JP7419807B2 - Low odor resin composition - Google Patents

Description

The present invention relates to a low odor resin composition.

Conventionally, radically reactive resin compositions have been produced by combining a radically reactive resin, which is a product of a ring-opening reaction between an epoxy compound and an unsaturated monobasic acid having a polymerizable unsaturated bond and a carboxy group, with a radically polymerizable monomer such as styrene. It is dissolved in The cured product obtained by curing the radically reactive resin composition has various excellent properties such as mechanical properties, electrical properties, corrosion resistance, heat resistance, photocuring properties, and adhesiveness. Fiber-reinforced plastics (FRP) have been used in chemical plant pipes, chemical storage tanks, concrete repair materials, etc.

Generally used radically reactive resin compositions contain about 30 to 60% by mass of styrene, which is a radically polymerizable monomer. Therefore, in open mold molding methods such as hand lay-up molding method and spray-up molding method, when FRP is molded, the styrene contained in the vinyl ester resin composition may volatilize, worsening the working environment.

In addition, due to concerns about carcinogenicity, styrene has been newly designated as a specified chemical substance due to the revision of the Specified Chemical Substance Hazard Prevention Ordinance (Specialized Regulations) in recent years. workers, health examinations, and records of the working environment. With the tightening of these regulations, there is a social demand for the development of non-styrene materials.

In order to solve the above odor problem, low odor resins made of (meth)acrylic acid esters are used as polymerizable monomers. Because it has the property of curing poorly in thinner films, poor curing is likely to occur during lining construction, etc.

Furthermore, in the curing of these acrylic resins, since oxygen in the air acts as a polymerization inhibitor, methods are used to block the permeation of oxygen in the air during the curing process of the coating resin and the lining resin. For example, as a conventional technique, there is a method of containing paraffin wax and a polymerizable diluent in a resin composition. In this case, when the polymerizable diluent evaporates as the polymerization in the coating progresses, the concentration of paraffin in the polymerizable diluent increases, and the undissolved paraffin wax forms the resin surface layer (the coating surface and lining). precipitates on the surface). The result is a thin layer of paraffin wax that acts as an air barrier and accelerates curing.

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

Japanese Patent Application Publication No. 05-230423 Japanese Patent Application Publication No. 11-255847 Japanese Patent Application Publication No. 2007-326934 Japanese Patent Application Publication No. 05-295862 Japanese Patent Application Publication No. 2004-10771 Japanese Patent Application Publication No. 2005-120305

On the other hand, the resin composition used as the material for the FRP layer is required to cure within an appropriate pot life depending on the area of the construction surface and the conditions at the construction site. When constructing a large area, a polymerization inhibitor (radical trap) is added to ensure a certain pot life, but if a large amount of polymerization inhibitor is added to extend the pot life, effective radicals will be Due to the trapping, the amount of heat generated decreases, making it easier for temperature differences to occur between the inside and the surface, resulting in variations. Furthermore, compositions that use (meth)acrylate monomers as diluents instead of styrene tend to cure quickly, resulting in noticeable variations and, as a result, the problem of wrinkles on the coating surface.

The present invention was made in view of the above circumstances, and provides FRP floors, wall base materials, coating materials, and coating materials that are low in odor, have a sufficient pot life, and are resistant to wrinkles on the coating surface. The object of the present invention is to provide a radically polymerizable resin composition used for.

（式（１）又は式（２）中、Ｒ１は水素原子またはメチル基である。Ｒ２は炭素数が０～１０の直鎖または分岐した２価の炭化水素基であり、水酸基、アルコキシ基から選ばれる少なくとも１つの置換基を有していても良い。但し、Ｒ２の炭素数が０で、Ａｒが酸素原子と直接結合していても良い。Ｒ３は炭素数が１～１０の直鎖または分岐した２価の炭化水素基であり、水酸基、アルコキシ基から選ばれる少なくとも１つの置換基を有していても良い。Ａｒはフェニル基、ナフチル基から選ばれる少なくとも１つを示し、水素原子の一部または全部がアルキル基、アルケニル基、アリール基、アセチル基、アルコキシ基、カルボキシ基、水酸基、またはヒドロキシアルキル基から選ばれる少なくとも１つで置換されていても良い。）
［５］ 前記（Ｄ）金属石鹸が、コバルト塩である［１］～［４］のいずれかにに記載の低臭気樹脂組成物。
［６］ 前記（Ｅ）ラジカル発生抑制剤が、乳酸及びグリセリンからなる群から選択される少なくとも１種である［１］～［５］のいずれかに記載の低臭気樹脂組成物。
［７］ 前記（Ａ）ラジカル反応性樹脂と前記（Ｂ）(メタ)アクリレート系モノマーの合計量１００質量部に対して、前記（Ｂ）(メタ)アクリレート系モノマーを２０～６０質量部含む［１］～［６］のいずれかに記載の低臭気樹脂組成物。
［８］ 前記（Ａ）ラジカル反応性樹脂と前記（Ｂ）(メタ)アクリレート系モノマーの合計量１００質量部に対して、前記（Ｄ）金属石鹸を０．１～３質量部含む［１］～［７］のいずれかに記載の低臭気樹脂組成物。
［９］ 前記（Ａ）ラジカル反応性樹脂と前記（Ｂ）(メタ)アクリレート系モノマーの合計量１００質量部に対して、前記（Ｅ）ラジカル発生抑制剤を０．０１～３質量部含む［１］～［８］のいずれかに記載の低臭気樹脂組成物。
［１０］ 前記（Ａ）ラジカル反応性樹脂と前記（Ｂ）(メタ)アクリレート系モノマーとの合計１００質量部に対して、（Ｃ）ワックスを０．０１～３．０質量部含む［１］～［９］のいずれかに記載の低臭気樹脂組成物。
［１１］ ＪＩＳ Ｋ ６９０１（２００８）、「５．９常温硬化特性（発熱法）」に記載の方法で測定した可使時間（ゲル化時間）は、３０分以上である［１］～［１０］のいずれかに記載の低臭気樹脂組成物。 The present invention includes the following aspects.
[1] (A) radically reactive resin;
(B) (meth)acrylate monomer;
(C) Wax;
(D) Metallic soap;
(E) a radical generation inhibitor, and (F) a resin composition substantially free of styrenic compounds,
A low-odor resin composition, wherein the radical generation inhibitor (E) is a compound having at least two substituents selected from the group consisting of a hydroxyl group and a carboxylic acid group.
[2] The low-odor resin composition according to [1], wherein the radical-reactive resin (A) is a bisphenol A vinyl ester resin.
[3] The low-odor resin composition according to [1] or [2], wherein the (meth)acrylate monomer (B) is a compound having an aromatic ring group.
[4] The low-odor resin composition according to any one of [1] to [3], wherein the (meth)acrylate monomer (B) is a compound represented by formula (1) or formula (2).

