JP4982987B2 - Resin composition for coating - Google Patents

Description

  The present invention relates to a coating resin composition that has a low odor and is excellent in surface dryness and topcoat compatibility throughout all seasons (5-35 ° C.) from spring to winter.

Conventionally, vinyl ester resins, vinyl urethane resins, methacrylic resins, unsaturated polyester resins, etc. are cured by radical polymerization, so they can be used as coating materials because the curing speed is fast and the construction time can be shortened. Has been.
However, these radically polymerizable resins are anaerobic and have problems in surface curability and curability in a thin film when cured in a natural environment.
To solve this problem, it has been proposed to add petroleum wax and use an air-drying resin (see, for example, Reference 1).

  However, the addition of petroleum wax has the effect of blocking air on the surface of the coating film, which contributes to the improvement of air drying properties, but still exists on the coating film surface after curing, and the secondary adhesion and appearance of the coating film May be affected.

  In response to this problem, when petroleum wax bleeds during coating curing, a polyoxyethylene alkylphenyl ether component is added to prevent the wax from contacting each other and forming a complete barrier coating, and secondary adhesion is performed. It has been proposed to improve the performance (see, for example, Reference 2).

  However, when a monomer having a phenyl group and a (meth) acrylate group having a number average molecular weight of 180 or more is used, good surface drying properties cannot be obtained in all seasons.

In addition, air-drying resins that can achieve surface hardening without using petroleum wax have been proposed for the problem of secondary adhesion (see, for example, Patent Documents 3 and 4).
However, there is a problem that the drying speed is greatly inferior to that of the blended with petroleum wax.

JP-A-11-209628 JP 2004-155936 A JP 2003-40949 A JP 2004-143393 A

  The present invention provides a resin composition for coating that has low odor and is excellent in surface dryness and topcoat suitability during all seasons (5-35 ° C.) from spring to winter.

As a result of intensive studies on the above-mentioned problems, the present inventors have found that the above-mentioned problems can be achieved by blending a mixture of petroleum waxes having specific different melting points. It came.
That is, the present invention provides (A) a reactive oligomer having at least two (meth) acryloyl groups at the molecular end, (B) a (meth) acrylate group having a phenyl group and a number average molecular weight of 180 or more. A coating resin composition comprising a monomer having (C) petroleum wax and (D) polyoxyethylene alkylphenyl ether, wherein the component (B) relative to the component (A) in the coating resin composition Is a weight ratio of 20/80 to 80/20, and the total amount [(A) + (B)] of the component (A) and the component (B) is 0.05 for the component (C). ~ 2% by weight, and the component (D) is 0. 2 to 1% by weight, wherein the (C) petroleum wax has a melting point measured according to JIS K 2235 of 115 to 155 ° F. (46.1 to 68.3 ° C.) , and the petroleum wax But Provided is a coating resin composition characterized by comprising a mixture of two or more kinds of petroleum wax having a melting point of 120 ° F. (48.9 ° C.) and a melting point of 150 ° F. (65.6 ° C.). It is.

  Since the coating resin composition of the present invention has a low odor and is excellent in surface drying properties and topcoat compatibility throughout the season, it is particularly useful as a coating material for civil engineering buildings used under natural conditions.

  The reactive oligomer (A) having at least two (meth) acryloyl groups at the molecular terminals used in the present invention is preferably a vinyl ester type resin, specifically a urethane (meth) acrylate resin, an epoxy. (Meth) acrylate resin, polyester (meth) acrylate resin, etc. are mentioned. The number average molecular weight of the reactive oligomer (A) is 500 to 10,000.

  The urethane (meth) acrylate resin is preferably obtained by reaction of polyol, polyisocyanate and (meth) acrylate having one or more hydroxyl groups per molecule, and two or more (meth) in one molecule. Has an acryloyl group.

  The polyol used for the urethane (meth) acrylate resin preferably has a number average molecular weight of 200 to 3,000, particularly preferably 400 to 2,000. Typical examples of this polyol include polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol and the like.

  Examples of the polyether polyol herein include polyols obtained by adding the above alkylene oxide to bisphenol A and bisphenol F, in addition to polyalkylene oxides such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

  Polyester polyol refers to a condensed polymer of dibasic acids and polyhydric alcohols or a ring-opening polymer of a cyclic ester compound such as polycaprolactone. Dibasic acids used here are, for example, 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. 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-cyclo Cyclohexanedicarboxylic methanol, paraxylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalin glycol, and 2,7-decalin glycol, and the like.

