JP2006028418A - Radical-curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition containing a radical-curable resin suitable for finishing materials for building materials in a construction field, etc., by virtue of an enough reduction in an amount of formaldehyde emission and in an amount of emission of highly volatile polymerizable monomers such as styrene, and full suppression of sanitary problems due to emission of chemical substances. <P>SOLUTION: This radical-curable resin composition comprises a radical-curable resin having a (meth)acryloyl group and an acetoacetyl group as essential ingredients, wherein the total amount of the (meth)acryloyl group is ≥1 pt.wt. and ≤40 pts.wt., and the total amount of the acetoacetyl group is ≥0.01 pt.wt. and ≤30 pts.wt. on the basis of the radical-curable resin of 100 pts.wt. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a radical curable resin composition. More specifically, the present invention relates to a radical curable resin composition suitable for various uses such as a lining material, a coated floor material, fiber reinforced plastic, resin concrete, a decorative board, a paint, a putty, a gel coat, a casting, and an adhesive.

Radical curable resins are used as finishing materials for building materials in the building field and the like. For example, those that can be applied to a room temperature curing system that cures at room temperature are widely used. As such a radical curable resin, radical polymerization is possible at room temperature, and since the cured product has performances such as toughness, strength, durability, waterproofness, for example, a waterproof material (waterproof lining material), Painted flooring, Fiber Reinforced Plastics (FRP) material, resin concrete, decorative board, paint, putty, gel coat, casting, adhesive, furniture material, anticorrosive, WPC (Wood Plastic Combination), bathtub (bathtub) ), Human-sized (artificial marble), and packaging products.

By the way, as a countermeasure against sick house for VOC (volatile organic compounds) emitted from building materials, the Ministry of Land, Infrastructure, Transport and Tourism has partially revised the Building Standards Law, etc., and technical standards regarding hygienic measures against the release of chemical substances in the living room Formaldehyde is mentioned as a chemical substance that may cause sanitary problems due to divergence. For example, regarding the rate of divergence of interior finishing materials, those that emit formaldehyde in an amount exceeding 0.12 milligrams per hour per square meter of surface area in the summer are formaldehyde-emitting building materials of the first type (not used for interior finishing) Therefore, there is a demand for a technology that can lower the amount of formaldehyde emitted from the standard value and meet the building standards in the field of interior finishing materials.
Regarding other chemical substances, styrene is included in the 13 chemical substances specified by the Ministry of Health, Labor and Welfare as the indoor concentration guideline values, and the Ministry of Education, Culture, Sports, Science and Technology revised the school environmental hygiene standards. Since it has become a measurement target substance, styrene, which is widely used as a polymerizable monomer for radical curable resins, is likely to be subject to restrictions in the future in the field of interior materials for homes and buildings. It is done. Therefore, a technique for reducing the amount of styrene emitted is also urgent.

An aldehyde adsorbent composed of an acetoacetyl group-containing unsaturated polyester resin has been disclosed for a conventional radical curable resin composition (see, for example, Patent Documents 1 and 2), and formaldehyde generated from a substrate is reduced. Making it possible. However, in Patent Document 1, a styrene monomer is used as the polymerizable monomer in the resin, and there is room for improvement to meet the indoor concentration guideline value for styrene of the Ministry of Health, Labor and Welfare. In Patent Document 2, the resin is a polymer obtained by polymerizing a (meth) acryloyl group, the (meth) acryloyl group does not remain in the resin, and the cured form is not radical polymerization.
JP 11-197502 A JP 11-89920 A

The present invention has been made in view of the above situation, and the amount of formaldehyde emission is sufficiently reduced, and the amount of emission when a highly volatile polymerizable monomer such as styrene is used can also be sufficiently reduced. An object of the present invention is to provide a resin composition containing a radical curable resin that is sufficiently suppressed in the possibility of causing sanitary hindrance to the release of chemical substances and is suitable for a finishing material of a building material in the building field or the like. To do.

The present inventors have made various studies on the radical curable resin composition, and found that by introducing an acetoacetyl group into the resin skeleton of the radical curable resin, an effect of sufficiently suppressing the emission of formaldehyde can be exhibited. When such a radical curable resin has a (meth) acryloyl group and an acetoacetyl group as essential, a coating layer having excellent physical properties such as mechanical strength and adhesiveness can be formed, and at the time of curing of the resin And found that the amount of formaldehyde emission can be sufficiently reduced after curing. And, by identifying the total content of (meth) acryloyl groups and acetoacetyl groups contained in the resin skeleton, it was found that the effect of reducing the amount of formaldehyde emission can be more fully exhibited, and the above problem The present inventors have arrived at the present invention by conceiving that the problem can be solved brilliantly. In addition, after the construction, the radical curable resin composition of the present invention is the “Act for Partial Revision of the Building Standards Act concerning Sick House Measures” in the revised Building Standards Law that came into effect on July 1, 2003. The final products such as building materials in the construction field and the like can sufficiently reduce the amount of formaldehyde emission. In addition, the indoor concentration guideline value of the Ministry of Health, Labor and Welfare can be adapted to the guideline value by reducing or not using the amount of styrene monomer in the radical curable resin composition of the present invention.

That is, the present invention is a radical curable resin composition containing a radical curable resin essentially comprising a (meth) acryloyl group and an acetoacetyl group, wherein the total content of the (meth) acryloyl group is a radical curable resin. 1 part by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the resin, and the total content of the acetoacetyl groups is 0.01 part by weight or more and 30 parts by weight with respect to 100 parts by weight of the radical curable resin. It is a radically curable resin composition that is not more than part.
The present invention is described in detail below.

In the radical curable resin composition of the present invention, the radical curable resin is an essential component of a (meth) acryloyl group and an acetoacetyl group, and the total content of acetoacetyl groups in the radical curable resin is: The amount is suitably 0.01 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the radical curable resin. If the amount is less than 0.01 parts by weight, the emission of formaldehyde may not be sufficiently suppressed. If the amount exceeds 30 parts by weight, there will be a problem in the storage stability of the liquid resin, and the resin cured machine There is a possibility that physical properties satisfying the required mechanical strength, drying property, water resistance, heat resistance and the like cannot be obtained. A preferable lower limit is 0.03 part by weight, and more preferably 0.05 part by weight. Moreover, a preferable upper limit is 15 weight part, More preferably, it is 10 weight part. Moreover, as a range, it is suitable that it is 0.01-30 weight part, Preferably it is 0.03-15 weight part, More preferably, it is 0.05-10 weight part.
The acetoacetyl group-containing form may be a form having an acetoacetyl group at both ends of the resin skeleton, or a form in which a hydroxyl group and an acetoacetyl group contained in the resin skeleton are combined. However, a form having an acetoacetyl group at one end is preferable.

