JP6134757B2 - Curable resin composition, concrete coating composition and lining material - Google Patents

Description

  The present invention is particularly excellent in low odor, adhesiveness, chemical resistance, surface air curing, heat resistance, wear resistance, high reactivity, durability, and lining for surface coating of concrete in sewerage treatment facilities. Curable resin composition suitable for formation of lining materials for repairing materials, inner surfaces of human holes, etc., and repair lining materials for concrete facilities in food factories, pharmaceutical factories, and electronic material factories, and this curable resin composition The present invention relates to a concrete coating composition and a lining material.

  The gas phase part of the concrete structure of the sewage treatment facility is sulphated by hydrogen sulfide by sulfur-oxidizing bacteria, and the surface is weakened by long-term use, affecting the structural strength of the facility.

  The repair method for an aging sewerage treatment facility is usually applied by applying a cross-section repair material to the deterioration layer thickness of the wall surface of an existing deteriorated concrete structure, applying a primer after curing, and then applying a base material for the purpose of adjusting unevenness. A method of applying a coating resin lining material to the adjusting material is used. In the case of a new structure, a method is used in which a primer is applied to a concrete base, and then a base material is applied for the purpose of adjusting unevenness, and then an anticorrosion coating resin lining material is applied.

  Many proposals have been made for the technology of the primer for the concrete base. The low odor primer resin composition includes (a) a vinyl ester or a modified product (0.5 to 4.5 parts by mass) obtained by reacting an epoxy resin with acrylic acid and / or methacrylic acid, and (b) a low volatile fat. 100 parts by weight of a reactive composition comprising a cyclic monofunctional acrylic monomer (99.5 to 95.5 parts by weight) contains (c) a solventless urethane resin (5 to 30 parts by weight), a curing agent and a curing accelerator. A primer material composition for a concrete, corrosion-proof and odorless coating is disclosed in Patent Document 1 (Japanese Patent Laid-Open No. 2002-60282), and the primer comprises a non-styrene type vinyl ester resin (70 to 95 parts by weight) and It consists of solvent-free urethane resin (5-30 parts by weight). As the non-styrene type vinyl ester resin, a composition containing 40 to 90 parts by weight of a vinyl ester and 60 to 10 parts by weight of a low volatile radical polymerization type monomer is disclosed in Japanese Patent Application Laid-Open No. 10-231453. And a non-styrene type vinyl ester resin is used alone as a primer for a steel material anticorrosion coating. As a constitution of the non-styrene type vinyl ester resin, a composition containing 40 to 90 parts by weight of a vinyl ester and 60 to 10 parts by weight of a low volatile radical polymerization type monomer is disclosed in JP-A-2000-63448. And a composition containing 40 to 90 parts by weight of a vinyl ester and 60 to 10 parts by weight of a low-volatile radical polymerization monomer as a non-styrene type vinyl ester resin, A primer for a sheet substrate obtained by curing an ester resin and a solventless urethane resin is disclosed in Patent Document 4 (Japanese Patent Laid-Open No. 2000-63449).

  In addition, many proposals have been made on low-odor resin compositions that suppress the odor caused by styrene. For example, a low-volatile polymerizable composition mainly using a polyester acrylate unsaturated polyester is disclosed in Patent Document 5 (Japanese Patent Laid-Open No. 6-211952). Polyacrylic urethane resins, resins having a (meth) methacryloyl group at the molecular ends such as epoxy acrylate, air-drying imparting polymers using a drying oil and / or fatty acid compounds thereof, and a molecular weight of 160 or more A resin composition comprising an ethylenically unsaturated monomer having a (meth) acryloyl group is disclosed in Patent Document 6 (Japanese Patent Laid-Open No. 8-283357). A vinyl ester resin obtained from methacrylic acid and Epicote 828 (manufactured by Yuka Shell Co., Ltd., bisphenol epoxy resin, epoxy equivalent 187) and the like, a polymerizable monomer such as styrene, and glycidoxysilane A lining composition obtained by heat-treating a composition containing it is disclosed in Patent Document 7 (Japanese Patent Application Laid-Open No. 11-12448), and vinyl ester (eg, reaction product of epicoat 828 and methacrylic acid), low A concrete anticorrosive coating material composition containing a non-styrene type vinyl ester resin containing a volatile radical polymerizable monomer and a flaky inorganic filler is disclosed in Patent Document 8 (Japanese Patent Laid-Open No. 10-231453). Has been.

  Bisphenol A and / or F and an aliphatic diglycidyl ether type epoxy compound, epoxy (meth) acrylate, epoxy (meth) acrylate, and a molecular weight of 160 or more and a viscosity at 25 ° C. of 100 mPa · s or less Curable resin composition containing polymerizable (meth) acrylic monomer (II) (Patent Document 9 (Japanese Patent Laid-Open No. 2001-240632)), vinyl ester obtained from epoxy resin and (meth) acrylic acid, and low volatility Alicyclic monofunctional (reactive composition comprising a methacrylic monomer, a solvent-free urethane resin, a primer composition for a rust-free coating for a rust-proof coating (Patent Document 10) (Japanese Patent Laid-Open No. 2002-60282)), a curable resin composition containing a compound obtained by reacting epoxy (meth) acrylic acid (special Document 11 (JP 2006-169311)) have 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, and further, patent literature 11 uses a compound obtained by reacting (meth) acrylic acid with an ethylene oxide adduct of bisphenol A. However, even if such a resin composition is used as a lining material for the surface coating of concrete in sewerage treatment facilities, it has low odor, water resistance, chemical resistance, durability, adhesion, and air drying properties. It is still not enough in performance.

Japanese Patent Laid-Open No. 2002-60282 JP-A-10-231453 JP 2000-63448 A JP 2000-63449 A JP-A-6-211952 JP-A-8-283357 Japanese Patent Laid-Open No. 11-12448 JP-A-10-231453 JP 2001-240632 A Japanese Patent Laid-Open No. 2002-60282 JP 2006-169311 A

  Conventionally, toluene and xylene have been used for moisture-curing urethane primers. Toluene and xylene are excellent in solubility in urethane resin, viscosity reduction, and drying properties, but are regulated by the Poisonous and Deleterious Substances Control Law (Ministry of Health, Labor and Welfare) and the Odor Control Law (Ministry of the Environment). It is also listed as a concentration guideline substance (Ministry of Health, Labor and Welfare) for indoor environmental pollution (sick house). Moreover, these solvents are listed as PRTR (Ministry of Economy, Trade and Industry and Ministry of the Environment) as Class 1 Designated Chemical Substances, and the Ministry of Education, Culture, Sports, Science and Technology has also been measuring concentrations at the time of handing over new construction / renovation works of schools since 2002. Mandatory. Thus, these solvents are expected to become more restrictive in the future due to toxicity problems. As countermeasures against toluene and xylene, water-based primers that use water as the main solvent and systems that use non-aromatic solvents have been proposed, but the former (water-based primer) is impregnated into the ground concrete. There are practical problems such as wettability, poor drying in low-temperature environment in winter, poor adhesion, etc. The latter (non-aromatic solvent) is derived from blister which expands the upper layer coating material when it remains without volatilizing in the primer layer In addition, there are problems such as a long touch drying time (a time until drying can be confirmed by touch when a finger touches) after primer application.

  In addition, as a curable resin composition used for a coating type resin lining material, an unsaturated polyester resin composition 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 an acid is used.

  In the known unsaturated polyester resin composition and vinyl ester resin composition used for the coating type lining material, a styrene monomer is generally used as a copolymerizable monomer. However, since this mixture of ester and styrene has a peculiar odor and diffuses to the environment around the construction, a method of adsorbing the generated styrene with an activated carbon adsorption device has been introduced. For styrene, the PRTR system (Chemical Emission Control Management Promotion Act) has been applied to the system for the release and transfer of the amount of designated type 1 designated chemical substances. Moreover, styrene has been designated as a specified chemical substance on November 1, 2014 (Ministry of Health, Labor and Welfare), and its management is necessary. In addition, styrene concentration in styrene-containing unsaturated polyester resins and vinyl ester resins is regulated. The situation is getting strict and measures are being urged.

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

  Therefore, the object of the present invention is to eliminate the above-mentioned drawbacks of the primer and the anticorrosion coating method of the anticorrosion coating material, and to have a low odor, water resistance, chemical resistance, durability, adhesion, and air drying properties. A resin composition is provided.

  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.

  As a result of intensive studies by the inventors on the above-mentioned problems, as an epoxy acrylate, by using a curable resin composition having an acid value lower than a specific value and in a specific molecular weight range, it has low odor. Thus, it has been clarified that a product excellent in the above characteristics can be easily obtained. Further, an ethoxylated bisphenol A dimethacrylate having 2 to 10 moles of ethylene oxide added and a cyclic hydrocarbon 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. A monofunctional (meth) acrylate monomer having a group containing a group is used in a specific ratio, and a polyol specified by an average molecular weight and a hydroxyl value and a carbodiimide-modified MDI are in a specific ratio. The curable resin composition contained in (1) has excellent adhesion to the concrete substrate, excellent low odor, and is excellent in water resistance, chemical resistance and air drying properties as an anticorrosive coating composition. As a result, the present invention has been reached. That is, the present invention is as follows.

(A) an epoxy (meth) acrylate containing a reaction product of an aromatic epoxy resin and (meth) acrylic acid, having a number average molecular weight in the range of 500 to 1100 and an acid value of 10 KOH mg / g or less;
(B) ethoxylated bisphenol A dimethacrylate of a bifunctional (meth) acrylate monomer having 2 to 10 moles of alkylene oxide addition,
(C) Monofunctional (meth) acrylate system 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 Monomer, and
(D) a polyol having a hydroxyl value of 160 KOHmg / g or less and a number average molecular weight of 1000 or more, and (E) with respect to a total of 100 parts by mass of (A), (B), (C) and (D) (E ) A curable resin composition containing 1 to 30 parts by mass of a polyisocyanate.

  The curable resin composition of the present invention realizes excellent adhesion strength, water resistance, fast-curing and drying film, and low odor to the concrete structure substrate, so that the primer resin composition for concrete anticorrosion coating And is particularly suitable as a curable composition for concrete anticorrosion coating.

  Preferred embodiments of the curable resin composition of the present invention are as follows.

