JP6372922B2 - Resin composition, coating method using the same, and coating structure coated by the method - Google Patents

Description

  The present invention relates to a resin composition suitable for a lining coating material and a waterproof coating material, a coating material containing the resin composition, and a coating method using the coating material. More specifically, it is a resin composition that has low odor, is excellent in coating film drying properties and secondary adhesiveness, and can be used for lining materials, waterproof materials, fiber reinforced plastics, and the like, and further, a coating containing the resin composition The present invention relates to a lining coating method and a waterproof coating method characterized by using the coating material and the coating material.

  In recent years, FRP (waterproof) lining that incorporates advantages such as moldability, water resistance, mechanical properties (strength, etc.) of FRP has been used for waterproofing and anticorrosion of floors such as rooftops, verandas, parking lots, and factories. ing.

  As the resin used for FRP waterproofing, a soft resin is used in consideration of adhesion to the base, followability to the base, and relaxation of curing shrinkage distortion. The soft resin used has a tensile strength of 10-50 MPa and a tensile elongation of 25-120% of the cured resin, as described in the building construction standard specification / comment JASS8 waterproofing construction. Those having the same performance after heat resistance, acid resistance and alkali resistance treatment and maintaining a specified retention rate are used. As an FRP waterproofing resin having these characteristics, a soft unsaturated polyester resin using a styrene monomer as a radical polymerizable monomer is used.

In FRP waterproofing construction work, styrene, which is a radical polymerizable monomer contained in the resin, is volatilized in the lining work process, resulting in a worse working environment and problems of odor.
Furthermore, in order to solve the odor problem, a low odor resin of (meth) acrylic acid ester is used as a polymerizable monomer, and a low odor resin using these is used as a (meth) acrylic acid ester. However, since it has a property of being harder to cure in a thin film than styrene, poor curing is likely to occur during lining construction.

  Further, in curing these acrylic resins, oxygen in the air acts as a polymerization inhibitor, and therefore a method of blocking the permeation of oxygen in the air during the curing process of the coating film resin and the lining resin is taken. Therefore, conventionally, the resin composition contains a paraffin wax and a polymerizable diluent, volatilizes the polymerizable diluent, and the concentration of paraffin in the polymerizable diluent as the polymerization in the coating proceeds. The paraffin wax that can no longer be dissolved is deposited on the resin surface layer (coating surface or lining surface), and as a result, a thin paraffin wax layer is formed and functions as an air barrier material to accelerate curing. ing.

  However, in the case of a resin using (meth) acrylic acid ester, the anaerobic property is very strong, so a large amount of paraffin wax must be added, which often affects the secondary adhesion of the coating film. For this reason, techniques for using (meth) acrylic acid esters and resins having air-drying performance in combination with specific (meth) acrylic acid esters have been proposed (see, for example, Patent Documents 1 to 6). As another solution, it has been desired to use a polymerizable monomer that is less anaerobic than (meth) acrylic acid ester.

Japanese Patent No. 3278001 Japanese Patent No. 3859857 Japanese Patent No. 497914 JP 05-295862 A Japanese Patent Laid-Open No. 2004-10771 JP 2005-120305 A

  The present invention solves the above-mentioned conventional problems by using a polymerizable monomer other than (meth) acrylic acid ester, and is excellent in low odor property, coating film drying property and secondary adhesiveness, and toughness of a cured product. It is another object of the present invention to provide a resin composition having excellent durability, a coating material containing the resin composition, and a coating method using the coating material.

