JP2002227110A - Resin pavement material and installation method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pavement material mainly constituted of a vinyl ester resin using a PET(polyethylene terephthalate) raw material and having improved sticking force of an aggregate. SOLUTION: A vinyl ester resin composition A containing the vinyl ester resin made of polyester containing a terephthalic acid component and an ethylene glycol components as essential components and having (metha)acrylic group at a molecular terminal, an ethylene monomer, and an air drying property applying polymer and an antiskid aggregate B are used as main components to form the resin pavement material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin-based pavement material having excellent adhesion to non-slip aggregates. A polyester (meth) acrylate-containing vinyl ester resin (a), an air-drying imparting polymer (b), an ethylenically polymerizable monomer (c), and a non-slip aggregate (B). The present invention relates to a resin-based pavement material and a method for constructing a resin-based pavement using the pavement material.

[0002]

2. Description of the Related Art Among resin-based pavement materials, a resin-based non-slip pavement resin is a thermosetting resin applied to an existing or new asphalt or concrete pavement surface, and abrasion-resistant resin is applied thereon. Non-slip aggregates are sprayed to fix the aggregates on the road surface. For the thermosetting resin having a vinyl ester resin, for example, JP-A-04-202410
And Japanese Patent Application Laid-Open No. 05-9245 are known.

[0003] These resins are faster in curing than thermosetting resins such as epoxy resins, and can be used for shortening the construction time, so that they are often used in winter or other low temperature periods. However, with the increase in traffic volume in recent years, there are many cases where abrasion-resistant non-slip aggregate adhesive force is required more than ever before to provide on roads with heavy traffic volume.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a pavement material in which the adhesion of aggregate is further improved.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, they have included a terephthalic acid component and an ethylene glycol component as essential components, and have a (meth) acryl group at a molecular terminal. The present inventors have found that a vinyl ester resin composition comprising a polyester (meth) acrylate having a higher adhesiveness to aggregate than existing vinyl ester resins has led to the completion of the present invention.

That is, the present invention relates to (a) a vinyl ester resin comprising a polyester (meth) acrylate containing a terephthalic acid component and an ethylene glycol component as essential components and having a (meth) acryl group at a molecular terminal, and (b)
An object of the present invention is to provide a resin-based pavement containing a vinyl ester resin composition (A) containing an ethylenic monomer and a non-slip aggregate (B) as main components, and a method for applying the same.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Polyethylene terephthalate (PET), which can be a raw material component of a terephthalic acid component and an ethylene glycol component in the present invention, is a polyester consisting of only terephthalic acid and ethylene glycol,
It is a polyester containing these as a main component, and is widely used as chemical fibers and engineering plastics. In addition, molded bottles such as PET bottles and PET sheets used as beverage containers,
Also includes crushed materials such as collected PET molded product waste. These recovered PET pulverized materials, preferably vertical and horizontal (1 to 2
0 mm × 1 to 20 mm).

The PET used in the present invention contains terephthalic acid and ethylene glycol as its main components, and a saturated dibasic acid such as isophthalic acid or other glycols such as cyclohexanedimethanol and diethylene glycol. It also includes those contained. This PET-derived component is preferably 5-70% by weight, more preferably 10-40% by weight in the vinyl ester resin.
It is.

The polyester (A) containing a terephthalic acid component and an ethylene glycol component as essential components of the resin composition (A) of the present invention and having a (meth) acryl group at a molecular terminal (hereinafter referred to as an acrylic group-containing polyester). )) Is preferably a vinyl ester resin
A saturated polyester and / or unsaturated polyester containing ET as an essential raw material component and having a (meth) acryl group at a molecular terminal, more preferably PET
It is a saturated polyester and / or unsaturated polyester containing a terephthalic acid ester oligomer produced by alcoholysis with a polyhydric alcohol as an essential raw material component and having a (meth) acryl group at a molecular end, and more preferably a saturated polyester and / or unsaturated polyester. A saturated polyester and / or unsaturated polyester having a (meth) acryl group at a molecular terminal obtained by subjecting a carboxyl group at the terminal of a saturated polyester to an acrylidyl group-containing acrylic compound (unsaturated epoxy compound) to undergo an addition reaction is exemplified.

[0010] A terephthalic acid component and an ethylene glycol component as the component (a) of the present invention are contained as essential components,
The vinyl ester resin composed of an acrylic group-containing polyester will be described in more detail. Including the terephthalic acid skeleton and ethylene glycol skeleton of the present invention as essential components,
The vinyl ester resin comprising an acrylic group-containing polyester is a saturated polyester and / or unsaturated polyester containing at least one (meth) acrylate group in one molecule.