When the curable composition is used as an undercoat (primer) that is applied directly to concrete in the case of concrete anticorrosion coating, the mixing ratio of components (A) to (D) is changed to (A) epoxy (meth) acrylate. -10 to 25 parts by mass of (B) ethoxylated bisphenol A dimethacrylate 5 to 15 parts by mass, (C) monofunctional (meth) acrylate monomer 50 to 70 parts by mass, (D) It is preferable to use 5 to 15 parts by mass of polyol.
Moreover, when using the said curable composition for concrete anticorrosion coating | cover of a film thicker than a primer, the mixture is (A) 30-60 mass parts of epoxy (meth) acrylate, (B) Ethoxylated bisphenol A dimethacrylate 10-30 parts by mass, (C) monofunctional (meth) acrylate monomer-20-40 parts by mass, (D) polyol 5-15 parts by mass Is preferred.

  The curable resin composition is preferably a main agent (main curing agent) containing components (A), (B), (C) and (D), and a secondary main agent (subagent, sub-curing) containing component (E). From the viewpoint of storability, it is preferable to make a so-called two-component main agent (two-component curing agent) that is mixed with the main agent and the auxiliary main agent immediately before use.

  In this curable resin composition, the alkylene oxide is preferably propylene oxide or ethylene oxide (particularly ethylene oxide). It is effective to suppress whitening of the cured resin composition due to room temperature water or hot water immersion. Furthermore, in the curable resin composition using propylene oxide or ethylene oxide (particularly ethylene oxide), the chemical resistance (oxidation resistance) of the cured product is improved.

  Moreover, this invention is also related with the lining material containing the said curable resin composition, Preferably the curable resin composition contains an organic peroxide.

  Furthermore, the present invention provides a concrete containing a filler containing fine particles and / or granular inorganic aggregate materials that are chemically inert to the components (A) to (E) in addition to the curable resin composition. G coating composition.

  The present invention also relates to a lining material containing a filler and preferably an organic peroxide in addition to the curable resin composition. The filler is not particularly limited, but one or more kinds of fine particles and / or granular inorganic aggregate materials that are inert to the resin composition can be used.

  Furthermore, the composition containing the curable resin composition of the present invention and a wax component and / or a paraffin component is used for a top coat layer covering a concrete structure, a primer layer, a lining material and / or another layer (film). It can be used as a composition. Since the composition containing wax (paraffin) is excellent in waterproofness, it is particularly suitable for a top coat layer exposed at the uppermost layer and exposed to water or air. In the case of a two-component main agent, the wax component (paraffin component) may be added to either the main agent or the auxiliary main agent. However, in consideration of dispersibility, if necessary, the wax component should be heated and completely dispersed in the main agent. Is desirable.

  The curable resin composition of the present invention is a non-styrene type vinyl ester resin to which styrene is not added, and is a specific resin having epoxy (meth) acrylate, high reactivity, imparting air drying properties and low volatility. Polymerizable monofunctional (meth) acrylic monomer, ethoxylated bisphenol A dimethacrylate having a specific number of added moles of alkylene oxide (ethylene oxide), and phenyl group for imparting water resistance, heat deterioration resistance and weather resistance A monofunctional (meth) acrylic monomer having a specific composition ratio is used. As a result, there is no styrene volatilization, surface dryness and curability are good, wear resistance of the cured product by increasing / decreasing the composition ratio with inorganic aggregate, when coated with concrete, and when immersed in warm water for a long time Adhesive strength stability is superior to existing styrene-type vinyl ester resin cured products.

  The primer of the present invention has low volatility and hardly causes environmental pollution. Moreover, the dryness of touching the surface of the cured product can be formed in a short time.

  Furthermore, the concrete coating composition and the lining material of the present invention do not generate 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.

  Hereinafter, components (A), (B), (C), (D) and (E) used in the curable resin composition of the present invention and other components which can be optionally added will be described in detail. The present invention is not limited to this.

<Component (A)>
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.

  The aromatic epoxy resin used as a raw material for the aromatic epoxy (meth) acrylate of the component (A) of the resin composition of the present invention is an epoxy resin having an aromatic in the molecule, For example, 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, and the like. These epoxy resins may be used alone or in combination of two or more. Of these, bisphenol A type epoxy resins are more preferred because they provide balanced properties to the concrete coating curable resin composition and the cured lining material.

  The unsaturated monobasic acid to be reacted with the epoxy resin is generally acrylic acid or methacrylic acid, but other unsaturated monobasic acids such as crotonic acid, sorbitan acid, cinnamic acid, acrylic acid dimer, monomethyl acrylate, A small amount of monomethyl fumarate, monocyclohexyl fumarate or sorbic acid can be used in combination. 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, and is an epoxy. The reaction ratio of the resin and (meth) acrylic acid is usually 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 performed at 80 to 130 ° C., and the reaction catalyst includes tertiary amines such as triethylamine and dimethylaniline, quaternary ammonium salts such as trimethylbenzylammonium chloride and pyridinium chloride, lithium hydroxide, lithium chloride and the like. Inorganic salts are used. A polymerization inhibitor is used as necessary.

  Polymerization inhibitors include hydroquinones such as hydroquinone and methylhydroquinone, benzoquinones such as benzoquinone and methyl-p-benzoquinone, catechols such as t-butyl catechol, 2,6-di-t-butyl-t- Examples include phenols such as methylphenol and 4-methoxyphenol, and phenothiazine. The esterification catalyst can be used in the range of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts per 100 parts by mass in total of the aromatic epoxy resin and (meth) acrylic acid. It is the range of mass parts. 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 amount of the aromatic epoxy (meth) acrylate (A) having a number average molecular weight of 500 to 1100 and an acid value of 10 KOHmg / g or less is not particularly limited, but it is a primer resin composition for concrete anticorrosion coating. In the use of the product, the total amount of the curable resin composition of (A), (B), (C) and (D), which is an essential component constituting the curable resin composition of the present invention, is 100 parts by mass (% by mass). ) To 10 to 25 parts by mass (mass%). If the amount is less than 10 parts by mass, the cured product of the resulting curable resin composition has low film strength, and whitening occurs when immersed in warm water for a long time. When the amount exceeds 25 parts by mass, the composition becomes highly viscous, so that the permeability to the concrete is low, and adhesion peeling tends to occur on the surface of the concrete.

  The amount of (A) used can be appropriately changed according to the application. For example, in the use of a curable resin composition for concrete anticorrosion coating, the amount of aromatic epoxy (meth) acrylate (A) used is (A) It is the range of 30-60 mass parts with respect to a total of 100 mass parts of (D) component. If the amount is less than 30 parts by mass, the cured product of the resulting curable resin composition causes a whitening phenomenon when immersed in warm water for a long time, and if it exceeds 60 parts by mass, a shrinkage crack is likely to occur during curing. In any case, if the number average molecular weight of the aromatic epoxy (meth) acrylate (A) is less than 500, there is a drawback that the terminal acryloyl group concentration becomes too high and the water absorption is increased. As the ester bond density increases, the alkali resistance decreases. On the other hand, if the number average molecular weight exceeds 1100, the viscosity of the curable resin composition during synthesis and the curable resin composition becomes too high, resulting in poor workability and poor solvent resistance. In the present invention, the number average molecular weight is a value measured using a high performance liquid chromatography GPC method (gel permeation chromatography method).

  In order to balance the above performance, 0.3 mol% to 0.7 mol% of a liquid type epoxy resin having a molecular weight of 500 or less and 0.7 wt% of a solid type epoxy resin having a molecular weight of 900 or more in 1 mol of an aromatic epoxy resin. Using a resin having a composition ratio of ˜0.3 mol%, an aromatic epoxy (meth) acrylate is obtained from a reaction product of this resin and (meth) acrylic acid. An acid value of 10 KOH mg / g or more is not preferable because an unsaturated monobasic acid acrylic acid or methacrylic acid monomer having an irritating odor remains in the aromatic epoxy (meth) acrylate. The molecular weight is a polystyrene equivalent value, and the acid value is a value measured according to JIS-K-2501-2003.

<Component (B)>
As the alkylene oxide addition constituting the resin composition (B) used in the present invention, in particular, as the ethoxylated bisphenol A dimethacrylate having 2 to 10 moles of ethylene oxide addition, bisphenol A and / or bisphenol- An ester compound of a divalent alcohol obtained by adding alkylene oxide to F and methacrylic acid may be mentioned. As for bisphenol, bisphenol A is preferable, and in this case, ethylene oxide is more preferable in consideration of reactivity.

  In the present invention, when the number of moles of ethylene oxide added to the ethoxylated bisphenol A dimethacrylate of (B) exceeds 10, the crosslinking density is unnecessarily lowered and the reactivity of the curable resin composition is only lowered. Instead, the water resistance of the cured product, particularly the rate of change in weight when immersed in room temperature water and warm water, is increased. In addition, chemical resistance, especially in the test methods specified by the guidelines of the Japan Sewerage Corporation, increases the penetration depth and decreases the affinity and adhesive strength with fiber reinforcements. Use proved unsuitable. In this test method, the cured product is immersed in a 10% sulfuric acid aqueous solution for 120 days, and the durability life prediction of the lining material is performed based on the penetration depth of sulfur in sulfuric acid with an electron beam microanalyzer (EPMA). . 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 too high and the work becomes difficult.

  In the present invention, the content of the alkylene oxide-added alkoxylated bisphenol A dimethacrylate (B) is not particularly limited. However, in the application of the primer resin composition for concrete anticorrosion coating, (A), (B), (C ) And (D) in a total amount of 100% by mass (parts by mass), preferably 5 to 15% by mass (parts by mass). That is, when it is less than 5% by mass, a whitening phenomenon occurs on the surface of the cured product of the resulting curable resin composition when immersed in normal temperature water and warm water. On the other hand, if it exceeds 15% 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.

  The usage-amount of (B) can be suitably changed according to a use. For example, in the use of the curable resin composition for concrete anticorrosion coating, it is 10-30 with respect to a total of 100 mass% of component (A)-(D). It is the range of mass%. If it is less than 10% by mass, a whitening phenomenon occurs on the surface of the cured product of the resulting curable resin composition when immersed in normal temperature water and warm water. On the other hand, if it exceeds 30% 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 can be produced by a known method described in JP-A-7-268079. Specifically, first, an ethylene oxide adduct of bisphenol A is prepared. As the diglycidyl ether, a nucleated polyol obtained by adding ethylene oxide to bisphenol A and an epihalohydrin are subjected to an ether reaction to obtain ethylene oxide-added bisphenol A diglycidyl. An esterification catalyst is then used to obtain ethoxylated bisphenol A di (meth) acrylate, which is a reaction product with methacrylic acid or acrylic acid.

