JPWO2011013532A1 - Radical curable resin composition, paving material using the same, and paving structure - Google Patents

Abstract

  The object of the present invention is radical polymerization comprising a radical curable resin (A) having both terminal (meth) acryloyl groups, a polymerizable unsaturated monomer (B), paraffin wax (C), and a curing accelerator (D). In the curable resin composition, by including a specific (meth) acrylic copolymer excellent in compatibility with the composition, the radical curable resin composition is improved in tire stain resistance after curing and excellent. It is intended to provide a radically polymerizable resin composition that can obtain excellent physical properties, a paving material using the same, and a paving structure.

Description

  The present invention relates to a radical curable resin composition capable of obtaining a cured product excellent in tire stain resistance, compatibility, and physical properties, a paving material using the same, and a paving 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, a low molecular weight component of a radically polymerizable air-drying component tends to remain during curing, and in order to increase the elongation rate of the unsaturated resin cured product, in particular, When the bond concentration is lowered, the surface curability is remarkably lowered, and after construction on an asphalt road, there is a problem that the tire surface is inferior in resistance to tire contamination, such as tire marks adhering to the road surface.

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

  An object of the present invention is to provide a radical curable resin composition that is excellent in compatibility and compatibility with tire tires with improved resistance to tire contamination after curing of a radical curable resin composition containing paraffin wax and a curing accelerator. An object of the present invention is to provide a paving material and a paving structure.

The inventors of the present invention performed addition of an acrylic polymer to a radical curable resin composition containing a wax and a curing accelerator, and found that the compatibility was poor. Therefore, as a result of earnest research on an acrylic polymer that is excellent in compatibility with a radical curable resin having a (meth) acryloyl group and can improve tire stain resistance, a specific monomer was used at a specific weight average molecular weight ( It has been found that the addition of a (meth) acrylic copolymer can solve the problems of compatibility, resistance to tire contamination, and physical properties, and the present invention has been completed.
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 polymerizable 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 having a (meth) acrylic copolymer (E) in the resin composition and a (meth) acrylic copolymer (E) having a weight average molecular weight of 20,000 to 50,000 A radical-polymerizable resin composition comprising butyl (meth) acrylate as a copolymer component in an amount of 5% by mass to less than 70% by mass, a paving material using the same, and a paving structure That.

  The present invention includes a specific (meth) acrylic copolymer excellent in compatibility with the resin composition in the radical polymerizable resin composition, so that the tire contamination resistance can be improved, and the tensile strength, elongation, etc. It is possible to provide a radical polymerizable resin composition from which a cured product having excellent physical properties can be obtained, a paving material using the same, and a paving structure.

  The radical curable resin (A) having both end (meth) acryloyl groups used in the present invention is a liquid at room temperature dissolved in the polymerizable unsaturated monomer (B), and an epoxy (meth) acrylate resin, One or more selected from urethane (meth) acrylate resins. Furthermore, a polyester (meth) acrylate resin may be used in combination as long as the effects of the present invention are not impaired. Specifically, the resin (A) includes an epoxy (meth) acrylate resin derived from an addition reaction product of an epoxy resin and an unsaturated monobasic acid, a polyisocyanate, a polyol having a terminal hydroxyl group, and a hydroxyl group-containing (meth) acrylate. It is 1 type chosen from urethane (meth) acrylate resin which consists of. The polyester (meth) acrylate resin is derived from a polyester resin at both acid ends and glycidyl (meth) acrylate.

  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 acrylate resin (also referred to as a vinyl ester resin) obtained by reacting an epoxy resin and 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, glycol Type glycidyl ether type, peracetic acid oxidation type and the like are exemplified, and each can be used alone or in combination. As unsaturated monobasic acids, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, HEMA (hydroxyethyl methacrylate), HEA (hydroxyethyl acrylate), HPMA (hydroxypropyl methacrylate), HPA (hydroxypropyl) Acrylate), DCPD (dicyclopentadiene), and the like, and maleate compounds composed of maleic anhydride, can be used alone or in combination.