The terephthalic acid component and the ethylene glycol component as the component (a) of the present invention are contained as essential components,
A vinyl ester resin comprising an acrylic group-containing polyester is a glycidyl group-containing acrylic compound at a terminal carboxyl group of a saturated polyester produced by the reaction of a glycol containing ethylene glycol as an essential component and a saturated dibasic acid containing terephthalic acid as an essential component. (Unsaturated epoxy compounds), preferably those obtained by an addition reaction of an epoxy (meth) acrylate such as glycidyl (meth) acrylate.

As the alcohol component of the acrylic group-containing polyester, it is preferable to use ethylene glycol as an essential component and to use other glycols in combination. Also,
As the acid component, terephthalic acid or its anhydride is an essential component, and another acid component can be used in combination. The molar ratio of ethylene glycol to other glycols was 1/1.
Is preferably from 10 to 10, more preferably from 1/1 to 2. When the molar ratio of the other glycol is in the above range, the ability to follow the road surface and the grip force of the non-slip aggregate are more excellent.

The alcohol unit in the acrylic group-containing polyester is preferably glycol, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, Alkylene represented by 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, dichlorohexanedimethanol, 2,4,4-trimethyl-1,3-pentanediol, etc. Glycols; polyalkylene glycols represented by diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polybutylene glycol, etc .; bisphenol A, bisphenol F, bisphenol S, tetrabromobi Addition reaction products of an alkylene oxide represented by dihydric phenols with ethylene oxide or propylene oxide typified by bisphenol A, etc., and the like.

The saturated dibasic acids include, for example, orthophthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid, nitrophthalic acid , Malonic acid, succinic acid, adipic acid, azelaic acid, 1,12-dodecane 2
Acid, hymic acid, hetonic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4 ′
-Biphenyldicarboxylic acid and acid anhydrides thereof. In use, they may be alkyl esterified compounds when used.

The epoxy (meth) acrylate used in the present invention includes glycidyl esters of unsaturated monobasic acids such as acrylic acid and methacrylic acid, for example, glycidyl acrylate and glycidyl methacrylate.
Glycidyl methacrylate is preferred as the glycidyl ester of the unsaturated monobasic acid.

The number average molecular weight of such an acrylic group-containing polyester is preferably from 1500 to 3000, particularly preferably from 1800 to 2800. When the molecular weight is in the above range, the resulting cured product can have reduced adhesiveness, high strength physical properties, and a relatively short curing time, resulting in excellent productivity.

Specific examples of the vinyl ester resin comprising an acrylic group-containing polyester as the component (a) of the resin composition (A) of the present invention include unsaturated unsaturated compounds formed by the reaction of glycol with a saturated or unsaturated dibasic acid. A polyester obtained by adding an epoxy (meth) acrylate such as glycidyl (meth) acrylate to a terminal carboxyl group of a polyester can be used.

As the glycol unit in the unsaturated polyester (meth) acrylate, the same units as those used in the saturated polyester (meth) acrylate can be used.

As the saturated dibasic acid unit in the unsaturated polyester (meth) acrylate, the same units as those used in the saturated polyester (meth) acrylate can be used.

Examples of the unsaturated dibasic acid unit in the unsaturated polyester (meth) acrylate include maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chlormaleic acid and the like.

The epoxy (meth) acrylate used in the present invention is preferably the same as that used for the saturated polyester (meth) acrylate, such as glycidyl acrylate and glycidyl methacrylate.

The number average molecular weight of the unsaturated polyester (meth) acrylate is preferably from 1500 to 3000, particularly preferably from 1800 to 2800, in order to reduce the tackiness after curing.

The (un) saturated polyester (meth) of the present invention
As a method for producing the acrylate resin composition, one mole or more, preferably 1 to 10 moles of a dihydric alcohol (preferably 1 mole to 10 moles) per mole of the pulverized PET (calculated as the molecular weight 192 of terephthalic acid / ethylene glycol 1 unit) Compounds listed as the glycol units of the saturated polyester acrylate) under a nitrogen atmosphere, preferably 200
Alcoholization at temperatures of ~ 260 ° C to produce terephthalic acid ester oligomer diols (dihydric alcohols), other dihydric alcohols (glycol units), saturated dibasic acids, (unsaturated polyester (meth) acrylate resins and In addition, an unsaturated dibasic acid is also added), and the esterification reaction is carried out under a nitrogen atmosphere, preferably at a temperature of 190 to 220 ° C., to form a terminal carboxyl group of the (un) saturated polyester produced. To an ethylenic monomer such as methyl methacrylate (MMA) by adding an unsaturated epoxy compound such as glycidyl methacrylate to the mixture, preferably at a temperature of 120 to 140 ° C. The vinyl ester resin composition can be obtained by dissolving in the monomer (b).