<Ingredient (C)>
In the present invention, a monofunctional (meth) acrylate system having a group containing a cyclic hydrocarbon group having one carbon-carbon double bond or one nitrogen atom as an alcohol residue in the ring represented by (C) A monomer having a molecular weight of 240 or more, a viscosity at 25 ° C. of 100 mPa · s or less (using a Brookfield viscometer described in 4.4.1 of JIS K6901), and a vapor pressure of 0.5 mmHg or less. preferable. Specifically, dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, pentamethylpiperidyl methacrylate, and Pentamethylpiperidyl acrylate and the like are listed, and these may be used alone or in combination of two or more. Among these, in the present invention, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyl methacrylate, because of low odor, reactivity, and properties of the cured product, It is preferable to use one or more selected from the group consisting of pentamethylpiperidyl methacrylate.

  Although the usage-amount of the said monofunctional (meth) acrylic-type monomer (C) is not specifically limited, In the use of the primer resin composition for concrete anticorrosion coating, it is an essential component (A), (B), (C) and It is the range of 50-70 mass parts (mass%) with respect to 100 mass parts (mass%) of the total amount of (D), and if it is less than 50 mass parts, the permeability to the concrete of the curable resin composition cured product. And surface finger touch dryness is inferior, and the viscosity of the curable resin composition becomes too high, resulting in poor workability. Moreover, when it exceeds 70 mass parts, a swelling will generate | occur | produce on the surface of hardened | cured material at the time of high temperature water immersion, and it will be inferior to durability. Therefore, it is preferable to use in the said range of 50-70 mass parts.

  (C) The usage-amount of a component can be suitably changed according to a use, for example, in the use of the curable resin composition for concrete anticorrosion coating, the usage-amount of monofunctional (meth) acrylic-type monomer (C) is, It exists in the range of 20-40 mass parts with respect to a total of 100 mass parts of component (A)-(D), and when it is less than 20 mass parts, the surface touch dryness of hardened | cured material is inferior, and the viscosity of curable resin composition Becomes too high, and workability is very poor. Moreover, when it exceeds 40 mass parts, the swelling of the cured | curing material surface will become large at the time of high temperature water immersion, and it will be inferior to durability. Therefore, it is more preferable to use in the said range 20-40 mass parts.

<Component (D)>
In the present invention, specific examples of the component represented by (D), that is, a polyol having a hydroxyl value of 160 KOH mg / g or less and a number average molecular weight of 1000 or more include polyoxypropylene diol and polyoxypropylene triol. Polyoxypropylene ethylene triol, and other triol derivatives such as polyether polyol such as glycerin, trimethylolpropane and hexanetriol can also be used. It is preferable to use a glycerol polyester polyol alone or a mixture of a triol and a diol, the average functional group number 2-3 of the polyol or a mixture thereof, a number average molecular weight of 1000 or more, A hydroxyl value of 160 or less (mgKOH / g) is preferred. Here, the average number of functional groups is the number of functional groups (active hydroxyl groups) that react with NCO groups per molecule of polyol. The hydroxyl value is a value measured by applying the method A described in JIS K1557-1: 2007 “Plastics—Polyurethane raw material polyol test method—Part 1: Determination of hydroxyl value”. For the number average molecular weight, the hydroxyl value is used and the following formula (1):
Average molecular weight = (56,110 × number of functional groups) / (hydroxyl value) (1)
Is a value calculated by

  When the polyol is a mixture, each polyol component preferably has the above-mentioned preferred hydroxyl value (160 or less). However, if the hydroxyl value measured by the above method for the entire mixture is 160 mgKOH or less, The hydroxyl value of one or more polyol components may exceed 160 mgKOH. Each polyol component preferably has a number average molecular weight of 1000 or less, but any number of polyols may have a number average molecular weight of less than 1000 as long as the number average molecular weight of the entire mixture is 1000 or less. . In the case of a mixture of n types of polyols (n is an integer of 1 or more), the product obtained by multiplying the number average molecular weight of each polyol by the molar ratio of the polyol (number of moles of a single polyol / number of moles of the entire polyol mixture). Each of the n types of polyols is calculated, and the sum of these calculated products is the number average molecular weight of the entire mixture.

  Preferably, the polyol (D) may be a polyoxypropylene triol alone or a mixture of a polyoxypropylene triol and a polyoxypropylene diol. A bifunctional diol alone is not preferable because the dry time of touching the surface of the cured product becomes long. In addition, the molar ratio (polyoxypropylene triol / polyoxypropylene diol) is preferably 1.0 / 0 to 0.4 / 0.6. The number average molecular weight of the polyol is preferably 1000 to 5000, more preferably 1000 to 4000, as the molecular weight per hydroxyl group. If the number average molecular weight is less than 1000, the curing rate becomes too fast, the cured product becomes brittle, and bulges are generated when immersed in water and warm water, which is not preferable. On the other hand, if the number average molecular weight exceeds 5,000, the curing rate becomes slow, the surface drying time becomes long, and the concrete adhesion strength also decreases, which is not preferable.

  The amount of the above-mentioned polyol (D) used is a total of 100 masses of (A), (B), (C) and (D) regardless of whether it is a primer for concrete anticorrosion coating, a concrete anticorrosion coating, or any other use. If it is less than 5 parts by mass, the cured primer product has poor adhesion strength. Moreover, since the surface drying property of a cured film will be inferior when it exceeds 15 mass parts, it is preferable to use in the said range of 5-15 mass parts.

<Ingredient (E)>
Component (E) is preferably at least a component separate from component (D), and when component (E) is a secondary agent, the secondary agent may contain additives other than component (E). . Below, a component (E) is demonstrated in detail.

  In the present invention, (E) polyisocyanate is a compound containing two or more isocyanate groups. For example, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate (TDI) ), 2,6-tolylene diisocyanate (TDI), 1-chloro-2,4-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4 , 4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 2,2'-diphenylmethane diisocyanate (2,2′-MDI), 3,3′-methoxy-4,4′-biphenylene diisocyanate, 2,2 ′, 5,5′-tetramethyl-4,4′-biphenylene diisocyanate -G, 1 5-naphthalene diisocyanate (NDI), 4,4′-diphenylpropane diisocyanate and the like, and derivatives of these isocyanates, carbodiimides, uretonimines, etc., polymethylene polyphenyl polyisocyanate One or more selected from the group consisting of aromatic polyisocyanates such as

  Among these, it is preferable to use at least one selected from isocyanurates of diphenylmethane diisocyanate MDI. These MDIs alone or 4,4′-diphenylmethane diisocyanate (4 , 4′-MDI) and 2,4′-diphenylmethane diisocyanate (2,4′-MDI) are preferably used.

  The amount of the polyisocyanate compound (E) of the present invention used is a primer for concrete anticorrosion coating, a concrete anticorrosion coating, or any other use, which constitutes the curable resin composition of the present invention (A), (B), (C) and (D) are in the range of 1 to 30 parts by mass with respect to 100 parts by mass in total, and if it is less than 1 part by mass, the cured product of the primer composition has poor adhesion strength, and 30 parts by mass If it exceeds 1, the surface drying property of the cured film is inferior. Therefore, the use within the above range is preferable.

<Other ingredients>
The resin composition of the present invention can be used only with the above components (A) to (E), but other components can also be added. When the curable resin composition is used as two or more drugs (eg, main and auxiliary main agents), these other components may be added to any one or more drugs. Specific examples of other components will be described below.

  Considering the sick house problem and the regulation of styrene emission concentration by the PRTR method, the chemical substance emission control management registration method (PRTR method) etc., the following polymerizable vinyl monomers for crosslinking are added as other components to greatly increase the polymerizable monomers for crosslinking. It may be used as a resin composition that alleviates the above. This component is preferably used by being added to the main agent.

  Examples of the polymerizable vinyl monomer for crosslinking include aromatic styrene, vinyl toluene, and α-methylstyrene. Further, methacrylic methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate and the like can be mentioned. These crosslinking polymerizable monomers may be used alone or in combination of two or more, but styrene is generally used. The compounding amount of the crosslinkable polymerizable vinyl monomer is 40 parts by mass with respect to a total of 100 parts by mass of (A), (B), (C) and (D) (content of polymerizable monomer for crosslinking is 30% or less). The following is preferred. Usually, the content of the crosslinkable polymerizable monomer of the vinyl ester resin is 40 to 50 parts by mass. For this reason, it can be applied as a low crosslinkable polymerizable monomer-containing resin composition capable of greatly reducing the content of the crosslinkable polymerizable monomer and significantly reducing the volatilization amount during operation.

  The resin composition of the present invention is characterized in that only the above components (A) to (D) and (E) are excellent in drying properties, but for the purpose of improving drying properties, paraffin and / or waxes are used. You may use together. When the curable resin composition is a two-component type, it is preferable to add the paraffin and / or wax to the main agent. Since the resin composition containing paraffin and / or waxes has high oxygen shielding properties, it is particularly suitable for a top coat layer covering the outermost surface.

  Examples of paraffins and / or waxes used in the resin composition of the present invention include paraffin wax, polyethylene wax, or higher fatty acids such as stearic acid and 1,2-hydroxystearic acid, preferably paraffin. Wax is used. 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 an addition rate, it is 0.1-5 mass parts with respect to 100 mass parts of resin compositions of component (A), (B), (C), and (D), Preferably it is 0.2-2 mass parts.

  Examples of inert fine particle and / or powdery inorganic aggregate materials that can be used in the present invention include sand, silica powder, crushed rock, calcium carbonate, alumina powder, clay, quartzite powder, talc, glass powder, and silica powder. -Aluminum hydroxide, silica sand, aluminum silicate, magnesium silicate, cement and the like can be used. When the curable composition is made into a two-component type, these inorganic bone materials can be added to either or both of the main agent and the auxiliary main agent, but are preferably added to the main agent in consideration of dispersibility. .

