JP5384715B1 - Curable resin composition, concrete coating composition and lining material - Google Patents

Abstract

The present invention provides a curable resin composition, a concrete coating composition, and a lining material excellent in low odor, water resistance, chemical resistance, durability, adhesion and air drying.
An epoxy (meta) comprising a reaction product of (A) an aromatic epoxy resin and (meth) acrylic acid, having a number average molecular weight in the range of 500 to 1,100 and an acid value of 10 KOH mg / g or less. ) 30 to 60 parts by mass of acrylate, (B) 10 to 30 parts by mass of ethoxylated bisphenol A dimethacrylate having 2 to 10 moles of ethylene oxide added, and (C) an alcohol residue having a molecular weight of 300 or less in the ring. A curable resin composition comprising 20 to 40 parts by mass of a monofunctional (meth) acrylate monomer having a double bond or a group containing a cyclic hydrocarbon group having one nitrogen atom.
[Selection figure] None

Description

  The present invention is particularly suitable for the formation of lining materials for surface coating of concrete in sewage treatment facilities, lining materials for repairing inner surfaces of manholes, and repair lining materials for concrete facilities in food factories, pharmaceutical factories, and electronic material related factories. The present invention relates to a suitable curable resin composition, and a concrete coating composition and a lining material containing the curable resin composition.

  In the gas phase part of a concrete structure of a sewerage treatment facility, hydrogen sulfide is sulfated by sulfur-oxidizing bacteria, and when used for a long period of time, the surface of the concrete becomes brittle and the structural strength of the facility decreases. As a method for repairing an aging sewerage treatment facility, a method of applying a coating type resin lining material to the wall surface of an existing facility is usually used.

  As the coating type resin lining material as described above, a curable resin composition containing an unsaturated polyester resin has been conventionally used. Recently, an unsaturated monobasic acid, particularly acrylic acid or methacrylic acid is used as an epoxy resin. A resin composition (generally a vinyl ester resin composition) containing an epoxy (meth) acrylate obtained by reacting is used.

  In known unsaturated polyester resin compositions and vinyl ester resin compositions used for coating type lining materials, styrene monomer is generally used as a copolymerizable monomer. However, since the mixture of ester and styrene has a peculiar odor, the odor diffuses to the surrounding area during construction. Therefore, a method of adsorbing styrene, which is the cause of odor, with an activated carbon adsorption device was introduced. ing. Styrene is also subject to the PRTR system (Chemical Substance Emission Control Management Promotion Act), which is a system for the release and transfer amount of first-class designated chemical substances, and management is also necessary from that point. In addition, regulations on styrene concentration in styrene-containing unsaturated polyester resins and vinyl ester resins are becoming stricter, and countermeasures are urgently required.

  A composition comprising a mixture of so-called epoxy acrylate (or epoxy methacrylate) and a monomer copolymerizable with this ester, obtained by reacting an epoxy resin with an unsaturated monobasic acid, particularly acrylic acid or methacrylic acid, is known. It is. This composition has heretofore been used, for example, as a matrix for fiber-reinforced plastics.

  Many proposals have been made on low-odor resin compositions that suppress the odor caused by styrene. For example, a low volatile polymerizable resin composition mainly using polyester acrylate and unsaturated polyester (Patent Document 1 (JP-A-6-211952)), polyether acrylic urethane resin, epoxy acrylate, etc. A resin composition comprising a resin having an acryloyl group, an air-drying imparting polymer using a drying oil and / or a fatty acid compound thereof, and an ethylenically unsaturated monomer having a (meth) acryloyl group having a molecular weight of 160 or more (patent) Polymeric monomers such as vinyl ester resin and styrene obtained from Document 2 (JP-A-8-283357), methacrylic acid and Epicoat 828 (Oilized Shell Co., Ltd., bisphenol epoxy resin, epoxy equivalent 187), etc. Rhini formed by heat-treating a composition comprising a monomer and glycidoxysilane Composition (Patent Document 3 (Japanese Patent Laid-Open No. 11-12448)), vinyl ester (eg, reaction product of Epicoat 828 and methacrylic acid), non-styrene type vinyl ester containing a low-volatile radical polymerizable monomer Concrete anticorrosion coating composition (Patent Document 4 (Japanese Patent Laid-Open No. 10-231453)) containing resin, scale-like inorganic filler, etc., obtained from bisphenol A and / or F and an aliphatic diglycidyl ether type epoxy compound A curable resin composition containing an epoxy compound, an epoxy (meth) acrylate, and a polymerizable (meth) acrylic monomer (II) having a molecular weight of 160 or more and a viscosity at 25 ° C. of 100 mPa · s or less (Patent Document 5 (special No. 2001-240632)), vinyl s obtained from epoxy resin and (meth) acrylic acid Primer composition for anticorrosion and odorless coating for concrete containing a reactive composition comprising a volatile alicyclic monofunctional (meth) acrylate monomer, a solventless urethane resin, a curing agent and the like (Patent Document 6 ( JP-A-2002-60282)), a curable resin composition comprising a compound obtained by reacting (meth) acrylic acid with an ethylene oxide adduct of epoxy (meth) acrylate and bisphenol A (Patent Document 7 (JP-A 2006)) -16931))) has been proposed.

  From the above, a combination of a low molecular weight epoxy acrylate obtained by reacting Epicoat 828 and (meth) acrylic acid and a low volatile radical polymerizable monomer is known. Further, Patent Document 7 discloses bisphenol A. A compound obtained by reacting (meth) acrylic acid with an ethylene oxide adduct of is used. However, even when such a resin composition is used as a lining material for concrete surface coating in sewerage treatment facilities, it has low odor, water resistance, chemical resistance, durability, adhesion, and air drying performance. Not enough.

Japanese Patent Laid-Open No. 6-211952 JP-A-8-283357 Japanese Patent Laid-Open No. 11-12448 Japanese Patent Laid-Open No. 10-231453 JP 2001-240632 A JP 2002-60282 A JP 2006-169911 A

  Accordingly, an object of the present invention is to provide a curable resin composition that eliminates the above-mentioned drawbacks and is excellent in low odor, water resistance, chemical resistance, durability, adhesion, and air drying.

  Moreover, the objective of this invention is providing the concrete coating composition which has the said characteristic using the said curable resin composition.

  Furthermore, the objective of this invention is providing the lining material which has the said characteristic using the said curable resin composition.

The inventors of the present invention have made extensive studies to obtain a curable resin composition having excellent low odor, water resistance, chemical resistance, durability, adhesion, and air drying properties. As a result, it is clear that by using an epoxy acrylate having an acid value lower than a specific value and having a specific molecular weight range, it is easy to obtain a low odor and excellent in the above characteristics, Further, an ethoxylated bisphenol A dimethacrylate having 2 to 10 moles of ethylene oxide added and a group containing a cyclic hydrocarbon group having one carbon-carbon double bond or one nitrogen atom in the ring as an alcohol residue having a molecular weight of 300 or less. By using a monofunctional (meth) acrylate monomer and a (meth) acrylate monomer having a phenyl group at a specific ratio, the above-mentioned low odor, water resistance, chemical resistance, durability, adhesion and air drying It became clear that the curable resin composition excellent in property was obtained, and it reached the present invention.

The present invention
(A) Epoxy (meth) acrylate 30 to 30 consisting of a reaction product of an aromatic epoxy resin and (meth) acrylic acid, having a number average molecular weight in the range of 500 to 1,100 and an acid value of 10 KOHmg / g or less. 60 parts by mass, (B) 10 to 30 parts by mass of ethoxylated bisphenol A dimethacrylate having 2 to 10 moles of ethylene oxide added, and (C) an alcohol residue having a molecular weight of 300 or less, or a carbon-carbon double bond or It contains 20 to 40 parts by mass of a monofunctional (meth) acrylate monomer having a group containing a cyclic hydrocarbon group having one nitrogen atom, and the total of components (A), (B) and (C) is 100 masses part der is,
Furthermore, it contains 5 to 40 parts by mass of (D) phenyl group-containing (meth) acrylate monomer with respect to a total of 100 parts by mass of (A), (B) and (C) . It is in.

The cured product of the curable resin composition of the present invention is particularly effective in suppressing whitening due to room temperature water or warm water immersion. Furthermore, in this curable resin composition, the chemical resistance (oxidation resistance) of the cured product is further improved.
By using (D), a cured product having a particularly high tensile strength is obtained, and the durability such as water resistance, heat deterioration resistance, and weather resistance is further improved. Moreover, since the viscosity of a composition falls, workability | operativity improves.

  The number average molecular weight of the epoxy (meth) acrylate is measured using a high performance liquid chromatography GPC method (gel permeation chromatography method). The molecular weight value is a conversion value of polystyrene. As a measuring device, a high-speed GPC device (HLC-8120GPC, manufactured by Tosoh Corporation) is used, and as a column, Showdex KF-805, 803, 802 (manufactured by Showa Denko Corporation) is used. The acid value is measured according to JIS-K-2501-2003.

  Preferred embodiments of the curable resin composition of the present invention are listed below.

  (2) (E) 1-30 mass parts of (meth) acrylate monomers which have an acetoacetoxyl group are further included with respect to 100 mass parts of total mass of (A), (B), and (C). In general, (E) is used in addition to (D). In this curable resin composition, the monofunctional (meth) acrylate monomer having an acetoacetoxyl group to be used generally has a molecular weight of 200 or more, a viscosity at 25 ° C. of 5 mPa · s or less, and a vapor pressure of 0.5 mmHg. Since it is the following, it has low volatility and has almost no environmental pollution, and the surface dryness to touch can be shortened. Moreover, since the viscosity of a composition falls, workability | operativity improves.

  (3) (C) having a group containing a cyclic hydrocarbon group having one carbon-carbon double bond or one nitrogen atom in the ring as an alcohol residue having a viscosity at 25 ° C. of 30 mPa · s or less and a molecular weight of 300 or less At least the monofunctional (meth) acrylate monomer is selected from dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, pentamethylpiperidyl methacrylate and pentamethylpiperidyl acrylate One kind of compound.

(4) The number of moles of ethylene oxide added in (B) is preferably 2 to 6 moles, particularly preferably 2 to 3 moles. Water resistance and chemical resistance are further improved. (5) 1 to 30 parts by mass of thermoplastic resin powder as a thickener with respect to 100 parts by mass of the total mass of (A), (B) and (C). To do.

  (6) The photopolymerization initiator is contained in an amount of 0.5 to 2.5 parts by mass with respect to 100 parts by mass of the total mass of the components used in (A) to (E).

  (7) The organic peroxide of 0.01-10 mass parts is contained with respect to 100 mass parts of total mass of the component used among (A)-(E).

  Moreover, this invention exists also in the concrete coating composition containing said curable resin composition of this invention.

  In the concrete coating composition, 100 powders of an inert powdery inorganic material having an average particle size of 0.2 mm to 10 mm with respect to 100 parts by mass of the total mass of (A) to (C) of the curable resin composition. It is preferable to contain -600 mass parts.

The preferred embodiment of the curable resin composition of the present invention can also be applied to the concrete coating composition.

  Furthermore, this invention exists also in the lining material containing said curable resin composition of this invention.

  In the said lining material, it is preferable to contain 5-50 mass parts of scale-like inorganic fillers with respect to 100 mass parts of total mass of (A)-(C).

  The suitable aspect of the curable resin composition of this invention is applicable also to the said lining material.

  The curable resin composition of the present invention is a non-styrene vinyl ester resin, a specific epoxy (meth) acrylate having a specific acid value and a specific number average molecular weight, imparting high reactivity, air drying property and low volatility. Specific polymerizable monofunctional (meth) acrylic monomer and ethoxylated bisphenol A dimethacrylate having an ethylene oxide addition mole number in a specific range are included in a specific composition ratio. As a result, there is no styrene volatilization, surface dryness and curability are good, physical properties of cast plates and laminates, wear resistance of hardened products due to increase / decrease of composition ratio with inorganic aggregate, coating layer on concrete The stability of the adhesion strength after long-term immersion in hot water is superior to the existing cured styrene-type vinyl ester resin. Moreover, there is little odor compared with the existing non-styrene type vinyl ester resin, and it is remarkably excellent in the adhesion strength stability of the coating layer in the long-term hot water immersion in concrete.

  In particular, by using a monofunctional (meth) acrylic monomer having a phenyl group at a specific composition ratio, water resistance, heat deterioration resistance, and weather resistance can be further improved. Furthermore, when a monofunctional (meth) acrylate monomer having an acetoacetoxyl group is used, environmental pollution can be further reduced, and surface dryness to the touch can also be shortened.

  Furthermore, the concrete coating composition and lining material of the present invention have no styrene odor before and after curing and do not cause environmental pollution. In addition, since the concrete coating composition and the lining material can be imparted with dryness to dryness after surface hardening at an early stage, the opening time after construction is shortened.

  In the present invention, the aromatic epoxy (meth) acrylate (A), which is one of the essential components of the curable resin composition, is obtained from an aromatic epoxy compound and (meth) acrylic acid.

  As a preferable aromatic epoxy resin used as a raw material of the aromatic epoxy (meth) acrylate of the component (A) of the resin composition of the present invention, for example, an epoxy resin having an aromatic in the molecule may be used. Phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alkylphenol type epoxy resin, resorcin type epoxy resin, N-glycidylamine type epoxy resin, brominated bisphenol A type epoxy resin, etc. Can be mentioned. These epoxy resins may be used alone or in combination of two or more. Of these, bisphenol A type epoxy resins are particularly preferred because they provide balanced properties to the concrete coating curable resin composition and the lining material cured product.

  As the unsaturated monobasic acid to be reacted with the epoxy resin, acrylic acid or methacrylic acid is generally used. However, other unsaturated monobasic acids such as crotonic acid, sorbitan acid, cinnamic acid, acrylic acid dimer, monomethyl acrylate, monomethyl fumarate, monocyclohexyl fumarate, sorbic acid and the like can be used in small amounts. These acids are used alone or in combination of two or more.

  The aromatic epoxy (meth) acrylate (A) used in the curable resin composition of the present invention is obtained from a normal reaction of the aromatic epoxy resin and (meth) acrylic acid, The reaction ratio of (meth) acrylic acid is generally in the range of 0.9 to 1.1: 1.1 to 0.9 in terms of molar ratio. The reaction at this time is usually carried out at 80 to 130 ° C., and as an esterification catalyst, tertiary amines such as triethylamine and dimethylaniline, quaternary ammonium salts such as trimethylbenzylammonium chloride and pyridinium chloride, lithium hydroxide, lithium chloride Inorganic salts such as are used. A polymerization inhibitor is used as necessary.

  Examples of the polymerization inhibitor include hydroquinones such as hydroquinone and methylhydroquinone; benzoquinones such as benzoquinone and methyl-p-benzoquinone; catechols such as t-ptylcatechol; 2,6-di-t-butyl-t- Examples thereof include phenols such as methylphenol and 4-methoxyphenol; phenothiazine and the like.

  The addition amount of the esterification catalyst can be used in a range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the total of the aromatic epoxy resin and (meth) acrylic acid. It is preferable to use in the range of 0.05 to 5 parts by mass. When the amount is less than 0.01 parts by mass, the esterification reaction is extremely slow. When the amount exceeds 10 parts by mass, the esterification reaction becomes extremely fast, and temperature control becomes difficult due to rapid heat generation, which is not preferable.

  In the present invention, the aromatic epoxy (meth) acrylate (A) component has a number average molecular weight in the range of 500 to 1,100 and an acid value of 10 KOHmg / g or less. A number average molecular weight in the range of 550 to 900, particularly a number average molecular weight in the range of 600 to 850 is preferable. When the number average molecular weight is less than 500, the terminal acryloyl group concentration increases and the water absorption increases, and when the terminal group and ester bond density increases, the alkali resistance decreases. On the other hand, when the number average molecular weight is 1,100 or more, the viscosity of the curable resin composition at the time of synthesis increases and workability deteriorates, and the solvent resistance also decreases.