The ethylenic monomer as the component (b) of the resin composition (A) of the present invention is a vinyl ester resin (a)
An unsaturated monomer or an unsaturated oligomer capable of undergoing a cross-linking reaction with acrylate is exemplified. A monomer or oligomer having an acryloyl group is particularly preferred, and a (meth) acrylate monomer is preferred. Specific examples of these monomers having an acryloyl group include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate Decyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, β-ethoxyethyl acrylate, 2-cyanoethyl acrylate, cyclohexyl acrylate, diethylaminoethyl acrylate,
Methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, 2-hydroxyethyl methacrylate,
2-hydroxypropyl methacrylate, pt-butylcyclohexyl methacrylate, phenyl carbitol methacrylate, nonylphenyl carbitol acrylate, nonifenoxypropyl acrylate, N-vinylpyrrolidone, polycaprolactone acrylate, acryloyloxyethyl phthalate,
Acryloyloxysuccinate, each derivative of dicyclopentanedien, tricyclodecane, and triazine for improving the surface drying property of the cured resin, such as dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tricyclodecanyl acrylate, and tricyclodecanyl acrylate Cyclodecanyl methacrylate, tris (2-hydroxyethyl) isocyanuryl acrylate, and the like are included. Styrene monomers can also be used, but since styrene monomers have asphalt cutback properties,
The range of use is limited only when the ground road is concrete.

As the ethylenic monomer (b) of the present invention, a compound having at least two polymerizable double bonds in one molecule can be used, and abrasion resistance and scratch resistance of the surface of a cured product can be used. It is preferably used for the purpose of improving the sliding resistance, chemical resistance and the like. The compound having at least two polymerizable double bonds in one molecule, that is, the polyfunctional unsaturated monomer is preferably a polyfunctional (meth) acrylate monomer, for example, ethylene glycol di (meth)
Alkanediol di- (meth) acrylates such as acrylate, 1,2-propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate; Propylene glycol di (meth)
Polyoxyalkylene-glycol di (meth) acrylates such as acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, divinylbenzene, diallyl phthalate, triallyl phthalate, triaryl Lucyanurate, triallyl isocyanurate, allyl (meth) acrylate, diallyl fumarate and the like can be mentioned, and these can be used alone or in combination of two or more.

As the (meth) acrylic acid ester monomer (b) of the present invention, an air-drying polymerizable unsaturated monomer may be used. For example, dicyclopentadiene,
Acrylic acid derivatives such as tricyclodecane, dicyclopentenyloxyethyl acrylate, tricyclo [5-2-1-
02,6] decanyl acrylate and the like, and drying oils and epoxy-reactive diluents described below can also be used.

As the ethylenic monomer (b) of the present invention, an unsaturated alcohol monomer may be used. This unsaturated alcohol monomer has an acryloyl group and a hydroxyl group, and specific examples thereof include methacrylic acid 2
-Hydroxyethyl, hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate and the like.

The air-drying-imparting polymer as the component (c) of the composition (A) of the present invention is obtained by introducing an air-drying-imparting component as an essential component into an unsaturated polyester resin or the like.

The above-mentioned air-drying imparting polymer will be described in more detail. The air-drying imparting polymer is a glycol having an allyl hydrogen-containing air-drying imparting component incorporated in the skeleton, glycol and α, β-
An unsaturated polyester comprising an unsaturated dibasic acid and a saturated dibasic acid.

The method for introducing an air-drying component as an essential component into the unsaturated polyester includes the following. 1) A compound containing an allyl ether group represented by -0-CH2-CH = CH2 is used in combination with the glycol component. 2) A compound containing a cycloaliphatic unsaturated polybasic acid and its derivative is used in combination with the acid component. 3) A compound containing dicyclopentadiene is used in combination. 4) Use drying oil and the like together.