As the radical curable resin, the total content of (meth) acryloyl groups in the radical curable resin is 1 part by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the radical curable resin. Is appropriate. Thereby, radical curable resin excellent in mechanical strength, adhesiveness, drying property, water resistance, heat resistance, etc. can be obtained. A preferred lower limit is 3 parts by weight and an upper limit is 30 parts by weight, a more preferred lower limit is 5 parts by weight, and an upper limit is 20 parts by weight. Moreover, as a range, although it is suitable that it is 1-40 weight part, Preferably it is 3-30 weight part, More preferably, it is 5-20 weight part.

A preferred form of the radical curable resin is a form comprising a compound obtained by reacting a compound having a (meth) acryloyl group in the molecule with a compound having an acetoacetyl group in the molecule. In such a compound, a compound having a (meth) acryloyl group in the molecule and a compound having an acetoacetyl group in the molecule have a group capable of reacting with each other. A radical curable resin containing a compound having a (meth) acryloyl group and an acetoacetyl group can be obtained.
As a more preferable form of the compound obtained by reacting a compound having a (meth) acryloyl group in the molecule with a compound having an acetoacetyl group in the molecule, the following general formula (1);

(Where n represents 0 or an integer of 1 or more). By using a radical curable resin containing such a compound in the radical curable resin composition of the present invention, a coating layer having excellent physical properties such as mechanical strength and adhesiveness is formed, and the resin composition is cured. It is possible to more sufficiently reduce the amount of formaldehyde emitted from the product.

The following method is exemplified as a reaction method for obtaining a compound obtained by reacting a compound having a (meth) acryloyl group in the molecule with a compound having an acetoacetyl group in the molecule.
That is, for example, (1) a compound having a (meth) acryloyl group in the molecule further has a carboxyl group, and a compound having an acetoacetyl group in the molecule further has a hydroxyl group. A method for obtaining a compound by condensation reaction of a carboxyl group and a hydroxyl group, (2) a compound having a (meth) acryloyl group in the molecule further having a hydroxyl group, and having an acetoacetyl group in the molecule Further having an alkyl ester group, a method of obtaining the compound by transesterifying the alkyl ester group of these compounds with a hydroxyl group, and (3) a compound having a (meth) acryloyl group in the molecule. The compound having an acetoacetyl group in the molecule further has an isocyanate group. (4) A compound having a (meth) acryloyl group in a molecule further has an epoxy group, and an acetoacetyl group in the molecule. The compound having a carboxyl group further has a carboxyl group, and examples thereof include a method of obtaining the compound by ring-opening addition reaction of the epoxy group of these compounds with a carboxyl group, but the present invention is particularly limited to these reaction methods. It is not something.

The compound having a (meth) acryloyl group in the molecule is not particularly limited as long as it is a compound having at least one (meth) acryloyl group in one molecule, and the form of the compound may be a polymer or a crosslinkable property. It may be in the form of a polymer (oligomer) or in the form of a monomer. Among these, at least one crosslinkable polymer selected from the group consisting of polyether (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and polyester (meth) acrylate is preferable. Moreover, as a crosslinkable polymer which has such a (meth) acryloyl group, it is preferable that a number average molecular weight is 350-7000. More preferably, it is 400-5000.
In addition, these molecular weight analysis conditions are analyzed from a peak having a molecular weight of 350 or more. In addition, these molecular weights are measured using a general-purpose gel permeation chromatography (GPC) apparatus, using TSK guard column Super H-H, TSK gel Super H2000, TSK gel Super HM-H manufactured by Tosoh Corporation, and known molecular weights. It can be easily measured by measuring polystyrene as a standard substance and a differential refractometer as a detector.
The compound having an acetoacetyl group in the molecule is not particularly limited as long as it is a compound having at least one acetoacetyl group in one molecule, for example, ethyl acetoacetate, methyl acetoacetate, or a compound having a hydroxyl group. A compound acetoacetylated with diketene is preferably used.

The radical curable resin preferably contains a radical polymerizable monomer. Examples of the radical polymerizable monomer include styrene, vinyl toluene, paramethyl styrene, chlorostyrene, and divinylbenzene. Vinyl acetate; monofunctional alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate; cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, isobol Monofunctional (meth) acrylates having a cyclic structure in the molecule such as nyl methacrylate, dicyclopentenyloxyethyl methacrylate, phenoxyethyl methacrylate; diethylene glycol di (meth) acrylate, Multifunctional (meth) acrylates such as ethylene glycol di (meth) acrylate, neopentyl glycol dimethacrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, etc. Can be used. These may be used alone or in combination of two or more. In addition, as a suitable form of a radically polymerizable monomer, the molecular weight is less than 350 and the viscosity at 25 ° C. is 100 mPa · s or less. If the viscosity exceeds 100 mPa · s, the viscosity of the resin composition increases, and the workability may not be sufficient.

In addition, when using a polymerizable monomer having a boiling point of 200 ° C. or lower, such as styrene or methyl (meth) acrylate, it is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the total amount of the radical curable resin. . If the polymerizable monomer exceeds 30 parts by weight, the odor at the time of construction on site etc. is strong, the working environment is deteriorated, and the amount of the polymerizable monomer emitted from the cured product may not be sufficiently reduced. is there. More preferably, it is 1 to 15 parts by weight, but it is most preferable not to use it.

Among the radical polymerizable monomers, it is preferable to use a (meth) acrylate monomer, and the amount of the (meth) acrylate monomer is 1 part by weight or more with respect to 100 parts by weight of the total amount of the radical curable resin. 60 parts by weight or less is preferable. Thereby, while being able to suppress the formaldehyde emission amount more fully, it becomes possible for hardened | cured material to exhibit sufficient basic performance in various uses, such as a flooring and a decorative board. As a lower limit, it is more preferable that it is 5 weight part, More preferably, it is 10 weight part. As an upper limit, it is more preferable that it is 50 weight part, More preferably, it is 30 weight part. Moreover, as a range, it is suitable that it is 1-60 weight part, However, More preferably, it is 5-50 weight part, More preferably, it is 10-30 weight part.
Thus, the radical curable resin contains a radical polymerizable monomer containing a (meth) acrylate monomer, and the (meth) acrylate monomer has a total amount of radical curable resin of 100. A form that is 1 part by weight or more and 60 parts by weight or less with respect to parts by weight is also a preferred form of the present invention.
In addition, in the said radically polymerizable monomer, when using a styrene-type monomer, it is preferable to set it as 1-50 weight part with respect to 100 weight part of total amounts of a radically polymerizable monomer.