  The amount of the aromatic epoxy (meth) acrylate (A) used is the total of the curable resin compositions (A), (B) and (C) which are essential components constituting the curable resin composition of the present invention. It is the range of 30-60 mass parts with respect to 100 mass parts. A range of 35 to 55 parts by mass, particularly a range of 35 to 50 parts by mass is preferable. When the amount used is less than 30 parts by mass, a cured product of the resulting curable resin composition will cause whitening when immersed in warm water for a long time, and when it is 60 parts by mass or more, a shrinkage crack is likely to occur during curing.

  In order to balance the above performance, 0.3 to 0.7 mol% of a liquid type epoxy resin having a molecular weight of 500 or less and 0 to a solid type epoxy resin having a molecular weight of 900 or more are usually added to 1 mol of an aromatic epoxy resin. An aromatic epoxy (meth) acrylate is obtained from a reaction product of a resin having a composition ratio in the range of 7 to 0.3 mol% and (meth) acrylic acid. An acid value of 10 KOH mg / g or more is not preferable because an unsaturated monobasic acrylic acid or methacrylic acid monomer having an irritating odor remains in the aromatic epoxy (meth) acrylate.

  As the ethoxylated bisphenol A dimethacrylate having 2 to 10 moles of ethylene oxide added, which is an essential component constituting the resin composition (B) used in the present invention, ethylene oxide is added to bisphenol A and / or bisphenol F. The thing of the ester compound of a bihydric alcohol and methacrylic acid can be mentioned. The number of moles of ethylene oxide added is preferably 2 to 6 moles, particularly preferably 2 to 3 moles. Thereby, the following water resistance and chemical resistance are further improved. Bisphenol A is preferred as the bisphenol. When the number of moles of ethylene oxide added to the ethoxylated bisphenol A dimethacrylate of (B) exceeds 10, the crosslinking density decreases, thereby reducing the reactivity of the curable resin composition, the water resistance of the cured product, particularly room temperature water. In addition, the weight change rate of immersion in hot water is increased, and as chemical resistance, the cured product is immersed in a 10% sulfuric acid aqueous solution specified by the guidelines of the Japan Sewerage Corporation for 120 days, and sulfuric acid is analyzed with an electron beam microanalyzer (EPMA). The test method for predicting the durability life of lining materials by the penetration depth of sulfur in the interior is unsuitable for use in a liquid phase environment because the penetration depth increases, the affinity with fiber reinforcement, and the adhesive strength decrease. . On the other hand, when the added mole number of ethylene oxide is less than 2, it is not preferable because the viscosity of the resin composition becomes high and the operation becomes difficult.

  In the present invention, the content of ethylene oxide-added alkoxylated bisphenol A dimethacrylate (B) is the sum of (A), (B), and (C), which are essential components constituting the curable resin composition of the present invention. It is the range of 10-30 mass parts with respect to 100 mass parts. A range of 10 to 25 parts by mass, particularly a range of 15 to 25 parts by mass is preferable. That is, when the amount is less than 10 parts by mass, the surface of the cured product of the obtained curable resin composition is whitened when immersed in room temperature water and warm water. On the other hand, when the amount exceeds 30 parts by mass, swelling is generated in the cured product of the curable resin composition when immersed in water or warm water, which is not preferable. Ethoxylated bisphenol A di (meth) acrylate is, for example, a known method described in JP-A-7-268079. First, a nucleated polyol obtained by adding ethylene oxide to bisphenol A and an epihalohydrin are subjected to ether reaction to add ethylene oxide. Bisphenol A diglycidyl can be obtained and then an esterification catalyst can be used to obtain ethoxylated bisphenol A di (meth) acrylate in reaction with methacrylic acid or acrylic acid.

  In the present invention, the monofunctional (meth) acrylic monomer has (C) a group containing a cyclic hydrocarbon group having one carbon-carbon double bond or one nitrogen atom in the ring as an alcohol residue having a molecular weight of 300 or less. Monofunctional (meth) acrylate monomers are used. Furthermore, the molecular weight is preferably 240 or more. Moreover, it is preferable that the viscosity at 25 ° C. is 100 mPa · s or less (particularly 30 mPa · s or less?) And the vapor pressure is 0.5 mmHg or less. Examples of such monofunctional (meth) acrylic monomers include dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, pentamethylpiperidyl methacrylate and pentamethylpiperidyl acrylate. Can be mentioned. These may be used alone or in combination of two or more. Among these, since the present invention is excellent in odor, reactivity, and cured product properties, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyl methacrylate, and pentamethylpiperidyl methacrylate are used. It is preferable.

  The usage-amount of the said monofunctional (meth) acrylic-type monomer (C) is 100 mass parts of total mass of (A), (B), and (C) which is an essential component which comprises the resin composition of this invention. It is the range of 20-40 mass parts, and the range of 25-40 mass parts is preferable. When the amount is less than 20 parts by mass, the cured product of the curable resin composition is inferior in surface touch drying property, and the curable resin composition has high viscosity and inferior workability. Moreover, when it exceeds 40 mass parts, it will be preferable to use in the above-mentioned range from the occurrence of swelling on the surface of the cured product when immersed in high-temperature water, resulting in poor durability.

  In the present invention, it is preferable to use a (meth) acrylate monomer having a phenyl group as the component (D). Examples include benzyl (meth) acrylate monomer, phenoxyethyl (meth) acrylate monomer, phenol ethylene oxide (EO) modified (meth) acrylate, nonylphenyl carbitol (meth) acrylate, nonylphenol EO modified (meth) acrylate, phenoxy Examples thereof include propyl (meth) acrylate, phenol propylene oxide (PO) -modified (meth) acrylate, (meth) acryloyloxyethyl phthalate, and the like. Among these, it is preferable to use phenoxyethyl (meth) acrylate in consideration of the odor of the monomer. By using a (meth) acrylate monomer having a phenyl group, a cured product having sufficient tensile strength can be obtained, and a cured product having excellent durability such as water resistance, heat deterioration resistance, and weather resistance can be obtained.

  The used amount of the (meth) acrylate monomer (D) having the phenyl group is 100 parts by mass with respect to a total mass of (A), (B) and (C) which are essential components constituting the resin composition of the present invention. The range is 5 to 40 parts by mass, and the range of 5 to 30 parts by mass is preferable. If the amount is less than 5 parts by mass, the cured product of the curable resin composition has poor tensile strength, and the curable resin composition has high viscosity and poor workability. On the other hand, if it exceeds 40 parts by mass, the water resistance and heat deterioration resistance will be poor.

  In the present invention, it is preferable to use a monofunctional (meth) acrylate monomer having an acetoacetoxyl group as the component (E) as the polymerizable monomer. This monofunctional (meth) acrylate monomer generally has a molecular weight of 200 or more, a viscosity at 25 ° C. of 5 mPa · s or less, a vapor pressure of 0.5 mmHg or less, low volatility, and almost no environmental pollution. There is nothing. Specific examples of the (meth) acrylate monomer having an acetoacetoxyl group include acetoacetoxyethyl methacrylate, acetylacetoxyethyl acrylate, acetoacetoxybutyl acrylate, and triacetoacetoxymethylpropane. Among these, it is preferable to select and use in consideration of the odor of the monomer. Preferably, acetoacetoxyethyl methacrylate is used.

  In the present invention, the content of acetoacetoxy (meth) acrylate (E) is an essential component constituting the curable resin composition of the present invention (A), (B) and (C) 100 mass parts in total. It is preferable that it is the range of 1-40 mass parts with respect to 1 to 30 mass parts especially. That is, if it is less than 1 part by mass, it takes a long time to dry the surface of the cured product of the curable resin composition obtained, and the viscosity is unfavorably high. On the other hand, if it exceeds 40 parts by mass, the crosslink density is increased and the wear resistance is lowered, which is not preferable.

  Although the resin composition of the present invention can be used alone, the following polymerizable vinyl for cross-linking is considered in consideration of the styrene discharge concentration regulation by the sick house problem and the chemical substance emission grasp management transfer registration method (PRTR method). A monomer may be used in combination as a resin composition that significantly reduces the polymerizable monomer for crosslinking.

  Examples of the polymerizable vinyl monomer for crosslinking include aromatic styrene, vinyl toluene, and α-methylstyrene. Examples of the methacrylic monomer include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and 2-ethylhexyl methacrylate. These crosslinking polymerizable monomers may be used alone or in combination of two or more, but generally styrene is used. The compounding amount of the crosslinkable polymerizable monomer is 40 parts by mass (the crosslinkable polymerizable monomer content is 30 parts or less) with respect to the total curable resin composition of 100 parts by mass of (A), (B) and (C). The following is preferred. Generally, since the content of the crosslinkable polymerizable monomer in the vinyl ester resin is 40 to 50% by mass, the content of the crosslinkable polymerizable monomer is greatly reduced, and the low crosslinkable polymerization that can significantly reduce the volatile amount during operation. It can be used as a functional monomer-containing resin composition.

  As a photoinitiator used for the curable resin composition of this invention, the visible light polymerization initiator which can harden | cure even a well-known ultraviolet-ray polymerization initiator and / or a fiber-containing curable composite material can be used. Examples of UV polymerization initiators include benzoin ether-based isopropyl benzoin ether, isobutyl benzoin ether, benvine ethyl ether, benzoin methyl ether, benzyl ketal hydrocyclohexyl phenyl ketone, benzyl methyl ketal, and ketone benzophenone. Benzyl, methyl-o-benzoin benzoate, 2-chlorothioxanthone, methyltooxanthone, benzophenone-based benzophenone / tertiary amine, 2,2-diethoxyacetophenone, α-hydroxyisobutylphenone, acylophosphine oxide, bisacylphosphine oxide As typical examples of camphorquinone, etc. can be mentioned. In the case of the photo-curing lining material used in the present invention, a coating method is adopted in which the surface of the lining material is irradiated with ultraviolet rays to be quickly cured. A photopolymerization initiator having absorption of 250 nm in the ultraviolet wavelength region to 450 nm in the visible wavelength region is preferable. 2,4,6-trimethylbenzoyldiphenylphosphine oxide and benzylmethyl ketal are preferred and may be used alone or in combination.

  An acyl phosphine oxide compound is effective as the visible light polymerization initiator. Examples include bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichlorobenzoyl). Examples include -4-ethoxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylbenzylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and the like. It may be used alone or in combination.

  The usage-amount of a photoinitiator is 0.01-20 mass with respect to 100 mass parts of total amounts of (A), (B), and (C) which are the essential components which comprise the resin composition used for this invention. Part range. If it is less than 0.01 parts by mass, the polymerization may not be sufficiently performed. If it exceeds 20 parts by mass, the curing time will be almost flat.

  By adding a thickener to the curable resin composition of the present invention, a suitable viscosity can be adjusted to form a prepreg sheet. Examples of the thickener include magnesium oxide, magnesium hydroxide, potassium oxide, calcium hydroxide and metal alkoxides of alkaline earth metals. Examples of metal alkoxides include aluminum isopropylate, methyl acetoacetate. Mention may be made of aluminum dibutyrate, methyl ethyl acetoacetate aluminum isopropylate, ethyl acetoacetate aluminum diethoxyethylate, ethyl acetoacetate aluminum diisopropylate and aluminum tris (ethyl acetoacetate). Furthermore, isocyanates such as toluylene diisocyanate and diphenylmethane diisocyanate can be used singly or in an appropriate mixture in combination with the ants.

  The alkaline earth metal oxide magnesium oxide usually used in styrene type unsaturated polyester resins and vinyl ester resins causes intermolecular cross-linking between carboxyl groups liberated from the resin composition. Although the viscosity is increased, since the crosslinking reaction is slow, a method of aging in a temperature environment of 40 ° C. or higher is usually employed after the resin composition is impregnated into the fiber and the viscosity is usually accelerated. However, since the low odor photocurable resin composition has no free carboxyl group and does not have a thickening effect, a thermoplastic resin is added to the curable resin composition, and the solution is heated and dissolved at a thickening temperature of 50 to 90 ° C. A method of exerting a thickening effect is taken.

  In addition, the curable resin composition of this invention can use a well-known thermoplastic resin powder as a thickener. The average single particle size of the thermoplastic resin powder is preferably 0.1 to 5.0 μm, particularly preferably 0.2 to 3.0 μm. When the average single particle size is less than 0.1 μm, the monofunctional (meth) acrylic monomer (B), which is the component (B), has a high absorption rate at room temperature and the viscosity becomes too high, so that the fibers are impregnated. May not be easy. On the other hand, when the average single particle diameter exceeds 5.0 μm, the absorption rate of the monofunctional (meth) acrylic monomer (B) and / or the polyfunctional (meth) acrylic monomer is slowed, and pseudo-curing is caused. Become slow. The weight average degree of polymerization is 1,000 to 150,000. When the weight average degree of polymerization exceeds 150,000, the absorption rate of the monofunctional (meth) acrylic monomer (B) and / or the polyfunctional (meth) acrylic monomer is slow, and the viscosity increases even after a long time. Giving is difficult. On the other hand, when the molecular weight is less than 1,000, the absorption rate of the monofunctional (meth) acrylic monomer and / or the polyfunctional (meth) acrylic monomer is high and the viscosity is rapidly increased. It becomes uniform, and the mechanical strength of the prepreg cured product is low, and the chemical resistance is remarkably lowered. In addition, when the thermoplastic resin powder is copolymerized with a crosslinkable monomer, if the crosslinking degree is too high, it tends to take a long time to form a prepreg sheet having an appropriate viscosity. It is preferable that the insoluble gel component when the plastic resin powder is dissolved in a solvent is 50% by weight or less.

  About the manufacturing method of thermoplastic resin powder, it is shown by well-known, for example, Unexamined-Japanese-Patent No. 9-188770. It is roughly divided into a homogeneous component polymer (homopolymer), a copolymer of two or more monomers, and a core / shell structure. A thermoplastic resin powder is a mixture of a curable resin composition and a (meth) acrylic monomer. Has a low viscosity immediately after the adjustment, rapidly increases in viscosity after the addition of the fibrous material, and thereafter shows stability over time of the viscosity.

  The thermoplastic resin powder swells by absorbing a monofunctional (meth) acrylic monomer and / or a polyfunctional (meth) acrylic monomer as disclosed in Japanese Patent Application Laid-Open No. 9-174781 If there is no particular limitation, it can be used. At least one monomer unit selected from acrylic acid ester, methacrylic acid ester and aromatic vinyl compound, although not particularly limited, selected from acrylic acid ester, methacrylic acid ester and aromatic vinyl compound Is preferably a thermoplastic resin powder having a carboxyl group or epoxy group-containing monomer unit of 1 to 20% by weight.

  Examples of the acrylic ester used as a monomer of the resin raw material of the thermoplastic resin powder include, for example, methyl acrylate, ethyl acrylate, n-pyropropyl acrylate, n-butyl acrylate, isopropyl acrylate, isobutyl acrylate, sec-butyl acrylate, Examples thereof include 2-ethylhexyl acrylate and n-octyl acrylate. As the methacrylic acid ester, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, and n-octyl methacrylate are preferable. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, divinylbenzene, and monomers in which a benzene nucleus of these monomers is substituted with a methyl group, an ethyl group, a propyl group, a butyl group, for example, And vinyltoluene and isobutylstyrene. These monomers can be used alone or in combination of two or more. If the content of the monomer units of these acrylic acid ester, methacrylic acid ester or aromatic vinyl compound in the thermoplastic resin powder is less than 50% by weight, the thermoplastic resin powder may not exhibit a sufficient thickening effect. There is.