As the allyl ether group-containing compound of 1), any of the known compounds can be used, and typical examples thereof include ethylene glycol monoallyl ether and diethylene glycol monoallyl. Ether, triethylene glycol monoallyl ether, polyethylene glycol monoallyl ether,
Propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether, hexylene glycol mono Of polyhydric alcohols such as allyl ether, octylene glycol monoallyl ether, trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether, glycerin monoallyl ether, glycerin diallyl ether, pentaerythritol monoallyl ether, and pentaerythritol triallyl ether; Allyl having an oxirane ring such as allyl ether compound and allyl glycidyl ether Ether compounds and the like.

Among the compounds 1) to 4), examples of the compound containing a cyclic aliphatic unsaturated polybasic acid and its derivative in the acid component 2) include, for example, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, Methyltetrahydrophthalic anhydride, cis-3-methyl-4-cyclohexene-cis-1,2-dicarboxylic acid and its anhydride, α
-Terhinene-maleic anhydride adduct, rosin, ester gum and the like.

Among these 1) to 4), as a method for introducing the compound containing dicyclopentadiene of 3), an addition product (sideca) of dicyclopentadiene and maleic acid, which is known as a method for producing unsaturated polyester, is used. There is a method in which phenol monomaleate is introduced as a monobasic acid into the polyester skeleton.

Of these 1) to 4), 4) drying oil,
As the epoxy-reactive diluent, any of known ones can be used. Typical examples thereof include linseed oil,
Examples include soybean oil, cottonseed oil, peanut oil, coconut oil and the like, or a reaction product of these fatty oils with a polyhydric alcohol such as glycerin.

The epoxy-reactive diluent includes a monoepoxy compound and a polyepoxy compound. The former includes allyl glycidyl ether, n-butyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, Khadura E and the like, and the latter includes UNOX 206, Epicoat 812, DG
E and BDO.

The glycol unit in the unsaturated polyester as the air-drying property imparting polymer includes, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol,
1,2-butanediol, 1,3-butanediol,
1,4-butanediol, neopentyl glycol,
Alkylene glycols represented by 1,6-hexanediol, dichlorohexanedimethanol, 2,4,4-trimethyl-1,3-pentanediol; diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polybutylene glycol Polyalkylene glycols represented by, for example;
There are addition reaction products of a dihydric phenol represented by bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A and an alkylene oxide represented by ethylene oxide or propylene oxide, and diethylene glycol and triethylene glycol are used. preferable.

The saturated dibasic acids include orthophthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid, nitrophthalic acid, malonic acid, Succinic acid, adipic acid, azelaic acid, 1,12-dodecane diacid, hymic acid, hetonic acid, 2,6-naphthalenedicarboxylic acid,
Examples include 2,7-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, and acid anhydrides thereof.

As the α, β-unsaturated dibasic acid or its acid anhydride in the above-mentioned air-drying property imparting polymer unsaturated polyester, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chlormaleic acid Acids and esters thereof.

When the above-mentioned saturated polyester (meth) acrylate (a), unsaturated polyester (meth) acrylate (a), and air-drying imparting polymer (c) are produced,
It is recommended to use a polymerization inhibitor for the purpose of preventing gelation and for controlling the storage stability or curability of the resulting resin. Here, typical examples of the polymerization inhibitor used include hydroquinones such as hydroquinone, pt-butylcatechol and mono-t-butylhydroquinone; hydroquinone monomethyl ether and di-t-butyl-p. -Phenols such as cresol: quinones such as p-benzoquinone, naphthoquinone and p-toluquinone; copper salts such as copper naphthenate;

The vinyl ester resin (a) of the present invention comprising a terephthalic acid skeleton and an ethylene glycol skeleton as essential components and comprising an acrylic group-containing polyester and (c) an air-drying-imparting polymer are represented by (a) / (c) ) Weight ratio is 9
/ 1 to 5/5. When the ratio of (a) to (c) is within the above range, the surface drying property of the cured resin is good, and the properties of the cured resin such as tensile strength, tear strength, water resistance, and heat and humidity resistance are also preferable.

The polymer component (a + c) containing the terephthalic acid component and the ethylene glycol component of the present invention as essential components, and adding the vinyl ester resin (a) composed of an acrylic group-containing polyester and the air-drying imparting polymer (c), The preferred weight ratio [(a + c) / b] of the ethylenically unsaturated monomer (b) is 2/8 to 8/2. With such a weight ratio, the curability of the cured resin material becomes good.