(In formula (1) or formula (2), R1 is a hydrogen atom or a methyl group. R2 is a straight chain or branched divalent hydrocarbon group having 0 to 10 carbon atoms, and is a hydroxyl group or an alkoxy group. It may have at least one selected substituent.However, R2 may have 0 carbon atoms and Ar may bond directly to the oxygen atom.R3 may have a straight chain or a carbon number of 1 to 10. It is a branched divalent hydrocarbon group, and may have at least one substituent selected from a hydroxyl group and an alkoxy group.Ar represents at least one substituent selected from a phenyl group and a naphthyl group; Part or all may be substituted with at least one selected from an alkyl group, an alkenyl group, an aryl group, an acetyl group, an alkoxy group, a carboxy group, a hydroxyl group, or a hydroxyalkyl group.)
[5] The low-odor resin composition according to any one of [1] to [4], wherein the metal soap (D) is a cobalt salt.
[6] The low-odor resin composition according to any one of [1] to [5], wherein the radical generation inhibitor (E) is at least one selected from the group consisting of lactic acid and glycerin.
[7] Contains 20 to 60 parts by mass of the (B) (meth)acrylate monomer based on 100 parts by mass of the total amount of the (A) radically reactive resin and the (B) (meth)acrylate monomer [ The low odor resin composition according to any one of [1] to [6].
[8] Contains 0.1 to 3 parts by mass of the metal soap (D) based on 100 parts by mass of the total amount of the (A) radically reactive resin and the (B) (meth)acrylate monomer [1] - The low odor resin composition according to any one of [7].
[9] Contains 0.01 to 3 parts by mass of the radical generation inhibitor (E) based on 100 parts by mass of the total amount of the radical-reactive resin (A) and the (meth)acrylate monomer (B) [ The low odor resin composition according to any one of [1] to [8].
[10] Contains 0.01 to 3.0 parts by mass of wax (C) based on a total of 100 parts by mass of the radically reactive resin (A) and the (meth)acrylate monomer (B) [1] - The low odor resin composition according to any one of [9].
[11] The pot life (gelling time) measured by the method described in "5.9 Room temperature curing characteristics (exothermic method)" of JIS K 6901 (2008) is 30 minutes or more [1] to [10] ] The low-odor resin composition according to any one of the above.

The low odor resin composition of the present invention comprises (A) a radically reactive resin, (B) a (meth)acrylate monomer, (C) a wax, (D) a metal soap, and (E) a radical generation inhibitor. including. The low odor resin composition of the present invention does not substantially contain (F) a styrene compound. The radical generation inhibitor (E) is a compound having at least two substituents selected from the group consisting of a hydroxyl group and a carboxylic acid group. Therefore, the low-odor resin composition of the present invention has a low odor, can secure a sufficient pot life, and can be used for FRP floors, wall base materials, coating materials, and coating materials that are resistant to wrinkles on the coating surface. It can be suitably used as a material.

1 is a photograph of a coating film produced using the low odor resin composition of Example 1. 1 is a photograph of a coating film produced using the resin composition of Comparative Example 1.

Hereinafter, the low odor resin composition of the present invention will be explained in detail. Note that the present invention is not limited only to the embodiments shown below.
The low odor resin composition of the present embodiment includes (A) a radically reactive resin, (B) a (meth)acrylate monomer, (C) a wax, and (D) Contains a metal soap and (E) a radical generation inhibitor. The low-odor resin composition of this embodiment does not substantially contain (F) a styrene compound. The radical generation inhibitor (E) is a compound having at least two substituents selected from the group consisting of a hydroxyl group and a carboxylic acid group.

<(A) Radical reactive resin>
(A) The radically reactive resin is copolymerized with (B) (meth)acrylate monomer to form a polymer. Examples of the radical polymerizable resin of component (A) used in this embodiment include vinyl ester resin (A1), polyester (meth)acrylate resin (A2), urethane (meth)acrylate resin (A3), etc. It will be done.

<Vinyl ester resin (A1)>
The vinyl ester resin (A1) of this embodiment generally consists of an epoxy group in an epoxy compound (a) having two or more epoxy groups, and an unsaturated monobasic acid having a polymerizable unsaturated bond and a carboxyl group. It is a compound having a polymerizable unsaturated bond obtained by a ring-opening reaction with a carboxy group (b). Such vinyl ester resin (A1) is described, for example, in the Polyester Resin Handbook (published by Nikkan Kogyo Shimbun, 1988).

Here, the structural pattern of the product resulting from the ring-opening reaction of the carboxy group of the unsaturated monobasic acid (b) with two or more epoxy groups of the epoxy compound (a) exists infinitely, so it cannot be uniquely determined. do not have. Therefore, it is almost impractical to comprehensively describe all the structures of the vinyl ester resin (A1), that is, to directly specify the structure of the vinyl ester resin (A1).

<Epoxy compound (a)>
The epoxy compound (a) is not particularly limited, but preferably contains at least one selected from bisphenol-type epoxy resins and novolac phenol-type epoxy resins. By using the above-mentioned epoxy compound (a) having two or more epoxy groups, the mechanical strength and corrosion resistance of the cured product are further improved.

Examples of bisphenol-type epoxy resins include those obtained by reacting bisphenols such as bisphenol A, bisphenol F, bisphenol S, and tetrabromobisphenol A with epichlorohydrin and/or methylepichlorohydrin, or those obtained by reacting bisphenol A, glycidyl ether, and the above. Examples include those obtained by reacting a condensate of bisphenols with epichlorohydrin and/or methylepichlorohydrin.

Examples of the novolak phenol type epoxy resin include those obtained by reacting phenol novolak or cresol novolak with epichlorohydrin and/or methylepichlorohydrin.