  Polyisocyanates used for urethane (meth) acrylate resins include 2,4-tolylene diisocyanate and its isomers or a mixture of isomers (hereinafter abbreviated as TDI), diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate. , Hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and the like. These can be used alone or in combination of two or more. Of the above polyisocyanates, diisocyanates, particularly TDI, are preferably used.

  Examples of the (meth) acrylate having one or more hydroxyl groups per molecule used for the urethane (meth) acrylate resin include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxybutyl. Mono (meth) acrylates such as (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, tris (hydroxyethyl) isocyanuric acid di (meth) acrylate, pentaerythritol tri (meth) acrylate, etc. And polyvalent (meth) acrylates.

  Examples of methods for producing urethane (meth) acrylate resins include: 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 ( A method of reacting a (meth) acrylate compound with an isocyanate group so that the hydroxyl groups are substantially equivalent, and 2) a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound are reacted at NCO / OH = 2 or more, and one end Examples thereof include a method in which an isocyanate compound is produced and then a polyol is added to react.

  The epoxy (meth) acrylate resin preferably has two or more (meth) acryloyl groups in one molecule, and is obtained by reacting an epoxy resin and an unsaturated monobasic acid in the presence of an esterification catalyst. It is what

  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.

  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. Examples thereof include epoxy resins, methyl glycidyl ether type epoxy resins obtained by reaction of methyl epichlorohydrin and bisphenol A or bisphenol F, or epoxy resins obtained from an alkylene oxide adduct of bisphenol A and epichlorohydrin or methyl epichlorohydrin. 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.

  Unsaturated monobasic acids used in epoxy (meth) acrylate resins include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, monopropyl maleate, mono (2-ethylhexyl) maleate or sorbic acid Etc. 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.

  The polyester (meth) acrylate resin is a saturated or unsaturated polyester having two or more (meth) acryloyl groups in one molecule, and has a (meth) acryl compound reacted at the terminal of the saturated or unsaturated polyester. It is. The number average molecular weight of the resin is preferably 500 to 5,000.

  Saturated polyester is obtained by condensation reaction of saturated dibasic acid and polyhydric alcohol, and unsaturated polyester is obtained by condensation reaction of dibasic acid containing α, β-unsaturated dibasic acid and polyhydric alcohol. Is.

  Examples of the saturated dibasic acid herein include the compounds shown in the above-mentioned polyester polyol, and examples of the unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride. Etc. Moreover, the compound shown to the term of the said polyester polyol can be mentioned also about polyhydric alcohol.

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

  As the air-drying component, a polymer containing an unsaturated group that has air-drying properties and can be crosslinked by radical polymerization can be used in combination with the component (A). This air-drying means that curing proceeds rapidly even in the air without being inhibited by oxygen molecules by introducing a specific functional group in the polymer. 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 unsaturated polyester, vinyl ester and the like.

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

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

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

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

  The monomer having a (meth) acryloyl group having a number average molecular weight of 180 or more and having a phenyl group as the component (B) used in the present invention is a reactive oligomer (A) having a (meth) acryloyl group at the molecular end. And a monomer having a phenyl group and a (meth) acryloyl group. Preferred is phenoxyethyl (meth) acrylate or phenoxypropyl (meth) acrylate. When a monomer having no phenyl group is used and the amount thereof is increased, the strength of the resulting cured product is not sufficient, and a monomer having no (meth) acryloyl group is used and the amount thereof is increased. In such a case, the copolymerization with the reactive oligomer (A) having a (meth) acryloyl group at the molecular terminal is deteriorated, resulting in a disadvantage that the curing time is prolonged.