  Furthermore, the amount of inert fine particles and / or granular inorganic aggregate material used depends on workability such as desired fluidity and is determined by the strength of the cured product of the concrete composition. The addition amount is set in a range of 30 to 600 parts by mass with respect to 100 parts by mass in total of components (A), (B), (C), and (D) of the curable resin composition. The average particle diameter of the inorganic aggregate is 0.02 to 10 mm, preferably 0.05 to 5 mm. Moreover, the silica sand of the aggregate is No. 1 silica sand (average particle diameter of 5 to 2.5 mm), No. 2 silica sand (particle diameter of 2.5 to 1.2 mm), No. 3 silica sand (particle diameter) specified by JISG5901-1968. 1.2-0.6 mm), No. 4 silica sand (particle size 0.6-0.3 mm), No. 5 silica sand (grain sand 0.3-0.15 mm), No. 6 silica sand (grain sand 0.15-0) 074 mm) and No. 7 silica sand (particle size of 0.074 mm or less) can also be used.

  Inactive fine particles and / or granular inorganic aggregate materials that can be used in addition to silica sand are calcium carbonate, fly ash, clay, alumina powder, silica powder, talc, silica powder, glass powder, mica, hydroxylation Aluminum, aluminum silicate, magnesium silicate, cement, marble and the like are preferable. The average particle diameter of the fine particles is preferably about 0.5 μm to 20 μm. This inert fine particle and / or granular inorganic aggregate material addition rate is 2. with respect to a total of 100 parts by mass of the components (A), (B), (C) and (D) of the curable resin composition. It is preferred to add 5 to 100 parts by weight of filler. Moreover, a filler may be used independently or may use 2 or more types together.

  The curable resin composition of the present invention can be used only with the resin compositions (A), (B), (C), (D) and (E), but the curable resin composition of the present invention Among these, it is related with the concrete lining material which added 5-50 mass parts scale-like inorganic filler with respect to a total of 100 mass parts of (A), (B), (C), and (D). When making a curable composition into a 2 liquid type, it is preferable to add a scaly inorganic filler to a main ingredient in consideration of dispersibility.

  Examples of the scale-like inorganic filler include glass flakes and mica flakes. Among these, it is more preferable to use glass flakes. As the flaky inorganic filler, those having an average particle diameter of 10 to 4000 μm can be usually used, but in order to keep the workability of the concrete coating composition well, the average particle diameter of 100 to It is more preferable to use one having a range of 1000 μm.

  The organic peroxide added to the curable resin composition, particularly the main agent in the present invention includes ketone peroxides such as methyl ethyl ketone peroxide; hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide. Peroxyesters such as t-butyl peroxyoctate and t-butyl peroxybenzoate; Dialkyl peroxides such as dicumyl peroxide; Diacyl peroxides such as lauroyl peroxide, benzoyl peroxide Known materials such as oxide are used.

  The amount of organic peroxide used is 0.01 with respect to 100 parts by mass of the total amount of (A), (B), (C) and (D) constituting the resin composition used in the present invention, particularly the main agent. It is the range of -10 mass parts.

  The present invention further includes 0.01 to 5 parts by mass of an aromatic amine accelerator and / or a polyvalent metal salt with respect to a total of 100 parts by mass of (A), (B), (C) and (D). / Or a complex is added to the curable resin composition (especially the main agent), and then a thermosetting resin composition (or main agent) mixed with an organic peroxide is formed, and this thermosetting resin composition (or main agent) is formed. And an auxiliary agent) are added to accelerate the curing of the lining material. If it is less than 0.01 part by mass, curing is not sufficient, and if it exceeds 5 parts by mass, no further effect is exhibited.

  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, examples of the polyvalent metal salt and / or complex include naphthenic acid and polyvalent metal salt of octenoic acid, and examples of the polyvalent metal include calcium, copper, manganese, cobalt, vanadium and the like. Particularly preferred are cobalt octylate and cobalt naphthenate.

  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. . When the curable composition is a two-component type, these additives may be added to either the main agent or the auxiliary main agent, but it is preferable to add them to the main agent in consideration of dispersibility.

  The present invention will be described by way of examples, but the present invention is not limited thereto. In the examples, “part” is “part by mass” unless otherwise specified.

-Production of aromatic epoxy methacrylate component (A):
As a epoxy resin, 148 g of jER828, 360 g of jER1001, and 240 g of jER1002 were added as epoxy resins to a 2 liter four-necked flask equipped with a stirrer, a condenser, a thermometer, and an air introduction tube. The temperature was raised to 130 ° C. while blowing 10 liters of dry air every minute. 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. The measurement of the acid value was started every 1 hour after 3 hours had passed after the completion of dropping, and after confirming that it was 10 KOHmg / g or less, the mixture was cooled to 100 ° C. to obtain component (A). It was about 750 when the number average molecular weight of this component (A) was measured by the method mentioned later.

-Blending of components (A) to (E) To 200 parts by mass of component (A) prepared in the above step, 2.6 mol of ethylene oxide addition ethoxylated bisphenol A dimethacrylate (B) (Shin Nakamura Chemical Co., Ltd.) 100 parts by mass of BPE-100), 600 parts by mass of dicyclopentenyloxyethyl methacrylate (C) (Hitachi Chemical Industry Co., Ltd., FA-512MT), and polyether polyol (D) (Asahi Glass Co., Ltd. Exanol E240) : Number average molecular weight 3000, hydroxyl value 56 mg KOH / g) 100 parts by mass was added and dissolved, and cooled to room temperature. A curable primer resin composition obtained by adding 10 parts by mass of a polyisocyanate compound as an auxiliary agent of component (E) to 100 parts by mass of this mixture (100 parts by mass of the mixture of components (A) to (D)). It was.

  The polyisocyanate compound is Cosmonate LK manufactured by Mitsui Chemicals, Inc., 15 to 25% carbodiimide-modified MDI, 70 to 80% methylenebis (4,1-phenylene) diisocyanate, 2,4 1-5% of diphenylmethane diisocyanate is contained (all by mass).

  Chop on a release-treated glass plate using a composition in which 6% cobalt naphthenate, peroxide (NOF Percure-K) and dimethylniline were mixed in the composition shown in Table 1 below. Strand mat MC-450 (manufactured by Nitto Boseki Co., Ltd.) 3 plies (3 sheets) were laminated on FRP having a glass content of 30% and cured at 25 ° C. for 72 hours to obtain a laminate. The following test was done about this laminated board and resin composition.

-Measurement method The amount of wear was 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.

  The number average molecular weight was measured by high performance liquid chromatography (GPC) and indicated as a polystyrene equivalent value.

  As the volatilization amount of styrene, 100 g of a mixture obtained by thoroughly mixing 6% cobalt naphthenate, peroxide, and dimethylniline with a curable resin composition in the composition shown in Table 1 was placed in a glass dish having a diameter of 145 mm, and 60 minutes After weight change rate was measured.

  The bar hardness of the hardness test was measured based on the measurement method specified in JIS K7060 (Barcol hardness test method of glass fiber reinforced plastic).

  EPMA (electron beam microanalyzer) was obtained by immersing the laminate in a 10% sulfuric acid aqueous solution for 120 days and measuring 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.

For the surface drying time, the blended compounds in the proportions shown in Table 1 were applied onto a glass plate at 20 ° C. room temperature using an applicator. For this coating film, a finger touch test is performed for surface drying. Furthermore, the evaluation method measured the time until the absorbent cotton did not remain on the coating film surface even if the absorbent cotton (the area of one side was about ² to 3 cm ² ) was pressed against the coating film surface.

  The concrete adhesion strength was measured by a Kenken tensile tester according to JIS A6916, and the adhesive strength was measured.

The concrete peeling test was conducted using a JIS 5304 standard sidewalk board (size: 300 mm x 300 mm) as a primer with the composition of the curable resin composition of each example (mixed in the proportions described in each table) as a primer. After coating at 150 g / m ² and touch-drying (touch with finger to confirm drying), 100 parts by mass of the curable resin composition of each example and 30 parts by mass of glass flake RCF-140 (manufactured by Nippon Sheet Glass Co., Ltd.) , Crystallite AA (silica stone powder manufactured by Tatsumori Co., Ltd.) 20 parts by mass, 1.5% by mass of 6% cobalt naphthenate, and 2.5 parts by mass of peroxide (NOF Percure-K) A base material prepared by applying 700 g / m ² as a substrate preparation material, dried by touching, and further adding 10 parts by weight of glass flake RCF-140 to 100 parts by weight of the primer curable resin composition. Surface protection 1 kg / ^{m 2} coated with (thickness 0.6 mm) was formed anticorrosive coating layer as. After curing at 25 ° C. for 72 hours, in an FRP plate of width × length × thickness = 20 mm × 90 mm × 2 mm, the unbonded portion was left at one end in the length direction and adhered with an epoxy adhesive. A hole with a diameter of 2 mm was formed 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 in accordance with the vulcanized rubber adhesion test method of JIS K6256.

  Regarding the rate of change in weight, 10 g of the resin composition having the blending ratio of Example 1 was thoroughly mixed, poured into a glass dish having a diameter of 40 mm (height 15 mm), cured at 25 ° C. for 72 hours, and then demolded. After the casting was immersed in warm water (80 ° C.) for 96 hours, the rate of weight change was measured. Moreover, EPMA, Barcol hardness, and abrasion amount were measured by the above-mentioned method.

-Measurement result of Example 1 As shown in Table 1, when the resin composition of Example 1 was used, the concrete adhesion strength and the concrete peeling strength were high. Moreover, when the specimen which laminated | stacked the primer which used the resin composition of Example 1, the base material preparation material, and the surface protection material on the concrete was immersed in the 80 degreeC warm water whole surface and observed 60 days later, primer was obtained. -No abnormality was observed between the layers, the base material adjusting material layer and the surface protective layer (warm water immersion test). The concrete adhesion strength and concrete peeling strength after the warm water immersion maintained the initial values. Moreover, warm water (80 degreeC) immersion water absorption showed the low value with 1.2%.

  150 parts by mass of the same aromatic epoxy methacrylate (A) as in Example 1, 100 parts by mass of ethylene oxide 6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Kyoeisha Chemical Co., Ltd. BP-6EM), 650 parts by mass of dicyclopentenyloxyethyl methacrylate (C) and 100 parts by mass of polyol (D) (Asahi Glass Co., Ltd. Exanol E240) were added and dissolved, then cooled to room temperature, and the above (A), ( 10 parts by mass of an isocyanate compound (Cosmonate LK manufactured by Mitsui Chemicals) was added to 100 parts by mass of the total of B), (C) and (D) to obtain a curable primer resin composition.