<Unsaturated monobasic acid (b)>
The unsaturated monobasic acid (b) is not particularly limited as long as it is a monocarboxylic acid having a polymerizable unsaturated bond, but preferably methacrylic acid, acrylic acid, crotonic acid, cinnamic acid, etc. Acrylic acid or methacrylic acid is preferred, and methacrylic acid is more preferred. By using methacrylic acid, the vinyl ester resin (A1) obtained by the reaction with the epoxy compound (a) is less likely to be hydrolyzed by acid or alkali, and the corrosion resistance of the cured product is improved.

When performing a ring-opening reaction between the epoxy compound (a) and the unsaturated monobasic acid (b), the amount of the unsaturated monobasic acid (b) is preferably 0.0. The amount is 3 to 1.5 equivalents, more preferably 0.4 to 1.2 equivalents, and still more preferably 0.5 to 1.0 equivalents. If the amount of the unsaturated monobasic acid (b) is 0.3 to 1.5 equivalents per equivalent of the epoxy group of the epoxy compound (a), sufficient hardness can be achieved by the radical polymerization reaction of the vinyl ester resin composition. A cured product with a certain amount of moisture is obtained.

<Synthesis method of vinyl ester resin (A1)>
The vinyl ester resin (A1) used in this embodiment can be synthesized by a known synthesis method.

As a method for synthesizing the vinyl ester resin (A1), for example, an epoxy compound (a) and an unsaturated monobasic acid (b) are synthesized at 70 to 150°C, preferably 80 to 140°C, in the presence of an esterification catalyst, and Preferred is a method in which the reaction is carried out at 90 to 130°C.

As the esterification catalyst, for example, known catalysts such as tertiary amines such as triethylamine, N,N-dimethylbenzylamine, N,N-dimethylaniline or cyazabicyclooctane, triphenylphosphine or diethylamine hydrochloride can be used. .

The content of the vinyl ester resin (A1) is preferably 40 to 80 parts by mass, more preferably The amount is 45 to 70 parts by weight, more preferably 50 to 65 parts by weight. If the content of the vinyl ester resin (A1) is 40 to 80 parts by mass based on the total of 100 parts by mass of the radically reactive resin (A) and the (meth)acrylate monomer (B), the mechanical Strength and corrosion resistance are further improved.

<Polyester (meth)acrylate resin (A2)>
The polyester (meth)acrylate resin in the present invention refers to (1) an α,β-unsaturated carboxylic acid ester in a polyester with a terminal carboxy group obtained from a saturated polybasic acid and/or an unsaturated polybasic acid and a polyhydric alcohol; (meth)acrylate obtained by reacting an epoxy compound containing a group, (2) a polyester with a terminal carboxy group obtained from a saturated polybasic acid and/or an unsaturated polybasic acid and a polyhydric alcohol, and a hydroxyl group-containing acrylate. (meth)acrylate obtained by reacting (3) a polyester with a terminal hydroxyl group obtained from a saturated polybasic acid and/or unsaturated polybasic acid and a polyhydric alcohol with (meth)acrylic acid; meth)acrylate.

Saturated polybasic acids used as raw materials for polyester (meth)acrylate resins include, for example, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid, which do not have polymerizable unsaturated bonds. Examples include polybasic acids or their anhydrides, and polymerizable unsaturated polybasic acids such as fumaric acid, maleic acid, and itaconic acid, or their anhydrides. Examples of the polyhydric alcohol component include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, etc. Can be mentioned. Glycidyl methacrylate is a typical example of the α,β-unsaturated carboxylic acid ester having an epoxy group used in the production of polyester (meth)acrylate.
Among the polyester (meth)acrylate resins obtained from the above raw materials, bisphenol A type polyester (meth)acrylate resins are preferred from the viewpoint of mechanical strength.

<Urethane (meth)acrylate resin (A3>
The urethane (meth)acrylate resin in the present invention can be produced by, for example, reacting a polyisocyanate with a polyhydroxy compound or a polyhydric alcohol, and then further adding a hydroxyl group-containing (meth)acrylic compound and, if necessary, a hydroxyl group-containing allyl ether compound. It is a radically polymerizable unsaturated group-containing oligomer that can be obtained by reaction. Further, after the hydroxyl group-containing (meth)acrylic compound and the polyhydroxy compound or polyhydric alcohol are reacted, a polyisocyanate may be further reacted.

Examples of the polyisocyanate used as a raw material for the urethane (meth)acrylate resin include 2,4-tolylene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate. Examples include diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, and triphenylmethane triisocyanate. These polyisocyanates may be used alone or in combination of two or more. Among these, diphenylmethane diisocyanate is preferred from the viewpoint of cost.

Examples of the polyhydroxy compound used as a raw material for the urethane (meth)acrylate resin include polyester polyols, polyether polyols, and the like. More specifically, glycerin-ethylene oxide adduct, glycerin-propylene oxide adduct, glycerin-tetrahydrofuran adduct, glycerin-ethylene oxide-propylene oxide adduct, trimethylolpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide adduct. , trimethylolpropane-tetrahydrofuran adduct, trimethylolpropane-ethylene oxide-propylene oxide adduct, dipentaesritol-ethylene oxide adduct, dipentaesritol-propylene oxide adduct, dipentaesritol-tetrahydrofuran adduct , dipentaesritol-ethylene oxide-propylene oxide adduct, and the like. These polyhydroxy compounds may be used alone or in combination of two or more.

Examples of polyhydric alcohols used as raw materials for the urethane (meth)acrylate resin include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3 Propanediol, 1,3-butanediol, adduct of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-butanediol, 1,2 -cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, paraxylene glycol, bicyclohexyl-4,4-diol, 2,6-decalin glycol, 2,7-decalin glycol and the like. These polyhydric alcohols may be used alone or in combination of two or more.

The hydroxyl group-containing (meth)acrylic compound used as a raw material for the urethane (meth)acrylate resin is preferably a hydroxyl group-containing (meth)acrylic acid ester, specifically, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, -Hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, tris(hydroxyethyl)isocyanursanodi(meth)acrylate, pentaesritol tri (meth)acrylate, glycerin (mono)(meth)acrylate, and the like. These hydroxyl group-containing (meth)acrylic compounds may be used alone or in combination of two or more.