The inventors of the present invention have intensively studied to solve the above problems, and as a result, have found that the above problems can be solved by using an itaconic acid ester.
Specifically, the present invention
[1] At least one resin selected from the group consisting of (A) polyester (meth) acrylate resin, urethane (meth) acrylate resin and epoxy (meth) acrylate resin, (B) dibenzyl itaconate , (C) styrene A radically polymerizable monomer excluding a monomer based on (D) a wax, and a resin composition ,
[ 2 ] The resin composition according to [1 ], wherein the component (A) is a glycidyl methacrylate-modified unsaturated polyester resin,
[ 3 ] The resin composition according to [1] or [2] , wherein the component (C) is a (meth) acrylic ester,
[4] A resin composite composition obtained by combining at least one of the resin composition according to any one of [1] to [ 3 ] and a fiber reinforcing material, a filler and an aggregate, A resin composite composition obtained by adding 1 to 300 parts by mass of at least one of a fiber reinforcement, a filler, and an aggregate with respect to 100 parts by mass of the resin composition;
[5] Waterproof coating for civil engineering buildings, comprising applying the resin composition according to any one of [1] to [ 3 ] or the resin composite composition according to [ 4 ] to a civil engineering building as a waterproof layer Construction method,
[6] A lining coating for civil engineering buildings comprising applying the resin composition according to any one of [1] to [ 3 ] or the resin composite composition according to [ 4 ] to a civil engineering building as a protective layer. Construction method,
[7] A covering structure provided with a waterproof layer using the resin composition according to any one of [1] to [ 3 ] or the resin composite composition according to [ 4 ], and
[8] A covering structure in which a protective layer is applied using the resin composition according to any one of [1] to [ 3 ] or the resin composite composition according to [ 4 ].

  Since it can refrain from using highly volatile monomers, it has low odor, and even if it is refrained from using highly volatile monomers, it has excellent coating surface drying and secondary adhesive properties, and is further cured. The cured product obtained has excellent strength characteristics, chemical resistance, and heat resistance, and is very useful for civil engineering and building materials such as waterproof coatings.

  In the present invention, at least one of (A) polyester (meth) acrylate resin, urethane (meth) acrylate resin and vinyl ester resin is used. Preferably, polyester (meth) acrylate having at least two (meth) acryloyl groups at the molecular terminals is used.

  The polyester (meth) acrylate resin used as the component (A) of the present invention is a saturated or unsaturated polyester having two or more (meth) acryloyl groups in one molecule, and the terminal of the saturated or unsaturated polyester. And (meth) acrylic compound. The number average molecular weight of the resin is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 500 to 5000.

  The saturated polyester used in the present invention is a condensation reaction between a saturated dibasic acid and a polyhydric alcohol, and the unsaturated polyester is a dibasic acid containing an α, β-unsaturated dibasic acid and a polyhydric alcohol. It is obtained by the condensation reaction.

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

  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, 1,3 -Butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, 1,6-hexanediol, an adduct of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, Glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cycl Hexane dimethanol, paraxylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalin glycol, and 2,7-decalin glycol, and the like.

  Examples of the (meth) acrylic compound used in the polyester (meth) acrylate resin used as (A) in the present invention include unsaturated glycidyl compounds, various unsaturated monobasic acids such as acrylic acid or methacrylic acid, and glycidyl esters thereof. Etc. Preferably, glycidyl (meth) acrylate is used.

The urethane (meth) acrylate resin used as (A) of the present invention is obtained by reacting and synthesizing polyalkylene glycol, polyisocyanate, and a (meth) acrylate monomer having one or more hydroxyl groups in one molecule ( A meth) acrylate is preferred. Even more preferred is a polyalkylene glycol having 2 to 4 carbon atoms in the repeating unit of the alkylene group of the polyalkylene glycol, and more preferred is polypropylene glycol.
Further, the number average molecular weight of the resin is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 500 to 5,000.

  The polyalkylene glycol (preferably polypropylene glycol) used preferably has a weight average molecular weight of 200 to 3000, more preferably 300 to 2000. When the weight average molecular weight is 200 or more, the flexibility (elongation rate) of the cured product can be sufficiently increased, and when the weight average molecular weight is 3000 or less, the strength of the cured product can be sufficiently maintained. Examples of polyalkylene glycols other than polypropylene glycol include polyether polyols such as polyethylene glycol, polytetramethylene ether glycol (polytetrahydrofuran), polyols obtained by adding alkylene oxide to bisphenol A and bisphenol F.