  Furthermore, in the process for producing an epoxy (meth) acrylate resin (vinyl ester resin), an epoxy oligomer can be synthesized by reacting a low molecular weight bisphenol type epoxy with bisphenol A, and then an unsaturated monobasic acid can be reacted. A part of the unsaturated monobasic acid can also be reacted with a dicarboxylic acid compound (eg, adipic acid, sebacic acid, dimer acid) or a corresponding terminal carboxyl liquid rubber (eg, liquid nitrile rubber). It is also possible to react the hydroxyl group of the vinyl ester resin with an isocyanate compound or a urethane prepolymer. 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, for example, an isocyanate group-terminated urethane prepolymer obtained by reacting a polyisocyanate with a polyol such as a polyether polyol, a polyester polyol, or a polyacryl polyol, and a hydroxyl group content such as a hydroxyalkyl (meth) acrylate (meta ) It is obtained by reacting with an acrylic compound. An ether bond-containing urethane (meth) acrylate 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, and is optionally produced by using an aromatic and aliphatic or aliphatic saturated dibasic acid as an acid component. Saturated polyester is mentioned. 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 has a hydroxyl group at both ends or side chains obtained by reacting from a polymerizable monomer such as 2-hydroxyalkyl (meth) acrylate and another acrylic polymerizable monomer (such as pentaerythritol triallyl ether). It is an acrylic polymer. Such a reaction can be obtained by using an ordinary 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 the aliphatic or alicyclic saturated dibasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof. There are compounds, etc., which are 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. , Used alone or in combination. In addition, adducts such as ethylene oxide and propylene oxide can be used in the same manner. 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, Crisbon NX (DIC Corporation product), Desmodur L (Sumitomo Bayer product), Coronate L (Nippon Polyurethane product) In particular, TDI is preferably used.

  Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and the like.

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

  The polyester (meth) acrylate resin production method includes α, β-unsaturated dibasic acid or acid anhydride thereof or aromatic saturated dibasic acid or acid anhydride thereof and polycondensation of glycols, and in some cases acid. After using aliphatic or aliphatic saturated dibasic acid as a component and reacting in a conventional manner with an acid component excess having an acid / glycol molar ratio of 1/1 to 1.1 / 1, the terminal acid It can be produced by reacting a glycidyl compound having a (meth) acryloyl group in the group.

  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. Examples of aliphatic or alicyclic saturated dibasic acids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof. Or used together.

  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 glycidyl compound having a (meth) acryloyl group include glycidyl acrylate and glycidyl methacrylate.

The polymerizable unsaturated monomer (B) is a (meth) acrylic compound and is a so-called (meth) acryloyl group-containing monomer. These include, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, decyl acrylate, lauryl acrylate, acrylic acid Stearyl, polycaprolactone acrylate, diethylene glycol monomethyl ether monoacrylate, dipropylene glycol monomethyl ether monoacrylate, 2-ethylhexyl carbitol acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate , Hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, decyl methacrylate, lauryl methacrylate, methacryl Stearyl, 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, nonylphenyl carbitol Tacrylate, nonylphenol EO modified methacrylate, phenoxypropyl methacrylate, phenol PO modified methacrylate, nonylphenoxypropyl methacrylate, nonylphenol PO modified methacrylate, methacryloyloxyethyl phthalate, dicyclopentenyloxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, etc. Is mentioned. 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.

The polymerizable unsaturated monomer (B) is a monomer having at least two ethylenically unsaturated groups, preferably (meth) acryloyl groups in one molecule, as long as the effects of the present invention are not impaired. May be used in combination. By using this monomer in combination, the wear resistance, scratch resistance, peristaltic resistance, chemical resistance, etc. of the cured product surface can be improved. 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 mixing ratio (% by mass) of the radical curable resin (A) and the polymerizable unsaturated monomer (B) is preferably (A) / (B) = 30/70 to 70/30 (% by 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. Further, when the amount of the monomer (B) is more than 70% by mass, the asphalt solidifying the aggregate of the asphalt pavement promotes the elution of the asphalt into the component (B) and the asphalt cutback, and the asphalt pavement structure. It itself causes damage and is not preferable.

  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 added is preferably 500 ppm to 10,000 ppm with respect to the resin composition. Furthermore, 2000 ppm to 8000 ppm is more preferable from the viewpoint of drying properties and viscosity.

  The curing accelerator (D) is preferably a cobalt compound. Examples of the cobalt compound include metal soaps such as cobalt naphthenate and cobalt octylate.