Specifically, examples of the hydroxyl group-containing allyl ether compound used as a raw material for the above-mentioned urethane (meth)acrylate resin include ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, and polyethylene glycol monoallyl ether. Glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether , hexylene glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropane diallyl ether, glycerin diallyl ether, pentaesritol triallyl ether, and the like. These hydroxyl group-containing allyl ether compounds may be used alone or in combination of two or more.

<(B) (meth)acrylate monomer>
The (meth)acrylate monomer used in the present invention as component (B) is important for improving molding workability. This (meth)acrylate monomer has a boiling point of 140°C or higher, preferably 140°C to 200°C, and 80°C or higher, preferably 140°C to 200°C at normal pressure (1 atm), in consideration of odor and other effects on the environment. preferably has a flash point of 80°C to 150°C. Specifically, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydro Furfuryl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,4-butanediol di( meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin Di(meth)acrylate, methoxytriethylene glycol(meth)acrylate, butoxyethyl(meth)acrylate, neopentylglycol di(meth)acrylate, perfluorooctylethyl(meth)acrylate, allyl(meth)acrylate, dicyclopentenyl( Examples include meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, acryloylmorpholine, 2-(acetoacetoxy)ethyl (meth)acrylate, and 2-methoxyethyl (meth)acrylate. These (meth)acrylate monomers may be used alone or in combination of two or more.

The (meth)acrylate monomer as component (B) used in the present invention preferably has an aromatic ring group. There are no particular limitations on the (meth)acrylate (B) having an aromatic ring group. Among these, compounds represented by formula (1) or formula (2) are preferred.

(In formula (1) or formula (2), R1 is a hydrogen atom or a methyl group. R2 is a straight chain or branched divalent hydrocarbon group having 0 to 10 carbon atoms, and is a hydroxyl group or an alkoxy group. It may have at least one selected substituent.However, R2 may have 0 carbon atoms and Ar may bond directly to the oxygen atom.R3 may have a straight chain or a carbon number of 1 to 10. It is a branched divalent hydrocarbon group, and may have at least one substituent selected from a hydroxyl group and an alkoxy group.Ar represents at least one substituent selected from a phenyl group and a naphthyl group; Part or all may be substituted with at least one selected from an alkyl group, an alkenyl group, an aryl group, an acetyl group, an alkoxy group, a carboxy group, a hydroxyl group, or a hydroxyalkyl group.)
The number of carbon atoms in R2 is 0 to 10, preferably 0 to 5, and more preferably 0 to 3. When the number of carbon atoms in R2 is "0", it means that R2 does not exist and Ar is directly bonded to the oxygen atom.

Ar may have substitution. The substituent is at least one selected from an alkyl group, an alkenyl group, an aryl group, an acetyl group, an alkoxy group, a carboxy group, a hydroxyl group, or a hydroxyalkyl group, and is preferably a methyl group. The number of substituents is preferably 1 or 2.

The number of carbon atoms in R3 is 1 to 10, preferably 1 to 5, and more preferably 1 to 3. Preferred substituents are the same as R2.

Specific examples of R2 and R3 include -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )-, -CH ₂ CH(CH ₃ )CH ₂ -. Can be mentioned.

The (meth)acrylate (B) having an aromatic ring group is more preferably a compound represented by formula (3) or formula (4).

(In formula (3) or formula (4), R1, R2, and R3 are the same as formula (1) and formula (2).)
Examples of the compound represented by formula (3) or formula (4) include benzyl methacrylate, phenyl methacrylate, 1-phenylethyl methacrylate, 2-phenylethyl methacrylate, phenoxyethyl methacrylate, and addition products of methacrylic acid and styrene oxide ( 1(2)-hydroxy-2(1)-phenylethyl methacrylate). Among them, benzyl methacrylate, phenyl methacrylate, and phenoxyethyl methacrylate are preferred.

Further, the (meth)acrylate monomer used as the component (B) used in the present invention preferably has a theoretical glass transition temperature (Tg) of 10° C. or higher when formed into a polymer. It is preferable that the theoretical glass transition temperature (Tg) is 10° C. or higher because durability will not be lowered more than necessary. The theoretical glass transition temperature Tg of a polymer can be calculated using the following formula described in "Structure and Physical Properties of Tobolsky Polymers" by Murakami et al., published by Tokyo Kagaku Dojin, p. 61.
Tg={(w1/Tg1)+(w2/Tg2)+...+(wn/Tgn)}-1
(In the formula, w1, w2, ..., wn are the mass fractions of each (meth)acrylate monomer, and Tg1, Tg2, ..., Tgn are the proportions of each (meth)acrylate monomer as a polymer. )
For the glass transition temperature of the polymer used in the above calculation, values described in literature can be used. For example, Mitsubishi Rayon Co., Ltd.'s acrylic ester catalog (1997 edition), Kyozo Kitaoka, "Shin Kobunshi Bunko 7 "Introduction to synthetic resins for paints", Kobunshi Publishing Association, pp. 168-169.

Furthermore, in the present invention, a (meth)acrylic acid ester compound having two or more (meth)acryloyl groups in the molecule may be used as a part of the (meth)acrylate monomer, and known compounds can be used. . Specific examples include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerin di(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl Examples include (meth)acrylic acid esters of various glycols such as (meth)acrylate and trimethylolpropane tri(meth)acrylate.

Among these, from the viewpoint of low odor, drying properties, and physical properties of cured products, dicyclopentenyloxyethyl (meth)acrylate, acryloylmorpholine, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and 2-methoxyethyl Preferred are (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, and diethylene glycol di(meth)acrylate. Among these, benzyl (meth)acrylate, phenyl (meth)acrylate, and phenoxyethyl (meth)acrylate are more preferred.

The (meth)acrylate monomer as component (B) is preferably 20 parts by mass to 60 parts by mass based on 100 parts by mass of the total amount of the (A) radically reactive resin and the (B) (meth)acrylate monomer. , more preferably from 30 parts by weight to 55 parts by weight, even more preferably from 35 parts by weight to 50 parts by weight. If the blending ratio of the (meth)acrylate monomer is 20 parts by mass or more, the viscosity of the low-temperature curable resin composition may increase, resulting in poor workability in a low-temperature atmosphere and poor wettability to aggregate. On the other hand, when the amount is 60 parts by mass or less, sufficient hardness and water resistance of the cured product can be obtained, which is preferable.