  Specific examples of the monomer having a phenyl group and a (meth) acryloyl group having a number average molecular weight of 180 or more include phenoxyethyl acrylate, phenol ethylene oxide (EO) -modified acrylate, nonylphenyl carbitol acrylate, nonylphenol EO-modified acrylate, Phenoxypropyl acrylate, phenol propylene oxide (PO) modified acrylate, nonylphenoxypropyl acrylate, nonylphenol PO modified acrylate, acryloyloxyethyl phthalate, phenoxyethyl methacrylate, phenol EO modified methacrylate, nonylphenyl carbitol methacrylate, nonylphenol EO modified meta Acrylate, phenoxypropyl methacrylate, phenol PO modification Methacrylate, nonylphenoxy propyl methacrylate, nonylphenol PO-modified methacrylate, methacryloyloxyethyl phthalate.

  In this invention, although the intensity | strength etc. of resin hardened | cured material are inferior, the monomer which has a (meth) acryloyl group which does not contain a phenyl group can be used together in the range which does not impair the effect of this invention. Specific examples include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, decyl acrylate, lauryl acrylate, acrylic Acid stearyl, polycaprolactone acrylate, diethylene glycol monomethyl ether monoacrylate, dipropylene glycol monomethyl ether monoacrylate, 2-ethylhexyl carbitol acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, T-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, decyl methacrylate, methacrylic acid Examples include uril, stearyl methacrylate, polycaprolactone methacrylate, diethylene glycol monomethyl ether monomethacrylate, dipropylene glycol monomethyl ether monomethacrylate, 2-ethylhexyl carbitol methacrylate, and the like. In order to maintain odor, a monomer having a number average molecular weight of 180 or more is preferable.

  It is also possible to use a compound having at least two polymerizable double bonds in one molecule together with the monomer (B) having a (meth) acryloyl group having a phenyl group of the present invention and having a number average molecular weight of 180 or more. It is preferably used for the purpose of improving the wear resistance, scratch resistance, peristaltic resistance, chemical resistance, etc. of the surface of the cured product. The compound having at least two polymerizable double bonds in one molecule is a polyfunctional (meth) acrylate, and specific examples thereof include ethylene glycol di (meth) acrylate, 1,2-propylene glycol di (meta). ) Acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate alkanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) ) Acrylate, tetraethylene glycol di (meth) acrylate, polyoxyalkylene-glycol di (meth) acrylate such as polyethylene glycol di (meth) acrylate, and the like. These may be used alone or in combination of two or more. .

The petroleum wax (C) used in the present invention forms a film on the laminated surface or painted surface when the resin composition is laminated or painted, and suppresses the inhibition of curing by oxygen. Specifically, there are paraffin wax, microcrystalline wax, petrolactam, etc.
Paraffin wax is particularly preferable.
Petroleum wax (C) has a melting point of 110 ° F. (43.3 ° C.) to 160 ° F. (71.1 ° C.), especially assuming use in all seasons (5-35 ° C.) from spring to winter. Is preferably from 115 ° F. (46.1 ° C.) to 155 ° F. (68.3 ° C.) .
The melting point here is a melting point measured based on JIS K 2235.
Furthermore, this invention mix | blends 2 or more types of petroleum wax which has the melting | fusing point which is 10 degrees F or more away at the point of the surface drying property in all the seasons (5-35 degreeC). And it is preferable to mix | blend the same quantity of paraffin wax which has melting | fusing point of the said range.

  Other synthetic waxes, that is, polyethylene wax, oxidized paraffin, alcohol type wax, and the like can be used. For example, liquid hydrocarbons such as mineral oil and liquid paraffin can be used in combination.

The polyoxyethylene alkyl phenyl ether (D) used in the present invention forms micelles in the resin composition with the above petroleum wax (C), and the petroleum wax is a wax that bleeds to the coating surface when the coating is cured. Components are brought into contact with each other to prevent the formation of a complete air barrier coating. Specific examples of the component (D) include polyoxyethylene alkylphenyl ethers, and in particular, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene dodecyl phenyl ether, and the like.
The HLB value of the polyoxyethylene alkylphenyl ether (D) is preferably from 8.0 to 18.0. The HLB value refers to a hydrophilic-lipophilic balance, and is a value according to the Griffin formula: HLB value = 20 × (weight% of hydrophilic group).
Moreover, it is preferable that the said (D) component is added 0.03-1.0 weight part with respect to 100 weight part of resin. In particular, the addition of 0.1 to 0.5 parts by weight is preferable from the viewpoint of surface drying properties and top coat compatibility.