  To this resin composition, 6% cobalt naphthenate, peroxide (Nippon Percure-K) and dimethylniline were added according to the formulation shown in Table 1, and the laminate was formed by the method described in Example 1. The laminate and the resin composition were prepared and tested in the same manner as in Example 1. The results are shown in Table 1. Also in Example 2, the concrete adhesion strength and the concrete peeling strength were high. Moreover, when the same hot water immersion test as Example 1 was done, there was no abnormality in each layer of a primer layer, a base material adjusting material layer, and a surface protective layer. Moreover, the hot water (80 degreeC) immersion water absorption showed the low value around 1%.

  200 parts by mass of the same aromatic epoxy methacrylate (A) as in Example 1, 50 parts by mass of ethylene oxide 6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Kyoeisha Chemical Co., Ltd. BP-6EM), 600 parts by mass of dicyclopentenyloxyethyl methacrylate (C) (Hitachi Chemical Industry Co., Ltd., FA-512MT), 150 parts by mass of polyol (D) (Asahi Glass Co., Ltd. Exenol E1030: number average molecular weight 1,000) In addition, after dissolution and cooling to room temperature, 20 mass of isocyanate compound (Cosmonate LK manufactured by Mitsui Chemicals) with respect to a total of 100 mass parts of (A), (B), (C) and (D). To make a resin composition, and then add 6% cobalt naphthenate, peroxide (Nissan Percure-K) and dimethylniline in the composition shown in Table 1 to make a composition. Made.

  Using this blend, a laminate was prepared under the same conditions as in Example 1, and this laminate and resin composition were tested in principle by the same method as in Example 1, but the concrete peeling test was performed. Was carried out except that the amount of 6% cobalt naphthenate was changed to 1.0 part by mass and the amount of Percure-K was changed to 2.0 parts by mass with respect to 100 parts by mass of the resin composition for the substrate conditioner. The conditions were the same as in Example 1.

  Ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Shin-Nakamura Chemical Co., Ltd. BPE-100) to 150 parts by mass of the same aromatic epoxy methacrylate (A) as in Example 1. 150 parts by mass, 550 parts by mass of dicyclopentenyloxyethyl methacrylate (C), 150 parts by mass of polyol (D) (Asahi Glass Co., Ltd. Exanol E240) were added and heated to 70 ° C. After adding 20% concentration 120 degrees F / (FA-512MT) paraffin wax in the formulation of Table 1 and dissolving, the mixture was cooled to room temperature, and a total of 100 of the above (A), (B), (C) and (D) 25 parts by mass of an isocyanate compound (Cosmonate LK manufactured by Mitsui Chemicals) was added to the mass part to obtain a curable resin composition.

  A laminate was prepared under the same conditions as in Example 1, using a composition in which 6% cobalt naphthenate, peroxide (Nissan Percure-K) and dimethylniline were further added to the above composition. About this laminated body and resin composition, each test was done on the same conditions as Example 1 except having changed the concrete peeling test into the same conditions as Example 3. FIG. The results are listed in Table 1.

<Comparative Example 1>
The same epoxy resin as in Example 1 (148 g of jER828 from Mitsubishi Chemical Corporation, 360 g of jER1001 and 240 g of jER1002) was stirred and heated under the same conditions as in Example 1 and heated to 130 ° C., and then hydroquinone (Polymerization inhibitor) 0.3 g and trimethylbenzylammonium chloride 2 g 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 became 17 KOH mg / g, the mixture was cooled to 100 ° C. and a component having a number average molecular weight of 750 ( A) was obtained. To 400 parts by mass of this aromatic epoxy (meth) acrylate (A), 2.6 parts by mass of ethylene oxide of Example 1, ethoxylated bisphenol A dimethacrylate (B) 500 parts by mass and dicyclopentenyloxyethyl 100 parts by weight of methacrylate (C) was added and dissolved, and then cooled to room temperature to obtain a resin composition. The blend obtained by adding 6% cobalt naphthenate, dimethylaniline and Percure-K in Table 1 to this resin composition was uncured even after 24 hours at 25 ° C.

<Comparative example 2>
The same amount of the aromatic epoxy (meth) acrylate (A) as in Comparative Example 1 was added to 200 parts by mass of the ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) of Example 1 and di The above-mentioned (A), (B) cooled to room temperature after adding 400 parts by mass of cyclopentenyloxyethyl methacrylate (C) and 350 parts by mass of polyol (D) (Asahi Glass Co., Ltd. Exanol E240) , (C) and (D) were added to 40 parts by mass of an isocyanate compound (Cosmonate LK manufactured by Mitsui Chemicals) with respect to 100 parts by mass in total to obtain a resin composition for a curable primer. The composition obtained by adding 6% cobalt naphthenate, dimethylaniline and Percure-K to the composition shown in Table 1 was uncured even after 24 hours at 25 ° C.

<Comparative Example 3>
After adding 500 parts by mass of the phenoxyethyl methacrylate (C) of Example 1 to 500 parts by mass of the same aromatic epoxy methacrylate (A) as in Comparative Example 1, the resin composition was cooled to room temperature. I got a thing. A blend obtained by adding 6% cobalt naphthenate, dimethylaniline and Percure-K in the blend of Table 1 to this resin composition was uncured after 24 hours at 25 ° C.

<Comparative example 4>
-Production of aromatic epoxy methacrylate (A) (number average molecular weight about 1300)
Into the same four-necked flask as in Example 1, 93 g of jER828 (Mitsubishi Chemical), 180 g of jER1002 (Mitsubishi Chemical) and 990 g of jER1004 were charged and heated to 130 ° C. while blowing 10 liters of dry air per minute with 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. The acid value measurement was started every hour after 3 hours from the end of the dropping, and after confirming that the acid value reached 18 KOH mg / g, the mixture was cooled to 100 ° C. and aromatic epoxy methacrylate having a number average molecular weight of about 1300. A product of rate was obtained.

-Composition of components (A) to (E) The components (B), (C) and (D) were added to the 40 parts by mass of the product in the following Table 1 and dissolved, and then cooled to room temperature (A ), (B), (C) and (D) in total, 100 parts by mass of (E) isocyanate compound was added to obtain a resin composition. For component (B), ethylene oxide 30 mol addition ethoxylated bisphenol A dimethacrylate (Shin-Nakamura Chemical Co., Ltd. NK Light Ester BPE-1300) was used, and components (C) and (D) were examples. The same type as 1 was used. To this resin composition, as shown in the following table, 6% cobalt naphthenate, dimethylaniline and Percure-K were added to prepare a blend. The cured product was characterized in the same manner as in Example 1. The value was measured. The results are shown in the table below.

  The resin composition obtained by adding 6% cobalt naphthenate, dimethylaniline, and Percure-K in the composition shown in Table 1 has low concrete adhesion strength and concrete peeling strength, and After the specimen, in which the primer, the base material adjusting material, and the surface protective material are laminated on the concrete, is immersed in warm water at 80 ° C. for 25 days, all layers of the primer layer, the base material adjusting material layer, and the surface protective layer are used. Innumerable minute blisters and peeling occurred. Moreover, the hot water (80 degreeC) immersion water absorption rate is as high as about 3 times of the resin composition of this invention, and the fall rate with respect to the initial value of the concrete adhesion strength and concrete peeling strength after warm water immersion is large.

<Comparative Example 5>
Ethylene oxide 30 mol addition ethoxylated bisphenol A dimethacrylate (Shin Nakamura Chemical Co., Ltd. NK) to 45 parts by mass of aromatic epoxy methacrylate (A) having a number average molecular weight of 1300 obtained in the production of Comparative Example 4 Light ester BPE-1300) (B) 3 parts by mass, dicyclopentenyloxyethyl methacrylate (C) 32 parts by mass, polyol (D) (Asahi Glass Co., Ltd. Exenol E240) 20 parts by mass are added and dissolved. Then, it cooled to room temperature. A curable primer obtained by adding 40 parts by mass of an isocyanate compound (Cosmonate LK manufactured by Mitsui Chemicals) to 100 parts by mass in total of the above (A), (B), (C) and (D). -A resin composition was obtained. A blend obtained by adding 6% cobalt naphthenate, dimethylaniline and Percure-K in Table 1 to this resin composition has a long surface drying time, a concrete adhesion strength and a peeling strength with a concrete. Decreased drastically after immersion in room temperature water and warm water. In addition, a specimen in which a primer, a base material adjusting material, and a surface protective material are laminated on a concrete is immersed in warm water at 80 ° C. for 7 days and then minutely between each layer of the primer layer, the base material adjusting material layer, and the surface protective layer. Numerous swelling and peeling occurred. Moreover, the warm water (80 degreeC) immersion weight change rate is as high as about 3 times the Example of this invention. About this curable resin composition, the cast material 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.

<Comparative Example 6>
In place of components (A) to (E), 6% cobalt naphthenate and methyl ethyl ketone peroxide (NOF Parmec NS) shown in Table 1 were added to 100 parts by mass of styrene type vinyl ester resin (Showa Denko Lipoxy R804). The concrete adhesion strength, peeling strength with concrete, and styrene volatilization amount were measured. The measurement results are shown in Table 1. The amount of styrene volatilized is as high as 80 g / m ² . A compound obtained by adding 6% cobalt naphthenate and methyl ethyl ketone peroxide (NOF Parmec NS) shown in Table 1 to 100 parts by mass of the styrene type vinyl ester resin was cast by the method described in Example 1. Articles and laminates were prepared and characteristic values were measured, and EPMA, Barcol hardness and wear were also measured. The results are shown in Table 1.

<Comparative Example 7>
Ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) (new) to 30 parts by mass of aromatic epoxy methacrylate (A) having a number average molecular weight of 1300 obtained in the production of Comparative Example 4 Nakamura Chemical Co., Ltd. BPE-100) 10 parts by mass, dicyclopentenyloxyethyl methacrylate (C) 40 parts by mass, polyol (D) (Asahi Glass Co., Ltd. Exanol E240) 20 parts by mass was added to 70 ° C. Further, 20% 120 degrees F / (FA-512MT) paraffin wax was dissolved in the formulation shown in Table 1 and dissolved, and then cooled to room temperature. The above (A), (B), (C) and ( D) 35 parts by mass of an isocyanate compound (Cosmonate LK manufactured by Mitsui Chemicals) (E) is added to 100 parts by mass of the total to obtain a wax-containing resin composition. 6% in combination Putian cobalt, dimethylaniline and Pas - give a formulation with the addition of curing -K, characteristic values were measured by the method described in Example 1. The results are shown in Table 1.