  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. The copolymer is preferably 5 to 60% by mass and other alkyl (meth) acrylates 95 to 30% by mass, 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, when the weight average molecular weight is smaller than the above range, the tire contamination resistance is inferior, and when 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. N-butyl methacrylate is preferred. Further, the (meth) acrylic copolymer (E) is preferably contained in an amount of 5% by mass to 20% by mass in the resin composition.

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. manufactured, C ₁₂ - / C ₁₃ methacrylate mixture), stearyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate , Isobornyl (meth) acrylate or 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% by mass to more than 30% by mass, preferably 95% by mass to 40% by mass in the copolymer. Outside this range, the radical curable resin (A) is incompatible with the storage stability.

  In the present invention, a known air-drying unsaturated resin may be used in combination. In that case, it is preferable that the non volatile matter (resin solid content) in the resin composition of this invention is 30-70 mass%. When the amount is less than this range, the coating layer strength on the pavement layer is inferior, and when the amount is large, the coating workability is inferior.

  The air-drying unsaturated resin 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, etc. (Meth) acrylate resin, air-drying epoxy (meth) acrylate, air-drying urethane (meth) acrylate, air-drying unsaturated polyester, etc. are mentioned. Among these, air-drying polyester (meth) acrylate is preferably mentioned in terms of easy physical property adjustment and yellowing resistance.

  As the curing accelerator (D) used in the present invention, a curing accelerator other than the cobalt-based compound that is preferably used may be added within a range that does not impair the effects of the present invention. For example, metal soaps such as zinc octylate, vanadium octylate, copper naphthenate, barium naphthenate, metal chelates such as vanadium acetyl acetate, cobalt acetyl acetate, iron acetylacetonate, aniline, N, N-dimethylaniline, N, N-diethylaniline, p-toluidine, N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p-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, diethylenetri N, N-substituted anilines such as amine, pyridine, phenylmorpholine, piperidine, N, N-bis (hydroxyethyl) aniline, diethanolaniline, N, N-substituted-p-toluidine, 4- (N, N-substituted) And amines such as amino) benzaldehyde. Of these, amines and metal soaps are preferred. You may use a hardening accelerator 1 type or in combination of 2 or more types. This curing accelerator 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 becomes like this. Preferably it is 0.1-5 mass parts in a total of 100 mass parts of a resin composition.

  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.

  The radical curing agent is preferably an organic peroxide, specifically, a diacyl peroxide type, a peroxy ester type, a hydroperoxide type, a dialkyl peroxide type, a ketone peroxide type, a peroxy ketal type. And publicly known ones such as alkyl peresters and percarbonates. 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 a resin composition.

  Examples of the photo radical initiator, i.e., photosensitizer, include benzoin ethers such as benzoin alkyl ether, benzophenone, benzophenone such as benzyl, methyl orthobenzoyl benzoate, benzyl dimethyl ketal, 2,2-diethoxyacetophenone, Acetophenones such as 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 1,1-dichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropyl Examples include thioxanthone series such as thioxanthone.

  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, silane coupling agents, thickeners, low shrinkage agents, anti-aging agents, plasticizers, and aggregates. In addition, flame retardants, antistatic agents, surfactants, antifoaming agents, leveling agents, heat shields, stabilizers, fiber reinforcing materials, and the like can be used.

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

  Further, 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 with respect to 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 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 composition of the present invention.

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

  Furthermore, in order to improve the surface appearance of the coating film, various antifoaming agents and leveling agents are added, or in order to improve the storage stability of the composition before coating, hydroquinone, hydroquinone monomethyl ether, 2,4-dimethyl- A polymerization inhibitor such as 6-t-butylphenol can be added to the 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 imparting heat shielding properties, and CIE 1976 L ^* a ^* b ^* color. A heat-shielding pigment having an L ^* value in space of 30 or less, more preferably an 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 pavement material of the present invention is obtained by mixing the resin composition as it is or with the components that can be added. Moreover, a pavement structure is what has this pavement material as a surface layer by apply | coating with the well-known application methods, such as a brush, a roller, and a spray. This pavement is a known asphalt pavement, concrete pavement, or the like.

  The resin composition of the present invention is excellent in compatibility and excellent in tire stain resistance and curability during use, and is particularly useful as a pavement material and road marking material for asphalt pavement structures. It is also useful when used as a covering material such as a flooring material, wall surface 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>
1850 g of epoxy resin having an epoxy equivalent of 185 obtained by the 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, 860 g of methacrylic acid, 1.36 g of hydroquinone and triethylamine 10.8 g was 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 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. Reaction was performed for 3 hours to obtain a urethane methacrylate resin having a residual NCO amount of 0.0343%.

