JP2005098022A - Coated composition for civil engineering/construction material, paving material, and pavement - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coated composition for a civil engineering/construction material, especially a paving material, which gives a coated body superior in surface driability and soil resistance. <P>SOLUTION: The coated composition has essential components, which consist of (A) one type of a resin having an air drying property that is selected from the group consisting of a vinyl ester resin, a vinyl urethane resin, and an unsaturated polyester resin, (B) a polymeric monomer, and (C) a thermoplastic resin, which is mainly composed of a methacrylic acid ester and has a number-average molecular weight of 5,000 to 200,000. The paving material and a pavement are provided by adding an aggregate (D) to the above coated composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention provides a coating structure for civil engineering and building materials, particularly a civil engineering and building material coating composition capable of obtaining a pavement, which is excellent in surface curability and soil resistance during curing.

  Conventionally, epoxy resins, polyurethane resins and the like are typically used as resins for civil engineering and building materials, but these resins have high viscosity and are used in a form dissolved in a solvent. In addition to these solvent-type resins for civil engineering and building materials, in civil engineering and building resin using unsaturated polyester resin and vinyl ester resin, the monomer used in combination also serves as a solvent, and the coating film is a general solvent-type civil engineering Unlike resin for building materials, it is 100% solidified. These resins are generally cured by radical polymerization, but when used as a civil engineering and building material coating composition, oxygen in the air inhibits radical polymerization, resulting in a coating material that has poor surface drying properties and is likely to remain dirty. There are drawbacks. In order to make up for these problems, the present situation is that a resin having a wax addition or air-drying performance is used (see, for example, Patent Document 1).

However, the addition of wax contributes to the improvement of air drying properties due to the air blocking action on the coating surface, but it is still present on the coating surface after curing, affecting the secondary adhesion and appearance of the coating. There are many cases. Moreover, when only the component which has air drying performance is used, there exists a problem that it will become easy to get dirty after hardening, if an uncured low molecular weight component remains.
JP-A-11-209628

  The objective of this invention is providing the coating composition for civil engineering and building materials excellent in surface drying property and stain resistance, especially a paving material.

  As a result of diligent research on these problems, the present inventors have found that the use of a thermoplastic polymer having a specific number average molecular weight improves the surface drying property and stain resistance, and thereby the present invention. Has been completed.

  That is, in the present invention, (A) at least one resin selected from the group consisting of a vinyl ester resin, a vinyl urethane resin and an unsaturated polyester resin, (B) a polymerizable monomer and (C) a number average molecular weight is 5 The present invention provides a coating composition for civil engineering and construction materials comprising a thermoplastic resin of 1,000,000 to 200,000 as an essential component. The present invention also includes (A) at least one resin selected from the group consisting of vinyl ester resins, vinyl urethane resins, and unsaturated polyester resins, (B) a polymerizable monomer, and (C) a number average molecular weight of 5, The present invention provides a paving material comprising 000 to 200,000 thermoplastic resin and aggregate as essential components. Furthermore, this invention provides the pavement formed by apply | coating the said pavement material to a pavement surface, and making it harden | cure.

Since the coating composition for civil engineering and building materials and the paving material of the present invention are excellent in surface drying property and stain resistance, it is useful for applications of civil engineering and building materials such as paving materials.

The present invention is described in further detail below.
The resin (A) used in the present invention is at least one resin among vinyl ester resins, vinyl urethane resins, and unsaturated polyester resins.

  Examples of the vinyl ester resin used as the resin (A) include an epoxy (meth) acrylate resin produced by a reaction between an epoxy resin and (meth) acrylic acid, and a (meth) acrylic compound at the terminal of a saturated or unsaturated polyester resin. Examples thereof include a polyester (meth) acrylate resin reacted, or a polybutadiene type vinyl ester resin produced by a reaction between polybutadiene having a terminal carboxyl group and glycidyl (meth) acrylate. These vinyl ester resins are excellent in corrosion resistance and mechanical strength.

  The epoxy (meth) acrylate resin used as the resin (A) is obtained by reacting an epoxy resin with a carboxylic acid having a (meth) acrylol group, for example, a bisphenol type epoxy resin and a (meth) acrylol group. And a carboxylic acid having a (meth) acrylolyl group and a novolac type epoxy resin.

  Examples of the bisphenol type epoxy resin include a glycidyl ether type epoxy resin having substantially two or more epoxy groups in one molecule obtained by reaction of epichlorohydrin and bisphenol A or bisphenol F, methyl epichlorohydrin and bisphenol A, for example. Or the dimethyl glycidyl ether type epoxy resin obtained by reaction with bisphenol F, the epoxy resin obtained from the alkylene oxide adduct of bisphenol A, and epichlorohydrin or methyl epichlorohydrin, etc. are mentioned.