  The thermoplastic resin powder, which is a component for imparting thickening of the curable resin composition of the present invention, may contain other monomer units copolymerizable with the above-mentioned monomers. As monomers, vinyl cyanides such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate, vinyl propionate, vinyl myristate, vinyl oleate, vinyl benzoate; acrylic acid, methacrylic acid, 2- Unsaturated dicarboxylic acids such as ethylpropionic acid, crotonic acid and cinnamic acid; unsaturated dicarboxylic acids such as maleic acid, itaconic acid, fumaric acid, citraconic acid and chloromaleic acid; monomethyl maleate, monomethyl maleate, monoethyl maleate; Monoesters of unsaturated dicarboxylic acids such as monobutyl itaconate; butadiene, isoprene, 1,3 Pentajen, conjugated diene compounds such as cyclopentadiene; 1,4-hexane, and the like non-conjugated diene compounds such as dicyclopentadiene. Furthermore, in order to adjust the solubility when the thermoplastic resin powder is used as a thickener in the process of preparing the prepreg of the curable vinyl ester resin composition, the polymer constituting the thermoplastic resin powder is appropriately crosslinked. can do. Examples of the copolymer component for giving a crosslinked structure include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 2 -Aminobutyl (meth) acrylate, (meth) acrylamide, N-2-aminopropyl (meth) acrylate, N-2-aminoethyl (meth) acrylamide, N-3-aminopropyl (meth) acrylamide, ethylene group number 1 -14 monomers such as polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, triallyl trimellitate, diallyl phthalate, allyl glycidyl ether, triallyl isocyanurate, and the like. The content of these crosslinkable monomers should not exceed 0.5% by weight in the copolymer. If the degree of crosslinking is too high, the absorption rate is slow, and the predetermined thickening effect cannot be exhibited. Other copolymerizable monomers can be used alone, but two or more can be used in combination.

  There is no particular limitation on the method for producing the thermoplastic resin powder, and a conventional method (for example, JP 9-188770 A) used for producing fine resin powder such as polymethyl methacrylate, for example, fine suspension polymerization method, An emulsion polymerization method, a seeding emulsion polymerization method, or the like can be employed. Among these methods, a polymerization method that can obtain a spherical particle size without being extremely fine is particularly preferable. For example, surfactants and dispersants are generally used in the fine suspension polymerization method. Examples of the surfactant include alkyl sulfates such as sodium lauryl sulfate and sodium myristyl sulfate; alkylaryl sulfonates such as sodium dodecylbenzenesulfonate and potassium dodecylbenzenesulfonate; sodium dioctylsulfosuccinate and dihexylsulfosuccinate. Sulfosuccinic acid ester salts such as sodium acid salt; fatty acid salts such as ammonium laurate and potassium stearate; polyoxyethylene alkylsulfuric acid ester salts, polyoxyethylene alkylarylsulfuric acid ester salts; and anionic surface activity such as sodium dodecyl diphenyl ether disulfonate Agents: Sorbitan monooleate, sorbitan monooleate, polyoxyethylene sorbitan monostearate, etc. Ethers; nonionic surfactants such as polyoxyethylene alkyl ethers; cetylpyridinium chloride, and the like cationic surface active agents such as cationic, such as cetyltrimethylammonium bromide. Examples of the dispersant include polyvinyl alcohol, methyl cellulose, and polyvinyl pyrrolidone. These surfactants and dispersants may be used alone. Or it can use combining 2 or more types. The amount used can be appropriately selected within the range of 0.05 to 10 parts by weight, preferably 0.2 to 7 parts by weight, based on 100 parts by weight of the monomer generally used.

  As for the method for producing the thermoplastic resin powder, for example, a homogeneous component polymer (homopolymer), a copolymer of two or more monomers and a core / shell structure disclosed in JP-A-9-188770 are widely used. Although different, the thermoplastic resin powder used in the present invention has a core / shell having a polymer containing 1 to 20% by weight of a carboxyl group-containing monomer unit or an epoxy group-containing monomer unit in a shell layer. A mold structure is preferred. When the core component is a (meth) acrylic acid ester-based polymer and / or a gen-based copolymer having a glass transition point of −30 ° C. or lower, preferably −40 ° C. or lower, the mechanical strength and elastic modulus of the molded product are It is preferable because it greatly improves.

  Although it is the characteristic that it is excellent in drying property only with the component of the resin composition of this invention, you may use paraffin and / or wax together in order to improve drying property more. Examples of paraffin and / or waxes used in the resin composition of the present invention include paraffin wax, polyethylene waxes, higher fatty acids such as stearic acid and 1,2-hydroxystearic acid. The use of paraffin wax is preferred. It is added for the purpose of improving the air blocking action and the stain resistance during the curing reaction on the paraffin and / or wax coating surface. As addition amount, 0.1-5 mass parts with respect to 100 mass parts of resin compositions of component (A), (B) and (C), especially 0.2-2 mass parts is preferable.

  The curable resin composition of the present invention can be used for a concrete coating composition.

  In the concrete coating composition of the present invention, inert fine particles and / or inert powdery inorganic aggregate materials can be used. Examples of inert powdery inorganic aggregate materials include, for example, sand, silica powder, crushed rock, calcium carbonate, alumina powder, clay, silica powder, talc, glass powder, silica powder, aluminum hydroxide, silica sand, Aluminum silicate, magnesium silicate, cement and the like can be used.

  Furthermore, the amount of the inorganic aggregate material used depends on workability such as desired fluidity and is determined by the strength of the hardened material of the concrete composition, but the added amount is the components (A) and (B). And it is preferable to set it as the range of 100-600 mass parts with respect to 100 mass parts of curable resin composition of (C), especially the range of 150-600 mass parts. The average particle size of the inorganic aggregate is generally 0.02 to 10 mm, preferably 0.05 to 5 mm. The aggregate is No. 1 silica sand (average particle size 5 to 2.5 mm), No. 2 silica sand (particle size 2.5 to 1.2 mm), No. 3 silica sand (particle size 1. 2 to 0.6 mm), No. 4 quartz sand (particle size 0.6 to 0.3 mm), No. 5 quartz sand (grain sand 0.3 to 0.15 mm), No. 6 quartz sand (grain sand 0.15 to 0.074 mm) ), No. 7 silica sand (particle size 0.074 mm or less) can also be used.

  In the concrete coating composition of the present invention, inert fine particles can also be used as described above. For example, calcium carbonate, fly ash, clay, alumina powder, silica powder, talc, silica powder, glass powder, mica, aluminum hydroxide, aluminum silicate, magnesium silicate, cement, marble and the like are preferable. The average particle size of the fine particles is preferably in the range of 0.5 μm to 20 μm. The addition amount of the inert fine particles is preferably 2.5 to 100 parts by mass with respect to 100 parts by mass of the curable resin composition of components (A), (B) and (C). The fine particles may be used alone or in combination of two or more.

  The curable resin composition of the present invention can be used for a lining material (particularly, a concrete lining material). Furthermore, the concrete lining material which added 5-50 mass parts scale-like inorganic filler with respect to 100 mass parts of curable resin composition of the component (A) of this invention, (B), and (C) is preferable.

  Examples of the scale-like inorganic filler include glass flakes and mica flakes, and among these, it is more preferable to use glass flakes. As the scale-like inorganic filler, those having an average particle diameter of 10 to 4000 μm are generally used. However, in order to maintain the workability of the concrete lining material satisfactorily, an average particle diameter of 100 to 1000 μm is used. It is preferable to use it.

  In general, an organic peroxide is used to thermally cure the curable resin composition. Organic peroxides to be mixed with the curable resin composition include ketone peroxides such as methyl ethyl ketone peroxide; hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide; peroxyesters such as t-Butylperoxyoctoate, t-butylperoxybenzoate and the like; Dialkyl peroxides such as dicumyl peroxide; Diacyl peroxides such as lauroyl peroxide and benzoyl peroxide are used.

  Generally the usage-amount of an organic peroxide is 0.01- with respect to 100 mass parts of total amounts of (A), (B), and (C) which are the essential components which comprise the resin composition used for this invention. The range is 10 parts by mass.

  In the present invention, 0.01 to 5 parts by mass of an aromatic amine accelerator and / or a polyvalent metal salt and / or a complex is further added to 100 parts by mass of the resin composition, and then an organic peroxide is added. It can mix | blend when forming the mixed thermosetting resin composition and accelerating | curing hardening of a lining material. If it is less than 0.01 parts by mass, curing is not sufficient, and if it exceeds 5 parts by mass, no further effect can be obtained.

  As the aromatic amine accelerator, one or more combinations of aniline, N, N-dimethylaniline, N, N-diethylaniline, toluidine, N, N-dimethyl-P-toluidine and the like can be used.

  Next, the polyvalent metal salt and / or complex is a polyvalent metal salt of naphthenic acid or octenoic acid, and the polyvalent metal is calcium, copper, manganese, cobalt, vanadium, or the like. In particular, cobalt octylate and cobalt naphthenate are preferable.

Examples of the complex include acetylacetone, cobalt acetylacetonate, and manganese acetylacetonate.
In addition, pigments, antioxidants, flow control agents, thixotropic agents, plasticizers, and the like can be added to these resin compositions, concrete coating compositions, and lining materials as necessary.

  The characteristic values in the examples were measured as follows.

  The amount of wear described in the examples is measured by the wear wheel method of JIS-A-1453 (abrasion test method for building materials and building components (abrasive paper method)), wear wheel CS-17, load 1 kg, rotation speed 1000 rpm. taking measurement.

  The number average molecular weight described in the Examples was measured using a high performance liquid chromatography GPC method (gel permeation chromatography method). The molecular weight value is a conversion value of polystyrene. A high-speed GPC device (HLC-8120GPC, manufactured by Tosoh Corporation) was used as a measuring apparatus, and Showdex KF-805, 803, 802 (made by Showa Denko Corporation) were used as columns.

  Regarding the volatilization amount of styrene, after sufficiently mixing the resin composition having the blending ratio of Example 1, 100 g was put in a glass petri dish of φ145 mm, and the weight change rate was measured after 60 minutes.

  The method for measuring the Barcol hardness in the hardness test is defined in JISK7060 (Barcol hardness test method for glass fiber reinforced plastics).

  EPMA (electron beam microanalyzer) immerses the laminate in a 10% sulfuric acid aqueous solution for 120 days, and measures the penetration depth of sulfur in sulfuric acid. Since the gas phase part of the concrete structure of the sewerage facility is placed in a sulfuric acid environment, the life of the resin coating thickness can be predicted from the sulfur penetration depth.

Next, although an example of the present invention explains, the present invention is not limited to this. In the examples, “part” is “part by mass” unless otherwise specified.
[Reference Example 1]

[Curable resin composition using aromatic epoxy methacrylate (A) and ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) and dicyclopentenyloxyethyl methacrylate (C) using the same]
[Production of aromatic epoxy methacrylate (A) having a number average molecular weight of about 750]
148 g of jER828 (manufactured by Mitsubishi Chemical Corporation), 360 g of jER1001 (manufactured by Mitsubishi Chemical Corporation) and jER1002 (manufactured by Mitsubishi Chemical Corporation) were added to a 2 liter four-necked flask equipped with a stirrer, a condenser, a thermometer and an air introduction tube. 240 g), and heated to 130 ° C. while blowing 10 liters of dry air per minute with stirring. After the temperature rise, 0.3 g of hydroquinone (polymerization inhibitor) and 2 g of trimethylbenzylammonium chloride were added, and 172 g of methacrylic acid was added dropwise over 2 hours. After 3 hours from the end of dropping, measurement of the acid value was started every hour, and after confirming that it was 10 KOH mg / g or less, the mixture was cooled to 100 ° C.

  Ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Shin Nakamura Chemical Co., Ltd. BPE-100) 20 parts by mass, dicyclopentenyloxyethyl methacrylate (C) (50 parts by mass of the product) 30 parts by mass of Hitachi Chemical Co., Ltd. FA-512MT) was added and dissolved, and then cooled to room temperature to obtain a curable resin composition.

This was mixed well in the proportion of the above resin composition of Example 1 in Table 1, then poured into a mold and cured at 25 ° C. for 72 hours, and a cured resin product having a thickness of 3 mm (cast product). Got. The resin cured product was subjected to a bending test (elastic modulus) according to JIS-K-6901 at a test speed of 1000 mm / min. The tensile test (elastic modulus and elongation) was measured according to JIS-K-7113. The laminated plate was formed by laminating FRP having a glass content of 30% on a release-treated glass plate using 3 plies of chop strand mat MC-450 (manufactured by Nitto Boseki Co., Ltd.). The laminate was obtained by curing at 25 ° C. for 72 hours. The bending strength (elastic modulus) was measured according to JIS-K-6911, and the tensile strength (tensile elastic modulus, elongation) was measured according to JIS-K-7113. The Barcol hardness and sulfur penetration depth were measured by the above methods. The results are shown in Table 1. The surface drying time is prepared using an applicator on a glass plate at room temperature of 20 ° C., and a finger touch test is performed on the surface drying property. The evaluation method measured the time until the absorbent cotton did not remain on the surface of the coating film due to adhesion even when about 2-3 cm ² of absorbent cotton was pressed against the surface of the coating film. The thermal deformation temperature of the laminate was measured according to JIS-K-6911. The concrete adhesion strength was tested according to JIS-A-6916 with a Kenken type tensile tester, and the adhesive strength was measured. In the concrete peeling test, the resin composition of Example 1 (the resin composition of each Example was also used in Examples 2 to 4) was applied to a JIS-A-5304 standard sidewalk board (size: 300 mm × 300 mm). As a primer, a coating amount of 150 g / m ² was applied, and after touch-drying, 100 parts by mass of the resin composition of Example 1 (in the case of Examples 2 to 4 also with respect to 100 parts by mass of the resin composition of each Example) Glass flake RCF-140 (manufactured by Nippon Sheet Glass Co., Ltd.) 30 parts by mass, crystallite AA (manufactured by Tatsumori quartzite powder) 20 parts by mass, 6% cobalt naphthenate 1.5 parts by mass, peroxide (Nippon Yushi Co., Ltd. Percure K) Applying 2.5 parts by weight of the composition as a substrate conditioner, 700 g / m ² , drying the touch, and then adding 100 parts by weight of the curable resin composition to glass flakes RCF- 10 masses for 140 The added formulation as a surface protective layer to form a corrosion prevention coating layer is 1 kg / m ² coating (thickness 0.6 mm). After curing at 25 ° C. for 72 hours, the inside of the FRP plate of width × length × thickness = 20 mm × 90 mm × 2 mm is bonded with an epoxy adhesive leaving 20 mm unbonded at one end in the length direction. In addition, a 2mm hole is opened at the center of the unbonded part, and a hook at the tip of the spring balance is inserted into this hole, and 90 degree peeling is performed in accordance with the vulcanized rubber adhesion test method of JIS-K-6256. It was measured. The weight change rate was 10 g after thoroughly mixing the resin composition having the blending ratio of Example 1 and poured into a glass petri dish with a diameter of 40 mm (height, 15 mm) and cured for 25 hours at 25 ° C. After the mold was immersed in warm water (80 ° C.) for 96 hours, the weight change rate was measured. Further, EPMA, Barcol hardness and wear amount were measured by the above-described methods.
[Reference Example 2]

  Ethylene oxide 6 mol addition ethoxylated bisphenol A dimethacrylate (B) (BP-6EM manufactured by Kyoeisha Chemical Co., Ltd.) was added to 50 parts by mass of the aromatic epoxy methacrylate (A) having a number average molecular weight of 750 obtained in the production of Example 1. ) 20 parts by mass and 30 parts by mass of dicyclopentenyloxyethyl methacrylate (C) were added and dissolved, and then cooled to room temperature to obtain a curable resin composition. The resin composition was poured into a mold and cured at 25 ° C. for 72 hours to obtain a cured resin product having a thickness of 3 mm. About this curable resin composition, the casting and the laminated board were created by the method as described in Example 1, and the characteristic value was measured. The results are shown in Table 1.