  In principle, each evaluation was performed using the composition of Comparative Example 7 under the same conditions as in Example 1. However, only the concrete peeling test was performed under the same conditions as in Example 3. The results are listed in Table 1 below.

<Comparative Example 8>
Ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) (new) to 30 parts by mass of aromatic epoxy methacrylate (A) having a number average molecular weight of 1300 obtained in the production of Comparative Example 4 Nakamura Chemical Co., Ltd. BPE-100) 10 parts by mass, dicyclopentenyloxyethyl methacrylate (C) 25 parts by mass, polyol (D) (Asahi Glass Co., Ltd. Exanol E240) 35 parts by mass The mixture was cooled to room temperature to obtain a mixture. 100 parts by mass of the mixture was heated to 70 ° C. to dissolve 2.0 parts by mass of 20% 120 ° F./(FA-512MT) paraffin wax. A curable primer obtained by adding 35 parts by mass of an isocyanate compound (Cosmonate LK manufactured by Mitsui Chemicals) to 100 parts by mass in total of the above (A), (B), (C) and (D). -A resin composition was obtained. A resin composition was prepared by adding 6% cobalt naphthenate, dimethylaniline and Percure-K in the formulation shown in Table 1, and the same items as in Example 1 and the surface drying property were measured.

-Production of aromatic epoxy methacrylate (A) having a number average molecular weight of about 750:
The four-necked flask used in Example 1 was charged with 148 g of jER828 (Mitsubishi Chemical), 360 g of jER1001 (Mitsubishi Chemical) and 240 g of jER1002, and heated to 130 ° C. while blowing 10 liters of dry air per minute with 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. The acid value measurement was started every 1 hour after 3 hours had passed after the completion of the dropwise addition, and after confirming that it was 10 KOH mg / g or less, the product was cooled to 100 ° C. to obtain the product (A). .

-Blending of resin composition 200 parts by mass of ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Shin-Nakamura Chemical Co., Ltd. BPE-100) to 450 parts by mass of the above product, dicyclopentenyloxy Isocyanate with respect to a total of 100 parts by mass of 250 parts by mass of ethyl methacrylate (C) (Hitachi Chemical Industry Co., Ltd. FA-512MT) and 100 parts by mass of polyol (D) (Asahi Glass Co., Ltd. Exanol E240). 20 parts by mass of Compound (E) (Cosmonate LK manufactured by Mitsui Chemicals) was added and dissolved, and then cooled to room temperature to obtain a curable resin composition. In Table 2, in the (E) polyisocyanate column, in addition to the mass part of the polyisocyanate, the mass% of the carbodiimide-modified MDI in the component (E) is also described in the lower part. In the formulation shown in Table 2, 6% cobalt naphthenate, peroxide (NOF Percure-K) and dimethylaniline were mixed well in the proportions shown in Table 2, and then poured into a mold at 25 ° C. And cured for 72 hours to obtain a cured resin (cast material) having a thickness of 3 mm. About this resin hardened | cured material, bar hardness and sulfur penetration depth were measured. The results are shown in Table 2.

  Using this resin composition, the test was performed under the same conditions as in Example 1 in principle. However, the concrete peeling test was performed under the same conditions as in Example 1 except that the amount of the glass flake RCF-140 of the surface protective layer was changed from 10 parts by mass to 15 parts by mass. The results are listed in Table 2. The resin composition containing 6% cobalt naphthenate, dimethylaniline and Percure-K with the composition shown in Table 2 has high concrete adhesion strength and concrete peeling strength. After 60 days of immersing the specimen, in which the primer, the base material adjusting material, and the surface protective material were 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 hot water (80 degreeC) immersion water absorption showed the low value with 1.2%.

  Ethylene oxide 6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Kyoeisha 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 5. BP-6EM) 20 parts by mass, dicyclopentenyloxyethyl methacrylate (C) 25 parts by mass, polyol (D) (Asahi Glass Co., Ltd. Exanol E240) 10 parts by mass, 20 parts by mass of an isocyanate compound (E) (Cosmonate LK manufactured by Mitsui Chemicals) was added and dissolved, and then cooled to room temperature to obtain a curable resin composition. 6% cobalt naphthenate, peroxide (NOF Percure-K) and dimethylaniline were mixed well in the blending ratio described in Example 6 in Table 2, and then poured into a mold. Curing was performed for a time to obtain a cured resin (cast material) having a thickness of 3 mm. This cured resin was measured for Barcol hardness and sulfur penetration depth by the methods described above. The results are shown in Table 2. The concrete peeling test was performed under the same conditions as in Example 1 except that the amount of glass flake RCF-140 used for the surface protective layer was changed to 15 parts by mass as in Example 5. This test was also performed under the same conditions as in Example 1.

  The composition obtained by adding 6% cobalt naphthenate, dimethylaniline and Percure-K to the resin composition of Example 6 in the proportions shown in Table 2 has high concrete adhesion strength and concrete peeling strength. After 60 days of complete immersion of the specimen in which the primer, base material adjusting material and surface protective material are laminated on the concrete in 80 ° C warm water, there is an abnormality between the primer layer, the base material adjusting material layer and the surface protective layer. There was nothing at all. Moreover, the hot water (80 degreeC) immersion water absorption showed the low value around 1%.

  Ethylene oxide 6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Kyoeisha 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 5. BP-6EM) 20 parts by mass, dicyclopentenyloxyethyl methacrylate (C) 25 parts by mass, polyol (D) (Asahi Glass Co., Ltd. Exanol E240) 10 parts by mass, 30 parts by mass of isocyanate compound (E) (Cosmonate LK manufactured by Mitsui Chemicals) was added and dissolved, and then cooled to room temperature to obtain a curable resin composition. After mixing 6% cobalt naphthenate, peroxide (Nissan Percure-K) and dimethylaniline with the formulation described in Example 6 column of Table 2, the mixture was poured into a mold and 72 hours at 25 ° C. Curing was performed to obtain a cured resin (cast material) having a thickness of 3 mm.

  Each test was conducted under the same conditions as in Example 1 except that the blending ratio of the surface protective layer in the concrete peeling test was the same as in Example 6. The results are shown in Table 2.

  The resin concrete was prepared by dissolving 2.0 parts by mass of 20% 120 ° F./(FA-512MT) paraffin wax in 100 parts by mass of the resin composition, and then, first, 1.0 part by mass of 6% cobalt naphthenate, dimethyl 0.5 parts by mass of aniline 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 described in Table 2) was added to obtain a blend. For 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 prepared by pouring into a rod-shaped mold having a diameter of 2.5 cm.

  The composition obtained by adding 6% cobalt naphthenate, dimethylaniline and Percure-K to the resin composition shown in Table 2 has high concrete adhesion strength and concrete peeling strength. The specimens laminated with the primer, the base material adjusting material, and the surface protective material were all immersed in warm water at 80 ° C. and after 60 days, there were no abnormalities between the primer layer, the base material adjusting material layer, and the surface protective layer. Moreover, the hot water (80 degreeC) immersion water absorption showed the low value around 1%.

  In 45 parts by mass of the aromatic epoxy methacrylate (A) (number average molecular weight of about 750, acid value of 10 mg KOH / g or less) obtained in the production of Example 5, 2.6 mol of ethylene oxide addition ethoxylated bisphenol- 20 parts by mass of A-dimethacrylate (B) (Shin-Nakamura Chemical Co., Ltd. BPE-100), 25 parts by mass of dicyclopentenyloxyethyl methacrylate (C), polyol (D) (Asahi Glass Co., Ltd. E240) A total of 100 parts by mass of 10 parts by mass is heated to 70 ° C., and a wax-containing composition is prepared by dissolving 2 parts by mass of a 20% concentration of 120 degrees F / (FA-512MT) paraffin wax. The total amount of (A) to (D) is 100 parts by mass, and after adding 20 parts by mass of the isocyanate compound (E) (Cosmonate LK manufactured by Mitsui Chemicals), the mixture is 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, 0.2 part by mass of dimethylaniline, and 2.0 parts by mass of Percure-K were added to obtain a blend. This compound was poured into a mold, cured at 25 ° C. for 72 hours, and then demolded to obtain a cured resin product (cast material) having a thickness of 3 mm. Although the conditions of this cured resin were changed as follows, in principle, the characteristic values were measured by the method described in Example 1. The results are shown in Table 2.

  The resin concrete evaluation test was performed under the same conditions as in Example 7 except that the inorganic aggregate material was changed from 450 parts by mass of mixed silica sand to 40 parts by mass of glass flake RCF-140 (manufactured by Nippon Sheet Glass Co., Ltd.). .

  For the concrete peeling test, the amount of 6% cobalt naphthenate was 1.0 parts by mass, and the amount of Percure-K was 2.0 parts by mass, as in Example 3, for the preparation for the base material. The conditions were the same as in Example 1 except that the part was changed to the part.

  Ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Shin-Nakamura Chemical Co., Ltd. BPE) was added to 45 parts by mass of the aromatic epoxy methacrylate (A) obtained in the production of Example 5. -100) 20 parts by mass, 25 parts by mass of dicyclopentenyloxyethyl methacrylate (C), and 10 parts by mass of polyol (D) (Asahi Glass Co., Ltd. Exanol E240) were added to 70 ° C in total. After warming and dissolving 2 parts by mass of 20% concentration of 120 ° F / (FA-512MT) paraffin wax, the isocyanate compound (E) (Mitsui Chemicals) is added to 100 parts by mass of (A) to (D). (Cosmonate LK) 20 parts by mass 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, 0.2 part by mass of dimethylaniline, and 2.0 parts by mass of Percure-K were added to obtain a blend. Also for this blend, a cured resin (cast product) was obtained under the same conditions as in Example 1, and the characteristic values thereof were measured. The results are shown in Table 2.

  For the resin concrete, the resin composition of Example 9 was used, a formulation was prepared with the same formulation as Example 8, and evaluated in the same manner as in Examples 7 and 8.

  In the concrete peeling test, in the same manner as in Example 8, the composition for the substrate preparation material was changed to 1.0 part by mass of 6% cobalt naphthenate and 2.0 parts by mass of Percure-K. The conditions were the same as in Example 1, except that Other tests were the same as in Example 1.