  Examples of the novolak type epoxy resin include an epoxy resin obtained by a reaction of a novolak type phenol resin or a novolac type cresol resin with epichlorohydrin or methyl epichlorohydrin.

  Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl malate, monobutene malate, sorbic acid, and mono (2-ethylhexyl) malate. Are used alone or in combination of two or more.

  Furthermore, as the polyester (meth) acrylate resin used as the resin (A), those obtained from a saturated polyester obtained by a condensation reaction of a saturated dibasic acid and a polyhydric alcohol and a (meth) acrylate compound, α, Some are obtained from an unsaturated polyester obtained by condensation of a dibasic acid containing a β-unsaturated dibasic acid with a polyhydric alcohol and a (meth) acrylate compound.

  Examples of the saturated dibasic acid herein include phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, Hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2 , 3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4′-biphenyldicarboxylic acid, or dialkyl esters thereof.

  Polyhydric alcohols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1, Examples include 3-butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, 1,6-hexanediol, and the like.

  Examples of the unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride and the like.

Examples of the (meth) acrylic compound include unsaturated glycidyl compounds, various unsaturated monobasic acids such as acrylic acid or methacrylic acid, and glycidyl esters thereof. Of these, glycidyl (meth) acrylate is preferred.

  The vinyl urethane resin used as the resin (A) used in the present invention is an oligomer of urethane (meth) acrylate used as a raw material with polyols, isocyanates, and hydroxyl group-containing (meth) acrylates.

  Such a urethane (meth) acrylate can be obtained by reacting the polyols with the isocyanate to obtain a terminal isocyanate group-containing prepolymer, and then reacting this with a hydroxyl group-containing (meth) acrylate.

  Examples of the polyols include polyether polyols and polyester polyols. Examples of such polyether polyols include polyoxypropylene diol, polytetramethylene glycol ether, and polyoxyethylene diol. Polyester polyols include dibasic acids or their anhydrides and polyhydric alcohols. A condensate is mentioned.

  Examples of such dibasic acids or acid anhydrides thereof include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, etc., and these may be used alone or in combination of two or more. It is done.

  Examples of the polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, Examples include triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, and the like. These may be used alone or in combination of two or more.

  Next, examples of the isocyanates include 2,4-tolylene diisocyanate and its isomer or a mixture of isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexylmethane diisocyanate, and tolidine. And polyisocyanates such as diisocyanate, naphthalene diisocyanate, and triphenylmethane triisocyanate. Of these polyisocyanates, diisocyanates are preferred. These can be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing (meth) acrylates described above include hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate, and these are used alone or in combination of two or more.

  Next, the unsaturated polyester resin used as the resin (A) used in the present invention is not particularly limited, and is a well-known unsaturated polyester resin conventionally used in general civil engineering coating materials. Can be used. Known unsaturated polyester resins include, for example, carboxylic acids having an α, β-ethylenically unsaturated double bond, or carboxylic acids having an α, β-ethylenically unsaturated double bond and an α, β-ethylenically unsaturated resin. An unsaturated polyester obtained by a condensation reaction between a saturated carboxylic acid having no saturated double bond and a polyhydric alcohol can be mentioned.

  Examples of the carboxylic acid having an α, β-ethylenically unsaturated double bond include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, and chloromaleic acid. Examples of the saturated carboxylic acid include Examples include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, oxalic acid, malonic acid, succinic acid, adipic acid, and sebacic acid. These may be used alone or in combination of two or more. Can be used.

  As the polyhydric alcohol, the polyhydric alcohol described above can be used.

  The air-drying property of the resin having air-drying property used in the present invention means that by introducing a specific functional group in the polymer, curing is not rapidly inhibited by oxygen molecules, but curing proceeds rapidly even in the air. say. Examples of the resin that can be used for this purpose include those obtained by introducing an air-drying group as an essential component into the vinyl ester, unsaturated polyester, and the like.

  Examples of the air-drying group include alkenyl groups including allylic groups, alkenyl ether groups, and dicyclopentadiene groups.

  Examples of the air-drying group introduction method include the following methods. That is, 1) A compound containing an allyl ether group is used in combination with a polyhydric alcohol component. 2) An alcoholysis compound obtained by a transesterification reaction between a polyhydric alcohol and a fatty oil such as drying oil is used in combination with the alcohol component. 3) A compound containing a cyclic unsaturated aliphatic polybasic acid and a derivative thereof is used in combination with the dibasic acid component. 4) A compound containing a dicyclopentadienyl group is used in combination.