In addition to polyalkylene glycol, other polyols can be used in combination as long as various physical properties are not impaired. Typical examples of the polyol that can be used include polyester polyol, polycarbonate polyol, polybutadiene polyol, and hydrogenated polybutadiene polyol.
The polyester polyol is a ring-opening polymer of a cyclic ester compound such as a condensation polymer of dibasic acids and polyhydric alcohols or polycaprolactone, and the dibasic acids and polyhydric alcohols used are And the compounds shown in the section of polyester (meth) acrylate.

  Furthermore, as the polyol that can be used in combination with the polyalkylene glycol, various polyhydric alcohols exemplified as the raw material for the polyester polyol can be used within a range where there is no problem.

  A polyisocyanate is used for the urethane (meth) acrylate resin used in the component (A) of the present invention. Examples of the polyisocyanate used include 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI) 2,4-tolylene diisocyanate and its isomer or a mixture of isomers, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and tetramethyl. Examples include xylylene diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and the like, and one or more of them may be used. it can. Of the polyisocyanates, diisocyanates are preferably used.

  Furthermore, the (meth) acrylate monomer which has a 1 or more hydroxyl group in 1 molecule is used for the urethane (meth) acrylate resin used for (A) component of this invention. Examples of the (meth) acrylate monomer having one or more hydroxyl groups in one molecule used include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and polyethylene. Mono (meth) acrylates such as glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate, polyvalent (meth) such as tris (hydroxyethyl) isocyanuric acid di (meth) acrylate and pentaerythritol tri (meth) acrylate Mention may be made of acrylate monomers.

  The urethane (meth) acrylate resin used for the component (A) can be produced by a known method. As an example of the production method, (1) First, a polyisocyanate and a polyol are preferably reacted at NCO / OH = 1.3 to 2 to form a terminal isocyanate compound, and then a hydroxyl group-containing (meth) acrylate compound is added thereto. A method of reacting so that the hydroxyl groups are substantially equal to the isocyanate group, and (2) reacting a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound at NCO / OH = 2 or more, Examples include a method of producing and then reacting by adding a polyol. These syntheses can be synthesized by reacting at a temperature of 50 ° C. to 100 ° C. and further using a known urethanization catalyst.

An epoxy (meth) acrylate resin can be used as the component (A) of the present invention. The epoxy (meth) acrylate resin that can be used preferably has two or more (meth) acryloyl groups in one molecule, and reacts an epoxy resin with an unsaturated monobasic acid in the presence of an esterification catalyst. Is obtained.
Examples of the epoxy resin mentioned here include a bisphenol type or novolac type epoxy resin alone, or a resin in which a bisphenol type and a novolac type epoxy resin are mixed, and the average epoxy equivalent is preferably from 150. It is in the range of 450.
Further, the number average molecular weight of the resin is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 500 to 5,000.

  Here, if a typical thing is mentioned as said bisphenol type epoxy resin, the glycidyl ether type | mold which has two or more epoxy groups in 1 molecule substantially obtained by reaction with epichlorohydrin and bisphenol A or bisphenol F will be mentioned. An epoxy resin, a methyl glycidyl ether-type epoxy resin obtained by reaction of methyl epichlorohydrin and bisphenol A or bisphenol F, an epoxy resin obtained from an alkylene oxide adduct of bisphenol A and epichlorohydrin or methyl epichlorohydrin, or the like. Typical examples of the novolak type epoxy resin include an epoxy resin obtained by a reaction of phenol novolak or cresol novolak with epichlorohydrin or methyl epichlorohydrin.

Typical examples of the unsaturated monobasic acid used for the epoxy (meth) acrylate resin include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, monopropyl maleate, and mono (2- Ethyl hexyl) or sorbic acid. These unsaturated monobasic acids may be used alone or in combination of two or more. The reaction between the epoxy resin and the unsaturated monobasic acid is preferably performed using an esterification catalyst at a temperature of 60 to 140 ° C, particularly preferably 80 to 120 ° C.
Examples of the esterification catalyst include known tertiary amines such as triethylamine, N, N-dimethylbenzylamine, N, N-dimethylanline and diazabicyclooctane, triphenylphosphine, and diethylamine hydrochloride. The catalyst can be used as it is.