<Comparative Example 9>
-Production of aromatic epoxy methacrylate (A) having a number average molecular weight of about 750:
The four-necked flask used in Example 1 is charged with the same epoxy resin as in Example 5 (jER828 (Mitsubishi Chemical) 148 g, jER1001 (Mitsubishi Chemical) 360 g and jER1002 240 g) and dried at 10 liters per minute with stirring. After raising the temperature to 130 ° C. while blowing air, 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 the dropwise addition, the acid value measurement was started every hour, and after confirming that the acid value became 17 KOHmg / g, the mixture was cooled to 100 ° C. Got. Ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) 50 parts by mass and dicyclopentenyloxyethyl 20 parts by mass of this aromatic epoxy (meth) acrylate (A) 30 parts by weight of methacrylate (C) was 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 in the blend of Table 2 to this resin composition was uncured even after 24 hours at 25 ° C.

<Comparative Example 10>
Ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) 20 masses of Example 1 to 70 mass parts of aromatic epoxy (meth) acrylate (A) obtained by manufacture of the comparative example 9. And 10 parts by mass of dicyclopentenyloxyethyl methacrylate (C), and an isocyanate compound (E) (Cosmonate LK manufactured by Mitsui Chemicals) with respect to a total of 100 parts by mass of (A) to (C) 50 parts by mass was 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 to the resin composition in the formulation shown in Table 2 was uncured after 24 hours at 25 ° C.

<Comparative Example 11>
Ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) 20 parts by mass to 50 parts by mass of the aromatic epoxy methacrylate (A) obtained in the production of Comparative Example 9 Polyol (D) (Asahi Glass Co., Ltd. Exenol E240: number average molecular weight 3000, hydroxyl value 56 mgKOH / g) was 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 in the blend of Table 2 to this resin composition was uncured even after 24 hours at 25 ° C.

<Comparative Example 12>
In Comparative Example 12, the aromatic epoxy methacrylate (A) was changed as follows.

-Production of aromatic epoxy methacrylate (A):
The four-necked flask used in Example 1 was charged with 93 g of jER828 (Mitsubishi Chemical), 180 g of jER1002 (Mitsubishi Chemical) and 990 g of jER1004, and heated to 130 ° C. while blowing 10 liters of dry air per minute with 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 KOH mg / g, the mixture was cooled to 100 ° C. and an aromatic epoxy having a number average molecular weight of about 1300. A product of methacrylate was obtained. 50 parts by mass of the product (A) and 40 parts by mass of dicyclopentenyloxyethyl methacrylate (C) (Hitachi Chemical Industry Co., Ltd. FA-512MT), polyol (D) (Asahi Glass Co., Ltd. Excell E240) 10 After adding mass parts, and further adding 20 mass parts of isocyanate compound (E) (Mitsui Chemicals Cosmonate LK) to 100 mass parts in total of (A), (C), (D), It cooled to room temperature and obtained curable resin composition.

  About this curable resin composition, the characteristic value was measured by the method of Example 5, and the test was done on the same conditions as Example 1 except others. The results are shown in Table 2.

  The concrete adhesion strength and concrete peeling strength of the composition obtained by adding 6% cobalt naphthenate, dimethylaniline and percure-K to the resin composition of Comparative Example 12 in the composition shown in Table 2 are low, A specimen in which a primer, a base material adjusting material, and a surface protective material are laminated on the concrete is immersed in warm water at 80 ° C. on the entire surface. After 25 days, all of the primer layer, the base material adjusting material layer, and the surface protective layer are microscopic. Innumerable swelling and peeling occurred. Moreover, warm water (80 degreeC) immersion water absorption is as high as about 3 times of the resin composition of this invention.

<Comparative Example 13>
Ethylene oxide 30 mol addition ethoxylated bisphenol A dimethacrylate (Shin-Nakamura Chemical Co., Ltd., NK Light Ester BPE-1300) to 50 parts by mass of the aromatic epoxy methacrylate (A) obtained in the production of Comparative Example 12 ) (B) 20 parts by mass, dicyclopentenyloxyethyl methacrylate (C) 20 parts by mass, polyol (D) (Asahi Glass Co., Exenol E240) 10 parts by mass (A), (B), (C) , (D) is added to 5 parts by mass of the isocyanate compound (E) (Cosmonate LK manufactured by Mitsui Chemicals), and then cooled to room temperature to obtain a curable resin composition. It was. A blend obtained by adding 6% cobalt naphthenate, dimethylaniline and Percure-K in the composition of Table 2 to this resin composition has a long surface drying time, a concrete adhesion strength and a peeling with a concrete. The strength decreased drastically after immersion in normal temperature water and warm water. In addition, a specimen in which a primer, a substrate conditioner, and a surface protective material are laminated on a concrete is immersed in warm water at 80 ° C. for 7 days after the entire surface of the primer layer, substrate conditioner layer, and surface protective layer. Numerous swelling and peeling occurred. 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. Further, casts and laminates were prepared by the same method as in Example 5, and characteristic values were measured. EPMA, bar hardness, and wear were measured by the methods described above. The results are shown in Table 2.

<Comparative example 14>
Concrete adhesion strength of a composition obtained by adding 6% cobalt naphthenate and methyl ethyl ketone peroxide (NOF Parmec NS) shown in Table 2 to 100 parts by mass of a styrene type vinyl ester resin (Showa Denko Lipoxy R804). Table 2 shows the measurement results such as the peeling strength with styrene and the volatile amount of styrene. The amount of styrene volatilized is as high as 80 g / m2. A compound obtained by adding 6% cobalt naphthenate and methyl ethyl ketone peroxide (NOF Parmec N) shown in Table 2 to 100 parts by mass of the above styrene type vinyl ester resin was subjected to a characteristic value by the method described in Example 5. It was measured. Further, EPMA, bar hardness and wear amount were measured by the above-described methods. These results are also shown in Table 2.

<Comparative Example 15>
Ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Shin-Nakamura Chemical Co., Ltd. BPE) was added to 55 parts by mass of the aromatic epoxy methacrylate (A) obtained in the production of Comparative Example 12. -100) 20 parts by mass and dicyclopentenyloxyethyl methacrylate (C) 25 parts by mass were dissolved and heated to 70 ° C. to dissolve 20% 120 ° F./(FA-512MT) paraffin wax. Thereafter, 6% cobalt naphthenate, dimethylaniline and Percure-K were added according to the formulation shown in Table 2 below, and the mixture was cooled to room temperature to obtain a formulation.

  This blend 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. It shows in following Table 2 with other evaluation results. In the evaluation test, the resin concrete was evaluated under the same conditions as in Example 7. The concrete peeling test was evaluated under the same conditions as in Example 1 except that the composition for the base material was changed to the same as in Example 3. Other tests were performed under the same conditions as in Example 1.

<Comparative Example 16>
Ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Shin-Nakamura Chemical Co., Ltd. BPE) was added to 55 parts by mass of the aromatic epoxy methacrylate (A) obtained in the production of Comparative Example 12. -100) 15 parts by mass, 20 parts by mass of dicyclopentenyloxyethyl methacrylate (C) and 10 parts by mass of polyol (D) (Asahi Glass Co., Ltd. Exenol E240) were mixed and heated to 70 ° C., and 20% 120 Degree F / (FA-512MT) paraffin wax was added and dissolved in the composition shown in Table 2 below, and then isocyanine was added to 100 parts by mass of (A), (B), (C), and (D). -To compound (E) (Cosmonate manufactured by Mitsui Chemicals, which does not contain carbodiimide-modified MDI) was dissolved by adding 40 parts by mass, and then cooled to room temperature with 6% cobalt naphthenate and dimethylanisate. Emissions and Pa - to obtain a formulation with the addition of curing -K the formulation shown in Table 2 below. The blend 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 5.

  The results are shown in Table 2 together with other evaluation results. The resin composition containing glass flakes was evaluated by conducting the same tests as those described in the resin concrete characteristics column of Example 7 in Table 2. Resin concrete was evaluated under the same conditions as in Example 7 except that the inorganic aggregate of the blend was changed as in Example 8. The concrete peeling test was carried out under the same conditions as in Example 1 except that the composition of the base material was changed in the same manner as in Example 3. Other tests were performed under the same conditions as in Example 1.

<Comparative Example 17>
Ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Shin-Nakamura Chemical Co., Ltd. BPE) was added to 55 parts by mass of the aromatic epoxy methacrylate (A) obtained in the production of Comparative Example 12. -100) 15 parts by mass, dicyclopentenyloxyethyl methacrylate (C) 20 parts by mass, (D) polyol (D) (Asahi Glass Co., Ltd., Exenol E240) 10 parts by mass are mixed and heated to 70 ° C. 20% 120 degrees F / (FA-512MT) paraffin wax was added and dissolved in the composition shown in Table 2 below, and the total amount of (A), (B), (C), and (D) was 100 parts by mass. On the other hand, 40 parts by mass of an isocyanate compound (E) (Cosmonate manufactured by Mitsui Chemicals, including carbodiimide-modified MDI) was added and dissolved, and then cooled to room temperature to obtain a curable resin composition. To this composition, 6% cobalt naphthenate, dimethylaniline, and Percure-K were added at the dividend shown in Table 2 and poured into a mold and cured at 25 ° C. for 72 hours to cure a resin having a thickness of 3 mm. A product (cast) was obtained. Characteristic values of the cured resin were measured by the method described in Example 5. The results are shown in Table 2 together with other evaluation results.

  Among other evaluation results, the resin concrete was evaluated under the same conditions as in Example 7 except that the inorganic aggregate of the blend was changed as in Example 8. The concrete peeling test was performed under the same conditions as in Example 1 except that the composition of the base material was changed as in Example 3. Other tests were performed under the same conditions as in Example 1.

  (D) Cosmonate LK (carbodiimide-modified MDI 15 to 25%, methylenebis (4,1-phenylene) diisocyanate 70 to 80%, 2,4 diphenylmethane diisocyanate manufactured by Mitsui Chemicals as polyisocyanate compound (E) Examples of resin compositions using 1 to 5%) will be described.

  To 150 parts by mass of the aromatic epoxy methacrylate (A) produced in Example 1, 2.6 parts of ethylene oxide addition ethoxylated bisphenol A dimethacrylate (B) (Shin-Nakamura Chemical Co., Ltd. BPE-100) 100 parts by mass , 650 parts by mass of dicyclopentenyloxyethyl methacrylate (C) (Hitachi Chemical Industry Co., Ltd., FA-512MT), polyol (D) (Asahi Glass Co., Ltd. Exenol E4030: number average molecular weight 4000, hydroxyl value 42 mg KOH / g ) After adding 100 parts by weight and dissolving, the total amount of 100 parts by weight of the above (A), (B), (C) and (D) cooled to room temperature is equivalent to an isocyanate compound (Cosmonate manufactured by Mitsui Chemicals). LK) 10 parts by mass were added to obtain a curable primer-resin composition.