In the radical curable resin of the present invention, the weight ratio of a compound obtained by reacting a compound having a (meth) acryloyl group in the molecule and a compound having an acetoacetyl group in the molecule to the radical polymerizable monomer The compound / polymerizable monomer is preferably (20 to 90) / (80 to 10). If the weight ratio of the polymerizable monomer exceeds 80% by weight, the resulting resin may not have sufficient chemical resistance and toughness. If it is less than 20% by weight, the cured product will have sufficient surface properties. In addition, the viscosity cannot be improved and the workability may not be excellent.
In the radical curable resin, a stable radical such as hydroquinone, catechol, t-butylcatechol, benzoquinone, cresol, t-butylhydroquinone, ferdazil, DPPH (diphenylpicrylhydrazyl) may be used as a stabilizer. it can.

Hereinafter, a compound having a (meth) acryloyl group, a compound having an acetoacetyl group, and a radical curable resin composition containing a compound obtained by reacting these compounds will be further described.
As the compound having a (meth) acryloyl group in the molecule, polyether (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate and polyester (meth) acrylate are preferable as described above, but these (meth) It is preferable that at least a part of the compound having an acryloyl group has a functional group capable of reacting with the compound having an acetoacetyl group together with the (meth) acryloyl group. By reacting such a compound having a (meth) acryloyl group with a compound having an acetoacetyl group, a compound having a (meth) acryloyl group and an acetoacetyl group in the skeleton which is a preferred form in the present invention. The radical curable resin composition to contain can be obtained.

The polyether (meth) acrylate is an esterified product obtained by an esterification reaction of a bivalent or higher-valent alcohol having an ether bond and (meth) acrylic acid, leaving at least a part of hydroxyl groups of the alcohol (meta A polyether (meth) acrylate having a hydroxyl group as a functional group capable of reacting with a compound having an acetoacetyl group is obtained by esterification with acrylic acid.

The esterification product of the bivalent or higher alcohol and (meth) acrylic acid is a compound having at least one (meth) acryloyl group in the molecule, such as diethylene glycol, polyethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, polypropylene glycol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1, 4-cyclohexanediol, 1,4-dimethylolcyclohexane, hydroxypivalylhydroxypivalate, triethylene glycol, tetraethylene glycol, bisphenol F, bisphenol Z, bisphenol S, bisphenol AF, bisphenol C, bisphenol FD Monoesters obtained by reacting one or more of dihydric alcohols such as hydrogenated bisphenol A and bisphenol A and their alkylene oxide adducts with (meth) acrylic acid; glycerin, trimethylolpropane, Monoesters obtained by reaction of one or more of trivalent or higher alcohols such as pentaerythritol, dipentaerythritol, novolak phenol, cresol novolak, etc. and their alkylene oxide adducts with (meth) acrylic acid , Diesters, triesters and the like, which may include only esterified compounds having a hydroxyl group, such as a compound having only a (meth) acryloyl group, for example, the above-described divalent or higher alcohol and (meth) acrylic acid Diesters obtained by the reaction of It may be a mixed form of.

The compound having one or more (meth) acryloyl groups has 1 to 3 terminal groups having (meth) acryloyl groups at the ends of the oxyalkylene chain in the molecule and 1 to 2 hydroxyl groups. Is preferred. The number of oxyalkylene units in one oxyalkylene chain is preferably 1 or more and 10 or less. If there is no oxyalkylene chain, the flexibility and base material followability of the film formed using the radical curable resin composition may not be sufficient, and if it exceeds 10, the cured product has excellent water resistance. There is a risk that it will not be. More preferably, they are 2 or more and 8 or less, More preferably, they are 4 or less.
The oxyalkylene unit is preferably composed of oxyalkylene units having 2 to 4 carbon atoms. That is, the oxyalkylene unit is preferably composed of at least one oxyalkylene unit selected from the group consisting of oxyethylene units, oxypropylene units and oxybutylene units. If the number of carbon atoms in the oxyalkylene unit exceeds 4, the viscosity of the radical curable resin composition increases, and there is a possibility that the work cannot be performed efficiently. More preferably, it is constituted by oxyalkylene units having 2 to 3 carbon atoms, and more preferably, it is constituted by oxyalkylene units having 2 carbon atoms, that is, oxyethylene units. In addition, when it has two or more oxyalkylene units, they may all be the same or different. In addition, the two or more oxyalkylene chains in the molecule may have the same or different oxyalkylene unit structure.

The (meth) acryloyl groups of the compound having one or more (meth) acryloyl groups may all be the same, or may be a combination of an acryloyl group and a methacryloyl group.
The compound having one or more (meth) acryloyl groups is preferably in a form having a phenol residue. The phenol residue means a residue having a structure in which active hydrogen is removed from the hydroxyl group of phenol. In addition, you may have one such residue in 1 molecule, and may have two or more.
A preferred form of such a compound having one or more (meth) acryloyl groups is one having a structure derived from bisphenol A, and among them, an alkylene oxide adduct of bisphenol A and (meth) acrylic acid. An esterified product is preferred. More preferably, the following general formula (2);

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² , R ³ , R ⁴ and R ⁵ are the same or different and represent a hydrogen atom or a methyl group. P and m are 0 to 10 respectively. And p + m is 1 or more and 10 or less.) A mono (meth) acrylate of an alkylene oxide adduct of bisphenol A having a structure represented by:
Thus, the form in which the esterified product includes an esterified product of an alkylene oxide adduct of bisphenol A and (meth) acrylic acid is also a preferred embodiment of the present invention.

As the epoxy (meth) acrylate, a crosslinkable polymer obtained by addition reaction of an epoxy compound having two or more epoxy groups in the molecule, (meth) acrylic acid and, if necessary, a polybasic acid ( An epoxy) having an epoxy group as a functional group capable of reacting with a compound having an acetoacetyl group by leaving at least a part of the epoxy group in the addition reaction with (meth) acrylic acid. ) Acrylate is obtained, and an epoxy (meth) acrylate having a carboxyl group as a functional group capable of reacting with a compound having an acetoacetyl group is obtained by addition reaction of a polybasic acid to the remaining epoxy group. Moreover, the epoxy (meth) acrylate which has a hydroxyl group as a functional group which can react with the compound which has an acetoacetyl group by the hydroxyl group produced by the ring-opening addition reaction with (meth) acrylic acid is obtained.