  In addition, the resin composition of this invention contains 30-80 mass% of resin of the said (A) component in resin of (A)-(C) component, Preferably it is 40-60 mass%. When the component (A) is 30% by mass or more in the resin of the components (A) to (C), sufficient durability can be maintained as an FRP waterproof layer, and when the content is 80% by mass or less, good lining workability is maintained can do.

The present invention contains itaconic acid ester as an essential component as component (B). Specific examples of itaconic acid esters include dimethyl itaconate, diethyl itaconate, dipropyl itaconate, dibutyl itaconate, dioctyl itaconate, diallyl itaconate, dibenzyl itaconate and the like. Among these, it is preferable to select and use in consideration of the odor of the monomer. Preferably, dibenzyl itaconate is used.
By using these itaconic acid esters, the surface drying property is improved, the amount of waxes used is reduced, and the secondary adhesiveness is improved. When itaconic acid ester is not used, the surface drying property is lowered and a large amount of wax is used, so that the secondary adhesive property is lowered.

  The resin composition of this invention contains 10-50 mass% of (B) itaconic acid ester in the resin of (A)-(C) component, Preferably 20-40 mass%. When the itaconic acid ester is 10% by mass or more in the resins of the components (A) to (C), the surface drying property can be obtained without adding a large amount of wax, so that the secondary adhesiveness is good and 50% by mass. If it is at most%, the viscosity will not increase and workability will be good.

  The present invention contains (C) a radical polymerizable monomer other than itaconic acid ester. As this (C) component, the radically polymerizable monomer except a styrene-type monomer with low volatility is used. Specific examples thereof include maleic acid esters, fumaric acid esters, and (meth) acrylic acid esters, with (meth) acrylic acid esters being preferred.

  (Meth) acrylic acid ester includes methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid lauryl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid benzyl, (meth) acrylic acid stearyl, (meth) acrylic acid tridecyl, dicyclopentenyloxyethyl (Meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monobutyl ether (meth) acrylate, ethylene glycol monohexyl ether (meth) acrylate, ethylene glycol Mono-2-ethylhexyl ether (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monobutyl ether (meth) acrylate, diethylene glycol monohexyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, acetoacetoxypropyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Triethylene glycol di (meth) acrylate Tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol Intramolecular such as di (meth) acrylate, 2-hydroxy 1,3 dimethacryloxypropane, isocyanuric acid EO-modified diacrylate, pentaerythritol diacrylate monostearate Monomers having an unsaturated double bond or the like oligomers thereof, and the like. Among these, it is preferable to select and use in consideration of the odor of the monomer. Preferably, phenoxyethyl (meth) acrylate is used.

  The resin composition of the present invention contains 10 to 50% by mass, preferably 20 to 40% by mass of the monomer (C) in the resins (A) to (C). When the component (C) is 10% by mass or more in the resins (A) to (C), the surface drying property can be obtained without adding a large amount of wax. When the content is less than or equal to mass%, the viscosity is not increased and the workability is good.

As long as the effects of the present invention are not impaired, a styrene monomer can be used in addition to the components (B) and (C). Styrene monomers are those in which a substituent such as an alkyl group, a halogen atom, or vinyl is bonded to styrene and styrene. Specific examples include vinyltoluene, α-methylstyrene, β-methylstyrene, chlorostyrene, Examples include dichlorostyrene, t-butylstyrene, and divinylbenzene.
Further, in addition to the above components (B) and (C), vinyl monomers such as ethyl vinyl ether and methyl vinyl ketone, and allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl succinate, triallyl cyanurate and oligomers thereof can be mentioned. . Among these, in order to maintain the low odor of the resin composition, it is preferable to select in consideration of the volatility and odor of the monomer.
However, it is preferable to refrain from using the above monomers as much as possible, and it is more preferable not to use them.