  Further, EPMA, Barcol hardness and wear amount were measured by the methods described above. The results are shown in Table 1.

Furthermore, the concrete adhesion strength and concrete peeling strength of this resin composition to which 6% cobalt naphthenate, dimethylaniline and Percure K are added as shown in Table 1 are high. After 60 days of immersing the test piece on which the protective material was laminated on the entire surface in 80 ° C. warm water, there was no abnormality between the primer layer, the base material adjusting material layer, and the surface protective layer. Moreover, the warm water (80 degreeC) immersion water absorption showed the low value around 1%.
[Reference Example 3]

  Ethylene oxide 6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Kyoeisha Chemical Co., Ltd.) was added to 50 parts by mass of the aromatic epoxy methacrylate (A) having a number average molecular weight of 750 and an acid value of 10 mgKOH / g obtained in the production of Example 1. BP-6EM) 20 parts by mass and dicyclopentenyloxyethyl methacrylate (C) 30 parts by mass were added and dissolved, and then cooled to room temperature to obtain a curable resin composition. The resin composition was poured into a mold and cured at 25 ° C. for 72 hours to obtain a cured resin (cast material) having a thickness of 3 mm. Characteristic values of the cured resin were measured by the method described in Example 1. The results are shown in Table 1.

  Resin concrete (concrete coating composition) is added to 100 parts by weight of the resin composition, and 1.0 parts by weight of 6% cobalt naphthenate, 0.5 parts by weight of dimethylaniline, and 2.0 parts by weight of Percure K are added and mixed. Subsequently, 450 parts by mass of an inorganic aggregate material (mixed silica sand having the composition shown in Table 1) was added to obtain a composition.

  With respect to this blend, a specimen for measuring compressive strength and bending strength was prepared by pouring the blend into a 40 × 40 × 160 mm mold. The tensile strength was cast into a 2.5 cmφ rod-shaped mold.

The concrete adhesion strength was tested according to JIS-A-6916 with a Kenken type tensile tester, and the adhesive strength was measured. The concrete peeling test was performed by applying a coating amount of 150 g / m ² on a JIS-A-5304 standard sidewalk board (size: 300 mm × 300 mm) using the resin composition of Example 3 as a primer, drying the touch, and then glass flake RCF. -140 (Nippon Sheet Glass Co., Ltd.) 30 parts by mass, Crystallite AA (manufactured by Tatsumori quartzite powder) 20 parts by mass, 6% cobalt naphthenate, 1.0 part by mass, Percure K 2.0 parts by mass 1 g / m ^{2 was} applied as a surface protective layer by applying 700 g / m ^{2 of the above} composition as a substrate conditioner, drying the touch and then adding 100 fl parts of the resin composition of Example 3 with glass flake RCF-140. The anticorrosion coating layer was formed by applying m ² (thickness 0.6 mm). After curing at 25 ° C. for 72 hours, the inside of the FRP plate of width × length × thickness = 20 mm × 90 mm × 2 mm is bonded with an epoxy adhesive leaving 20 mm unbonded at one end in the length direction. In addition, a 2mm hole is opened at the center of the unbonded part, and a hook at the tip of the spring balance is inserted into this hole, and 90 degree peeling is performed in accordance with the vulcanized rubber adhesion test method of JIS-K-6256. It was measured. The weight change rate was 10 g after thoroughly mixing the resin composition of the blending ratio of Example 3, poured into a glass petri dish of φ40 mm (height, 15 mm), cured at 25 ° C. for 72 hours, and then demolded. After the mold was immersed in warm water (80 ° C.) for 96 hours, the weight change rate was measured.

Further, EPMA, Barcol hardness and wear amount were measured by the above-described methods.
[Reference Example 4]

  Ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (50 parts by mass of aromatic epoxy methacrylate (A) having a number average molecular weight of about 750 and an acid value of 10 mgKOH / g or less obtained in the production of Example 1 ( B) 20 parts by mass (BPE-100 manufactured by Shin-Nakamura Chemical Co., Ltd.) and 30 parts by mass of dicyclopentenyloxyethyl methacrylate (C) were added and dissolved, and then cooled to room temperature to obtain a curable resin composition. . To 100 parts by mass of the resin composition, 1.0% by mass of 6% cobalt naphthenate and 2.0 parts by mass of Percure K were added to obtain a blend.

  The blend was poured into a mold, cured at 25 ° C. for 72 hours, and demolded to obtain a cured resin product (cast material) having a thickness of 3 mm. Characteristic values of the cured resin were measured by the method described in Example 1. The results are shown in Table 1.

  A glass flake-containing resin composition (lining material) was prepared as described in the formulation column of Example 4 in Table 1. That is, the composition of the resin composition containing glass flakes was first added to 100 parts by mass of the resin composition, 1.0 parts by mass of 6% cobalt naphthenate, 0.5 parts by mass of dimethylaniline, and 2.0 parts by mass of Percure K. Next, 40 parts by mass of glass flake RCF-140 (manufactured by Nippon Sheet Glass Co., Ltd.) was added to obtain a blend. With respect to this blend, a specimen for measuring compressive strength and bending strength was prepared by pouring the blend into a 40 × 40 × 160 mm mold. The tensile strength was cast into a 2.5 cmφ rod-shaped mold.

The concrete adhesion strength was tested according to JIS-A-6916 with a Kenken type tensile tester, and the adhesive strength was measured. The concrete peeling test was conducted by applying a coating amount of 150 g / m ² on a JIS-A-5304 standard sidewalk board (size: 300 mm × 300 mm) using the resin composition of Example 4 as a primer, drying the touch, and then glass flake RCF. -140 parts (manufactured by Nippon Sheet Glass Co., Ltd.), 20 parts by mass of Crystallite AA (manufactured by Tatsumori quartzite powder), 1.0 part by mass of 6% cobalt naphthenate and 2.0 parts by mass of Percure K 700 g / m ^{2 was} applied as a substrate conditioner, and after touch drying, 100 kg by weight of the resin composition of Example 4 was added with glass flake RCF-140 as a surface protective layer at 1 kg / m. ^Two coatings (thickness 0.6 mm) were applied to form an anticorrosion coating layer. After curing at 25 ° C. for 72 hours, the inside of the FRP plate of width × length × thickness = 20 mm × 90 mm × 2 mm was bonded with an epoxy adhesive leaving 20 mm unbonded at one end in the length direction. . In addition, a 2mm hole is opened at the center of the unbonded part, and a hook at the tip of the spring balance is inserted into this hole, and 90 degree peeling is performed in accordance with the vulcanized rubber adhesion test method of JIS-K-6256. It was measured. The rate of weight change was 10 g after thoroughly mixing the resin composition of the blending ratio of Example 4, poured into a glass petri dish of φ40 mm (height, 15 mm), cured at 25 ° C. for 72 hours, and then demolded. After the mold was immersed in warm water (80 ° C.) for 96 hours, the weight change rate was measured.

Further, EPMA, Barcol hardness and wear amount were measured by the above-described methods.
100 parts by mass of this resin composition is heated to 70 ° C., and 0.6 parts by mass of 135 ° F paraffin wax is dissolved. Then, 6% cobalt naphthenate, dimethylaniline and Percure K shown in Table 1 are added and blended. Got. About this formulation, the item similar to Example 1 and surface dryness were measured.

[Comparative Example 1]
Manufactured in the same manner as in Example 1, and 2.6 mol of the ethylene oxide of Example 1 was added to 20 parts by mass of an aromatic epoxy (meth) acrylate (A) having a number average molecular weight of 750 obtained with an acid value of 17 KOH mg / g. 50 parts by mass of ethoxylated bisphenol A dimethacrylate (B) and 30 parts by mass of dicyclopentenyloxyethyl methacrylate (C) were added and dissolved, and then cooled to room temperature to obtain a resin composition. A blend obtained by adding 6% cobalt naphthenate, dimethylaniline and Percure K shown in Table 1 to this resin composition was uncured after 24 hours at 25 ° C.

[Comparative Example 2]
The ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) 20 mass of Example 1 to 70 mass parts of aromatic epoxy (meth) acrylate (A) of the number average molecular weight 750 obtained by manufacture of the comparative example 1 And 10 parts by mass of dicyclopentenyloxyethyl methacrylate (C) were added and dissolved, and then cooled to room temperature to obtain a resin composition. A blend obtained by adding 6% cobalt naphthenate, dimethylaniline and Percure K shown in Table 1 to this resin composition was uncured after 24 hours at 25 ° C.

[Comparative Example 3]
50 parts by mass of the phenoxyethyl methacrylate (C) of Example 1 was added to 50 parts by mass of the aromatic epoxy methacrylate (A) obtained in the production of Comparative Example 1 and dissolved, and then cooled to room temperature to obtain a resin composition. It was.

  A blend obtained by adding 6% cobalt naphthenate, dimethylaniline and Percure K shown in Table 1 to this resin composition was uncured after 24 hours at 25 ° C.

[Comparative Example 4]
[Curable resin composition using aromatic epoxy methacrylate (A) having a number average molecular weight of 1,300 and dicyclopentenyloxyethyl methacrylate (C)]
[Production of aromatic epoxy methacrylate (A) having a number average molecular weight of about 1,300]
In a 2-liter four-necked flask equipped with a stirrer, condenser, thermometer, and air introduction tube, 93 g of jER828 (Mitsubishi Chemical), 180 g of jER1002 (manufactured by Mitsubishi Chemical) and 990 g of jER1004 (manufactured by Mitsubishi Chemical) The temperature was raised to 130 ° C. while blowing 10 liters of dry air per minute while charging and stirring. After the temperature increase, 0.3 g of hydroquinone (polymerization inhibitor) and 2 g of trimethylbenzylammonium chloride were added, and 172 g of methacrylic acid was added dropwise over 2 hours. After 3 hours from the end of dropping, measurement of the acid value was started every hour, and after confirming that the acid value reached 18 KOHmg / g, the mixture was cooled to 100 ° C. and an aromatic having a number average molecular weight of about 1,300 A product of an epoxy methacrylate was obtained. To 50 parts by mass of the product, 50 parts by mass of dicyclopentenyloxyethyl methacrylate (C) (FA-512MT manufactured by Hitachi Chemical Co., Ltd.) was added and dissolved, and then cooled to room temperature to obtain a curable resin composition. .

  About this curable resin composition, the casting and the laminated board were created by the method of Example 1, and the characteristic value was measured. The results are shown in Table 1.

Further, EPMA, Barcol hardness and wear amount were measured by the methods described above. The results are shown in Table 1.
Furthermore, the concrete adhesion strength and concrete peeling strength of this resin composition to which 6% cobalt naphthenate, dimethylaniline and Percure K are added as shown in Table 1 are low. After 25 days on the entire surface of the specimen laminated with the protective material immersed in 80 ° C. warm water, countless bulges and peeling occurred between the primer layer, the base material adjusting material layer, and the surface protective layer. Moreover, warm water (80 degreeC) immersion water absorption is as high as about 3 times of the resin composition of this invention.

[Comparative Example 5]
Ethylene oxide 30 mol addition ethoxylated bisphenol A dimethacrylate (Shin Nakamura Chemical Co., Ltd. NK light ester) to 50 parts by mass of 1,300 aromatic epoxy methacrylate (A) obtained in the production of Comparative Example 4 BPE-1300) (B) 20 parts by mass and dicyclopentenyloxyethyl methacrylate (C) 30 parts by mass were added and dissolved, and then cooled to room temperature to obtain a resin composition. The composition obtained by adding 6% cobalt naphthenate, dimethylaniline and Percure K shown in Table 1 to this resin composition has a long surface drying time, and the concrete adhesion strength and the peeling strength with concrete are extreme after immersion in normal temperature water and warm water. Declined. In addition, a specimen in which a primer, a substrate conditioner, and a surface protective material are laminated on concrete is immersed in warm water at 80 ° C for 7 days, and then minute swelling or peeling occurs between the primer layer, the substrate conditioner layer, and the surface protective layer. There were countless occurrences. Moreover, the warm water (80 degreeC) immersion weight change rate is as high as about 3 times of the Example of the resin composition of this invention.

  About this curable resin composition, the casting and the laminated board were created by the method of Example 1, and the characteristic value was measured. The results are shown in Table 1. Further, EPMA, Barcol hardness and wear amount were measured by the methods described above. The results are shown in Table 1.

[Comparative Example 6]
Concrete of a composition obtained by adding 6% cobalt naphthenate and methyl ethyl ketone peroxide (Permec NS manufactured by Nippon Oil & Fats Co., Ltd.) in Table 1 to 100 parts by mass of styrene type vinyl ester resin (Lipoxy R804 manufactured by Showa Denko KK). Table 1 shows the measurement results such as adhesion strength, peeling strength with concrete, and styrene volatilization amount. The amount of styrene volatilized is as high as 80 g / m ² .

  According to the method described in Example 1, a composition in which 6% cobalt naphthenate and methyl ethyl ketone peroxide (Permec NS manufactured by Nippon Oil & Fats Co., Ltd.) in Table 1 were added to 100 parts by mass of the above styrene type vinyl ester resin. Cast articles and laminates were prepared and the characteristic values were measured. The results are shown in Table 1.

  Further, EPMA, Barcol hardness and wear amount were measured by the methods described above. The results are shown in Table 1.

[Comparative Example 7]
Ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Shin Nakamura Chemical Co., Ltd.) was added to 55 parts by mass of the aromatic epoxy methacrylate (A) having a number average molecular weight of 1,300 obtained in the production of Comparative Example 4. ) BPE-100) 20 parts by mass and 25 parts by mass of dicyclopentenyloxyethyl methacrylate (C) were added and dissolved, and then cooled to room temperature to obtain a resin composition.

  The resin composition was poured into a mold and cured at 25 ° C. for 72 hours to obtain a cured resin (cast material) having a thickness of 3 mm. Characteristic values of the cured resin were measured by the method described in Example 1. The results are shown in Table 1.

  Resin concrete (concrete coating composition) is prepared by dissolving 2.0 parts by mass of 20% (FA512-MT) wax in 100 parts by mass of the resin composition, and then first 1.0 parts by mass of 6% cobalt naphthenate and dimethylaniline. 0.5 parts by mass and 2.0 parts by mass of Percure K were added and mixed, and then 450 parts by mass of an inorganic aggregate material (mixed silica sand having the composition shown in Table 1) was added to obtain a blend.

  With respect to this blend, a specimen for measuring compressive strength and bending strength was prepared by pouring the blend into a 40 × 40 × 160 mm mold. The tensile strength was cast into a 2.5 cmφ rod-shaped mold.