Examples of the polybasic acid include α, β-unsaturated dibasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid; phthalic acid, phthalic anhydride, isophthalic acid, Terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic acid, methyltetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, cyclohexanedicarboxylic acid, succinic acid, succinic anhydride, malonic acid, glutaric acid, Adipic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, dimer acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid Saturated diacids such as acid anhydrides and 4,4'-biphenyldicarboxylic acid In addition to basic acids, pyromellitic acid, trimellitic acid, trimer acid, polybutadiene having a carboxyl group, butadiene-acrylonitrile copolymer having a carboxyl group, α, β-unsaturated dibasic acid and / or saturated dibasic acid And a compound having a carboxyl group at the terminal obtained by esterification of a polyhydric alcohol and one or more of these can be used. In addition, when two or more of the above polybasic acids are used in combination, a vinyl ester compound rich in flexibility can be obtained.

Examples of the epoxy compound include two or more epoxy groups in the molecule, such as phenol novolac type epoxy resin, cresol novolak type epoxy resin, bisphenol type epoxy resin, tris (2,3-epoxypropyl) isocyanurate, and the like. A compound is mentioned, These 1 type (s) or 2 or more types can be used.

In the above epoxy (meth) acrylate, an addition reaction catalyst is usually used for the addition reaction of an epoxy compound having two or more epoxy groups in the molecule, (meth) acrylic acid and, if necessary, a polybasic acid. It is preferable to heat in the range of 50-150 degreeC in presence of this. As the addition reaction catalyst, a commonly used synthesis catalyst can be used, but tertiary amines, onium salts, metal soaps and the like are preferably used.

Urethane (meth) acrylate is a crosslinkable polymer (oligomer) obtained by urethanizing polyisocyanate, (meth) acrylate having a hydroxyl group, and, if necessary, polyol, and (meth) acrylic acid. The urethane (meth) acrylate having an isocyanate group as a functional group capable of reacting with a compound having an acetoacetyl group is obtained by leaving at least a part of the isocyanate group in the polyisocyanate in the addition reaction with the remaining isocyanate group. A urethane (meth) acrylate having a hydroxyl group as a functional group capable of reacting with a compound having an acetoacetyl group is obtained by urethanizing a polyol.

Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol. One or two of mono (meth) acrylates such as mono (meth) acrylate and polyvalent (meth) acrylates such as tris (hydroxyethyl) isocyanuric acid di (meth) acrylate and pentaerythritol tri (meth) acrylate More than species are preferred.

As said polyol, 1 type (s) or 2 or more types, such as a polyether polyol, a polyester polyol, a polycarbonate polyol, a polybutadiene polyol, are suitable, for example, and the number average molecular weight is 200-3000. More preferably, the number average molecular weight is 400 to 2000. The polyether polyol may be a polyol obtained by adding an alkylene oxide to bisphenol A or bisphenol F in addition to a polyalkylene oxide such as polyethylene glycol, polypropylene glycol, or polytetramethylene glycol. The polyester polyol is a condensation polymer of a dibasic acid component and a polyhydric alcohol component, or a ring-opening polymer of a cyclic ester compound such as polycaprolactone.

Examples of the polyisocyanate include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, and hydrogenation. Tolylene diisocyanate, hydrogenated xylylene diisocyanate, aliphatic diisocyanate such as hydrogenated diphenylmethane diisocyanate, tolylene diisocyanate trimer, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer An isocyanate etc. are mentioned. These polyisocyanate compounds can be used alone or in combination of two or more.

In the urethane (meth) acrylate, in order to urethanize the polyisocyanate and the (meth) acrylate compound having a hydroxyl group and, if necessary, the polyol, the equivalent ratio of the hydroxyl group and the isocyanate group is approximately 1. Thus, it is preferable to adjust the amount used and to heat in the range of 40 to 140 ° C. In order to promote the urethanization reaction, a commonly used urethanization catalyst can be used, and it is preferable to use a tin compound such as tertiary amines, dibutyltin dilaurate and tin chloride.

The polyester (meth) acrylate is a crosslinkable polymer (oligomer) obtained by esterifying a polyhydric alcohol, a polybasic acid, and (meth) acrylate. By leaving a carboxyl group, a polyester (meth) acrylate having a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with a compound having an acetoacetyl group is obtained.
Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5 -Pentanediol, 1,6-hexanediol, neopentyl glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2-methylpropane-1 , 3-diol, trimethylolpropane, hydrogenated bisphenol A, alkylene oxide (eg, ethylene oxide, propylene oxide, etc.) adducts of bisphenol A, and the like.
Examples of the basic acid other than the (meth) acrylic acids include the above-described α, β-unsaturated dibasic acid and its anhydride, saturated dibasic acid and its anhydride, and the like.

In the above polyester (meth) acrylate, the method of esterifying the (meth) acrylic acid, the polyhydric alcohol, and, if necessary, a basic acid other than the (meth) acrylic acid is not particularly limited, and the reaction temperature There are no particular limitations on the catalyst and catalyst.

As the compound having an acetoacetyl group, a compound having at least one acetoacetyl group in one molecule, a compound having a hydroxyl group, a compound having a carboxyl group, a compound having an alkyl ester group, and a compound having an isocyanate group Etc.
Examples of the compound having an alkyl ester group include methyl acetoacetate, ethyl acetoacetate, and compounds obtained by acetoacetylating a compound having a hydroxyl group with diketene.
Examples of the compound having a hydroxyl group include ethylene glycol monoacetoacetate, diethylene glycol monoacetoacetate, propylene glycol monoacetoacetate, and dipropylene glycol monoacetoacetate.
Examples of the compound having a carboxyl group include ethylene glycol monoacetoacetate ester, diethylene glycol monoacetoacetate ester, propylene glycol monoacetoacetate ester, dipropylene glycol monoacetoacetate ester, dibasic acid, and / or acid anhydride thereof. And half-esterified products.
Examples of the compound having an isocyanate group include ethylene glycol monoacetoacetate, diethylene glycol monoacetoacetate, propylene glycol monoacetoacetate, dipropylene glycol monoacetoacetate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, There are semi-urethane compounds with diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate.