  Among these 1) to 4), any known compound can be used as the allyl ether group-containing compound of 1). Typical examples thereof include ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, Ethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1, 3-butylene glycol monoallyl ether, trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether, glycerin monoallyl ether, glycerin di Rirueteru, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, allyl ether compounds of polyhydric alcohols such as pentaerythritol triallyl ether, allyl ether compound having such oxirane ring, such as allyl glycidyl ether.

  The drying oil used in the above 2) is preferably an oil having an iodine value of 130 or more, and examples thereof include linseed oil, soybean oil, cottonseed oil, peanut oil, and palm oil. Examples of the polyhydric alcohol used in the alcoholysis compound obtained by the transesterification include trihydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, trishydroxymethylaminomethane, and tetrahydric alcohols such as pentaerythritol. .

  The compound containing the cycloaliphatic unsaturated polybasic acid and its derivative used in the above 3) is tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, α-terhinene / maleic anhydride adduct And trans-piperylene / maleic anhydride adduct.

  Typical examples of the compound (4) containing a dicyclopentadienyl group include hydroxylated dicyclopentadiene.

Examples of the polymerizable monomer (B) used in the present invention include styrene, hydroxyethyl methacrylate, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Examples include (meth) acrylic acid derivatives such as isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, and phenoxyethyl methacrylate. Furthermore, if necessary, polyfunctional polymerizable monomers such as ethylene glycol dimethacrylate and diethylene glycol dimethacrylate can be used in combination.

Examples of the thermoplastic resin (C) used in the present invention include those obtained by polymerizing styrene, vinyl chloride, vinyl acetate, fumaric acid ester, (meth) acrylic acid ester, and these are used alone or in combination of two or more. Used in combination. Of these, those obtained by polymerizing methyl (meth) acrylate as a main component are preferable.

  The molecular weight of the thermoplastic resin (C) is a number average molecular weight of 5,000 to 200,000, preferably 8,000 to 50,000. Those having a number average molecular weight of less than 5,000 cannot exhibit sufficient surface drying properties and stain resistance.

  The ratio of (A), (B) and (C) used in the present invention can be changed depending on the desired application and is not particularly limited. However, from the viewpoint of workability and obtained effects, (A) :( B) is preferably 10 to 80:90 to 20 by weight, and more preferably 40 to 70:60 to 30. Further, the ratio of (C) is 0.1 parts by weight or more, preferably 3 parts by weight or more with respect to 100 parts by weight of (A) + (B).

The paving material of the present invention has (A) at least one resin selected from vinyl ester resins, vinyl urethane resins, and unsaturated polyester resins, (B) a polymerizable monomer, and (C) a number average molecular weight of 5,000. ˜200,000 thermoplastic resin and (D) aggregate are essential components.
The aggregate (D) used in the present invention is, for example, silica sand, river sand, cryolite, marble waste, crushed stone, hydraulic silicate material, calcium carbonate powder, clay, alumina powder, silica powder, talc, barium sulfate, Examples thereof include silica powder, glass powder, glass beads, mica, and aluminum hydroxide.

  The blending ratio of the aggregate (D) can be added in an amount of 10 to 900 parts by weight, preferably 50 to 500 parts by weight, based on a total of 100 parts by weight of (A) + (B) + (C).

As necessary, the coating composition for civil engineering and building materials and the paving material containing the components (A), (B) and (C) as essential components in the present invention, paraffin wax, dispersant, thixotropic agent, organic acid metal soaps , And a polymerization inhibitor can be added.

  In order to cure the coating composition for civil engineering and building materials and the paving material of the present invention, a radical curing agent, a photo radical initiator, and a curing accelerator can be used.

  Examples of radical curing agents include organic peroxides. Specific examples include known and publicly available ones such as diacyl peroxides, peroxyesters, hydroperoxides, dialkyl peroxides, ketone peroxides, peroxyketals, alkyl peresters, and carbonates. .

  The photo radical initiator is a photo sensitizer, and specific examples include benzoin ethers such as benzoin alkyl ethers and benzophenone.

  Examples of the curing accelerator include metal soaps such as cobalt naphthenate and cobalt octylate, metal chelates such as cobalt acetyl acetate, and N, N-substituted anilines such as aniline and N, N-dimethylaniline. It is done. Of these, aniline-based and metal soap-based curing accelerators are preferred. In the present invention, amine-based and metal soap-based accelerators are preferred. You may use a hardening accelerator in the combination of 2 or more types. Further, it may be added to the resin in advance or may be added at the time of use.

  It is preferable that the addition amount of a hardening | curing agent is 0.1-6 weight part with respect to 100 weight part of total amounts of the coating composition of component (A) + (B) + (C). Moreover, 0.1-5 weight part is used for the addition amount of a hardening accelerator.