Synthesis Example 3 <(Meth) acrylic copolymer> Polymer (11)
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.
After completion of the dropping, the solution was kept at 120 ° C. for 8 hours to obtain a polymer (11) solution having a nonvolatile content of 40%. Thereafter, the temperature was raised to 170 ° C. and the pressure was reduced to obtain a polymer (11) having a weight average molecular weight of 35,000.

Synthesis Example 4 <(Meth) acrylic copolymer> Polymers (1) to (10), (12) to (18)
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 (1) to (10) and (meth) acrylic copolymers (12) to (18) having the weight average molecular weight and composition ratio shown in Table 1 below were obtained. The weight average molecular weights of the polymers (1) to (10) and (12) to (18) are (1) 12,000, (2) 34,000, (3) 110,000, (4) 11,000, (5) 35,500, (6) 110,000, (7) 11,000, (8) 34,500, (9) 110,000, (10) 11,000, (12) 100, 500, ( 13) 12,000, (14) 36,500, (15) 110,000, (16) 11,000, (17) 36,000, (18) 110,000.

Synthesis Example 5 <Air-drying polyester (meth) acrylate resin>
5 mol of phthalic anhydride, 6.2 mol of triethylene glycol, 3.3 mol of diethylene glycol and 5 mol of cis-3-methyl-4-cyclohexene-cis-1,2-dicarboxylic anhydride were added to a thermometer, stirrer, Into a four-necked flask equipped with an active gas inlet and a reflux condenser, 0.5% by mass of dibutyltin oxide was added as an esterification catalyst and reacted at 205 ° C. for 11 hours.
Thereafter, the mixture was cooled to 140 ° C., and then a predetermined amount of 1.3 mol of glycidyl methacrylate was added and reacted for 10 hours to obtain polyester methacrylate. This resin is referred to as [air-drying resin a].

Examples 1-9, Comparative Examples 1-11
Using the (meth) acrylic copolymers (1) to (18) shown in Table 1, the following evaluation methods were tested in the formulations of Examples 1 to 9 and Comparative Examples 1 to 11 shown in Tables 2 to 4. went.

(Evaluation method)
<Tire resistance>
Tire contamination resistance was measured by weighing 50 g of the resin compositions of Examples and Comparative Examples in a 100 ml capacity cup and adjusting the temperature of the resin composition to 5 ° C., followed by curing agent (40% benzoyl peroxide, 40% BPO). ) Was added and mixed. 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 (room temperature 5 ° C., humidity 80%). Curing agent, after 60 minutes, 90 minutes, 120 minutes, and after that, rub the black rubber plug by hand on the coating film, determine whether the rubbed marks can be removed with an eraser, and after mixing The elapsed time of was measured.

<Compatibility>
Tables 2, 3 and 4 Examples and Comparative Examples A to D (curing agent: excluding 40% BPO) were all blended, and there was no separation for one month or more, especially solidified It was visually confirmed that there was nothing.

<Viscosity>
After adjusting the resin composition to 5 ° C., it was measured with a rotary viscometer according to JIS K6901-5.5.

<Tensile properties>
Two parts of a curing agent (40% benzoyl peroxide) was added to and mixed with the resin composition. After curing at 25 ° C. for 3 days, the tensile properties were measured according to JIS K6911-5.18. The tensile test speed is 5 mm / min.

<Evaluation of resistance to tire contamination>
○: Marks can be erased with an eraser within 2 hours.
Δ: Marks can be erased with an eraser in excess of 2 hours and in less than 4 hours.
X: The mark cannot be erased with an eraser even after 4 hours or more.