The concrete adhesion strength was tested according to JIS-A-6916 with a Kenken type tensile tester, and the adhesive strength was measured. The concrete peeling test was performed on a JIS-A-5304 standard sidewalk board (size: 300 mm × 300 mm), using the resin composition of Comparative Example 7 as a primer, an application amount of 150 g / m ^2, and after drying with the finger, Glass flake RCF-140 (manufactured by Nippon Sheet Glass Co., Ltd.) 30 parts by mass, crystallite AA (manufactured by Tatsumori quartzite powder) 20 parts by mass, 6% cobalt naphthenate, 1.0 part by mass Then, a mixture of 2.0 parts by mass of benzoyl peroxide was applied as a base material adjusting material at 700 g / m ^2, and after dry to the touch, a glass flake RCF-140 was added to 100 parts by weight of the resin composition of Comparative Example 7. As a surface protective layer, 1 kg / m ^{2 was} applied (thickness 0.6 mm) to form an anticorrosion coating layer. After curing at 25 ° C. for 72 hours, the inside of the FRP plate of width × length × thickness = 20 mm × 90 mm × 2 mm is bonded with an epoxy adhesive leaving 20 mm unbonded at one end in the length direction. In addition, a 2mm hole is opened at the center of the unbonded part, and a hook at the tip of the spring balance is inserted into this hole, and 90 degree peeling is performed in accordance with the vulcanized rubber adhesion test method of JIS-K-6256. It was measured. The rate of change in weight was 10 g after thoroughly mixing the resin composition having the blending ratio of Comparative Example 7, poured into a glass petri dish having a diameter of 40 mm (height, 15 mm), cured at 25 ° C. for 72 hours, and then demolded. After the mold was immersed in warm water (80 ° C.) for 96 hours, the weight change rate was measured.

Further, EPMA, Barcol hardness and wear amount were measured by the above-described methods.
After heating 100 parts by mass of this resin composition to 70 ° C. and dissolving 2.0 parts by mass of 20% 120 degrees F / (FA-512MT) paraffin wax, 6% cobalt naphthenate and dimethylaniline in Table 1 were dissolved. And Percure K was added to obtain a formulation. About this formulation, the item similar to Example 1 and surface dryness were measured.

[Comparative Example 8]
Ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Shin Nakamura Chemical Co., Ltd.) was added to 55 parts by mass of the aromatic epoxy methacrylate (A) having a number average molecular weight of 1,300 obtained in the production of Comparative Example 4. BPE-100) 20 parts by mass and 25 parts by mass of dicyclopentenyloxyethyl methacrylate (C) were added and dissolved, and then cooled to room temperature to obtain a resin composition. This resin composition was poured into a mold and cured at 25 ° C. for 72 hours to obtain a cured resin (cast material) having a thickness of 3 mm. Characteristic values of the cured resin were measured by the method described in Example 1. The results are shown in Table 1.

  The resin composition containing glass flakes was prepared as described in the resin concrete blending column of Comparative Example 8 in Table 1. That is, the resin composition containing glass flakes was prepared by dissolving 20 parts by mass of 20% 120 degrees F / (FA-512MT) paraffin wax in 100 parts by mass of the resin composition, and then adding 6% cobalt naphthenate 1 0.0 parts by mass, 0.5 parts by mass of dimethylaniline, and 2.0 parts by mass of Percure K were added and mixed, and then 40 parts by mass of glass flake RCF-140 (manufactured by Nippon Sheet Glass Co., Ltd.) was added to obtain a blend. .

  With respect to this blend, a specimen for measuring compressive strength and bending strength was prepared by pouring the blend into a 40 × 40 × 160 mm mold. The tensile strength was cast into a 2.5 cmφ rod-shaped mold.

The concrete adhesion strength was tested according to JIS-A-6916 with a Kenken type tensile tester, and the adhesive strength was measured. The concrete peeling test was carried out by applying a coating amount of 150 g / m ² on a JIS-A-5304 standard sidewalk board (size: 300 mm × 300 mm) using the resin composition of Comparative Example 8 as a primer, drying the touch, and then glass flake RCF. -140 (Nippon Sheet Glass Co., Ltd.) 30 parts by mass, Crystallite AA (Tatsumori silica stone powder) 20 parts by mass, 6% cobalt naphthenate, 1.0 part by mass, Percure K 2.0 parts by mass 700 g / m ^{2 was} applied as a substrate conditioner, and after drying with the touch, 100 kg by weight of the resin composition of Comparative Example 8 was added with glass flake RCF-140 as a surface protective layer at 1 kg / m. ² Apply (thickness 0.6 mm) to complete the anticorrosion coating layer. After curing at 25 ° C. for 72 hours, the inside of the FRP plate of width × length × thickness = 20 mm × 90 mm × 2 mm was bonded with an epoxy adhesive leaving 20 mm unbonded at one end in the length direction. . In addition, a 2mm hole is opened at the center of the unbonded part, and a hook at the tip of the spring balance is inserted into this hole, and 90 degree peeling is performed in accordance with the vulcanized rubber adhesion test method of JIS-K-6256. It was measured. The weight change rate was 10 g after thoroughly mixing the resin composition having the blending ratio of Comparative Example 8, poured into a glass petri dish with a diameter of 40 mm (height, 15 mm), cured at 25 ° C. for 72 hours, and then demolded. After the mold was immersed in warm water (80 ° C.) for 96 hours, the weight change rate was measured. Further, EPMA, Barcol hardness and wear amount were measured by the above-described methods.

  After heating 100 parts by mass of this resin composition to 70 ° C. and dissolving 2.0 parts by mass of 20% 120 degrees F / (FA-512MT) paraffin wax, 6% cobalt naphthenate and dimethylaniline in Table 1 were dissolved. And Percure K was added to obtain a formulation. About this formulation, the item similar to Example 1 and surface dryness were measured.

Ethylene oxide 4.0 mol addition ethoxylated bisphenol A dimethacrylate (B) (Shin-Nakamura Chemical Co., Ltd.) was added to 40 parts by mass of the aromatic epoxy methacrylate (A) having a number average molecular weight of 750 obtained in the production of Example 1. BPE-200) 15 parts by mass, 25 parts by mass of dicyclopentenyloxyethyl methacrylate (C) and 20 parts by mass of phenoxyethyl methacrylate (D) were added and dissolved, and 100 parts by mass of the resin composition was subjected to photopolymerization. Initiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BASF's Lucillin TPO) 1.5 parts by mass was thoroughly stirred and mixed, then dissolved, cooled to room temperature, and then average particle size 1.9 μm, Polymethylmethacrylate resin powder having a weight average degree of polymerization of 30,000 (Zeffire manufactured by Ganz Kasei Co., Ltd.) F320) 30 parts by mass were added heating to 80 ° C., dissolved to obtain a resin composition. First, a 0.2 mm thick polyurethane elastomer film 790M60K (manufactured by Nippon Valqua Industries, Ltd.) is laid on this photocurable resin composition for prepreg, and a chop strand mat (REM450-) having a unit weight of 450 g / m ² is placed thereon. G5; made by Nippon Sheet Glass Co., Ltd.) and impregnated with the resin mixture, and coated with a polyurethane elastomer film of 790M60K (made by Nippon Valqua Industries Co., Ltd.) having the same thickness as the first 0.2 mm. Then, ultraviolet irradiation (metal halide lamp: Ga-based, 240 W, irradiation intensity 80 mW / cm ² ) was performed for 3 minutes, and the physical properties of the laminate are shown in Table 2.

[Comparative Example 9]
Ethylene oxide 30 mol addition ethoxylated bisphenol A dimethacrylate (B) (manufactured by Shin-Nakamura Chemical Co., Ltd.) was added to 40 parts by mass of the aromatic epoxy methacrylate (A) having a number average molecular weight of 1300 obtained in the production of Comparative Example 4. NK light ester BPE-1300) 15 parts by mass, 10 parts by mass of dicyclopentenyloxyethyl methacrylate (C) and 35 parts by mass of phenoxyethyl methacrylate (D) were added and dissolved, and then 100 parts by mass of light was added to 100 parts by mass of the resin composition. The polymerization initiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BASF's Lucillin TPO) 1.5 parts by mass is well stirred and mixed, dissolved, cooled to room temperature, and then average particle size 1.9 μm. , Polymethyl methacrylate resin powder having a weight average polymerization degree of 30,000 (Gantz Kasei) Ltd.), Zefaiakku F320) 30 parts by mass were added heating to 80 ° C., dissolved to obtain a resin composition.

First, a 0.2 mm thick polyurethane elastomer film 790M60K (manufactured by Nippon Valqua Industries, Ltd.) is laid on this photocurable resin composition for prepreg, and a chop strand mat (REM450-) having a unit weight of 450 g / m ² is placed thereon. G5; made by Nippon Sheet Glass Co., Ltd.) and impregnated with the resin mixture, and coated with a polyurethane elastomer film of 790M60K (made by Nippon Valqua Industries Co., Ltd.) having the same thickness as the first 0.2 mm. Then, ultraviolet irradiation (metal halide lamp: Ga-based, 240 W, irradiation intensity 80 mW / cm ² ) was performed for 3 minutes, and the physical properties of the laminate are shown in Table 2.

  As shown in Table 2, in Comparative Example 9, the surface whitening occurrence and sulfur penetration depth in the concrete-coated hot water immersion was as large as 50 μm in Example 5 compared to 2 μm or less, and there was a problem as long-term life. Moreover, the hot water immersion water absorption was slightly more than three times that of Example 5.

  Into 45 parts by mass of the aromatic epoxy methacrylate (A) having a number average molecular weight of 750 and an acid value of 10 KOH mg / g obtained in the production of Example 1, 2.6 mol of ethylene oxide addition ethoxylated bisphenol A dimethacrylate (B) (new) Nakamura Chemical Co., Ltd. BPE-100) 15 parts by mass, dicyclopentenyloxyethyl methacrylate (C) (Hitachi Chemical Industry Co., Ltd. Funkuru FA-512MT) 30 parts by mass, phenoxyethyl methacrylate (D) ( 10 mass parts of Kyoeisha Chemical Co., Ltd. light ester PO) was added and melt | dissolved, it cooled to room temperature, and the curable resin composition was obtained.

  This was mixed well in the proportion of Example 6 in Table 3 to obtain a curable resin composition. About this curable resin composition, the casting and the laminated board were created by the method of Example 1, and the characteristic value was measured. The results are shown in Table 3.

  Table 3 shows the results of EPMA, Barcol hardness and wear measured by the methods described above.

  Moreover, the concrete adhesion strength and concrete peeling strength of this resin composition to which 6% cobalt naphthenate, dimethylaniline and Percure K shown in Table 3 are added are high. After 60 days of immersing the test piece on which the protective material was laminated on the entire surface in 80 ° C. warm water, there was no abnormality between the primer layer, the base material adjusting material layer, and the surface protective layer. Moreover, the warm water (80 degreeC) immersion water absorption showed the low value around 1%.

  To 45 parts by mass of the aromatic epoxy methacrylate (A) having a number average molecular weight of 750 and an acid value of 10 KOHmg / g obtained in the production of Example 1, 6.0 mol of ethylene oxide added ethoxylated bisphenol A dimethacrylate (B) (new 15 parts by mass of BPE-100 manufactured by Nakamura Chemical Co., Ltd., 30 parts by mass of dicyclopentenyloxyethyl methacrylate (C) (Funkle FA-512MT manufactured by Hitachi Chemical Co., Ltd.), and phenoxyethyl methacrylate (D) ( 10 mass parts of Kyoeisha Chemical Co., Ltd. light ester PO) was added and melt | dissolved, it cooled to room temperature, and the curable resin composition was obtained.

  This was mixed well in the proportion of Example 7 in Table 3, and then a curable resin composition was obtained. About this curable resin composition, the casting and the laminated board were created by the method of Example 1, and the characteristic value was measured. The results are shown in Table 3.

  Further, EPMA, Barcol hardness and wear amount were measured by the methods described above. The results are shown in Table 3.

  To 45 parts by mass of the aromatic epoxy methacrylate (A) having a number average molecular weight of 750 and an acid value of 10 KOHmg / g obtained in the production of Example 1, 6.0 mol of ethylene oxide added ethoxylated bisphenol A dimethacrylate (B) (Kyoeisha) BP-6EM manufactured by Kagaku Co., Ltd., 15 parts by mass, 30 parts by mass of dicyclopentenyloxyethyl methacrylate (C), and 10 parts by mass of phenoxyethyl methacrylate (D) were added and dissolved, and then cooled to room temperature. A composition was obtained. The resin composition was poured into a mold and cured at 25 ° C. for 72 hours to obtain a cured resin (cast material) having a thickness of 3 mm. Characteristic values of the cured resin were measured by the method described in Example 1. The results are shown in Table 3.

  Resin concrete (concrete coating composition) is added to 100 parts by weight of the resin composition, and 1.0 parts by weight of 6% cobalt naphthenate, 0.5 parts by weight of dimethylaniline, and 2.0 parts by weight of Percure K are added and mixed. Subsequently, 450 parts by mass of an inorganic aggregate material (mixed silica sand having the composition shown in Table 1) was added to obtain a composition.

  With respect to this blend, a specimen for measuring compressive strength and bending strength was prepared by pouring the blend into a 40 × 40 × 160 mm mold. The tensile strength was cast into a 2.5 cmφ rod-shaped mold.

The concrete adhesion strength was tested according to JIS-A-6916 with a Kenken type tensile tester, and the adhesive strength was measured. The concrete peeling test was carried out by applying a coating amount of 150 g / m ² to a JIS A 5304 standard sidewalk board (size: 300 mm × 300 mm) using the resin composition of Example 8 as a primer, drying the touch, and then glass flake RCF-140 (Japan). A composition of 6% cobalt naphthenate, 1.0 part by mass, and Percure K 2.0 parts by mass is added to 30 parts by mass of Sheet Glass Co., Ltd. and 20 parts by mass of Crystallite AA (silica stone powder of Tatsumori Co., Ltd.). Applying 700 g / m ² as a conditioning material, drying the touch, and then applying 1 kg / m ² (thickness) as a surface protective layer with a composition obtained by adding glass flake RCF-140 to 100 parts by weight of the resin composition of Example 8 0.6 mm) to form an anticorrosion coating layer. After curing at 25 ° C. for 72 hours, the inside of the FRP plate of width × length × thickness = 20 mm × 90 mm × 2 mm is bonded with an epoxy adhesive leaving 20 mm unbonded at one end in the length direction. In addition, a 2mm hole is opened at the center of the unbonded part, and a hook at the tip of the spring balance is inserted into this hole, and 90 degree peeling is performed in accordance with the vulcanized rubber adhesion test method of JIS-K-6256. It was measured. The weight change rate was 10 g after thoroughly mixing the resin composition having the blending ratio of Example 8, poured into a glass petri dish of φ40 mm (height, 15 mm), cured at 25 ° C. for 72 hours, and then demolded. After the mold was immersed in warm water (80 ° C.) for 96 hours, the weight change rate was measured. Further, EPMA, Barcol hardness and wear amount were measured by the above-described methods.

  To 40 parts by mass of an aromatic epoxy methacrylate (A) having a number average molecular weight of about 750 and an acid value of 10 KOH mg / g or less obtained in the production of Example 1, ethylene oxide 6.0 mol addition ethoxylated bisphenol A dimethacrylate ( B) (Shin-Nakamura Chemical Co., Ltd. BPE-100) 15 parts by mass, dicyclopentenyloxyethyl methacrylate (C) 25 parts by mass and phenoxyethyl methacrylate (D) 20 parts by mass were dissolved and cooled to room temperature. Then, a curable resin composition was obtained. To 100 parts by mass of the resin composition, 1.0% by mass of 6% cobalt naphthenate and 2.0 parts by mass of Percure K were added to obtain a blend. This blend was poured into a mold, cured at 25 ° C. for 72 hours, and demolded to obtain a cured resin (cast material) having a thickness of 3 mm. Characteristic values of the cured resin were measured by the method described in Example 1. The results are shown in Table 1.

  The resin composition containing glass flakes was prepared as described in the formulation column of Example 9 in Table 3. That is, the composition of the resin composition containing glass flakes was first added to 100 parts by mass of the resin composition, 1.0 parts by mass of 6% cobalt naphthenate, 0.5 parts by mass of dimethylaniline, and 2.0 parts by mass of Percure K. Next, 40 parts by mass of glass flake RCF-140 (manufactured by Nippon Sheet Glass Co., Ltd.) was added to obtain a blend.