In addition, regarding the reaction form of a compound having a (meth) acryloyl group and a compound having an acetoacetyl group in the molecule, as a compound having a (meth) acryloyl group, polyether (meth) acrylate, epoxy (meth) acrylate, urethane ( Although the case where a meth) acrylate and polyester (meth) acrylate are used is illustrated below, respectively, this invention is not limited only to these forms.

(In the formula, R ⁶ and R ⁷ are the same or different and represent a hydrogen atom or an alkyl group. Q represents 0 or an integer of 1 or more.)

The radical curable resin composition of the present invention can be cured by irradiation with radiation or ultraviolet rays and / or addition of a curing agent.
Examples of the curing agent include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, hydroperoxides such as cumene hydroperoxide, diacyl peroxides such as benzoyl peroxide, dicumyl peroxide, and t-butylcumyl peroxide. Dialkyl peroxides such as oxide, alkyls such as 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxybenzoate Peresters, peroxides such as bis (4-tert-butylcyclohexyl) peroxydicarbonate; azos such as 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile One kind of compound It can be used or two or more.

The amount of the curing agent used may be set as appropriate depending on the type of the curing agent and the use of the radical curable resin composition, but should be 0.1 parts by mass or more with respect to 100 parts by mass of the radical curable resin. In addition, the amount is preferably 10.0 parts by mass or less. More preferably, it is 0.2 parts by mass or more and 5 parts by mass or less. Moreover, a hardening accelerator can be used together as needed. Curing accelerators include metal soaps such as cobalt octylate and manganese octylate; metal chelate compounds such as cobalt acetylacetonate and vanadium acetylacetonate; amine compounds such as dimethylaniline and dimethyltoluidine; ethyl acetoacetate and acetylacetone 1 type (s) or 2 or more types can be used.

The radical curable resin composition preferably also contains paraffin. Paraffin is at least one wax selected from paraffin wax and microcrystalline wax, and is a mixture of hydrocarbons that are present in crude oil and are solid or semi-solid at room temperature.
Examples of the paraffin wax include paraffin wax 150 (trade name, manufactured by Nippon Seiwa Co., Ltd., melting point: 66 ° C.), paraffin wax 140 (trade name, manufactured by Nippon Seiwa Co., Ltd., melting point: 61 ° C.), and paraffin wax 130 (trade name). , Nippon Seiwa Co., Ltd., melting point 55 ° C.) and paraffin wax 115 (Nippon Seiwa Co., Ltd., melting point 47 ° C.). Examples of the microcrystalline wax include Hi-Mic-2065 (trade name, manufactured by Nippon Seiwa Co., Ltd., melting point 75 ° C.), Hi-Mic-2045 (trade name, manufactured by Nippon Seiwa Co., Ltd., melting point 64 ° C.), etc. Is mentioned. Only one type of these paraffins may be used, or two or more types may be appropriately mixed and used.

When the paraffin is used in the radical curable resin composition of the present invention, it is preferable to use a paraffin wax dispersant in combination. The dispersant for the paraffin wax is preferably a wax having at least one structure selected from, for example, a hydroxyl group, a carboxyl group, and an ester bond site. Specifically, for example, fatty acids having 12 or more carbon atoms and derivatives thereof such as dodecanoic acid, stearic acid, 12-hydroxystearic acid, octadecyl stearate; Nonipol 160 (trade name, manufactured by Sanyo Chemical Industries), Emalmine 200 Alkylphenols (trade name, manufactured by Sanyo Kasei Kogyo Co., Ltd.) and other alcohols in which alkylene oxides such as ethylene oxide and propylene oxide are added to higher alcohols; NPS-9125, NPS-9210, NPS-6010, HAD-5080, NSP Modified wax derived from paraffin wax or microcrystalline wax such as -80070, OX-020T, OX-1949 (trade names, all manufactured by Nippon Seiwa Co., Ltd.) by oxidation reaction, etc .; diamond wax (trade name, Shin Nippon Rika) Animal and vegetable oils and fats Derivatives; ceramer 67 (trade name, manufactured by Toyo Petororairo Co.), ceramer 1608 (trade name, Toyo Petororairo Co.) polymer and the like of a carboxyl group-containing monomer and olefin, and the like. Only one type of these paraffin wax dispersants may be used, or two or more types may be appropriately mixed and used.

In the present invention, the ratio of paraffin to the paraffin wax dispersant may be appropriately set according to the type, molecular weight, and composition of the radical curable resin used, but the mass ratio (paraffin mass / paraffin wax dispersant) Is preferably in the range of 500 to 1. If the ratio of the paraffin wax dispersant is larger than this range, the drying property may not be sufficient. If the ratio of the paraffin wax dispersant is smaller than this range, the adherence of the laminated resin layer to the cured product is likely to occur. Therefore, if it deviates from the above range, it is not possible to obtain a radical curable resin composition that can sufficiently satisfy both the drying property and the adherence of the laminated resin layer. There is a fear. More preferably, it exists in the range of 300-2, More preferably, it exists in the range of 200-2. By setting to such a range, it becomes possible to further improve the drying property and the adherence of the laminated resin layer in the cured product.

The amount of the wax used, that is, the total amount of the paraffin and the paraffin wax dispersant is preferably set as appropriate according to the esterified product, the crosslinkable polymer, the type and composition of the paraffin, and the like. It may be set sometimes so that a wax thin film (film) can be formed on the cured surface of the radical curable resin composition. For example, 0.005 to 2 parts per 100 parts by mass of the radical curable resin. It is preferable to use parts by mass. If the amount is less than 0.005 parts by mass, the resulting radically curable resin composition may not be sufficiently dried. If the amount exceeds 2 parts by mass, the resulting radically curable resin composition is cured. There is a possibility that the strength properties of the cured product may not be sufficient. More preferably, it is 0.02 to 0.6 parts by mass from the viewpoints of dry handling and strength properties of a cured product obtained by curing the obtained radical curable resin composition.

As the above-mentioned radical curable resin composition, additives (materials) such as thixotropic agents, fillers, drying improvers, thickeners, colorants, fiber reinforcing materials, aggregates, etc., if necessary 1 type or 2 types or more may be included. Moreover, you may mix 1 type, or 2 or more types of other types of thermosetting resins. Furthermore, you may mix a solvent and a diluent for viscosity adjustment. The amount of these used is suitably set according to the use of the radical curable resin composition.
Examples of the thixotropic agent include anhydrous fine powder silica, asbestos, clay and the like. Examples of the filler include aluminum hydroxide, talc, silica sand, calcium carbonate, and antimony oxide.
As the filler, aluminum hydroxide (ATH), calcium carbonate, calcium sulfate, barium sulfate, alumina, clay, talc, glass powder, milled fiber, cristobalite, mica, silica, river sand, diatomaceous earth, mica powder, gypsum, glass Examples include inorganic fillers such as powders; organic fillers and the like.
Examples of the drying improver include unsaturated or saturated polyester oligomers having an allyloxy group such as drying oil, allyl glycidyl ether, diethylene glycol and maleic anhydride addition polymers.
Examples of the thickener include metal oxides such as magnesium oxide, calcium oxide and zinc oxide; isocyanates; oxazolines.