The coating composition for civil engineering and building materials of the present invention is used as a coating material for concrete, asphalt, and the like, specifically for flooring, caulking materials, paving materials, lining materials and formwork, etc. It is done.
The pavement material of the present invention is preferably used as a pavement such as concrete or asphalt, particularly as a top coat pavement.

The pavement of the present invention is obtained by applying the pavement material to a pavement surface such as concrete or asphalt and curing it. As a method of applying to the painted surface, there are a method of spraying on the pavement surface, a method of applying evenly with a rubber rake, and the like. Moreover, when apply | coating, although it can apply | coat directly on an asphalt concrete pavement surface, when applying on a cement concrete pavement or a steel plate, it is preferable to apply after performing a primer process.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. Also, “parts” in the text indicates parts by weight.

(Example 1)
80 parts by weight of HTP-502W (manufactured by Dainippon Ink & Chemicals, Inc.), which is a methyl methacrylate solution of vinyl ester resin, is a 30% polymethyl methacrylate solution having a number average molecular weight of about 10,000 in advance. 20 parts by weight was added and mixed with stirring. To this was added 1.5 parts by weight of benzoyl peroxide as a curing agent, and the mixture was sufficiently stirred and mixed to obtain a coating composition. This coating composition was tested for drying and stain resistance. The results are shown in Table-1.

(Example 2)
Evaluation was performed in the same manner as in Example 1 except that HTP-563W [manufactured by Dainippon Ink & Chemicals, Inc.] was used as the vinyl ester resin.

(Example 3)
Evaluation was performed in the same manner as in Example 1 except that VU-180 [Dainippon Ink Chemical Co., Ltd.] was used as the urethane acrylate resin.

Example 4
Evaluation was performed in the same manner as in Example 1 except that HTP-506W (produced by Dainippon Ink & Chemicals, Inc.) having no air-drying component was used as the vinyl ester resin.

(Example 5)
After 100 parts by weight of No. 7 silica sand was added to 100 parts by weight of the coating composition of Example 2 and sufficiently stirred, drying and soil resistance were similarly confirmed for those coated and cured to a thickness of 5 mm. did.

(Comparative Examples 1-5)
Of the coating compositions of Examples 1 to 5, except for polymethylmethacrylate, the same operations as in the above example were performed and cured, and the drying property and stain resistance were confirmed. The results are shown in Table-2.
(Comparative Example 6)
Evaluation was performed in the same manner as in Example 1 except that polymethyl methacrylate having a number average molecular weight of 10,000 in the coating composition of the above example was replaced with polymethyl methacrylate having a number average molecular weight of 4,000. .

[Dry and stain resistance test and evaluation]
The mixture obtained in Example 1 was applied to a slate plate with a 0.5 mm applicator, and the touch-drying property and stain resistance when the coating film was cured were confirmed.
Regarding the dryness to touch, the presence or absence of stickiness was confirmed by touching the coating film after 2 hours had passed since the curing agent was added. The case where no stickiness was recognized was “no tack”, and the case where stickiness was recognized was “tack”.
Moreover, about stain resistance, the rubber | gum at the time of rubbing a rubber piece to a coating film was evaluated in five steps. "5" for non-stained material, "4" for almost non-stained material, "3" for soiled but wiped with a cloth, "2" for slightly unsuccessfully wiped, and "1" for blackly soiled "

Claims (7)

Thermoplastic having at least one resin (A) selected from the group consisting of vinyl ester resin, vinyl urethane resin and unsaturated polyester resin, polymerizable monomer (B), and number average molecular weight of 5,000 to 200,000. A coating composition for civil engineering and building materials comprising resin (C) as an essential component. The coating composition for civil engineering and building materials according to claim 1, wherein the thermoplastic resin (C) having a number average molecular weight of 5,000 to 200,000 is a polymer mainly composed of a methacrylic ester. The said resin (A) contains an air-drying component, The coating composition for civil engineering and building materials of Claim 1 or 2 characterized by the above-mentioned. The civil engineering building material according to any one of claims 1 to 3, wherein a content of the thermoplastic resin (C) having a number average molecular weight of 5,000 to 200,000 is 0.1 to 50% by weight. Coating composition. At least one resin (A) selected from the group consisting of vinyl ester resins, vinyl urethane resins and unsaturated polyester resins, polymerizable monomers (B), thermoplastic resins having a number average molecular weight of 5,000 or more (C ) And aggregate (D) as an essential component. The aggregate (D) is 10 to 10 parts by weight with respect to a total of 100 parts by weight of the resin (A), the polymerizable monomer (B) and the thermoplastic resin (C) having a number average molecular weight of 5,000 to 200,000. The pavement material according to claim 5, containing 900 parts by weight. A pavement formed by applying the pavement material according to claim 5 or 6 to a pavement surface and curing it.