A thermoplastic resin can be added to the resin composition (A) of the present invention for the purpose of improving the air curability of the cured resin and reducing the cure shrinkage. Specific examples of the thermoplastic resin include lower alkyl esters of acrylic acid or methacrylic acid such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, and ethyl acrylate, and styrene, vinyl chloride, and vinyl acetate. Homopolymers or copolymers, at least one of the above-mentioned vinyl monomers, lauryl methacrylate, isovinyl methacrylate, acrylamide, methacrylamide, hydroxyalkyl (meth) acrylate, acrylonitrile, methacrylonitrile, In addition to at least one copolymer of a polymer consisting of acrylic acid, methacrylic acid, and cetylstearyl methacrylate, cellulose acetate butyrate, cellulose acetate propionate, polyether It may be mentioned alkylene, polypropylene, saturated polyester. The amount added is preferably from 0 to 50 parts by weight, particularly preferably from 0 to 35 parts by weight, per 100 parts by weight of the resin composition (A).

The composition (A) of the present invention is characterized by being excellent only in the resin component and the monomer component and excellent in drying property. However, in order to further improve the drying property, paraffin and / or wax are used in combination. You may.

Examples of the paraffin and / or wax used in the present invention include paraffin wax, polyethylene wax, and higher fatty acids such as stearic acid and 1,2-hydroxystearic acid. Preferably, paraffin wax is used. This paraffin and / or wax is added for the purpose of improving the air blocking effect during the curing reaction on the coating film surface and improving the stain resistance. The amount added is 0.1 to 5 parts by weight, preferably 0.2 to 2 parts by weight, based on 100 parts by weight of the total of components (a), (b) and (c).

The resin composition (A) of the present invention is usually cured by adding a curing agent. As a curing agent that can be added, a thermosetting agent is used. In some cases, an ultraviolet curing agent or a light curing agent is used. The amount of the curing agent to be used is generally 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the resin composition.

The thermosetting agent includes an organic peroxide,
Specifically, known materials such as diacyl peroxide, peroxyester, hydroperoxide, dialkyl peroxide, ketone peroxide, peroxyketal, alkylperester, and percarbonate are used. , Kneading conditions, curing temperature and the like are appropriately selected.

The ultraviolet curing agent is a photosensitizing substance,
Specific examples thereof include benzoin ethers such as benzoin alkyl ether, benzophenones such as benzophenone, benzyl and methyl orthobenzoyl benzoate, benzyldimethyl ketal, 2,2-
Acetophenones such as diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone and 1,1-dichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone And thioxanthones such as 2-isopropylthioxanthone.

The photo-curing agent includes a hydroxyalkylphenone compound, an alkylthioxanthone compound, and a sulfonium salt compound.

It is also possible to add a curing accelerator, that is, a substance capable of decomposing the organic peroxide of the curing agent by a redox reaction and facilitating the generation of active radicals. Examples of the curing accelerator include cobalt-based, vanadium-based, and manganese-based metal soaps, tertiary amines, quaternary ammonium salts, and mercaptans.

Specific examples of the curing accelerator include organic metal salts such as cobalt naphthenate, cobalt octylate, vanadyl octylate, copper naphthenate and barium naphthenate, and amines such as dimethylaniline and the like.
N, N-diethylaniline, N, N-dimethylparatoluidine, N, N-dihydroxyethylparatoluidine,
N-ethyl-methtoluidine, triethanolamine,
Examples include metatoluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, diethanolaniline and the like.

The addition amount is a commonly used amount, and is preferably 0.1 to 100 parts by weight of the resin composition.
It is 01 to 4 parts by weight. The above curing agents may be used in combination.

The resin composition (A) according to the present invention may contain a fiber reinforcing material, a filler (d), and a coloring agent such as a pigment or a dye, in addition to the above additives.

The filler (d) used in the present invention includes:
Calcium carbonate powder, clay, alumina powder, silica stone powder, talc, barium sulfate, silica powder, glass powder, glass beads, mica, aluminum hydroxide, cellulose yarn,
Examples thereof include silica sand, river sand, cold water stone, marble chips, crushed stone, and known substances such as silica such as Aerosil and asbestos as a thixotropic agent.

Further, as a coloring pigment or a dye, titanium oxide, barium sulfate, carbon black, chromium vermillion, red bean, ultramarine blue, cobalt blue, phthalocyanine blue, phthalocyanine green and the like can also be used as the filler (d).

The preferred compounding weight ratio [d / (a + b + c)] of the filler (d) and the liquid resin component ((a) + (b) + (c)) is 10/100 to 1000 /
100. With such a weight ratio, the viscosity of the resin composition (A) is appropriate, the sedimentation of the filler is suppressed, the workability is good, the anti-slip aggregate is less sunk, and a sufficient grip force can be obtained. it can.

