and tensile properties and has low flammability, low odor, and low viscosity that passes the Fire Fighting Act No. 2 petroleum is obtained. And a pavement structure using the same.

That is, the present invention is a radical polymerization comprising a radical curable resin (A) having both terminal (meth) acryloyl groups, a polymerizable unsaturated monomer (B), a paraffin wax (C), and a curing accelerator (D). In the functional resin composition,
The radical curable resin (A) is at least one selected from an epoxy (meth) acrylate resin and a urethane (meth) acrylate resin, and the polymerizable unsaturated monomer (B) is a (meth) acrylic compound. And a flash point of 70 ° C. or higher which is one selected from the group consisting of 2-hydroxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, cyclohexyl methacrylate and tetrahydrofurfuryl methacrylate. The acrylic compound (B-1) and the (meth) acrylic compound (B-2) having a flash point smaller than 21 ° C. are 9/1 to 5/5, and the weight average molecular weight is 20000 to 50000, and butyl (meta ) A (meth) acrylic polymer (E) containing 5% by mass to less than 70% by mass of acrylate as a copolymerization component is included. The present invention relates to a radical curable resin composition, a pavement material containing the same, and a pavement structure using the same.

That is, the present invention, radical curable resin having both ends meth acryloyl group (A), the polymerizable unsaturated monomer (B), the radical polymerizable composition comprising a paraffin wax (C), the curing accelerator (D) In things,
The radical curable resin (A), epoxy meta acrylate resin is at least one selected from urethane meta acrylate resins, polymerizable unsaturated monomer (B) is at methacrylic compounds, dicyclopentenyloxy ethyl acrylate (B-1) and flash point of 21 ° C. less than methacrylic compound (B-2) = 9 / is 1-5 / 5, further weight-average molecular weight of 3 0000-4 0000, butyl methacrylate acrylate 5 wt% to 70 wt% less than copolymer component to methacrylic polymer radical curable resin composition, characterized in that it is intended to include (E), paving material containing it, and pavement structure using it About.

Claims (7)

In a radically polymerizable resin composition containing a radical curable resin (A) having both terminal (meth) acryloyl groups, a polymerizable unsaturated monomer (B), a paraffin wax (C), and a curing accelerator (D),
The radical curable resin (A) is at least one selected from an epoxy (meth) acrylate resin and a urethane (meth) acrylate resin, and the polymerizable unsaturated monomer (B) is a (meth) acrylic compound. In a mixture of a (meth) acrylic compound (B-1) having a flash point of 70 ° C. or higher and a (meth) acrylic compound (B-2) having a flash point lower than 21 ° C., the mixing mass ratio thereof is ( B-1) / (B-2) = 9/1 to 5/5, the weight average molecular weight is 20000 to 50000, and butyl (meth) acrylate is copolymerized with 5% by mass to less than 70% by mass. A radical polymerizable resin composition comprising a (meth) acrylic copolymer (E). The radical curable resin (A) is a mixture of an epoxy (meth) acrylate resin and a urethane (meth) acrylate resin, and a mixing mass ratio thereof is 7/3 to 3/7. 1. The radical polymerizable resin composition according to 1. The radically polymerizable resin composition according to claim 1, wherein the (meth) acrylic copolymer (E) is contained in an amount of 5 to 20% by mass in the resin composition. The radical polymerizable resin composition according to any one of claims 1 to 3, wherein the (meth) acrylic compound (B-2) having a flash point lower than 21 ° C is methyl methacrylate. The (meth) acrylic copolymer is characterized in that (E) is composed of 5 to 70% by mass of butyl (meth) acrylate and 95 to 30% by mass of another alkyl (meth) acrylate. The radically polymerizable resin composition of any one of Claims 1-4. A paving material comprising the resin composition according to any one of claims 1 to 5. A pavement structure comprising a cured product layer of the resin composition according to any one of claims 1 to 5 and an asphalt pavement layer.