With respect to this blend, a specimen for measuring compressive strength and bending strength was prepared by pouring the blend into a 40 × 40 × 160 mm mold. The tensile strength was cast into a 2.5 cmφ rod-shaped mold. The concrete adhesion strength was tested according to JIS-A-6916 with a Kenken type tensile tester, and the adhesive strength was measured. The concrete peeling test was performed on a JIS-A-5304 standard sidewalk board (size: 300 mm × 300 mm), using the resin composition of Example 9 as a primer, applying a coating amount of 150 g / m ² , drying the touch, and then glass flake RCF. -140 (Nippon Sheet Glass Co., Ltd.) 30 parts by mass, Crystallite AA (Tatsumori silica stone powder) 20 parts by mass, 6% cobalt naphthenate, 1.0 part by mass, Percure K 2.0 parts by mass 700 g / m ^{2 was} applied as a substrate conditioner, and after touch drying, a composition obtained by adding glass flake RCF-140 to 100 parts by weight of the resin composition of Example 9 as a surface protective layer was 1 kg / m. ² Apply (thickness 0.6 mm) to complete the anticorrosion coating layer. After curing at 25 ° C. for 72 hours, the inside of the FRP plate of width × length × thickness = 20 mm × 90 mm × 2 mm was bonded with an epoxy adhesive leaving 20 mm unbonded at one end in the length direction. . In addition, a 2mm hole is opened at the center of the unbonded part, and a hook at the tip of the spring balance is inserted into this hole, and 90 degree peeling is performed in accordance with the vulcanized rubber adhesion test method of JIS-K-6256. It was measured. The weight change rate was 10 g after thoroughly mixing the resin composition having the blending ratio of Example 9 and poured into a glass petri dish having a diameter of 40 mm (height, 15 mm), cured at 25 ° C. for 72 hours, and then demolded. After the mold was immersed in warm water (80 ° C.) for 96 hours, the weight change rate was measured. Further, EPMA, Barcol hardness and wear amount were measured by the above-described methods.

  After heating 100 parts by weight of this resin composition to 70 ° C. and dissolving 0.6 parts by weight of 20% concentration 120 ° F./(FA-512MT) paraffin wax, 6% cobalt naphthenate and dimethyl in Table 3 were used. Aniline and Percure K were added to obtain a formulation. About this formulation, the item similar to Example 1 and surface dryness were measured.

[Comparative Example 10]
The number average molecular weight obtained in the production of Comparative Example 4 is about 1,300, the acid value is 18 KOH mg / g or less, 25 parts by mass of an aromatic epoxy methacrylate (A), 6.0 mol of ethylene oxide addition ethoxylated bisphenol A di After dissolving 40 parts by weight of methacrylate (B) (BPE-100, manufactured by Shin-Nakamura Chemical Co., Ltd.), 32 parts by weight of dicyclopentenyloxyethyl methacrylate (C) and 3 parts by weight of phenoxyethyl methacrylate (D), It cooled to room temperature and obtained curable resin composition. To 100 parts by mass of the resin composition, 1.0% by mass of 6% cobalt naphthenate and 2.0 parts by mass of Percure K were added to obtain a blend. This blend was poured into a mold, cured at 25 ° C. for 72 hours, and demolded to obtain a cured resin (cast material) having a thickness of 3 mm. Characteristic values of the cured resin were measured by the method described in Example 1. The results are shown in Table 3.

The concrete adhesion strength was tested according to JIS-A-6916 with a Kenken type tensile tester, and the adhesive strength was measured. The concrete peeling test was carried out by applying a coating amount of 150 g / m ² to a JIS-A-5304 standard sidewalk board (size: 300 mm × 300 mm) using the resin composition of Comparative Example 10 as a primer, drying the touch, and then glass flake RCF. -140 (Nippon Sheet Glass Co., Ltd.) 30 parts by mass, Crystallite AA (Tatsumori silica stone powder) 20 parts by mass, 6% cobalt naphthenate, 1.0 part by mass, Percure K 2.0 parts by mass 700 g / m ^{2 was} applied as a substrate conditioner, and after drying by touch, 1 kg / m as a surface protective layer was obtained by adding glass flake RCF-140 to 100 parts by weight of the resin composition of Comparative Example 10 ^Two coatings (thickness 0.6 mm) were applied to form an anticorrosion coating layer. After curing at 25 ° C. for 72 hours, the inside of the FRP plate of width × length × thickness = 20 mm × 90 mm × 2 mm is bonded with an epoxy adhesive leaving 20 mm unbonded at one end in the length direction. In addition, a 2mm hole is opened at the center of the unbonded part, and a hook at the tip of the spring balance is inserted into this hole, and 90 degree peeling is performed in accordance with the vulcanized rubber adhesion test method of JIS-K-6256. It was measured. The rate of weight change was 10 g after thoroughly mixing the resin composition having the blending ratio of Comparative Example 10, poured into a glass petri dish of φ40 mm (height, 15 mm), cured at 25 ° C. for 72 hours, and then demolded. After the mold was immersed in warm water (80 ° C.) for 96 hours, the weight change rate was measured.

  Further, EPMA, Barcol hardness and wear amount were measured by the above-described methods.

[Comparative Example 11]
After adding 50 parts by mass of phenoxyethyl methacrylate (D) to 50 parts by mass of the aromatic epoxy (meth) acrylate (A) having a number average molecular weight of 750 obtained in the production of Comparative Example 1, the mixture was cooled to room temperature, A composition was obtained. A blend obtained by adding 6% cobalt naphthenate, dimethylaniline and Percure K shown in Table 1 to this resin composition was uncured after 24 hours at 25 ° C.

[Comparative Example 12]
Ethoxy oxide 30 mol addition ethoxylated bisphenol A dimethacrylate (NK light ester made by Shin-Nakamura Chemical Co., Ltd.) to 40 parts by mass of aromatic epoxy methacrylate (A) having a number average molecular weight of 1,300 obtained in the production of Comparative Example 4 BPE-1300) (B) 20 parts by mass and dicyclopentenyloxyethyl methacrylate (C) 40 parts by mass were added and dissolved, and then cooled to room temperature to obtain a resin composition. The composition obtained by adding 6% cobalt naphthenate, dimethylaniline and Percure K shown in Table 3 to this resin composition has a long surface drying time, and the concrete adhesion strength and the peeling strength with concrete are extreme after immersion in normal temperature water and warm water. Declined. In addition, a specimen in which a primer, a substrate conditioner, and a surface protective material are laminated on concrete is immersed in warm water at 80 ° C for 7 days, and then minute swelling or peeling occurs between the primer layer, the substrate conditioner layer, and the surface protective layer. There were countless occurrences. Moreover, the warm water (80 degreeC) immersion weight change rate is as high as about 3 times of the Example of the resin composition of this invention.

  About this curable resin composition, the casting and the laminated board were created by the method of Example 1, and the characteristic value was measured. The results are shown in Table 3. Further, EPMA, Barcol hardness and wear amount were measured by the methods described above. The results are shown in Table 3.

[Comparative Example 13]
Ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (40 parts by mass of aromatic epoxy methacrylate (A) having a number average molecular weight of about 750 and an acid value of 17 KOHmg / g or less obtained in the production of Comparative Example 1 ( B) 15 parts by mass (BPE-100 manufactured by Shin-Nakamura Chemical Co., Ltd.) and 45 parts by mass of dicyclopentenyloxyethyl methacrylate (C) were added and dissolved, and then cooled to room temperature to obtain a curable resin composition. . To 100 parts by mass of the resin composition, 1.0% by mass of 6% cobalt naphthenate and 2.0 parts by mass of Percure K were added to obtain a blend. This blend was poured into a mold, cured at 25 ° C. for 72 hours, and demolded to obtain a cured resin (cast material) having a thickness of 3 mm. Characteristic values of the cured resin were measured by the method described in Example 1. The results are shown in Table 3.

  The resin composition containing glass flakes was prepared as described in the formulation column of Comparative Example 13 in Table 3. The resin composition containing glass flakes was prepared by adding and mixing 100 parts by mass of the resin composition with 1.0 part by mass of 6% cobalt naphthenate, 0.5 parts by mass of dimethylaniline, and 2.0 parts by mass of Percure K. Subsequently, 40 parts by mass of glass flake RCF-140 (manufactured by Nippon Sheet Glass Co., Ltd.) was added to obtain a blend.

With respect to this blend, a specimen for measuring compressive strength and bending strength was prepared by pouring the blend into a 40 × 40 × 160 mm mold. The tensile strength was cast into a 2.5 cmφ rod-shaped mold. The concrete adhesion strength was tested according to JIS-A-6916 with a Kenken type tensile tester, and the adhesive strength was measured. The concrete peeling test was performed by applying a coating amount of 150 g / m ² to a JIS-A-5304 standard sidewalk board (size: 300 mm × 300 mm) using the resin composition of Comparative Example 13 as a primer, drying the touch, and then glass flake RCF. -140 (Nippon Sheet Glass Co., Ltd.) 30 parts by mass, Crystallite AA (Tatsumori silica stone powder) 20 parts by mass, 6% cobalt naphthenate, 1.0 part by mass, Percure K 2.0 parts by mass 700 g / m ^{2 was} applied as a substrate conditioner, and after drying by touch, 1 kg / m was used as a surface protective layer with a composition obtained by adding glass flake RCF-140 to 100 parts by weight of the resin composition of Comparative Example 13. ² Apply (thickness 0.6 mm) to complete the anticorrosion coating layer. After curing at 25 ° C. for 72 hours, the inside of the FRP plate of width × length × thickness = 20 mm × 90 mm × 2 mm is bonded with an epoxy adhesive leaving 20 mm unbonded at one end in the length direction. In addition, a 2mm hole is opened at the center of the unbonded part, and a hook at the tip of the spring balance is inserted into this hole, and 90 degree peeling is performed in accordance with the vulcanized rubber adhesion test method of JIS-K-6256. It was measured. The weight change rate was 10 g after thoroughly mixing the resin composition having the blending ratio of Comparative Example 13 and poured into a glass petri dish having a diameter of 40 mm (height, 15 mm) and cured for 25 hours at 25 ° C. After the mold was immersed in warm water (80 ° C.) for 96 hours, the weight change rate was measured.

  Further, EPMA, Barcol hardness and wear amount were measured by the above-described methods.

  After heating 100 parts by weight of this resin composition to 70 ° C. and dissolving 0.6 parts by weight of 20% concentration 120 ° F./(FA-512MT) paraffin wax, 6% cobalt naphthenate and dimethyl in Table 3 were used. Aniline and Percure K were added to obtain a formulation. About this formulation, the item similar to Example 1 and surface dryness were measured.

[Comparative Example 14]
Ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Shin Nakamura) was added to 40 parts by mass of the aromatic epoxy methacrylate (A) having a number average molecular weight of 1,300 obtained in the production of Comparative Example 4. Chemical Industry Co., Ltd. BPE-100) 15 parts by mass and dicyclopentenyloxyethyl methacrylate (C) 45 parts by mass were added and dissolved, and then cooled to room temperature to obtain a resin composition.

  The resin composition was poured into a mold and cured at 25 ° C. for 72 hours to obtain a cured resin (cast material) having a thickness of 3 mm. Characteristic values of the cured resin were measured by the method described in Example 1. The results are shown in Table 3.

  Resin concrete is added to and mixed with 100 parts by weight of the resin composition, 1.0 parts by weight of 6% cobalt naphthenate, 0.5 parts by weight of dimethylaniline and 2.0 parts by weight of Percure K, and then mixed with inorganic aggregate material. (Mixed silica sand blended in Table 3) 450 parts by mass was added to obtain a blend.

With respect to this blend, a specimen for measuring compressive strength and bending strength was prepared by pouring the blend into a 40 × 40 × 160 mm mold. The tensile strength was cast into a 2.5 cmφ rod-shaped mold. The concrete adhesion strength was tested according to JIS-A-6916 with a Kenken type tensile tester, and the adhesive strength was measured. The concrete peeling test was performed on a JIS-A-5304 standard sidewalk board (size: 300 mm × 300 mm), using the resin composition of Comparative Example 14 as a primer, an application amount of 150 g / m ^2, and after dry to the touch, Glass flake RCF-140 (manufactured by Nippon Sheet Glass Co., Ltd.) 30 parts by mass, crystallite AA (silica stone powder from Tatsumori Co., Ltd.) 20 parts by mass, 6% cobalt naphthenate, 1.0 part by mass, A blend of 2.0 parts by weight of benzoyl oxide as a substrate conditioner was applied at 700 g / m ^2, and after dry-to-touch, a blend of glass flake RCF-140 was added to 100 parts by weight of the resin composition of Comparative Example 14. As the surface protective layer, 1 kg / m ^{2 is} applied (thickness 0.6 mm) to complete the anticorrosion coating layer. After curing at 25 ° C. for 72 hours, the inside of the FRP plate of width × length × thickness = 20 mm × 90 mm × 2 mm is bonded with an epoxy adhesive leaving 20 mm unbonded at one end in the length direction. A 2 mm hole was opened in the center of the unbonded portion, and a hook at the tip of the spring balance was inserted into this hole, and 90 ° peeling was measured according to the vulcanized rubber adhesion test method of JIS K6256. The weight change rate was 10 g after thoroughly mixing the resin composition of the blending ratio of Comparative Example 14, poured into a glass petri dish of φ40 mm (height, 15 mm), cured at 25 ° C. for 72 hours, and then demolded. After the mold was immersed in warm water (80 ° C.) for 96 hours, the weight change rate was measured. Further, EPMA, Barcol hardness and wear amount were measured by the above-described methods.

  After heating 100 parts by mass of this resin composition to 70 ° C. and dissolving 2.0 parts by mass of 20% 120 ° F / (FA-512MT) paraffin wax, 6% cobalt naphthenate and dimethylaniline in Table 4 were used. And Percure K was added to obtain a formulation. About this formulation, the item similar to Example 1 and surface dryness were measured.

[Comparative Example 15]
[Using aromatic epoxy methacrylate (A) and ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B), dicyclopentenyloxyethyl methacrylate (C) and phenoxyethyl methacrylate (D) using the same Mixing of curable resin composition]
[Production of aromatic epoxy methacrylate (A) having a number average molecular weight of about 450]
453 g of jER828 (Mitsubishi Chemical Corporation) was charged into a 2 liter four-necked flask equipped with a stirrer, condenser, thermometer and air inlet tube, and the temperature was raised to 130 ° C. while blowing 10 liters of dry air per minute with stirring. Warm up. After the temperature rise, 0.3 g of hydroquinone (polymerization inhibitor) and 2 g of trimethylbenzylammonium chloride were added, and 411 g of methacrylic acid was added dropwise over 2 hours. After 3 hours from the end of dropping, measurement of the acid value was started every hour, and after confirming that the acid value reached 18 KOHmg / g, the product was cooled to 100 ° C. (aroma having a number average molecular weight of about 450). Group epoxy methacrylate (A)) was obtained. Ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Shin-Nakamura Chemical Co., Ltd. BPE-100) 10 parts by mass, dicyclopentenyloxyethyl methacrylate (C) ( 20 parts by mass of Hitachi Chemical Co., Ltd. FA-512MT) and 45 parts by mass of phenoxyethyl methacrylate (D) (manufactured by Kyoeisha Chemical Co., Ltd., Light Ester PO) were dissolved, cooled to room temperature, and curable resin composition I got a thing.

  This was mixed well in the proportion of the above resin composition of Comparative Example 15 in Table 3, and then poured into a mold and cured at 25 ° C. for 72 hours to obtain a cured resin product having a thickness of 3 mm. Got. About this curable resin composition, the casting and the laminated board were created by the method as described in Example 1, and the characteristic value was measured. The results are shown in Table 3.