  In this invention, a wax is contained as an essential component as (D) component. Examples of the wax used include at least one selected from the group consisting of petroleum wax, olefin wax, polar wax, and special wax.

Examples of the petroleum wax include paraffin wax and microcrystalline wax. Examples of the olefin wax include polyethylene and polypropylene. Further, examples of polar waxes include waxes obtained by introducing polar groups (such as hydroxyl groups and ester groups) into these petroleum waxes and olefin waxes, and unsaturated fatty acid esters such as oleic acid, linoleic acid, and linolenic acid. Examples of the special wax include Byk S-750 and Byk S-780 manufactured by BYK Chemie.
By using these waxes, when the resin is cured, it precipitates on the surface of the coating film or the lining layer and effectively acts as an oxygen blocking agent, so that the surface drying property of the coating film or the lining layer can be obtained. Without these waxes, it is difficult to obtain good surface drying properties.

  The resin composition of the present invention contains 0.05 to 0.80 mass%, preferably 0.10 to 0.50 mass% of the wax (D) in the resins (A) to (D). When the wax is 0.05% by mass or more in the resins (A) to (D), the surface dryness is good, and when it is 0.80% by mass or less, the secondary adhesiveness is good.

  In the present invention, it is preferable to use organic acid metal soaps such as cobalt-based, vanadium-based and manganese-based soaps for the purpose of improving the surface drying property, and among them, an organic acid salt of cobalt can be preferably used. The addition amount is preferably 0.1 to 3 parts by mass with respect to 100 parts by mass in total of the component (A) + the component (B) + the component (C).

In the composition of the present invention, a radical curing agent, a photo radical initiator, a curing accelerator, and a polymerization inhibitor can be used for curing the resin composition and adjusting the curing rate.
Examples of the radical curing agent include organic peroxides, specifically, diacyl peroxides, peroxyesters, hydroperoxides, dialkyl peroxides, ketone peroxides, peroxyketals, alkyl peroxides. Known and publicly used ones such as ester-based and percarbonate-based ones are used.

  Photoradical initiators are photosensitizers, specifically benzoin ethers such as benzoin alkyl ether, benzophenones such as benzophenone, benzyl, methyl orthobenzoylbenzoate, benzyl dimethyl ketal, 2,2-diethoxy. Acetophenones such as acetophenone, 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 1,1-dichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2 -Thioxanthone series such as isopropylthioxanthone and the like can be mentioned.

  Examples of the curing accelerator include metal soaps such as cobalt naphthenate, cobalt octylate, zinc octylate, vanadium octylate, copper naphthenate, and barium naphthenate, and metals such as vanadium acetyl acetate, cobalt acetyl acetate, and iron acetylacetonate. Chelates, 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-toluene N, N-substituted anilines such as idin, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N, N-bis (hydroxyethyl) aniline, diethanolaniline, N, N-substituted-p- Examples include amines such as toluidine and 4- (N, N-substituted amino) benzaldehyde, and β-diketones such as acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetylbutyllactone, and dimethylacetoacetamide.

  Examples of the polymerization inhibitor include trihydrobenzene, toluhydroquinone, 1,4-naphthoquinone, parabenzoquinone, hydroquinone, benzoquinone, hydroquinone monomethyl ether, p-tert-butylcatechol, 2,6-di-tert-butyl-4- Examples thereof include methylphenol and phenothiazine. Preferably, 10 to 1000 ppm can be added to the resin composition.

  The addition amount of the curing agent is preferably 0.1 to 6 parts by mass with respect to 100 parts by mass of the total amount of the resin composition. In the present invention, it is preferable to use diacyl peroxide-based benzoyl peroxide, peroxy ester-based and hydroperoxide-based t-butyl peroxybenzoate, and cumene hydroperoxide. Moreover, the addition amount of a hardening accelerator is used in 0.1-5 mass parts. In the present invention, it is preferable to use a β-diketone accelerator and a cobalt metal soap accelerator. The curing accelerator may be used in a combination of two or more, and may be added to the resin in advance or may be added at the time of use.