Examples of the colorant include organic pigments, inorganic pigments, dyes, and the like.
Examples of the fiber reinforcing material include inorganic fibers such as glass fibers and carbon fibers; organic fibers such as aramid fibers, polyester fibers, and nylon fibers. Examples of the shape of the fiber reinforcing material include a mat shape, a chop shape, and a roving shape.
Examples of the other types of thermosetting resins include unsaturated polyester resins, urethane (meth) acrylates, and polyester (meth) acrylates.
Known solvents and diluents can be used, and examples include toluene, xylene, butyl acetate and the like. Moreover, you may use the monomer which has polymerizable unsaturated groups, such as styrene, vinyl toluene, methyl methacrylate, vinyl acetate, as a diluent. From the viewpoint of odor, those having a boiling point of 150 ° C. or higher at normal pressure are preferred. More preferably, the boiling point is 200 ° C. or higher.

In the radical curable resin composition of this invention, it becomes possible to fully suppress generation | occurrence | production of formaldehyde from hardened | cured material. The formaldehyde emission amount in the cured product of the resin composition is preferably 1.0 mg / L or less. More preferably, it is 0.5 mg / L or less, More preferably, it is 0.1 mg / L or less.

In the present invention, the raw material of the resin composition or the adjusted resin composition may be bubbled in the step of adjusting the radical curable resin composition or the step after the adjustment. As a result, for example, even if formaldehyde is mixed into the raw material, or formaldehyde is generated in the resin composition adjustment process or after the adjustment process, the amount of formaldehyde emitted from the cured resin composition is sufficiently reduced. Therefore, the effects of the present invention can be more fully exhibited.

The radical curable resin composition of the present invention can sufficiently reduce the emission of formaldehyde from the cured product, and is excellent in basic performance such as strength and elongation, flexibility, substrate followability, etc. Since it is difficult for cracks of the cured product and peeling from the base material to occur, and the resin sagging of the standing surface hardly occurs, it can be preferably used for various applications. Further, when a highly volatile polymerizable monomer such as styrene is used, the odor can be sufficiently suppressed. As a use of such a radical curable resin composition, it is particularly suitable as a cover material for civil engineering and building construction, for the purpose of waterproofing, anticorrosion, maintaining strength and aesthetics on the rooftop, floor surface, wall surface, etc. of various buildings. It can be used as a material for forming a lining material or a flooring material to be applied. In such lining materials and coating floor materials, a multilayer structure such as a primer layer, an intermediate layer, and a top coat layer is generally applied. The primer layer sufficiently adheres the base material and the coating material. It is a layer provided for the purpose, and it is suitable to mix | blend the urethane prepolymer obtained by making isocyanate and glycol react with a primer layer. An intermediate | middle layer is a layer used as the main material of a coating | covering material, and is a layer for expressing durability and mechanical strength. The intermediate layer preferably contains aggregate, mortar, fiber reinforcement, thixotropic agent, drying improver and the like. The top coat is a layer provided for the purpose of protecting the intermediate layer, weather resistance, design properties, slip resistance, etc., and the top coat preferably contains a pigment, a drying improver, and the like. As the radical curable resin composition, among these covering materials for civil engineering and construction, it is particularly suitable as a material for forming an intermediate layer and a top coat layer, and is most suitable as a material for forming a top coat layer. It is. In addition, when using as an intermediate | middle layer and / or a topcoat layer, it is preferable to add a paraffin.
The radical curable resin composition of the present invention is also a coating material for civil engineering and construction such as a lining material and a coating floor material, as well as a fiber reinforced plastic such as a vehicle, a hull, a bathtub, a water tank, and an electric part, a resin concrete, a gel coat, It can also be suitably used for various applications such as paints, putty, decorative boards, adhesives, casting materials; concrete, asphalt, mortar, steel sheets, glass, thermoplastics and other coating materials.

As a method of forming a film (coating film) with the radical curable resin composition of the present invention, for example, a method of forming a film by applying the resin composition to a substrate and then curing it, or a mat shape In the case of using the above-mentioned fiber reinforcing material, a method of forming a film by impregnating the resin composition with a fiber reinforcing material by hand lay-up or the like to form a coating material and curing the resin composition may be used.
Examples of the base material include inorganic base materials such as glass, slate, concrete, mortar, ceramic, and stone; a metal plate made of aluminum, iron, zinc, tin, copper, titanium, stainless steel, tinplate, and tin; Metal base materials such as metal plated with zinc, copper, chromium, etc., metal with surface treated with chromic acid, phosphoric acid, etc .; polyethylene, polyvinyl chloride, ABS (acrylonitrile-butadiene-styrene), FRP (textile reinforced plastic) ), Polyethylene terephthalate, polycarbonate, polymethyl methacrylate, polystyrene, polypropylene, polyester, polyolefin, acrylic resin, epoxy resin, nylon resin, and other plastic substrates; synthetic leather; cypress, cedar, pine, plywood and other wood; fiber, Examples include organic materials such as paper. In addition, these base materials may be coated with a commonly used primer or a coating material such as an undercoat, an intermediate coat, or a metallic base before the radical curable resin composition of the present invention is applied. Good.

The method for applying the radical curable resin composition to the substrate and the curing method may be appropriately selected depending on the use for which the resin composition is used. Examples of the application method include dip coating and brushing. Examples include coating, roll brush coating, spray coating, roll coating, spin coating, dip coating, bar coating, flow coating, electrostatic coating, die coating, film lamination, gel coating, and the like. Moreover, as a hardening method, the method of hardening at normal temperature, the method of hardening by heating, the method of irradiating and irradiating an ultraviolet-ray etc. are mentioned, You may carry out combining these suitably.
In addition, what is necessary is just to set suitably as a film thickness of the coating film formed from the said radical curable resin composition by the use used.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Note that “%” means “mass%” unless otherwise specified.