  Further, EPMA, Barcol hardness and wear amount were measured by the methods described above. The results are shown in Table 3.

  Moreover, the concrete adhesion strength and concrete peeling strength of this resin composition to which 6% cobalt naphthenate, dimethylaniline and Percure K shown in Table 3 are added are high. After 60 days of the entire surface immersion of the test piece on which the protective material was laminated in 80 ° C. warm water, there was no abnormality among the primer layer, the base material adjusting material layer, and the surface protective layer. Moreover, warm water (80 degreeC) immersion water absorption showed the low value with 3%.

  Regarding the volatilization amount of styrene, after thoroughly mixing the resin composition of the blending ratio of Comparative Example 15, 100 g was put in a glass petri dish of φ145 mm, and the weight change rate was measured after 60 minutes. Further, EPMA, Barcol hardness and wear amount were measured by the above-described methods.

[Comparative Example 16]
[Curing using aromatic epoxy methacrylate (A) and ethylene oxide 17 mol addition ethoxylated bisphenol A dimethacrylate (B), dicyclopentenyloxyethyl methacrylate (C) and phenoxyethyl methacrylate (D) using the same Of Resin Composition]
Ethylene oxide 17 mol addition ethoxylated bisphenol A dimethacrylate (B) to 25 parts by mass of aromatic epoxy methacrylate (A) having a number average molecular weight of about 450 obtained in the same manner as in Comparative Example 14 (Shin Nakamura Chemical Co., Ltd.) BPE-900) 10 parts by mass, dicyclopentenyloxyethyl methacrylate (C) (Hitachi Chemical Industry Co., Ltd. FA-512MT) 20 parts by mass and phenoxyethyl methacrylate (D) 45 parts by mass were added and dissolved, then room temperature. Was cooled to obtain a curable resin composition.

  This was mixed well in the proportion of the above resin composition of Comparative Example 16 in Table 3, and then poured into a mold and cured at 25 ° C. for 72 hours to obtain a cured resin product having a thickness of 3 mm. Got. About this curable resin composition, the casting and the laminated board were created by the method as described in Example 1, and the characteristic value was measured. The results are shown in Table 3.

  Further, EPMA, Barcol hardness and wear amount were measured by the methods described above. The results are shown in Table 3.

  Moreover, the concrete adhesion strength and concrete peeling strength of this resin composition containing 6% cobalt naphthenate, dimethylaniline and Percure K shown in Table 3 are high. After 60 days of immersing the test piece on which the protective material was laminated on the entire surface in 80 ° C. warm water, there was no abnormality between the primer layer, the base material adjusting material layer, and the surface protective layer. Moreover, warm water (80 degreeC) immersion water absorption showed the low value with 3.1%.

  Regarding the volatilization amount of styrene, after thoroughly mixing the resin composition of the blending ratio of Comparative Example 16, 100 g was put in a glass petri dish of φ145 mm, and the weight change rate was measured after 60 minutes. Further, EPMA, Barcol hardness and wear amount were measured by the above-described methods.

  Into 45 parts by mass of an aromatic epoxy methacrylate (A) having a number average molecular weight of 750 and an acid value of 10 KOHmg / g or less obtained in the production of Example 1, 2.6 mol of ethylene oxide added ethoxylated bisphenol A dimethacrylate (B) ( Shin-Nakamura Chemical Co., Ltd. BPE-100) 15 parts by mass, dicyclopentenyloxyethyl methacrylate (C) (Hitachi Chemical Co., Ltd. Funkuru FA-512MT) 30 parts by mass, phenoxyethyl methacrylate (D) (Kyoeisha Chemical Co., Ltd. 10 parts by mass of ester PO) and 10 parts by mass of acetoacetoxylethyl methacrylate (E) were added and dissolved, and then cooled to room temperature to obtain a curable resin composition.

  After thoroughly mixing this in the proportion of Example 10 in Table 4, a curable resin composition was obtained. About this curable resin composition, the casting and the laminated board were created by the method of Example 1, and the characteristic value was measured. The results are shown in Table 4.

  Further, EPMA, Barcol hardness and wear amount were measured by the methods described above. The results are shown in Table 4.

  Furthermore, the concrete adhesion strength and concrete peeling strength of this resin composition containing 6% cobalt naphthenate, dimethylaniline and Percure K shown in Table 4 are high. After 60 days of immersing the test piece on which the protective material was laminated on the entire surface in 80 ° C. warm water, there was no abnormality between the primer layer, the base material adjusting material layer, and the surface protective layer. Moreover, the warm water (80 degreeC) immersion water absorption showed the low value around 1%.

  45 parts by mass of an aromatic epoxy methacrylate (A) having a number average molecular weight of 750 and an acid value of 10 KOHmg / below obtained in the production of Example 1, ethylene oxide 6.0 mol addition ethoxylated bisphenol A dimethacrylate (B) 15 mass Part, dicyclopentenyloxyethyl methacrylate (C) 30 parts by mass, phenoxyethyl methacrylate (D) 10 parts by mass and acetoacetoxylethyl methacrylate (E) 10 parts by mass, cooled to room temperature, and cured. A composition was obtained.

  This was mixed well in the proportion of Example 11 in Table 4 to obtain a curable resin composition. About this curable resin composition, the casting and the laminated board were created by the method of Example 1, and the characteristic value was measured. The results are shown in Table 4.

  Further, EPMA, Barcol hardness and wear amount were measured by the methods described above. The results are shown in Table 4.

  Moreover, the concrete adhesion strength and concrete peeling strength of this resin composition containing 6% cobalt naphthenate, dimethylaniline, and Percure K shown in Table 4 are high. After 60 days of immersing the test piece on which the protective material was laminated on the entire surface in 80 ° C. warm water, there was no abnormality between the primer layer, the base material adjusting material layer, and the surface protective layer. Moreover, the warm water (80 degreeC) immersion water absorption showed the low value around 1%.

  45 parts by mass of an aromatic epoxy methacrylate (A) having a number average molecular weight of 750 and an acid value of 10 KOHmg / g obtained in the production of Example 1, 2.6 mol of ethylene oxide and 15 masses of ethoxylated bisphenol A dimethacrylate (B) And 30 parts by mass of dicyclopentenyloxyethyl methacrylate (C), 10 parts by mass of phenoxyethyl methacrylate (D) and 10 parts by mass of acetoacetoxymethacrylate (E) were added and dissolved, and then cooled to room temperature to obtain a curable resin composition. Obtained. This resin composition was poured into a mold and cured at 25 ° C. for 72 hours to obtain a cured resin (cast material) having a thickness of 3 mm. Characteristic values of the cured resin were measured by the method described in Example 1. The results are shown in Table 4.

  Resin concrete was prepared by dissolving 2.0 parts by mass of 20% concentration (FA-512MT) 120 degree F paraffin wax in 100 parts by mass of this resin composition, and then, first, 1.0 part by mass of 6% cobalt naphthenate and 0% dimethylaniline. 0.5 parts by mass and 2.0 parts by mass of Percure K were added and mixed, and then 450 parts by mass of an inorganic aggregate material (mixed silica sand having a composition shown in Table 4) was added to obtain a blend.

With respect to this blend, a specimen for measuring compressive strength and bending strength was prepared by pouring the blend into a 40 × 40 × 160 mm mold. The tensile strength was cast into a 2.5 cmφ rod-shaped mold. The concrete adhesion strength was tested according to JIS-A-6916 with a Kenken type tensile tester, and the adhesive strength was measured. The concrete peeling test was performed by applying a coating amount of 150 g / m ² to a JIS-A-5304 standard sidewalk board (size: 300 mm × 300 mm) using the resin composition of Example 12 as a primer, drying the touch, and then glass flake RCF. -140 (Nippon Sheet Glass Co., Ltd.) 30 parts by mass, Crystallite AA (Tatsumori silica stone powder) 20 parts by mass, 6% cobalt naphthenate, 1.0 part by mass, Percure K 2.0 parts by mass 700 g / m ^{2 was} applied as a substrate conditioner, and after touch drying, 100 kg by weight of the resin composition of Example 12 was added with glass flake RCF-140 as a surface protective layer at 1 kg / m. ^Two coatings (thickness 0.6 mm) were applied to form an anticorrosion coating layer. After curing at 25 ° C. for 72 hours, the inside of the FRP plate of width × length × thickness = 20 mm × 90 mm × 2 mm is bonded with an epoxy adhesive leaving 20 mm unbonded at one end in the length direction. In addition, a 2mm hole is opened at the center of the unbonded part, and a hook at the tip of the spring balance is inserted into this hole, and 90 degree peeling is performed in accordance with the vulcanized rubber adhesion test method of JIS-K-6256. It was measured. The rate of weight change was 10 g after thoroughly mixing the resin composition of the blending ratio of Example 12, poured into a glass petri dish of φ40 mm (height, 15 mm), cured at 25 ° C. for 72 hours, and then demolded. After the mold was immersed in warm water (80 ° C.) for 96 hours, the weight change rate was measured. Further, EPMA, Barcol hardness and wear amount were measured by the above-described methods.

  Ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (50 parts by mass of aromatic epoxy methacrylate (A) having a number average molecular weight of about 750 and an acid value of 10 mgKOH / g or less obtained in the production of Example 1 ( B) 15 parts by mass and 10 parts by mass of dicyclopentenyloxyethyl methacrylate (C), 15 parts by mass of phenoxyethyl methacrylate (D) and 10 parts by mass of acetoacetoxyethyl methacrylate (E) were added and dissolved, and then cooled to room temperature. A curable resin composition was obtained. To 100 parts by mass of the resin composition, 1.0% by mass of 6% cobalt naphthenate and 2.0 parts by mass of Percure K were added to obtain a blend.

  This blend was poured into a mold, cured at 25 ° C. for 72 hours, and demolded to obtain a cured resin (cast material) having a thickness of 3 mm. Characteristic values of the cured resin were measured by the method described in Example 1. The results are shown in Table 4.

  The resin composition containing glass flakes was prepared as described in the formulation column of Example 13 in Table 4. That is, the composition of the resin composition containing glass flakes was first added to 100 parts by mass of the resin composition, 1.0 parts by mass of 6% cobalt naphthenate, 0.5 parts by mass of dimethylaniline, and 2.0 parts by mass of Percure K. Next, 40 parts by mass of glass flake RCF-140 (manufactured by Nippon Sheet Glass Co., Ltd.) was added to obtain a blend.

  With respect to this blend, a specimen for measuring compressive strength and bending strength was prepared by pouring the blend into a 40 × 40 × 160 mm mold. The tensile strength was cast into a 2.5 cmφ rod-shaped mold.

The concrete adhesion strength was tested according to JIS-A-6916 with a Kenken type tensile tester, and the adhesive strength was measured. The concrete peeling test was carried out by applying a coating amount of 150 g / m ² on a JIS-A-5304 standard sidewalk board (size: 300 mm × 300 mm) using the resin composition of Example 13 as a primer, drying the touch, and then glass flake RCF. -140 (Nippon Sheet Glass Co., Ltd.) 30 parts by mass, Crystallite AA (Tatsumori silica stone powder) 20 parts by mass, 6% cobalt naphthenate, 1.0 part by mass, Percure K 2.0 parts by mass 700 g / m ^{2 was} applied as a substrate conditioner, and after touch drying, 100 kg by weight of the resin composition of Example 13 was added with glass flake RCF-140 as a surface protective layer at 1 kg / m. ^Two coatings (thickness 0.6 mm) were applied to form an anticorrosion coating layer. After curing at 25 ° C. for 72 hours, the inside of the FRP plate of width × length × thickness = 20 mm × 90 mm × 2 mm is bonded with an epoxy adhesive leaving 20 mm unbonded at one end in the length direction. In addition, a 2mm hole is opened at the center of the unbonded part, and a hook at the tip of the spring balance is inserted into this hole, and 90 degree peeling is performed in accordance with the vulcanized rubber adhesion test method of JIS-K-6256. It was measured. The rate of weight change was 10 g after thoroughly mixing the resin composition having the blending ratio of Example 13 and poured into a glass petri dish having a diameter of 40 mm (height, 15 mm) and cured at 25 ° C. for 72 hours. After the mold was immersed in warm water (80 ° C.) for 96 hours, the weight change rate was measured. Further, EPMA, Barcol hardness and wear amount were measured by the above-described methods.

  After heating 100 parts by mass of this resin composition to 70 ° C. and dissolving 2.0 parts by mass of a 20% concentration (FA-512MT) 120 ° F paraffin wax, 6% cobalt naphthenate and dimethylaniline in Table 4 were used. And Percure K was added to obtain a formulation. About this formulation, the item similar to Example 1 and surface dryness were measured.

[Comparative Example 17]
To 45 parts by mass of the aromatic epoxy methacrylate (A) having a number average molecular weight of 750 and an acid value of 17 KOHmg / g obtained in the production of Comparative Example 1, 2.6 mol of ethylene oxide added ethoxylated bisphenol A dimethacrylate (B) (new Nakamura Chemical Co., Ltd. BPE-100) 20 parts by mass, dicyclopentenyloxyethyl methacrylate (C) (Hitachi Chemical Industry Co., Ltd. Funcle FA-512MT) 20 parts by mass, phenoxyethyl methacrylate (D) (Kyoeisha Chemical) 15 parts by mass of Light Ester PO (manufactured by Co., Ltd.) was added and dissolved, and then cooled to room temperature to obtain a curable resin composition.

  This was mixed well in the proportion of Comparative Example 17 in Table 4, and then a curable resin composition was obtained. About this curable resin composition, the casting and the laminated board were created by the method of Example 1, and the characteristic value was measured. The results are shown in Table 4.

  Further, EPMA, Barcol hardness and wear amount were measured by the methods described above. The results are shown in Table 3.

  Moreover, the concrete adhesion strength and concrete peeling strength of this resin composition containing 6% cobalt naphthenate, dimethylaniline, and Percure K shown in Table 4 are high. After 60 days of immersing the test piece on which the protective material was laminated on the entire surface in 80 ° C. warm water, there was no abnormality between the primer layer, the base material adjusting material layer, and the surface protective layer. Moreover, the warm water (80 degreeC) immersion water absorption showed the low value around 1%.

[Comparative Example 18]
Ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) 10 to 30 parts by mass of the aromatic epoxy methacrylate (A) having a number average molecular weight of 750 and an acid value of 17 KOHmg / g or less obtained in the production of Comparative Example 1 Mass parts, 10 parts by mass of dicyclopentenyloxyethyl methacrylate (C), 5 parts by mass of phenoxyethyl methacrylate (D) and 45 parts by mass of acetoacetoxylethyl methacrylate (E) are added and dissolved, and then cooled to room temperature and cured. A resin composition was obtained.

  After mixing this well in the proportion of Comparative Example 18 in Table 4, a curable resin composition was obtained. About this curable resin composition, the casting and the laminated board were created by the method of Example 1, and the characteristic value was measured. The results are shown in Table 4.

  Further, EPMA, Barcol hardness and wear amount were measured by the methods described above. The results are shown in Table 4.

  Moreover, the concrete adhesion strength and concrete peeling strength of this resin composition containing 6% cobalt naphthenate, dimethylaniline, and Percure K shown in Table 4 are high. After 60 days of immersing the test piece on which the protective material was laminated on the entire surface in 80 ° C. warm water, there was no abnormality between the primer layer, the base material adjusting material layer, and the surface protective layer. Moreover, the warm water (80 degreeC) immersion water absorption showed the low value around 1%.