<(C) component wax>
The wax component (C) used in the present invention is blended for the purpose of improving drying properties. As waxes, known waxes can be used without restriction, such as petroleum waxes (paraffin wax, microcrystalline, etc.), vegetable waxes (candelilla wax, rice wax, wood wax, etc.), animal waxes (beeswax, etc.). , spermaceti wax, etc.), mineral waxes (montan wax, etc.), synthetic waxes (polyethylene wax, amide wax, etc.), etc. can be used. More specifically, paraffin wax with a melting point of about 20°C to 80°C, BYK-S-750, BYK-S-740, BYK-LP-S6665 (manufactured by BYK Chemie Co., Ltd.), etc. You may use a combination of things. As component (C), petroleum wax is preferred, and paraffin wax is particularly preferred. Further, in order to effectively bring out the effect of paraffin wax added for the purpose of improving drying properties, a drying properties imparting agent as described in JP-A No. 2002-97233 may be used in combination. The amount of waxes is preferably 0.01 to 3 parts by mass based on the total of 100 parts by mass of the radically polymerizable resin as component (A) and the (meth)acrylate monomer as component (B), The amount is more preferably 0.2 to 2 parts by weight, and even more preferably 0.5 to 2 parts by weight. Furthermore, a solvent can be used to improve the solubility and dispersibility of paraffin wax. Known solvents can be used, such as alkyl ether acetates such as ethyl acetate, ethers such as tetrahydrofuran, acetone, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, benzene, toluene, and xylene. , hydrocarbons such as octane, decane, and dodecane, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha, lactic acid esters such as methyl lactate, ethyl lactate, and butyl lactate, dimethylformamide, N- Examples include methylpyrrolidone.

<(D) Metal soap>
The metal soap of component (D) used in the present invention acts as a metal soap and a drying property imparting agent. Examples of metal soaps include cobalt-based, vanadium-based, manganese-based metal soaps, tertiary amines, quaternary ammonium salts, mercaptans, etc., which may be used alone or in combination of two or more. .

The metal soap of component (D) is preferably a cobalt metal salt. Examples of the cobalt metal salt include cobalt naphthenate, cobalt octylate, cobalt hydroxide, and cobalt naphthenate and cobalt octylate.
The cobalt metal salt can be used within the range that achieves the object of the present invention, but preferably based on 100 parts by mass of the total amount of the radical-reactive resin (A) and the (meth)acrylate monomer (B). The amount is preferably 0.1 to 3 parts by weight, more preferably 0.2 to 2 parts by weight, and even more preferably 0.3 to 1 part by weight.
It is preferable that the blending ratio of the cobalt metal salt as component (D) is within the above range, since there will be no prolongation of curing time, poor curing, or poor drying properties.

<(E) Radical generation inhibitor>
The radical generation inhibitor (E) used in this embodiment is a compound having at least two substituents selected from the group consisting of a hydroxyl group and a carboxylic acid group. Methods of suppressing the generation of radicals in order to delay the curing of low-odor resin compositions and extend their pot life as necessary include, for example, trapping the generated radicals or inhibiting metal soaps to suppress the generation of radicals. There are ways to suppress it. As will be described later, from the viewpoint of being able to maintain good curing properties while ensuring pot life, a radical generation inhibitor that can inhibit metal soaps is preferred.

(E) Examples of the radical generation inhibitor include polyhydric alcohols having a valence of two or more, hydroxy acids which are carboxylic acids having a hydroxy group, and the like. Specific examples of the polyhydric alcohol having a valence of 2 or more include ethylene glycol, propylene glycol, and glycerin. Specific examples of the hydroxy acid include glycolic acid, lactic acid, glyceric acid, hydroxybutyric acid, malic acid, tartaric acid, and citric acid. (E) As the radical generation inhibitor, only one type may be selected from the above, or two or more types may be used. Among the above-mentioned radical generation inhibitors, (E) has good solubility in (A) radical-reactive resins and (B) (meth)acrylate monomers, is easily available, and is inexpensive; Preferably, it is at least one selected from the group consisting of lactic acid and glycerin.

(E) The radical generation inhibitor is preferably contained in an amount of 0.01 to 3 parts by mass, based on a total of 100 parts by mass of (A) the radical-reactive resin and (B) the (meth)acrylate monomer. It is more preferable to contain 1 to 1.5 parts by weight, and even more preferably 0.1 to 1.0 parts by weight. When the content of the (E) radical generation inhibitor is 0.1 part by mass or more, the (E) radical generation inhibitor binds to the (D) metal soap, thereby inhibiting the generation of radicals from the (D) metal soap. The effect of inhibiting the initiation of radical polymerization between (A) the radically reactive resin and (B) the (meth)acrylate monomer and delaying the polymerization rate of the radical polymerization becomes remarkable. (E) The content of the radical generation inhibitor is 3 parts by mass or less, and the content of (D) the metal soap is 100 parts by mass in total of (A) the radical-reactive resin and (B) the (meth)acrylate monomer. When the amount is 0.1 to 3 parts by mass, the amount of radicals generated from the metal soap (D) does not become too small, which is preferable.

"(E) Effect of suppressing radical generation more than a radical generation inhibitor"
The low odor resin composition of this embodiment has low odor and can be cured with a sufficient pot life. Although this mechanism has not been clarified, as shown below, the low odor resin composition of this embodiment is obtained due to the synergistic effect of containing (E) a radical generation inhibitor and (D) a metal soap. It is thought that it will be possible.

The radical generation inhibitor (E) contained in the low-odor resin composition of this embodiment combines with the metal soap (D) in the resin composition. For example, when (E) the radical generation inhibitor is lactic acid and (D) the metal soap is a metal salt, the acid groups -OH and -COOH in the lactic acid bond to the metal element in the metal salt. It forms a complex and inhibits the production of metal ions in the resin composition. As a result, the generation of radicals from (D) metal soap is suppressed, and for example, compared to the case where (E) radical generation inhibitor is not included, (A) radical-reactive resin and (B) (meth) The initiation of radical polymerization with acrylate monomers and the rate of radical polymerization are suppressed.