  In the present invention, as with the components (C) and (D), organic acid metal soaps such as cobalt, vanadium and manganese are preferably used in combination for the purpose of improving the surface drying property. Organic acid salts can be suitably used. The amount added is preferably 0.1 to 3 parts by weight, more preferably 0.3 to 1 part by weight, based on 100 parts by weight of the components (A) and (B).

  The composition ratio of the present invention is preferably such that the ratio of the component (B) to the component (A) is 20/80 to 80/20 by weight, and the total amount of the component (A) and the component (B), The component (C) is preferably 0.05 to 2% by weight, and the component (D) is preferably 0.01 to 2% by weight. If the component (A) is less than 20% by weight, the mechanical strength of the cured product is insufficient, and if it exceeds 80% by weight, the composition has a high viscosity and is difficult to use as a liquid resin. On the other hand, if the amount of the component (C) is less than the lower limit, the air drying property is deteriorated. If the upper limit is exceeded, the secondary adhesive property of the cured product is deteriorated and the appearance of the coating film is deteriorated. Furthermore, when the amount of the component (D) is less than the lower limit, the top coat compatibility and the secondary adhesive property are deteriorated, and when the upper limit is exceeded, the drying property is deteriorated and the coating film appearance is also deteriorated.

  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 to adjust 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, 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- And amines such as toluidine and 4- (N, N-substituted amino) benzaldehyde.

  Examples of the polymerization inhibitor include trihydrobenzene, toluhydroquinone, 14-naphthoquinone, parabenzoquinone, hydroquinone, benzoquinone, hydroquinone monomethyl ether, p-tert-butylcatechol, 2,6-di-tert-butyl-4-methylphenol. Etc. 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 weight with respect to 100 parts by weight of the total amount of the resin composition. Moreover, 0.1-5 weight part is used for the addition amount of a hardening accelerator. In the present invention, amine-based and metal soap-based accelerators are preferred. 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.

  In the present invention, various additives such as fillers, ultraviolet absorbers, pigments, thickeners, low shrinkage agents, anti-aging agents, plasticizers, aggregates, flame retardants, stabilizers, reinforcing materials, etc. are used. Also good.

  Examples of fillers include hydraulic silicate materials, calcium carbonate powder, clay, alumina powder, meteorite powder, talc, barium sulfate, silica powder, glass powder, glass beads, mica, aluminum hydroxide, cellulose-based, silica sand, Examples include river sand, cold water stone, marble waste, and crushed stone.

  The resin composition of the present invention has a low odor and is excellent in surface drying and topcoat compatibility in all seasons (5 to 35 ° C.) from spring to winter. Therefore, FRP molded product, putty, paint, cast product, floor It can be used for materials, wall coating materials, road marking materials, pavement materials, lining materials and the like. It is particularly useful for civil engineering and building materials that are used in a natural environment and have a problem of odor during curing.

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

Reference Example 1 Synthesis of Urethane Methacrylate Polymer [VU] Polypropylene glycol (number average molecular weight 984.2) was placed in a 5-liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser. ) 2461 parts, tolylene diisocyanate 739.5 parts, isophorone diisocyanate 166.8 parts, heated to 80 ° C. in a nitrogen atmosphere, reacted for 3 hours, when NCO equivalent 697 was reached, cooled to 50 ° C. Thereafter, 0.337 parts of toluhydroquinone and 657.7 parts of hydroxyethyl methacrylate are added under a nitrogen / air (flow ratio 1/1) mixed gas stream, and the temperature is raised again to 90 ° C. The reaction was carried out for 3 hours to obtain a urethane methacrylate polymer having a residual NCO amount of 0.0343%. This polymer is hereinafter referred to as [VU].

Reference Example 2 Synthesis of Epoxy Methacrylate Polymer [VE] Epiklon 830 (Dainippon Ink Chemical Co., Ltd.) was added to a 5-liter four-necked flask equipped with a thermometer, stirrer, gas inlet, and reflux condenser. Epoxy resin: reaction product of epichlorohydrin and bisphenol A: number average molecular weight 344) 2970 parts, 1456 parts methacrylic acid, 1.55 parts 2,6-di-tert-butyl-4-methylphenol, 13.3 parts triethylamine The mixture is charged and heated to 90 ° C. in a nitrogen / air (flow rate ratio 1/1) mixed gas stream and reacted for 2 hours. Next, the reaction temperature was raised to 105 ° C. and the reaction was continued for 30 hours to obtain an acid value of 8.87 and an epoxy equivalent of 23900. This polymer is hereinafter referred to as [VE].