Further, when the resin composition of the present invention is used as a coating material, a thixotropic agent, a thixotropic agent, a thickener, a colorant, a plasticizer, and the like are inhibited as necessary. It may be included within the range not to be.
Specific examples of the thixotropic agent include anhydrous fine powder silica, asbestos, and clay. As the thixotropic agent, specifically, polyethylene glycol, glycerin, polyhydroxycarboxylic acid amide, organic quaternary ammonium salt, BYK-R-605 (trade name; manufactured by Big Chemie Japan Co., Ltd.), etc. Is mentioned.
Specific examples of the thickener include metal oxides such as magnesium oxide, calcium oxide, and zinc oxide.
Specific examples of the colorant include organic pigments, inorganic pigments, dyes, and the like.
Specific examples of the plasticizer include chlorinated paraffin, phosphate ester, and phthalate ester.

  In the present invention, a resin composite composition is prepared by mixing at least one of a fiber reinforcing material, a filler, and an aggregate with a resin composition containing components (A) to (D). Examples of the fiber reinforcing material used include glass fibers, amides, aramids, vinylons, polyesters, phenols, and other organic fibers, carbon fibers, metal fibers, ceramic fibers, and mixtures thereof. In consideration of workability and economy, glass fibers and organic fibers are preferable, and glass fibers are particularly preferable. The fiber may be plain weave, satin weave, non-woven fabric, mat, roving, chop, knitted fabric, braided fabric, or a composite structure thereof. The mat shape is preferable due to construction method, thickness maintenance, and the like. Moreover, it is also possible to cut glass roving into 20-100 mm and use it as a chopped strand. The fiber reinforcement component is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin composition containing the components (A) to (D).

  Specific examples of the filler include calcium carbonate, aluminum hydroxide, fly ash, barium sulfate, talc, clay, and glass powder. Examples of the aggregate include quartz sand, gravel, and crushed stone. When these are used for mortar, those having a particle size of about 5 mm or less are preferable. As a compounding quantity of a filler or an aggregate, it is preferable to use 1-300 mass parts of fillers and an aggregate component with respect to 100 mass parts of resin compositions containing the said (A)-(D) component. .

  The waterproof coating structure or lining coating structure comprising the resin composition of the present invention is a urethane-based, epoxy-based, polyester-based, etc. on a civil engineering building base using a waterproof material and a lining material composition or composite composition. Applying a primer appropriately selected in consideration of workability, substrate condition, etc. from various things, after primer drying, hand lay-up or spray-up method of the waterproof composition, lining composition or composite composition of the present invention It is formed through a process consisting of a process of coating and the like.

  The resin composition of the present invention is used in combination with various materials on a waterproof coating structure or lining coating structure depending on the intended use. When used as a waterproof material, a top coating material called a well-known and commonly used top coat such as a fluorine-based, acrylic-based, urethane-based, or acrylic-silicon-based material having excellent weather resistance is applied on the waterproof coating structure. In addition, when the surface is used for running a vehicle, a method of preventing slipping by spraying dredged sand or wall sand on the surface of the runway is also employed.

  In the present invention, the substrate means, for example, a cement concrete, asphalt concrete, ALC plate, PC plate, FRP, plastic, wood, metal, or the like, and any shape thereof may be used. As long as it is a surface of a civil engineering building, any of a spherical surface, a curved surface, a cylindrical surface, a flat surface, a vertical surface, a slope, a ceiling surface and the like may be used. In the case of a solid substrate such as concrete or metal, it is advisable to perform base treatment, primer treatment or the like as necessary.

  The resin composition of the present invention suppresses the volatilization amount of the reactive monomer and can reduce the odor, so that the odor at the time of construction is a problem in new construction or repair work in densely populated houses, new establishment or repair work in stores, etc. The waterproof covering structure of civil engineering buildings using this material retains the durability of FRP, so it can be used for building roofs, rooftops, open corridors, verandas, exterior walls, underground exterior walls, indoors. And a waterproof structure for aquariums and a waterproof structure for membranes. In particular, outdoor waterproofing can be used as a covering material for heavy walk waterproofing, parking lots, and the like because it has sufficient durability even when a person or a vehicle passes over it.

  EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

[Synthesis Example 1] Synthesis of polyester methacrylate [PMA-1] Into a 5-liter four-necked flask equipped with a thermometer, a stirrer, a gas inlet, and a reflux condenser, 1142 g of dipropylene glycol and 1868 g of phthalic anhydride were added. The mixture was charged, heated to 205 ° C. in a nitrogen atmosphere, reacted for 3 hours, and cooled to 100 ° C. Under air, 0.6 g of methylhydroquinone and 1076 g of glycidyl methacrylate were added thereto, reacted at 120 to 130 ° C. for 2 hours, and cooled to obtain 4000 g of polyester methacrylate having a number average molecular weight of 1150. This polymer was hereinafter referred to as [PMA-1].

[Synthesis Example 2] Synthesis of urethane methacrylate [UMA-1] In a 5-liter four-necked flask equipped with a thermometer, a stirrer, a gas inlet, and a reflux condenser, 1695 g of polypropylene glycol (weight average molecular weight 1000), 847 g of 4,4′-diphenylmethane diisocyanate, 847 g of light ester L-8 (mixture of (meth) acrylate monomers having a long-chain alkyl group having 12 to 15 carbon atoms) and 0.6 g of hydroquinone were charged in a dry air atmosphere at 70 ° C. The temperature was raised to. When the internal temperature reached 70 ° C., 1.5 g of dibutyltin dilaurate was added as a catalyst, and after stirring for 1 hour, 365 g of polypropylene glycol (weight average molecular weight 400), 456 g of 4,4′-diphenylmethane diisocyanate, dibutyltin dilaurate 1 .8 g was added and stirring was continued. After 1 hour and 1.5 hours, the IR peak of the reaction product was measured to confirm that there was no change, and then 790 g of hydroxypropyl methacrylate was added over 30 minutes. Stirring was continued, and after 1 hour, the isocyanate peak was confirmed to have disappeared by IR, followed by cooling to obtain 5000 g of urethane methacrylate resin having a number average molecular weight of 2400. This polymer was hereinafter referred to as [UMA-1].

[Synthesis Example 3] Synthesis of epoxy methacrylate resin [EPMA-1] A 5-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was reacted with bisphenol A and epichlorohydrin. 2750 g of Araldite AER-2063 (Asahi Kasei E-Materials Co., Ltd.) having an epoxy equivalent weight of 189 was obtained, 1251 g of methacrylic acid, 1.2 g of methylhydroquinone and 12 g of triethylamine were added, the temperature was raised to 130 ° C., and 4 hours at the same temperature. It was made to react, it cooled by the acid value 10, and 4000 g of epoxy methacrylate resin of the number average molecular weight 700 was obtained. This polymer was designated as [EPMA-1] below.

Synthesis Example 5 Preparation of Dibenzyl Itaconic Acid In a 5 liter four-necked flask equipped with a thermometer, stirrer, gas inlet, and reflux condenser, itaconic acid 1660 g, benzyl alcohol 2800 g, and paratoluenesulfonic acid 22 as a catalyst .3 g was added, and the reaction was performed at 120 ° C. for 25 hours in a nitrogen atmosphere, followed by cooling with an acid value of 6.8 to obtain 4000 g of dibenzyl itaconate.

[Examples 1 to 4]
PMA-1 synthesized in the synthesis example was mixed and dissolved at a blending ratio shown in Table 2 to obtain a resin solution.
The drying property of the coating film and the secondary adhesion during lining were measured, and the results are shown in Table 2.
Table 4 shows the tensile test results and accelerated deterioration test results of the cured product of Example 4.