Specifically, when (D) the metal soap is a cobalt salt, in the low odor resin composition of this embodiment, radicals are generated from the (D) metal soap by the reaction represented by the following formula, and a curing reaction occurs. progresses.
ROOH+Co ²⁺ →RO・+OH-+Co ³⁺
At this time, the radical generation inhibitor (E) contained in the low-odor resin composition of the present embodiment combines with the metal soap (D) to suppress the generation of radicals in the resin composition. This delays the curing of the low odor resin composition and extends its pot life.

Therefore, in the low-odor resin composition of the present embodiment, the curing reaction proceeds mainly by radicals generated from the (D) metal soap that has not combined with the (E) radical generation inhibitor. (E) The radical generation inhibitor hardly reacts with radicals generated in the resin composition and does not trap radicals. Therefore, the radical generation inhibitor (E) does not interfere with the function of promoting radical polymerization by radicals generated in the resin composition by the reaction represented by the above formula.

Furthermore, in the low-odor resin composition of the present embodiment, radicals are slowly generated from the complex formed by combining the (E) radical generation inhibitor and (D) metal soap during the progress of the curing reaction. . As a result, a total amount of radicals sufficient to complete the curing reaction is supplied to the resin composition. Therefore, sufficient curing heat generation accompanying radical polymerization can be obtained. Therefore, the low-odor resin composition of this embodiment is unlikely to suffer from poor curing and is finally sufficiently cured.

<(F) Styrene compound>
The low odor resin composition of this embodiment does not substantially contain styrenic compounds. "Substantially free" means that the amount is less than 1 part by mass based on the total of 100 parts by mass of (A) the radically reactive resin and the (B) (meth)acrylate monomer.
Styrenic compounds are compounds with a styrene skeleton, including styrene, o, m, p-methylstyrene, dimethylstyrene, ethylstyrene, chlorostyrene, and other nuclear-substituted styrenes; α-methylstyrene, α-chlorostyrene. Also included are styrene derivatives such as , β-chlorostyrene.

<Other ingredients>
The low-odor resin composition of the present embodiment may contain other additives as necessary within a range that does not impair the effects of the present invention. Examples of additives include photopolymerization initiators, polymerization inhibitors, curing accelerators, and peroxides.

<Photopolymerization initiator>
Examples of the photopolymerization initiator having photosensitivity in the visible light to near-infrared light region include Irgacure 1800 (manufactured by Ciba Specialty Chemicals). The photopolymerization initiator is preferably 0.01 parts by weight to 15 parts by weight, and more It is preferably blended in a proportion of 0.05 parts by mass to 10 parts by mass. It is preferable that the blending ratio of the photopolymerization initiator is within this range, since surface drying properties and physical properties of the cured product do not deteriorate.

<Polymerization inhibitor>
A polymerization inhibitor is contained as necessary in order to suppress the polymerization of (A) radically reactive resin and (B) (meth)acrylate monomer.
(F) Polymerization inhibitors include tert-butylcatechol, p-methoxyphenol, hydroquinone, tert-butylhydroquinone, p-benzoquinone, chloranil, m-dinitrobenzene, nitrobenzene, p-phenyldiamine, and sulfur. , diphenylpicrylhydrazyl, di-p-fluorophenylamine, tri-p-nitrophenylmethyl, and the like.

<Curing accelerator aid>
The curing accelerator is included as necessary in order to promote curing of the low odor resin composition.
Specific examples of the curing accelerator include aniline, N,N-dimethylaniline, N,N-diethylaniline, p-toluidine, N,N-dimethyl-p-toluidine, and 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-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N,N-bis Examples include N,N-substituted anilines such as (hydroxyethyl)aniline and diethanolaniline, N,N-substituted-p-toluidine, and 4-(N,N-substituted amino)benzaldehyde.

<Peroxide>
Peroxide can be included as a curing agent when curing the resin composition. As the peroxide, it is preferable to use one that functions as a room temperature radical polymerization initiator by being included together with (D) the metal soap and the curing accelerator.
Specifically, the peroxides include methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, 1,1-bis(t -butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3,3-isopropylhydroperoxide, t-butylhydroperoxide , dicumyl hydroperoxide, acetyl peroxide, bis(4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide , azobisisobutyronitrile, azobiscarbonamide, and the like. Among these, methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, and cumene hydroperoxide are preferred. In particular, when used in combination with metal salts and aromatic tertiary amines, it is preferable to use methyl ethyl ketone peroxide, which functions as an excellent room temperature radical polymerization initiator. Only one type of peroxide may be selected and used, or two or more types may be used.

The peroxide is preferably contained in an amount of 0.1 to 7 parts by mass, and preferably 0.5 to 5 parts by mass, based on a total of 100 parts by mass of (A) radically reactive resin and (B) (meth)acrylate monomer. It is more preferable to include part. When the content of peroxide is 0.1 part by mass or more, the effect of accelerating the curing of the resin composition by peroxide becomes remarkable. If the peroxide content is 7 parts by mass or less, the curing speed of the resin composition will be too fast even when the resin composition is used as a material for the FRP layer in a high-temperature environment such as outdoors in summer. This is preferable because it prevents the construction from being hindered.

The low-odor resin composition of the present invention may contain various additives other than those mentioned above, such as fiber reinforcing materials, fillers, thixotropic agents, reinforcing materials, pigments, ultraviolet absorbers, thickeners, low-shrinkage agents, and anti-aging agents. Agents, plasticizers, aggregates, stabilizers, etc. can be used in combination within the range that achieves the purpose of the present invention.

Such fiber reinforcing materials include, for example, glass fibers, organic fibers such as amide, alanide, vinylon, polyester, and phenol, carbon fibers, metal fibers, ceramic fibers, or a combination thereof. In consideration of workability and economy, glass fibers and organic fibers are preferred. Further, the form of the fibers includes plain weave, satin weave, nonwoven fabric, and mat form.

Such fillers include, for example, hydraulic silicate materials, calcium carbonate powder, clay, alumina powder, silica powder, talc, barium sulfate, silica powder, glass powder, glass beads, mica, aluminum hydroxide, cellulose, silica sand. , river sand, kansui stone, marble waste, crushed stone, etc.