<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

<Evaluation of elongation (25 ° C)>
○: Elongation rate of 3.0% or more
Δ: Elongation of 1.0 to less than 3.0% ×: Elongation of less than 1.0%

(Abbreviation explanation)
Curing accelerator: PTD-2EO: paratoluidine ethylene oxide 2 mol adduct Curing accelerator: Cobalt: Cobalt octylate (DIC NAT 208V manufactured by DIC)
Radical curing agent: 40% BPO: Benzoyl peroxide (NIPPER NS, manufactured by NOF Corporation)
MMA: Methyl methacrylate DCPD-MA: Dicyclopentenyloxyethyl methacrylate

  When the (meth) acrylic copolymer (E) is not used as in Comparative Example 1, the tire contamination resistance is inferior, and as in (E) as in Comparative Examples 2 to 4, butyl methacrylate is not used. In addition, tire contamination resistance, compatibility, and viscosity are not sufficient, and if the weight average molecular weight is not as in Comparative Examples 5 to 8, tire contamination resistance, compatibility, and viscosity are not sufficient, as in Comparative Example 9. In addition, 70% by mass of butyl methacrylate (E) is inferior in resistance to tire contamination. If radical curable resin (A) is not used like Comparative Examples 10-11, it will be inferior to a viscosity, tensile strength, and elongation rate.

  The resin composition of the present invention is excellent in compatibility, and can provide a cured product with improved physical properties and tire stain resistance. Therefore, it is possible to provide a paving material and a paving structure on which the paving material is constructed.

The inventors of the present invention performed addition of an acrylic polymer to a radical curable resin composition containing a wax and a curing accelerator, and found that the compatibility was poor. Therefore, as a result of earnest research on an acrylic polymer that is excellent in compatibility with a radical curable resin having a (meth) acryloyl group and can improve tire stain resistance, a specific monomer was used at a specific weight average molecular weight ( It has been found that the addition of a (meth) acrylic polymer can solve the problems of compatibility, resistance to tire contamination, and physical properties, and the present invention has been completed.
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), epoxy (meth) acrylate resin is at least one selected from urethane meta acrylate resins, polymerizable unsaturated monomer (B) is a methacrylic compound, curing accelerator (D) is a cobalt-based compound, wherein comprises the resin composition methacrylic polymer (E), methacrylic copolymer (E) is a weight average molecular weight 20,000～50000, butyl methacrylate 5% by mass to less than 70% by mass, and 5 to 20% by mass of the methacrylic copolymer (E) is contained in the resin composition.
, Mixing ratio of the radical-curable resin (A) and the polymerizable unsaturated monomer (B) (mass%) of the (A) / (B) = 50 / 50~70 / 30 der Rukoto A characteristic radical curable resin composition. The present invention relates to a paving material and a paving structure using the same.

Synthesis Example 4 <methacrylic copolymer> Polymer (1) to (10), (12) - (18)
In the same reaction vessel and reaction conditions as in Synthesis Example 3, the weight-average molecular weight was di-tert- at a compounding ratio of methyl methacrylate (MMA) and n-butyl methacrylate (n-B M A) as shown in Table 1. It was synthesized by adjusting the blended amount of butyl peroxide (15 parts for 10,000 to 15,000 is 1.0 part for 100,000 or more). The weight average molecular weight shown in Table 1, other methacrylic copolymer polymer having a composition ratio (1) to (10), and obtain a methacrylic copolymer (12) to (18). The weight average molecular weights of the polymers (1) to (10) and (12) to (18) are (1) 12,000, (2) 34,000, (3) 110,000, (4) 11,000, (5) 35,500, (6) 110,000, (7) 11,000, (8) 34,500, (9) 110,000, (10) 11,000, (12) 100,500, ( 13) 12,000, (14) 36,500, (15) 110,000, (16) 11,000, (17) 36,000, (18) 110,000.

Claims (6)

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. And the resin composition contains (meth) acrylic copolymer (E), (meth) acrylic copolymer (E) has a weight average molecular weight of 20,000 to 50,000, and butyl (meth) acrylate Is a radically polymerizable resin composition characterized by comprising 5% by mass to less than 70% by mass of a copolymerization component. The radically polymerizable resin composition according to claim 1, wherein the (meth) acrylic copolymer (E) is contained in an amount of 5 to 20 mass% in the resin composition. Furthermore, a hardening accelerator (D) is a cobalt type compound, The radically polymerizable resin composition in any one of Claims 1-2 characterized by the above-mentioned. The (meth) acrylic copolymer (E) comprises 5% by mass to less than 70% by mass of butyl (meth) acrylate and more than 30% by mass to 95% by mass of another alkyl (meth) acrylate. The radically polymerizable resin composition according to claim 1, wherein the radically polymerizable resin composition is present. A paving material comprising the resin composition according to any one of claims 1 to 4. It has a hardened material layer of the resin composition of any one of Claims 1-4, The pavement structure characterized by the above-mentioned.