[Comparative Examples 1-4]
The resin liquid which mixed and dissolved PMA-1, UMA-1, and EPMA-1 which were synthesize | combined by the synthesis example similarly to the Example by the compounding ratio shown in Table 3 was obtained. The drying property of the coating film and the secondary adhesion during lining were measured, and the results are shown in Table 3.

Each evaluation method and evaluation criteria are shown below.
[Measurement of coating film drying time (dryness to touch)]
A curing agent and an accelerator shown below are mixed with a resin adjusted to have a gelation time of 30 minutes at 25 ° C., and a part of the composition is 300 mm × 300 mm (length × width) in thickness. It apply | coated to the thickness of 0.3 mm on a 50 mm concrete board. The dryness of the coated film of the cured product was confirmed based on the dryness to the touch, and the time when the tack became free was measured.

○ Curing agent 328E (made by Kayaku Akzo) 1.5%
○ Accelerator 8% Cobalt octylate 1.0%
Acetyl butyl lactone 0.5%

[Evaluation of secondary adhesion]
A hardener is mixed with a low odor vinyl ester resin NSR-112 (manufactured by Showa Denko) as a primer on a concrete plate of 300 mm x 300 mm (length x width) and thickness 50 mm to a thickness of 0.3 mm. After confirming that the coating film was dried after 2 hours, a curing agent was mixed with the prepared resin composition, and a one-ply lamination (FRP lining) was performed using a 450 g / m ² glass mat. went. Three days after drying, the surface treatment is not performed, and the resin composition prepared as it is is mixed with a curing agent and an accelerator, and a second layer is laminated using a 450 g / m ² glass mat (FRP lining). Went. The next day after the second layer was laminated, the adhesiveness was confirmed by a peeling test, and the failure mode was measured. Base material destruction was marked with ○, and interface peeling was marked with ×.

[Evaluation of cured product (tensile test / accelerated deterioration test)]
After mixing the cured resin with the prepared resin composition and degassing, the resin is poured into a mold that has been subjected to a mold release treatment of 300 mm × 300 mm × 3 mm (length × width × thickness) and cured at room temperature for 8 hours. After that, it was further cured for 24 hours in a curing furnace at 40 ° C. to prepare a cast plate. Test pieces were prepared according to JISK7113, and the tensile strength and elongation were measured.
Furthermore, the accelerated deterioration process shown in Table 1 described in JASS8 was performed, and the tensile strength and the elongation rate were measured for the test pieces after the process to evaluate the durability. The results are shown in Table 4.

  The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2012-285455 filed on Dec. 27, 2012 are incorporated herein as the disclosure of the specification of the present invention. It is.

Claims (8)

(A) at least one resin selected from the group consisting of a polyester (meth) acrylate resin, a urethane (meth) acrylate resin, and an epoxy (meth) acrylate resin, (B) dibenzyl itaconate , and (C) a styrene monomer. A resin composition comprising a radically polymerizable monomer to be removed and (D) a wax. The resin composition according to claim 1, wherein the component (A) is a glycidyl methacrylate-modified polyester methacrylate resin. The component (C) (meth) resin composition according to claim 1 or 2, characterized in that the acrylic acid ester. A resin composite composition obtained from at least one of the resin composition according to any one of claims 1 to 3 and a fiber reinforcing material, a filler, and an aggregate, wherein 100 parts by mass of the resin composition On the other hand, a resin composite composition obtained by adding 1 to 300 parts by mass of a fiber reinforcing material, a filler, and an aggregate. A waterproof coating method for civil engineering buildings, wherein the resin composition according to any one of claims 1 to 3 or the resin composite composition according to claim 4 is applied to a civil engineering building as a waterproof layer. . A lining coating method for civil engineering buildings, wherein the resin composition according to any one of claims 1 to 3 or the resin composite composition according to claim 4 is applied to a civil engineering building as a protective layer. . A covering structure provided with a waterproof layer using the resin composition according to any one of claims 1 to 3 or the resin composite composition according to claim 4 . The coating structure in which the protective layer was given using the resin composition of any one of Claims 1-3 , or the resin composite composition of Claim 4 .