A thixotropic agent is blended for the purpose of imparting thixotropy. Examples of thixotropic agents include inorganic ones such as silica powder (Aerosil type), mica powder, calcium carbonate powder, and short fiber asbestos, and organic ones such as hydrogenated castor oil. Preferably, it is a silica-based thixotropic agent. In addition, especially in the Aerosil type, a thixotropy aid such as BYK R605 (manufactured by BYK Chemie Co., Ltd.) may be used in combination.

Examples of reinforcing materials include short fibers such as carbon, ceramics, and stainless steel.

The low-odor resin composition of the present invention can be used for waterproofing roofs, walls, floors, underground waterproofing, or floors of multi-story parking lots, factories, warehouses, etc., and can also be used for waterproofing concrete structures such as buildings, piers of elevated bridges, and floors. It is also useful for waterproofing plates, etc.

The coating film forming method according to the present invention is characterized in that the above-described low-odor resin composition is applied onto a base such as concrete, asphalt concrete, mortar, wood, metal, etc., and then cured. The coating film forming method of the present invention can form an excellent coating film and has low odor during operation, so it is suitable for repairing floors of storage facilities and inner walls of storage containers.
Moreover, a fiber-reinforced resin can also be obtained by impregnating a fiber-reinforced material with the above-mentioned low-odor resin composition and curing it. Examples of the fiber reinforcing material include glass fiber, amide fiber, aramid fiber, vinylon fiber, polyester fiber, phenol fiber, carbon fiber, metal fiber, and ceramic fiber.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Note that the present invention is not limited to the following examples.

(Synthesis example 1)
"Synthesis of bisphenol A vinyl ester resin"
1890 g of jER828 (epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 189), 285 g of bisphenol A, and 3.3 g of triethylamine were charged into a reaction apparatus equipped with a stirrer, a reflux condenser, a gas inlet pipe, and a thermometer, and the mixture was heated under a nitrogen atmosphere. , and reacted at 150°C for 1 hour. After the reaction was completed, it was cooled to 90°C, and 645 g of methacrylic acid, 9 g of tetradecyldimethylbenzyl ammonium chloride, 0.9 g of hydroquinone, and 944 g of phenoxyethyl methacrylate (Light Ester PO, manufactured by Kyoeisha Chemical Co., Ltd.) were added to the reaction product, and air was added. The reaction was further carried out at 120° C. for 2 hours while blowing, and the reaction was terminated when the acid value reached 10 mgKOH/g, to obtain a bisphenol A-based vinyl ester resin as the radical-reactive resin (A) of the present invention.

(Synthesis example 2)
"Synthesis of urethane acrylate resin"
In a 1 L four-necked flask equipped with a stirrer, reflux condenser, gas inlet tube, and thermometer, 340 g of polypropylene glycol (Actcol D-1000 manufactured by Mitsui Chemicals SKC Co., Ltd.) with a weight average molecular weight of 1,00 and diphenylmethane diisocyanate were added. 170 g of Millionate MT manufactured by Tosoh Corporation, 256 g of phenoxyethyl methacrylate (Light Ester PO manufactured by Kyoeisha Chemical Co., Ltd.), and 0.18 g of hydroquinone were heated to 80°C and the mixture was stirred for 1.5 hours. Reacted to produce a terminal isocyanate-containing prepolymer. Next, 88 g of 2-hydroxyethyl acrylate was added dropwise over 0.5 hours, and the reaction was carried out until the absorption peak of the isocyanate group disappeared in the infrared absorption spectrum to obtain the urethane acrylate as the (A) radically reactive resin of the present invention. Resin was obtained.

(Adjustment example 1)
"Preparation of bisphenol A vinyl ester resin solution A"
To the bisphenol A vinyl ester resin obtained in Synthesis Example 1, 472 g of phenoxyethyl methacrylate (Light Ester PO, manufactured by Kyoeisha Chemical Co., Ltd.) as the (B) (meth)acrylate monomer of the present invention, and benzyl methacrylate (Kyoeisha Chemical Co., Ltd.) were added. 472 g of Light Ester BZ) manufactured by Co., Ltd. was added to obtain a bisphenol A vinyl ester resin solution A containing 60% by mass of a bisphenol A vinyl ester resin (A) as the radically reactive resin.

(Adjustment example 2)
"Preparation of bisphenol A vinyl ester resin solution B"
To the bisphenol A vinyl ester resin obtained in Synthesis Example 1, 944 g of diethylene glycol dimethacrylate (Light Ester 2EG manufactured by Kyoeisha Chemical Co., Ltd.) as the (B) (meth)acrylate monomer of the present invention was added, and 60% by mass of (A) A bisphenol A vinyl ester resin solution B containing a bisphenol A vinyl ester resin as a radically reactive resin was obtained.

(Adjustment example 3)
"Preparation of urethane acrylate resin solution"
To the urethane acrylate resin obtained in Synthesis Example 2, 46 g of phenoxyethyl methacrylate (Light Ester PO, manufactured by Kyoeisha Chemical Co., Ltd.) as the (B) (meth)acrylate monomer of the present invention, and benzyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) were added. 100 g of Light Ester BZ) was added to obtain a urethane acrylate resin solution containing 60% by mass of urethane acrylate resin as (A) radically reactive resin.

(Example 1 to Example 9, Comparative Example 1 to Comparative Example 9)
(C) wax, (D) metal soap, and (E ) The resin compositions of Examples 1 to 9 were obtained by mixing radical generation inhibitors in the proportions shown in Table 1 and stirring uniformly. In addition, (E) Comparative Examples 1 to 5 were adjusted using a polymerization inhibitor instead of a radical generation inhibitor, and Comparative Examples 6 to 5 were adjusted using (D) the amount of metal soap instead of (E) a radical generation inhibitor. A resin composition of Comparative Example 9 was obtained by adding styrene to the mixture of Comparative Example 8 and (A) to (E).

*The amount of each component shown in Table 1 is the amount (unit: parts by mass) based on 100 parts by mass of the total amount of (A) radically reactive resin and (B) (meth)acrylate monomer.

The thus-obtained resin compositions of Examples 1 to 9 and Comparative Examples 1 to 9 were evaluated by the following methods to determine their curability, appearance, drying properties, and odor. Detection was measured and evaluated according to the criteria shown below. The results are shown in Table 1.