Production Example 1 Preparation of acetoacetyl group-containing polyether methacrylate resin <Resin (1)>
(First step)
In a flask equipped with a stirrer, Dean-Stark type water separator, gas introduction tube and thermometer, 580 g of BA-8U glycol (trade name, bisphenol A8EO adduct, manufactured by Nippon Emulsifier Co., Ltd.), 414 g of phenoxyethanol, 81 g of methyl acetoacetate, 444 g of methacrylic acid, 97 g of cyclohexane, 0.24 g of 2-methylhydroquinone, 0.40 g of phenothiazine and 8 g of paratoluenesulfonic acid are charged, heated while blowing air, reacted at 80 to 90 ° C. for 3 hours, and then 120 ° C. The mixture was heated to 120 ° C. and held for 6 hours to conduct a transesterification reaction and a condensation reaction.
The mixture of condensed water and methanol that flowed out was 93 g (94% of the theoretical effluent), of which methanol was 22 g (95% of the theoretical effluent).
Thereafter, the temperature was lowered to 110 ° C., and cyclohexane was distilled off under reduced pressure (0.06 MPa or less) for 3 hours.
The acid value of the reaction mixture at this time was 39 mgKOH / g.
(Second step)
Next, 129 g of phenylglycidyl ether, 0.09 g of 2-methylhydroquinone, 0.23 g of phenothiazine, and 4.7 g of triethylamine were added to this reaction product, and the temperature was raised again to 115 ° C., and the reaction was performed while blowing air. Six hours after raising the temperature to 115 ° C., the reaction product had an acid value of 8.9 mgKOH / g, and a resin (1) having a viscosity of 120 mPa · s was obtained.

Production Example 2 Preparation of acetoacetyl group-containing polyether methacrylate resin <Resin (2)>
(First step)
In a flask equipped with a stirrer, Dean-Stark type water separator, gas inlet tube and thermometer, BA-8U glycol (trade name, bisphenol A8EO adduct, manufactured by Nippon Emulsifier Co., Ltd.) 1160 g, diketene 118 g, cyclohexane 100 g, paratoluene While charging 4 g of sulfonic acid and maintaining the temperature at 60 to 65 ° C. for 2 hours, 35% acetoacetylation of the hydroxyl group of BA-8U glycol was carried out.
As a result of measurement of the hydroxyl value, it was confirmed that the hydroxyl value was 114 mgKOH / g and the reaction rate was 98%.
(Second step)
Next, 291 g of methacrylic acid, 0.25 g of 2-methylhydroquinone, 0.42 g of phenothiazine, and 4.34 g of paratoluenesulfonic acid were added to the reaction product, and heated to 120 ° C. while blowing air. The condensed water that flowed out 6 hours after reaching 120 ° C. became 43 g (91% of the theoretical water output).
Thereafter, the temperature was lowered to 110 ° C., and cyclohexane was distilled off under reduced pressure (0.06 MPa or less) for 3 hours.
The acid value of the reaction mixture at this time was 34 mg KOH / g.
(Third process)
Next, 117 g of phenylglycidyl ether, 0.1 g of 2-methylhydroquinone, 0.25 g of phenothiazine, and 5 g of triethylamine were added to the reaction product, and the temperature was raised again to 115 ° C. while blowing air, followed by reaction for 4 hours. Thereafter, 412 g of diethylene glycol dimethacrylate was added to obtain a resin (2) having an acid value of 7.9 mgKOH / g and a viscosity of 110 mPa · s.

Production Example 3 Preparation of acetoacetyl group-containing polyether methacrylate resin <Resin (3)>
(First step)
In a flask equipped with a stirrer, Dean-Stark type water separator, gas introduction tube and thermometer, 808 g of BA-4 glycol (trade name, bisphenol A4EO adduct, manufactured by Nippon Emulsifier Co., Ltd.), 224 g of methacrylic acid, 77 g of cyclohexane 6.4 g of paratoluenesulfonic acid, 0.19 g of 2-methylhydroquinone and 0.32 g of phenothiazine were charged and heated to 120 ° C. while blowing air. Condensed water that flowed out after 5 hours from reaching 120 ° C. was 45 g (95% of theoretical water output).
(Second step)
Subsequently, 179 g of methyl acetoacetate was added to the reaction product, and the transesterification reaction was performed while blowing air and maintaining the temperature at 80 to 90 ° C. for 4 hours and 100 to 110 ° C. for 2 hours. Thereafter, the temperature was lowered to 110 ° C., and cyclohexane was distilled off under reduced pressure (0.06 MPa or less) for 3 hours. The mixture of methanol and condensed water that flowed out was 42 g, and a reaction product (3) having a hydroxyl value of 6.2 mgKOH / g and an acid value of 3.9 mgKOH / g was obtained.
(Third process)
80 parts by weight of the reaction product (3) was diluted with 20 parts by weight of phenoxyethyl methacrylate to obtain a resin (3) having a viscosity of 110 mPa · s.

Production Example 4 Preparation of acetoacetyl group-containing polyether methacrylate resin <Resin (4)>
(First step)
In a flask equipped with a stirrer, Dean-Stark type water separator, gas introduction tube and thermometer, 632 g of BA-2 glycol (trade name, bisphenol A2EO adduct, manufactured by Nippon Emulsifier Co., Ltd.), 325 g of methyl acetoacetate, p-toluenesulfone 3 g of acid was charged, and the ester exchange reaction of 70% hydroxyl group of BA-4U glycol was performed while raising the temperature and maintaining at 150 ° C. for 4 hours at 140 ° C. for 2 hours. The amount of methanol that flowed out was 85 g. As a result of measuring the hydroxyl value, it was confirmed that the hydroxyl value was 192 mgKOH / g and the reaction rate was 95%.
(Second step)
Next, 70 g of cyclohexane, 134 g of methacrylic acid, 0.17 g of 2-methylhydroquinone, 0.29 g of phenothiazine and 3 g of paratoluenesulfonic acid were added to the reaction product, and heated to 120 ° C. while blowing air.
The condensed water which flowed out 6 hours after reaching 120 ° C. became 20 g (90% of the theoretical water output).
Thereafter, the temperature was lowered to 110 ° C., and cyclohexane was distilled off under reduced pressure (0.06 MPa or less) for 3 hours.
The acid value of the reaction mixture at this time was 24 mgKOH / g.
(Third process)
Next, 54 g of phenylglycidyl ether, 0.07 g of 2-methylhydroquinone, 0.17 g of phenothiazine, and 3.3 g of triethylamine were added to the reaction product, and the temperature was raised again to 115 ° C., and the reaction was performed while blowing air. 4 hours after raising the temperature to 115 ° C., the acid value of the reaction product was 7.4 mg KOH / g, and a resin (4) having a viscosity of 400 mPa · s was obtained.