The resin composition (A) of the present invention includes unsaturated polyester resin, vinyl urethane resin, vinyl ester urethane resin, polyisocyanate, polyepoxide, acrylic resin, alkyd resin, urea resin, melanin resin, Vinyl acetate, vinyl acetate copolymers, polydiene elastomers, saturated polyesters, saturated polyethers, cellulose derivatives such as nitrocellulose, cellulose acetate butyrate, linseed oil, tung oil, soybean oil, castor oil, epoxidized oil, etc. Other conventional natural and synthetic high molecular compounds such as oils and fats can be added.

As the non-slip aggregate (B) used in the resin-based pavement of the present invention, hard aggregates such as colored porcelain aggregates such as silica sand, emery, and cerasand are preferable. The particle size of the aggregate is not particularly limited, but is preferably A1 to B, that is, 0.5 to 3.3 mm. Further, for the purpose of improving visibility, a luminous aggregate such as obsidian or a phosphorescent aggregate can be used. The weight ratio between the vinyl ester resin composition (A) and the non-slip aggregate (B) is preferably from 1/1 to 10.

The resin-based pavement material of the present invention has excellent adhesiveness to asphalt and can be applied directly on an asphalt concrete (ascon) pavement surface, but can be applied on a cement concrete pavement or a steel plate. In this case, it is desirable to apply the non-slip pavement material after the primer treatment.

Regarding the method of applying resin-based pavement using the resin-based pavement material of the present invention, a method of spraying on a pavement surface,
For example, there is a method in which the solution is spread by a rubber lake or the like and uniformly applied.

As a specific example of the construction procedure, the road surface is cleaned with a broom, an electric vacuum cleaner or the like, and tape curing is performed as necessary. In the case of cement concrete, a urethane or acrylic primer is applied, and a vinyl ester resin composition of 1.5 to 2.0 kg / m ² is applied by spraying or casting. After the vinyl ester resin composition is applied, before the resin is cured, 6 to 7 kg / m ² of non-slip aggregate is sprayed using a scoop or a special spraying device. To collect.

An object of the present invention is to provide an excellent non-slip resin-based pavement using a vinyl ester resin composition having a performance excellent in aggregate adhesion as compared with existing vinyl ester resins. Can be. Also, the present invention
As a method of treating waste PET bottles, which has become a major problem from the viewpoint of environmental protection, we have also provided an effective use method by chemical recycling as a raw material of vinyl ester resin.

[0062]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Further, “parts” in the text indicates parts by weight, and “%” is based on weight unless otherwise specified.

Synthesis Example 1 [Synthesis of Saturated Polyester Methacrylate (A-1)] In a 5 L three-necked flask equipped with a thermometer, a stirrer and a condenser, 1229.6 g of diethylene glycol (11.
6 mol), 1536 g of a pulverized PET bottle (equivalent to 8 mol of terephthalic acid / ethylene glycol each) and 1.38 g of dibutyltin oxide were charged in a nitrogen atmosphere at 220 ° C.
The reaction was continued at the same temperature for 4 hours. When the solid acid value reached 3.5, the mixture was cooled to 120 ° C, and 1776 g (12.0 mol) of phthalic anhydride was charged, and the temperature was lowered to 210 ° C.
The reaction was continued for 6.5 hours at the same temperature. When the 70% styrene (hereinafter abbreviated as SM) solution had an acid value of 23.5 and a Gardner viscosity of U-V2, 0.514 g of toluhydroquinone was added. In addition, the mixture was cooled to 130 ° C., and 379.7 g (2.67 mol) of glycidyl methacrylate was charged under an atmosphere of nitrogen / air = 1/1.
The reaction was performed for 2 hours at C, and a 75% methyl methacrylate (hereinafter abbreviated as MMA) solution was sampled to obtain an acid value of 2.0
Was cooled to 90 ° C, and MMA1568.
4 g, 5% copper naphthenate 0.087 g and t-butylcatechol 0.291 g were added to obtain a liquid resin having a nonvolatile content of 75%.