[Comparative Example 19]
50 parts by mass of the aromatic epoxy methacrylate (A) having a number average molecular weight of about 750 and an acid value of 17 KOHmg / g or less obtained in the production of Comparative Example 1, 40 parts by mass of dicyclopentenyloxyethyl methacrylate (C), phenoxy 10 parts by mass of ethyl methacrylate (D) was added and dissolved, and then cooled to room temperature to obtain a curable resin composition. To 100 parts by mass of the resin composition, 1.0% by mass of 6% cobalt naphthenate and 2.0 parts by mass of Percure K were added to obtain a blend.

  This blend was poured into a mold, cured at 25 ° C. for 72 hours, and demolded to obtain a cured resin (cast material) having a thickness of 3 mm. Characteristic values of the cured resin were measured by the method described in Example 1. The results are shown in Table 4.

  The resin composition containing glass flakes was prepared as described in the resin concrete properties column of Example 3 in Table 1. That is, the resin composition containing glass flakes was prepared by dissolving 2 parts by mass of a 20% concentration of 120 degrees F / (FA-512MT) paraffin wax in 100 parts by mass of the resin composition, and then, first, 6% cobalt naphthenate 1 0.0 parts by mass, 0.5 parts by mass of dimethylaniline, and 2.0 parts by mass of Percure K were added and mixed, and then 40 parts by mass of glass flake RCF-140 (manufactured by Nippon Sheet Glass Co., Ltd.) was added to obtain a blend. .

With respect to this blend, a specimen for measuring compressive strength and bending strength was prepared by pouring the blend into a 40 × 40 × 160 mm mold. The tensile strength was cast into a 2.5 cmφ rod-shaped mold. The concrete adhesion strength was tested according to JIS-A-6916 with a Kenken type tensile tester, and the adhesive strength was measured. The concrete peeling test was carried out by applying a coating amount of 150 g / m ² on a JIS-A-5304 standard sidewalk board (size: 300 mm × 300 mm) using the resin composition of Comparative Example 19 as a primer, drying the touch, and then glass flake RCF. -140 (Nippon Sheet Glass Co., Ltd.) 30 parts by mass, Crystallite AA (Tatsumori silica stone powder) 20 parts by mass, 6% cobalt naphthenate, 1.0 part by mass, Percure K 2.0 parts by mass 700 g / m ^{2 was} applied as a substrate conditioner, and after drying with the touch, 100 kg by weight of the resin composition of Comparative Example 19 was added with glass flake RCF-140 as a surface protective layer at 1 kg / m. ^Two coatings (thickness 0.6 mm) were applied to form an anticorrosion coating layer. After curing at 25 ° C. for 72 hours, the inside of the FRP plate of width × length × thickness = 20 mm × 90 mm × 2 mm is bonded with an epoxy adhesive leaving 20 mm unbonded at one end in the length direction. In addition, a 2mm hole is opened at the center of the unbonded part, and a hook at the tip of the spring balance is inserted into this hole, and 90 degree peeling is performed in accordance with the vulcanized rubber adhesion test method of JIS-K-6256. It was measured. The weight change rate was 10 g after thoroughly mixing the resin composition having the blending ratio of Comparative Example 19, poured into a glass petri dish having a diameter of 40 mm (height, 15 mm), cured at 25 ° C. for 72 hours, and then demolded. After the mold was immersed in warm water (80 ° C.) for 96 hours, the weight change rate was measured. Further, EPMA, Barcol hardness and wear amount were measured by the above-described methods.

  100 parts by mass of this resin composition was heated to 70 ° C., and 6% cobalt naphthenate, dimethylaniline and Percure K shown in Table 4 were added to obtain a blend. About this formulation, the item similar to Example 1 and surface dryness were measured.

[Comparative Example 20]
To 50 parts by mass of an aromatic epoxy methacrylate (A) having a number average molecular weight of 1,300 and an acid value of 18 KOH mg / g or less obtained in the production of Comparative Example 5, 2.6 mol of ethylene oxide addition ethoxylated bisphenol A dimethacrylate (B ) 20 parts by mass, 20 parts by mass of dicyclopentenyloxyethyl methacrylate (C) and 10 parts by mass of phenoxyethyl methacrylate (D) were added and dissolved, and then cooled to room temperature to obtain a curable resin composition. The resin composition was poured into a mold and cured at 25 ° C. for 72 hours to obtain a cured resin (cast material) having a thickness of 3 mm. Characteristic values of the cured resin were measured by the method described in Example 1. The results are shown in Table 4.

  Resin concrete is obtained by dissolving 2.0 parts by mass of 20% concentration (FA-512MT) 120 degree F paraffin wax in 100 parts by mass of the resin composition, and then adding 1.0 part by mass of 6% cobalt naphthenate and 0% dimethylaniline. 0.5 parts by mass and 2.0 parts by mass of Percure K were added and mixed, and then 450 parts by mass of an inorganic aggregate material (mixed silica sand having a composition shown in Table 4) was added to obtain a blend.

With respect to this blend, a specimen for measuring compressive strength and bending strength was prepared by pouring the blend into a 40 × 40 × 160 mm mold. The tensile strength was cast into a 2.5 cmφ rod-shaped mold. The concrete adhesion strength was tested according to JIS-A-6916 with a Kenken type tensile tester, and the adhesive strength was measured. The concrete peeling test was carried out by applying a coating amount of 150 g / m ² to a JIS-A-5304 standard sidewalk board (size: 300 mm × 300 mm) using the resin composition of Comparative Example 20 as a primer. -140 (Nippon Sheet Glass Co., Ltd.) 30 parts by mass, Crystallite AA (Tatsumori silica stone powder) 20 parts by mass, 6% cobalt naphthenate, 1.0 part by mass, Percure K 2.0 parts by mass 700 g / m ^{2 was} applied as a substrate conditioner, and after drying with the touch, 100 kg by weight of the resin composition of Comparative Example 20 was added with glass flake RCF-140 as a surface protective layer at 1 kg / m. ² Apply (thickness 0.6 mm) to complete the anticorrosion coating layer. After curing at 25 ° C. for 72 hours, the inside of the FRP plate of width × length × thickness = 20 mm × 90 mm × 2 mm is bonded with an epoxy adhesive leaving 20 mm unbonded at one end in the length direction. In addition, a 2mm hole is opened at the center of the unbonded part, and a hook at the tip of the spring balance is inserted into this hole, and 90 degree peeling is performed in accordance with the vulcanized rubber adhesion test method of JIS-K-6256. It was measured. The rate of weight change was 10 g after thoroughly mixing the resin composition having the blending ratio of Comparative Example 20, poured into a glass petri dish of φ40 mm (height, 15 mm), cured at 25 ° C. for 72 hours, and then demolded. After the mold was immersed in warm water (80 ° C.) for 96 hours, the weight change rate was measured. As for the volatilization amount of styrene, after sufficiently mixing the curable resin composition, 100 g was put in a glass petri dish having a diameter of 145 mm, and the weight change rate was measured after 60 minutes.

  Further, EPMA, Barcol hardness and wear amount were measured by the above-described methods.

  Ethylene oxide 4.0 mol addition ethoxylated bisphenol A dimethacrylate (B) (Shin Nakamura Chemical Co., Ltd.) was added to 45 parts by mass of the aromatic epoxy methacrylate (A) having a number average molecular weight of 750 obtained in the production of Example 1. BPE-200) 15 parts by mass, 20 parts by mass of dicyclopentenyloxyethyl methacrylate (C), 10 parts by mass of phenoxyethyl methacrylate (D), and 10 parts by mass of acetoacetochitoethyl methacrylate (E) are added and dissolved. Thereafter, 100 parts by mass of the resin composition was thoroughly stirred and mixed with 1.5 parts by mass of a photopolymerization initiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BASF's Lucillin TPO). After cooling to room temperature, polymethyl having an average particle size of 1.9 μm and a weight average degree of polymerization of 30,000 30 parts by weight of a methacrylate resin powder (manufactured by Gantz Kasei, Zefiac F320) was added and heated to 80 ° C. and dissolved to obtain a resin composition.

First, a 0.2 mm thick polyurethane elastomer film 790M60K (manufactured by Nippon Valqua Industries, Ltd.) is laid on this photocurable resin composition for prepreg, and a chop strand mat (REM450-) having a unit weight of 450 g / m ² is placed thereon. G5; manufactured by Nippon Sheet Glass) and impregnated with a resin mixture thereon, and coated with a polyurethane elastomer film of 790M60K (manufactured by Nippon Valqua Industries, Ltd.) having the same thickness of 0.2 mm as the first one, UV irradiation (metal halide lamp: Ga-based, 240 W, irradiation intensity 80 mW / cm ² ) was carried out for 3 minutes, and the physical properties of the laminate are shown in Table 5.

Table 5 shows the appearance of EPMA, Barcol hardness, hot water (80 ° C.) immersion water absorption, and concrete-coated hot water immersion (after 60 days).

[Comparative Example 21]
Ethylene oxide 30 mol addition ethoxylated bisphenol A dimethacrylate (B) (Shin Nakamura Chemical Co., Ltd.) was added to 45 parts by mass of the aromatic epoxy methacrylate (A) having a number average molecular weight of 1,300 obtained in the production of Comparative Example 4. BPE-200) 15 parts by mass, 20 parts by mass of dicyclopentenyloxyethyl methacrylate (C) and 20 parts by mass of phenoxyethyl methacrylate (D) were added and dissolved, and then 100 parts by mass of the resin composition was subjected to photopolymerization. Initiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BASF's Lucillin TPO) 1.5 parts by mass was well stirred and mixed, then dissolved, cooled to room temperature, then average particle size 1.9 μm, Polymethylmethacrylate resin powder having a weight average degree of polymerization of 30,000 320) 30 parts by mass were added heating to 80 ° C., dissolved to obtain a resin composition.

First, a 0.2 mm thick polyurethane elastomer film 790M60K (manufactured by Nippon Valqua Industries, Ltd.) is laid on this photocurable resin composition for prepreg, and a chop strand mat (REM450-) having a unit weight of 450 g / m ² is placed thereon. G5; manufactured by Nippon Sheet Glass) and impregnated with a resin mixture, and coated with a polyurethane elastomer film of 790M60K (manufactured by Nippon Valqua Industries) having the same thickness as that of the first one, and then irradiated with ultraviolet rays ( Metal halide lamp: Ga-based, 240 W, irradiation intensity 80 mW / cm ² ) 3 minutes, physical properties of the laminate are shown in Table 5.

Table 5 shows the appearance of EPMA, Barcol hardness, hot water (80 ° C.) immersion water absorption, and concrete-coated hot water immersion (after 60 days).

  In Table 1, in Comparative Examples 1 to 3 in which the blending ratio of the curable resin composition of the present invention is different, the curing is poor, and the ethylene of Comparative Example 3 and (B) which does not use the specific monomer (C) In Comparative Example 5 in which the number of moles of oxide added was large, swelling occurred and a long time was required for surface drying, and satisfactory results were not obtained. In addition, when the acid value of the bisphenol A glycidyl ether methacrylic acid adduct of (A) is 10 or more, there is an irritating odor. Furthermore, epoxy acrylates having a number average molecular weight of 1,100 of (A) exhibit whitening cracking phenomenon. Put out.

  In Comparative Example 6 using a styrene type vinyl ester resin, there is a problem in environmental pollution due to an increase in the amount of styrene volatilized. Further, as shown in Table 2, in Comparative Example 9 in which the mixing ratio of (C), which is an essential component of the present invention, is not included in the photocurable resin composition, surface whitening occurs and sulfur penetration depth occurs when the concrete-coated hot water is immersed. That is, Example 5 is as large as 50 μm with respect to 2 μm or less, and there is a problem as long-term life. Moreover, the hot water immersion water absorption was slightly more than three times that of Example 5.

  In Table 3, in Comparative Example 11 of the blending ratio of the curable resin composition different from the essential constituents of the present invention, Comparative Examples 10 and 12 to 12 showing curing failure and not using the specific monomer (D). No. 14, cracking in hot water immersion, increase in sulfur penetration depth, surface drying property takes a long time, and when the acid value is 10 or more, an irritating odor is generated, and the number average molecular weight is long-term outside the scope of the present invention. When immersed in warm water, the water absorption increases, the concrete adhesion strength, and the concrete peeling strength decrease significantly from the initial values when immersed in warm water. Furthermore, when the epoxy acrylate (A) having a number average molecular weight of less than 500 is used, various strength reductions are observed.

  In Table 4, Comparative Examples 17 to 20 of the composition of the curable resin composition not using the specific monomer (E) different from the essential component of the present invention and Examples 10 to 10 of the curable resin composition of the present invention. Compared with No. 13, the difference between the two is large in the hot water immersion water absorption rate, the occurrence of swelling, the surface drying property for a long time, and the sulfur penetration depth.

  In Table 5, in Comparative Example 21 in which (E) which is an essential component of the present invention is not added, whitening occurs in the immersion of the concrete-coated hot water, the sulfur penetration depth increases, the hot water absorption rate, the irritating odor, and the like. The effect of the curable resin composition is clear.

  From Tables 1 to 5, the curable resin composition as an essential component of the present invention solves the long-term life function of the lining material and the concrete coating composition.

Claims (10)

(A) Epoxy (meth) acrylate 30 to 30 consisting of a reaction product of an aromatic epoxy resin and (meth) acrylic acid, having a number average molecular weight in the range of 500 to 1,100 and an acid value of 10 KOH mg / g or less. 60 parts by mass, (B) 10 to 30 parts by mass of ethoxylated bisphenol A dimethacrylate having 2 to 10 moles of ethylene oxide added, and (C) an alcohol residue having a molecular weight of 300 or less, or a carbon-carbon double bond or It contains 20 to 40 parts by mass of a monofunctional (meth) acrylate monomer having a group containing a cyclic hydrocarbon group having only one nitrogen atom, and the total of components (A), (B) and (C) is 100 Mass part,
Furthermore, it contains 5 to 40 parts by mass of (D) phenyl group-containing (meth) acrylate monomer with respect to a total of 100 parts by mass of (A), (B) and (C). .   The curing according to claim 1, further comprising (E) 1 to 40 parts by weight of a (meth) acrylate monomer having an acetoacetoxyl group, with respect to a total of 100 parts by weight of (A), (B) and (C). Resin composition. (C) a monofunctional (meth) acrylate monomer having a group containing a cyclic hydrocarbon group having only one carbon-carbon double bond or one nitrogen atom in the ring as an alcohol residue having a molecular weight of 300 or less is dicyclo 3. The compound according to claim 1, wherein the compound is at least one compound selected from pentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, pentamethylpiperidyl methacrylate, and pentamethylpiperidyl acrylate. Curable resin composition.   In any one of Claims 1-3 which contains 1-30 mass parts of thermoplastic resin powder as a thickener further with respect to a total of 100 mass parts of (A), (B), and (C). The curable resin composition described.   The photopolymerization initiator is further contained in an amount of 0.5 to 2.5 parts by mass with respect to 100 parts by mass in total of (A), (B) and (C). The curable resin composition according to any one of the above.   The organic peroxide of 0.01-10 mass parts is further contained with respect to a total of 100 mass parts of (A), (B), and (C), Any one of Claims 1-5 characterized by the above-mentioned. 2. The curable resin composition according to item 1.   The concrete coating composition containing the curable resin composition of any one of Claims 1-6.   (A), (B), and 100 parts by mass of (C), and further contains 100 to 600 parts by mass of an inert powdery inorganic aggregate material having an average particle size of 0.02 to 10 mm. The concrete coating composition according to claim 7, wherein The lining material containing the curable resin composition of any one of Claims 1-6 .

  The lining material according to claim 9, further comprising 5 to 50 parts by mass of a flaky inorganic filler with respect to a total of 100 parts by mass of (A), (B) and (C). .