Production Example 5 Preparation of polyether methacrylate resin <Resin (5)>
(First step)
In a flask equipped with a stirrer, Dean-Stark type water separator, gas introduction tube and thermometer, 580 g of BA-8U glycol (trade name, bisphenol A8EO adduct, manufactured by Nippon Emulsifier Co., Ltd.), 414 g of phenoxyethanol, 516 g of methacrylic acid, cyclohexane 100 g, 8 g of paratoluenesulfonic acid monohydrate, 0.25 g of 2-methylhydroquinone and 0.4 g of phenothiazine were charged and heated to 120 ° C. while blowing air. After reaching 120 ° C., the condensed water that flowed out after 8 hours was 81 g (91% of the theoretical water output).
Thereafter, the temperature was lowered to 110 ° C., and cyclohexane was distilled off under reduced pressure (0.06 MPa or less) for 3 hours. The acid value of the reaction mixture at this time was 36 mgKOH / g.
(Second step)
Next, 0.25 g of phenothiazine, 0.1 g of 2-methylhydroquinone, 8 g of N, N, N-triethylbenzeneammonium chloride and 150 g of phenylglycidyl ether are added to the reaction product, and the temperature is raised to 115 ° C. again while blowing air. Reaction was performed.
After raising the temperature to 115 ° C., 4 hours later, an acid value of the reaction mixture became 4.5 mgKOH / g, and a resin (5) containing 60% by weight of a crosslinkable polymer having a viscosity of 75 mPa · s was obtained.

Table 1 shows the viscosity, acid value, acetoacetyl group content and (meth) acryloyl group content of the resins (1) to (5) obtained in Production Examples 1 to 5.

Examples 1-11, Comparative Examples 1-2
The secondary adhesion and cured product properties of the resin were evaluated as follows. The results are shown in Tables 2 and 3.
<Secondary adhesiveness>
1. Resin for use FRP layer resin: It was obtained by kneading with the blends shown in Tables 2 and 3 and shaking.
Coating resin: 3 parts by weight of Aerosil # 200 (trade name, manufactured by Nippon Aerosil Co., Ltd.) and 0.3 part by weight of BYK R605 (trade name, manufactured by Big Chemie) are added to resin (5), and the mixture is stirred with a homomixer. 130 F (trade name, manufactured by Nippon Seiwa Co., Ltd.) 0.05 parts by weight, paraffin 115F (trade name, manufactured by Nippon Seiwa Co., Ltd.) 0.05 parts by weight and paraffin dispersant NPS9125 (product name, manufactured by Nippon Seiwa Co., Ltd.) It was obtained by adding and mixing 001 parts by weight.
2. Preparation of test piece On a concrete plate of 30 cm x 30 cm that was left overnight after applying urethane primer NS-YP (trade name, manufactured by Japan Composite), 100 parts by weight of resin (for FRP layer), dimethylaniline, octylic acid Cobalt and park mill H-80 (trade name, manufactured by NOF Corporation) were mixed, and 80 g of the resin was impregnated into a glass mat (25 cm × 25 cm) and laminated. After standing at room temperature for 1 week, the coating resin was applied at a rate of 500 g / m ² with a brush.
After standing overnight, a 4 cm square iron jig was adhered to the coated surface with an epoxy adhesive, and the adhesion between the FRP layer and the coated layer was evaluated with a Kenken-type adhesive strength tester.
3. Evaluation ○: Concrete or FRP layer breaks Δ: Partially peeled between FRP layer and coating layer ×: Stripped at interface between FRP layer and coating layer

<Physical properties of cured product>
1 part by weight of Aerosil # 200 (trade name, manufactured by Nippon Aerosil Co., Ltd.) and BYK R605 (trade name, manufactured by Big Chemie) are added to the resins (1) to (5), stirred with a homomixer, and paraffin 135F. , Paraffin 120F and paraffin dispersant NPS-9125 (all trade names, manufactured by Nippon Seiwa Co., Ltd.) were added at the ratios shown in Tables 2 and 3 to obtain a resin composition.
Furthermore, after applying urethane primer NS-YP (trade name, manufactured by Nippon Shokubai Co., Ltd.) in advance, the resin composition, cobalt octylate (metal content 8% by weight) on a 30 cm × 30 cm concrete plate left overnight, N, N-dimethylaniline and park mill H-80 (trade name, manufactured by NOF Corporation) were mixed in the ratios shown in Tables 2 and 3, and 80 g of the resulting mixture was impregnated into 25 cm × 25 cm of the glass fiber mat. And lined up.
Then, the concrete board was stood upright and the surface drying property after leaving it in a 20 degreeC atmosphere for 5 hours was evaluated by finger touch.
Moreover, about each of the obtained mixture, the formaldehyde emission amount was measured using the following formaldehyde determination method. The results are shown in Tables 2 and 3.

(Formaldehyde determination)
1: Preparation of test plate A resin (obtained mixture) was brushed onto a glass plate having a length of 75 mm and a width of 50 mm with a wet thickness of 0.5 mm, cured at room temperature, and then cured at room temperature for 2 days to obtain a test plate.
2: Test method ・ A glass bottle with a capacity of 900 ml with an inner lid that can be sealed is prepared.
・ Place 50 g of water in a glass bottle.
As shown in FIG. 1, a test plate is supported on the inner lid of the glass bottle with a clip attached to the tip of the wire. On the other hand, a test plate is not attached to another glass bottle for a blank test.
• Cover the glass bottle and start the emission test.
The time for one emission test was 24 hours, and the formaldehyde concentration was measured by acetylacetone spectrophotometry according to JIS K5601-4-1.

(Evaluation of surface drying)
The surface dryness was evaluated by touch as follows.
◯: There is no stickiness.
Δ: Slightly sticky and fingerprints remain on the surface.
X: Stickiness remains.

It is a conceptual diagram which illustrates the form in the glass bottle used at the time of the measurement of the formaldehyde emission amount in an Example.

Explanation of symbols

1: 900 ml glass bottle 2: clip 3: test plate 4: 50 g of water

Claims (1)

A radical curable resin composition containing a radical curable resin essentially comprising a (meth) acryloyl group and an acetoacetyl group,
The total content of the (meth) acryloyl group is 1 part by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the radical curable resin.
The radical curable resin composition, wherein the total content of the acetoacetyl group is 0.01 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the radical curable resin.

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