Synthesis Example 2 [Synthesis of Unsaturated Polyester Methacrylate (A-2)] In a 5 L three-necked flask equipped with a thermometer, a stirrer and a condenser, 763.2 g (7.2 mol) of diethylene glycol and a PET bottle were crushed. 691.2 g (equivalent to 3.6 moles of terephthalic acid / ethylene glycol) and 0.73 g of dibutyltin oxide were charged under nitrogen atmosphere.
The reaction was continued for 4.5 hours at the same temperature, and when the acid value reached 0.2, the mixture was cooled to 120 ° C., and 801.4 g (7.56 mol) of diethylene glycol and 1598.4 g of phthalic anhydride were obtained. (10.8 mol), maleic anhydride 4
41 g (4.5 mol), trimethylhydroquinone
148 g was charged and heated to 210 ° C.
The reaction was continued for 5.5 hours, and when the 70% SM solution had an acid value of 12.3 and a Gardner viscosity of YZ2 by sampling, 0.558 g of toluhydroquinone was added, and the mixture was cooled to 130 ° C and nitrogen / air = 1. Glycidyl methacrylate (182.4 g, 1.28 mol) was charged under an atmosphere of 1, and reacted at 130 ° C. for 1 hour.
When the% MMA solution reached an acid value of 1.4, the solution was cooled to 90 ° C., and 1267.7 g of MMA and 0.1% of 5% copper naphthenate were used.
12 g was added to obtain a liquid resin having a nonvolatile content of 75%.

Synthesis Example 3 [Synthesis of air-drying type saturated polyester (C-1)] In a 5 L three-necked flask equipped with a thermometer, a stirrer, and a condenser, 1407 g (9.38 mol) of triethylene glycol and 489.72 g of diethylene glycol were placed. (4.62
Mol), 752.2 g (4.9 mol) of phthalic anhydride,
1162 g (7.0 mol) of PMAA, 1.88 g of dibutyltin oxide and 0.51 g of toluhydroquinone were charged and heated to 205 ° C. under a nitrogen atmosphere. The reaction was continued at the same temperature for 12 hours, and a 70% SM solution was sampled. Acid value
When the temperature reached 10.2, the solution was cooled to 120 ° C, 205.8 g (2.1 mol) of maleic anhydride was charged, the temperature was raised to 190 ° C, the reaction was continued at the same temperature for 5.5 hours, and sampling was performed. When the 75% MMA solution had an acid value of 19.2 and a Gardner viscosity of V, 1245.9 g of MMA, 0.074 g of 5% copper naphthenate, and 0.25 g of t-butylcatechol
Was added to obtain a liquid resin having a nonvolatile content of 75%.

Comparative Synthesis Example 1 [Synthesis of Saturated Polyester Methacrylate (Ea-1)] In a 5 L three-necked flask equipped with a thermometer, a stirrer and a condenser, 1302 g (8.68) of triethylene glycol was added.
Mol), 589.72 g of diethylene glycol (4.6)
2 mol), 2072 g (14 mol) of phthalic anhydride and 1.93 g of dibutyltin oxide were charged under nitrogen atmosphere.
The temperature was raised to 5 ° C., and the reaction was continued at the same temperature for 16 hours. When the 70% SM solution had an acid value of 19.1 and a Gardner viscosity of QR, 0.5% of toluhydroquinone was added.
Add 28 g, cool to 110 ° C, nitrogen / air = 1/1
255.3 g of glycidyl methacrylate under an atmosphere
(1.8 mol), reacted at 130 ° C. for 2.5 hours, sampled, and when the 75% MMA solution had an acid value of 1.9, cooled to 90 ° C. to obtain MMA 1293.2.
g, 5% copper naphthenate 0.079 g and t-butylcatechol 0.264 g were added to obtain a liquid resin having a nonvolatile content of 75%.

Comparative Synthesis Example 2 [Synthesis of Unsaturated Polyester Methacrylate (Ea-2)] In a 5 L three-necked flask equipped with a thermometer, a stirrer and a condenser, 1590 g (15 mol) of diethylene glycol and 1776 g (12 mol) of phthalic anhydride were added. ), 367.5 g (3.75 mol) of maleic anhydride, 1.795 g of trimethylhydroquinone, 1.7 dibutyltin oxide
95 g was charged and heated to 210 ° C. in a nitrogen atmosphere, and the reaction was continued at the same temperature for 4.5 hours. When the acid value reached 0.2, the mixture was cooled to 120 ° C., and diethylene glycol 80
1.4 g (7.56 mol) was charged, the temperature was raised to 210 ° C., the reaction was continued at the same temperature for 35 hours, and a 70% SM solution was sampled to obtain an acid value of 10.2 and a Gardner viscosity of Y2-Z.
When it became, it was cooled to 90 ° C and nitrogen / air = 1 /
129.8 g of glycidyl methacrylate under one atmosphere
(0.91 mol), reacted at 130 ° C. for 1 hour, sampled, and when the 75% MMA solution had an acid value of 2.5, cooled to 90 ° C. to obtain MMA 1199.36.
g, 5% copper naphthenate 0.15 g, and a nonvolatile content of 75%
% Liquid resin was obtained.