Reference Example 3 Synthesis of Air-Dry Unsaturated Polyester [UPE] Polymer Thermometer, Stirrer, Inert Gas Inlet, and 2 liter Four-necked Flask equipped with a reflux condenser, 576 parts of diethylene glycol and anhydrous phthalate 285 parts of acid, 81 parts of maleic anhydride and 457 parts of piperylene / maleic anhydride adduct were subjected to heat dehydration condensation under known conditions to obtain an air-drying polyester resin having an acid value of 10.2. This polymer is hereinafter referred to as [UPE].

(Examples 1-4 and Comparative Examples 1-4)
The solid obtained in the above reference example was diluted with an arbitrary amount of phenoxyethyl methacrylate [hereinafter: PHOEMA] or styrene [hereinafter: SM], and petroleum wax and polyoxyethylene nonylphenyl ether were dissolved and dispersed therein to cover the solid. A curable resin composition was obtained.

[Evaluation of surface drying]
To 100 parts of the curable resin composition for coating obtained in Examples 1 to 4 and Comparative Examples 1 to 4, 8% cobalt octylate was 1 part at 35 ° C, 1 part at 25 ° C, and 1.5 parts at 15 ° C. 1.5 parts at 5 ° C was added and stirred, and then 55% methyl ethyl ketone peroxide was 1 part at 35 ° C, 1.5 parts at 25 ° C, 2 parts at 15 ° C, 2 parts at 5 ° C, and α-acetyl- A product containing 0.4 part of γ-butyrolactone was applied onto a fiber reinforced cement board with an applicator having a thickness of 0.15 mm, and the dried state of the coating film surface was observed.
The curing time of the resin is set to 15 minutes at each temperature by blending the above accelerators and curing agents, and “◯” indicates that the resin is dried within 45 minutes. “△” indicates a product dried within 90 minutes. What was needed for drying for 90 minutes or more was made into "x".

[Evaluation of topcoat compatibility]
Using the dried coating films obtained in Examples 1 to 4 and Comparative Examples 1 to 4 as a base, Diover NS-800 (manufactured by Dainippon Ink & Chemicals, Inc.) was applied at 0.15 kg / m ² and JIS K was applied. According to 5600-3-4, visual observation was mainly performed for the presence or absence of cissing.
Those with no repelling were marked with “◯”, those with slight repelling were marked with “△”, and those with repelling were marked with “×”.

[Odor evaluation]
From the coating films obtained in Examples 1 to 4 and Comparative Examples 1 to 4, those that did not smell at a distance of 1 m were indicated as “◯”, those that slightly smelled “Δ”, and those that smelled “x”.

Claims (3)

(A) a reactive oligomer having at least two (meth) acryloyl groups at the molecular end, (B) a monomer having a (meth) acrylate group having a phenyl group and a number average molecular weight of 180 or more, (C) A coating resin composition comprising petroleum wax and (D) polyoxyethylene alkylphenyl ether, wherein the ratio of component (B) to component (A) in the coating resin composition is: The ratio is 20/80 to 80/20, and the total amount of the component (A) and the component (B) [(A) + (B)] is 0.05 to 2% by weight of the component (C). Yes, component (D) is 0. 2 to 1% by weight, wherein the (C) petroleum wax has a melting point measured according to JIS K 2235 of 115 to 155 ° F. (46.1 to 68.3 ° C.) , and the petroleum wax But A coating resin composition comprising a mixture of two or more kinds of petroleum wax having a melting point of 120 ° F. (48.9 ° C.) and a melting point of 150 ° F. (65.6 ° C.) . 0.05 to 0.1% by weight of petroleum wax having a melting point of 120 ° F. (48.9 ° C.) with respect to the total amount of the component (A) and the component (B) [(A) + (B)] The coating resin composition according to claim 1, wherein the petroleum wax at 150 ° F. (65.6 ° C.) is 0.2% by weight. The resin composition for coating according to claim 1, wherein the reactive oligomer (A) having at least two (meth) acryloyl groups at the molecular terminals contains an air-drying unsaturated polyester.