"Evaluation of hardenability"
25° C. curability: Measured according to JIS K 6901 (2008) 5.9 Room temperature curing characteristics (exothermic method).
Weigh 50g of the sample into a ^150cm3 beaker using a top scale, add a predetermined amount of accelerator, stir evenly with a glass rod, and place the sample in a constant temperature bath at (25±0.2)°C. It was fixed so that the surface was located approximately 10 mm below the bath liquid level. When the temperature of the sample reached (25 ± 0.2) °C, a curing accelerator (ethyl acetoacetate) was added to t-butyl peroxybenzoate and cumene hydroperoxide. Add 0.5 g of the sample), stir well, and pour the sample to a height of 100 mm into a test tube previously placed in a constant temperature bath at (25 ± 0.2) °C. Insert a thermocouple in the center of the sample. was fixed. The time from mixing the curing agent to the sample until the sample gels was defined as the pot life (gelling time), the time until reaching the maximum temperature was defined as the minimum curing time, and the maximum temperature was defined as the maximum exothermic temperature. The results are shown in Table 1. Curability is judged as ◎ if the pot life is 30 minutes or more and the maximum exothermic temperature is 80℃ or more, ○ if the pot life is 30 minutes or more but the maximum exotherm temperature is less than 80℃, and 10 if the pot life is 10 minutes or more. If the pot life was more than 30 minutes, it was rated as △, and if the pot life was less than 10 minutes, it was rated as ×.

"Evaluation of appearance of cured product"
Using the resin compositions of each example and comparative example, a resin containing curing agent 328E in the same proportion as in the "curability evaluation" experiment was applied to a Mylar film to a thickness of 300 μm at 25°C and 24°C. Visually observe the surface condition after the elapse of time. 1 and 2 are photographs of coating films made of the resin compositions of Example 1 and Comparative Example 1, respectively. As shown in Figure 1, if the surface is smooth, the appearance of the paint film is marked as "◎" with no wrinkles, and as shown in Figure 2, if wrinkles are observed visually, the appearance of the paint film is marked as "x" with wrinkles. And so. The results are shown in Table 1.

"Evaluation of dryness"
A resin containing curing agent 328E in the same proportion as in the above "curability evaluation" experiment was applied to a thickness of 300 μm, and the surface condition was observed by touch after 24 hours had elapsed. ○ indicates that there is no stickiness, △ indicates that the wax is floating but stickiness remains, and × indicates that the wax does not float sufficiently and drying is poor.

"Evaluation of odor presence"
Odor was judged by a sensory test. In the above-mentioned "curability evaluation" experiment, resin compositions that did not emit the odor of styrene monomer during curing were rated ○, and those that had the odor of styrene monomer were rated x.

As can be seen from Table 1, in Examples 1 to 9 in which the radical generation inhibitor was used, good surface appearance was obtained even with formulations that ensured a pot life suitable for large-area construction.
On the other hand, in Comparative Examples 1 to 5, in which pot life was ensured with a polymerization inhibitor, although drying properties were obtained, wrinkles appeared on the surface and the appearance was poor.
Further, as in Comparative Example 6, unless a radical generation inhibitor is used, the pot life cannot be obtained, which makes the work difficult. If the pot life is adjusted by lowering the amount of metal soap without using a radical generation inhibitor as in Comparative Examples 7 and 8, the wax will not perform its function and drying will be poor.
Furthermore, even if a small amount of styrene is added as in Comparative Example 9, an odor is felt, making it impossible to obtain a low-odor resin.

Claims (10)

(A) a radically reactive resin;
(B) (meth)acrylate monomer;
(C) Wax;
(D) Metallic soap;
(E) a radical generation inhibitor, and (F) a resin composition substantially free of styrenic compounds,
A low-odor resin composition, wherein the radical generation inhibitor (E) is at least one selected from the group consisting of lactic acid and glycerin . The low-odor resin composition according to claim 1, wherein the radical-reactive resin (A) is a bisphenol A vinyl ester resin. The low-odor resin composition according to claim 1 or 2, wherein the (meth)acrylate monomer (B) is a compound having an aromatic ring group. The low-odor resin composition according to any one of claims 1 to 3, wherein the (meth)acrylate monomer (B) is a compound represented by formula (1) or formula (2).

(In formula (1) or formula (2), R1 is a hydrogen atom or a methyl group. R2 is a straight chain or branched divalent hydrocarbon group having 0 to 10 carbon atoms, and is a hydroxyl group or an alkoxy group. It may have at least one selected substituent.However, R2 may have 0 carbon atoms and Ar may bond directly to the oxygen atom.R3 may have a straight chain or a carbon number of 1 to 10. It is a branched divalent hydrocarbon group, and may have at least one substituent selected from a hydroxyl group and an alkoxy group.Ar represents at least one substituent selected from a phenyl group and a naphthyl group; Part or all may be substituted with at least one selected from an alkyl group, an alkenyl group, an aryl group, an acetyl group, an alkoxy group, a carboxy group, a hydroxyl group, or a hydroxyalkyl group.) The low-odor resin composition according to any one of claims 1 to 4, wherein the metal soap (D) is a cobalt salt. A claim comprising 20 to 60 parts by mass of the (B) (meth)acrylate monomer based on 100 parts by mass of the total amount of the (A) radically reactive resin and the (B) (meth)acrylate monomer. The low odor resin composition according to any one of claims 1 to 5 . Claims 1 to 3, wherein the metal soap (D) is contained in an amount of 0.1 to 3 parts by mass based on 100 parts by mass of the total amount of the radical-reactive resin (A) and the (meth)acrylate monomer (B). The low odor resin composition according to claim 6 . 2. A method according to claim 1, wherein the radical generation inhibitor (E) is contained in an amount of 0.01 to 3 parts by mass based on 100 parts by mass of the total amount of the radical-reactive resin (A) and the (meth)acrylate monomer (B). The low odor resin composition according to any one of claims 1 to 7 . Claims 1 to 3 contain 0.01 to 3.0 parts by mass of wax (C) based on a total of 100 parts by mass of the radically reactive resin (A) and the (meth)acrylate monomer (B). 8. The low odor resin composition according to any one of 8 . Any of claims 1 to 9 , wherein the pot life (gelling time) measured by the method described in JIS K 6901 (2008), "5.9 Room temperature curing characteristics (exothermic method)" is 30 minutes or more. The low odor resin composition according to item (1).