Examples 1 and 2 and Comparative Examples 1 and 2 (Evaluation of Aggregate Grip Property) Additives shown in Table 1 were added to the resins obtained in Synthesis Examples 1 and 2 and Comparative Synthesis Examples 1 and 2, respectively. Add 30c
1.5 kg / m on a mx30 cm dense-grained ascon specimen
² application, 6.5 kg / m ² of aggregate (Cerasand H type R-A made by Misyu Kosan Co., Ltd.) was sprayed before the resin hardened,
Aggregate that did not adhere after the resin was cured was wiped off, and the amount of aggregate attached was measured. Table 1 shows the evaluation results.

[0069]

[Table 1]

(Note) The unit of the compounding amount in the table is part. Tensile elongation (%) of vinyl ester resin composition: Tensile elongation of cured product of resin not containing aggregate

The abbreviations in the above tables are as follows. C-1 Air-drying type saturated polyester of Synthesis Example 3 MMA methyl methacrylate n-BA n-butyl acrylate 2-EHA 2-ethylhexyl acrylate 6% Co-Nap 6% cobalt naphthenate PTD-2EO N, N-dihydroxy Ethyl paratoluidine WAX paraffin wax (melting point in parentheses)

As is clear from the results in Table 1, Example 1
In any one of Comparative Examples 1 and 2, the aggregate adhesion was superior to Comparative Examples 1 and 2.

[0073]

The pavement material of the present invention has an excellent adhesion to aggregate and has a particularly good anti-slip effect as compared with the existing pavement material, and has a great problem from the viewpoint of environmental protection. It can be obtained by using PET bottles effectively by chemical recycling.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Rie Tashiro 4-5-401 Tanakacho, Izumiotsu-shi, Osaka (72) Inventor Mitsuyuki Kanzaki 500-2 Hatamachi, Kishiwada-shi, Osaka F-term (reference) 2D051 AA08 AD02 AF01 AF07 AF09 AG09 AG14 AG15 AG16 AG17 AG20 AH02 EA06 EB04 EB06 4J011 PA13 PA88 PB18 PB40 PC02 PC08 4J027 AB02 AB03 AB10 AB15 AB23 AB28 AB29 BA05 BA07 BA08 BA13 BA15 BA17 BA18 BA19 BA20 BA21 BA22 BA29 CA06 CA18 CC01 CD00 CD18

Claims (9)

[Claims] 1. (a) a terephthalic acid component and an ethylene glycol component as essential components, and (meth)
A vinyl ester resin composition (A) comprising a vinyl ester resin comprising an acrylic group-containing polyester, (b) an ethylenic monomer, and (c) an air-drying imparting polymer.
And a non-slip aggregate (B) as a main component. 2. The resin-based pavement material according to claim 1, wherein a tensile elongation when the vinyl ester resin composition (A) is cured is 60% or more. 3. The resin-based pavement material according to claim 1, wherein the terephthalic acid component and the ethylene glycol component are obtained by subjecting polyethylene terephthalate to alcoholysis with a dihydric alcohol. 4. A vinyl ester (a) obtained by using polyethylene terephthalate as an essential raw material component,
A saturated polyester having a carboxyl group at a terminal and / or
The resin-based pavement material according to any one of claims 1 to 3, which is obtained by reacting an unsaturated polyester with a glycidyl group-containing acrylic compound. 5. The resin-based pavement material according to claim 1, wherein the vinyl ester (a) contains an ethylene glycol component and another glycol component as essential components as alcohol components. 6. The resin-based pavement material according to claim 5, wherein the molar ratio of ethylene glycol component / other glycol component is from 1/1 to 1/10. 7. The method according to claim 1, wherein the total amount or part of the ethylenic monomer (b) is (meth) acrylate.
The resin-based pavement material according to any of the above. 8. A resinous pavement comprising a vinyl ester resin composition (A) according to claim 1 and a filler (d). 9. A method for constructing a resin-based pavement, comprising performing pavement using the resin-based pavement material according to any one of claims 1 to 8.