  To this composition, 6% cobalt naphthenate, peroxide (Nissan Percure-K) and dimethylniline were mixed well in the formulation of Example 10 in Table 3. Using this formulation, a laminate was obtained under the same conditions as in Example 1. The bar hardness and sulfur penetration depth were measured by the above methods. The results are shown in Table 3. The concrete peeling test and other tests were also evaluated under the same conditions as in Example 1, and the results are shown in Table 3.

  The composition shown in Table 3 with 6% cobalt naphthenate, dimethylaniline and Percure-K added has high concrete adhesion strength and concrete peel strength. The specimens laminated with the material and the surface protective material were completely immersed in warm water at 80 ° C. After 60 days, no abnormality was found between the primer layer, the base material adjusting material layer, and the surface protective layer. The concrete adhesion strength and concrete peeling strength after immersion in warm water maintain initial values. Moreover, the hot water (80 degreeC) immersion water absorption showed the low value with 1.2%.

  150 parts by mass of the same aromatic epoxy methacrylate (A) as in Example 10, 100 parts by mass of ethylene oxide 6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Kyoeisha Chemical Co., Ltd. BP-6EM), After adding 650 parts by weight of dicyclopentenyloxyethyl methacrylate (C) and 100 parts by weight of polyol (D) (Asahi Glass Co., Ltd. Exanol E1030: number average molecular weight 1000, hydroxyl value 160 mg KOH / g), Addition of 20 parts by mass of an isocyanate compound (Cosmonate LK manufactured by Mitsui Chemicals) to a total of 100 parts by mass of the above (A), (B), (C) and (D) cooled to room temperature. A primer-resin composition was obtained. Using this composition, a laminate was prepared under the same conditions as in Examples 1 and 10, and the characteristic values were measured. Other tests were also performed under the same conditions as in Examples 1 and 10. These results are shown in Table 3.

  The concrete adhesion strength and concrete peeling strength of the blend obtained by adding 6% cobalt naphthenate, dimethylaniline and Percure-K to the resin composition of Example 11 in the blend shown in Table 3 are high. After 60 days of complete immersion of the specimen in which the primer, base material adjusting material and surface protective material are laminated on the concrete in 80 ° C warm water, there is an abnormality between the primer layer, the base material adjusting material layer and the surface protective layer. There was nothing at all. Moreover, the hot water (80 degreeC) immersion water absorption showed the low value around 1%.

  200 parts by mass of the same aromatic epoxy methacrylate (A) as in Example 10, 50 parts by mass of ethylene oxide 6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Kyoeisha Chemical Co., Ltd., BP-6EM) 600 parts by mass of dicyclopentenyloxyethyl methacrylate (C) (Hitachi Chemical Industry Co., Ltd., FA-512MT), polyol (D) (Asahi Glass Co., Ltd. Exanol E240: number average molecular weight 3000-triol and exeno- (E) 2020: molar ratio of the number average molecular weight 2000 of 0.7 / 0.3, number average molecular weight 2,700) 150 parts by mass was added and dissolved, and then cooled to room temperature (A), (B), ( C) and (D) are added to 20 parts by mass of an isocyanate compound (Cosmonate LK manufactured by Mitsui Chemicals) for a total of 100 parts by mass of the curable primer tree. To obtain a composition. To this composition, 6% cobalt naphthenate, peroxide (NOF Percure-K) and dimethylniline were added according to the formulation shown in Table 3 to prepare a formulation. The characteristic values of the cured resin were measured by the method described in Example 10. The results are shown in Table 3. The concrete peeling test was carried out in the same manner as in Example 1 except that the composition of the base material was the same as in Example 3 (6% cobalt naphthenate, 1.0 part by mass, Percure-2.0 parts by mass). An evaluation test was performed under the same conditions as those described above. Other tests were performed under the same conditions as in Example 1.

  Ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Shin-Nakamura Chemical Co., Ltd. BPE-100) to 150 parts by mass of the same aromatic epoxy methacrylate (A) as in Example 10 150 parts by mass and 550 parts by mass of dicyclopentenyloxyethyl methacrylate (C), polyol (D) (Asahi Glass Co., Ltd. Excell E240: number average molecular weight 3000-triol and Excell E2020: number average 150 parts by mass of a molar ratio of 0.5 / 0.5 and a number average molecular weight of 2500) having a molecular weight of 2000 are added and heated to 70 ° C., and a 20% concentration of 120 degrees F / (FA-512MT) paraffin wax is shown in the table below. After adding and dissolving, the mixture was cooled to room temperature, and the isocyanate was added to 100 parts by mass of the total of (A), (B), (C) and (D). 25 parts by mass of a compound (Cosmonate LK manufactured by Mitsui Chemicals) was added to obtain a curable primer resin composition. To this composition, 6% cobalt naphthenate, peroxide (NOF Percure-K) and dimethylniline were mixed according to the composition shown in Table 3, and the cured resin was measured for the characteristic values by the method described in Example 10. It was measured. The results are shown in Table 3 together with other evaluation results.

  The concrete peeling test was carried out in the same manner as in Example 1 except that the composition of the base material was the same as in Example 3 (1.0 part by mass of 6% cobalt naphthenate, 2.0 parts by mass of Percure-K). An evaluation test was performed under the same conditions. Other tests were performed under the same conditions as in Example 1.

<Comparative Example 18>
Production of aromatic epoxy methacrylate (A) having a number average molecular weight of about 750:
148 g of jER828 (Mitsubishi Chemical), 360 g of jER1001 (Mitsubishi Chemical) and 240 g of jER1002 were charged into the same four-necked flask as in Example 1, and the temperature was raised 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. The acid value measurement was started every 1 hour after 3 hours had passed after the completion of the dropwise addition, and after confirming that it was 17 KOH mg / g, 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) 100 parts by mass, dicyclopentenyloxyethyl methacrylate (150 parts by mass) C) 650 parts by mass (Hitachi Chemical Industry Co., Ltd. FA-512MT), polyol (D) (Asahi Glass Co., Ltd. Excell E837: number average molecular weight 6000, hydroxyl value 28 mg KOH / g) 100 parts by mass were added and dissolved, then room temperature 10 parts by mass of an isocyanate compound (Cosmonate LK manufactured by Mitsui Chemicals) to a total of 100 parts by mass of the above (A), (B), (C) and (D) cooled to a curable primer A resin composition was obtained.

  To this composition, 6% cobalt naphthenate, peroxide (NOF Percure-K) and dimethylniline were mixed well in the blending ratios described in the column of Comparative Example 18 in Table 3, and then Example 1 and A laminate was prepared under the same conditions. Each evaluation test was performed under the same conditions as in Example 1, and the results are shown in Table 3. The initial values of the concrete adhesion strength and concrete peeling strength of the blends containing 6% cobalt naphthenate, dimethylaniline and Percure-K shown in Table 3 are low. After 60 days of immersing the test piece on which the adjusting material and the surface protective material were laminated in 80 ° C. warm water, swelling occurred in each of the primer layer, the base material adjusting material layer, and the surface protective layer. The concrete adhesion strength and concrete peeling strength after immersion in warm water were greatly reduced from the initial values. Moreover, warm water (80 degreeC) immersion water absorption showed the high value with 3.5%. Furthermore, the surface drying time was long, and the measurement result was 24 hours or more for tack elimination.

<Comparative Example 19>
150 parts by mass of the same aromatic epoxy methacrylate (A) as in Comparative Example 18, 100 parts by mass of ethylene oxide 6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Kyoeisha Chemical Co., Ltd. BP-6EM), 650 parts by mass of dicyclopentenyloxyethyl methacrylate (C), polyol (D) (Asahi Glass Co., Ltd. Excell E430: number average molecular weight 400-triol, hydroxyl value 400 mg KOH / g, Excell E1020- Diol: Number average molecular weight 1000, hydroxyl value 112 mg KOH / g, triol / diol molar ratio 0.3 / 0.7, number average molecular weight 820) Add 100 parts by mass and cool to room temperature The isocyanate compound (Cosmonate LK manufactured by Mitsui Chemicals) 20 with respect to a total of 100 parts by mass of the above (A), (B), (C) and (D) Curable primer added an amount unit - to obtain a resin composition. A laminate was prepared for this composition with 6% cobalt naphthenate, peroxide (NOF Percure-K) and dimethylniline under the same conditions as in Examples 1 and 10, and the characteristic values were measured. The results are shown in Table 3.

  The resin composition of Comparative Example 19 was subjected to an evaluation test under the same conditions as in Example 1. The results are shown in Table 3. In the composition shown in Table 3, the initial values of the concrete adhesion strength and concrete peeling strength of the composition in which 6% cobalt naphthenate, dimethylaniline and Percure-K were added were low. -After immersing the specimen in which the base material-adjusting material and the surface protective material were laminated in 80 ° C warm water all over 60 days, swelling occurred in each of the primer layer, the base material-adjusting material layer, and the surface protective layer. The concrete adhesion strength and concrete peeling strength after immersion in warm water were greatly reduced from the initial values. Moreover, the hot water (80 degreeC) immersion water absorption showed the high value as 6.0%.

  An aromatic epoxy methacrylate (A) was produced under the same conditions as in Example 1, and 2.6 mol of ethylene oxide added ethoxylated bisphenol A dimethacrylate (B) (Shin-Nakamura Chemical Co., Ltd.) was added to 400 parts by mass of the product. BPE-100) 200 parts by mass, dicyclopentenyloxyethyl methacrylate (C) (Hitachi Chemical Industry Co., Ltd. FA-512MT) 300 parts by mass, polyol (D) (Asahi Glass Co., Ltd. Excell E820: number average After adding and dissolving 20 parts by mass of isocyanate compound (E) (Cosmonate LK manufactured by Mitsui Chemicals) to 100 parts by mass of 100 parts by mass of molecular weight 4900 and hydroxyl value 34 mgKOH / g), the mixture is cooled to room temperature. A curable resin composition was obtained. After mixing at the blending ratio of 6% cobalt naphthenate, peroxide (NOF Percure-K) and dimethylaniline in the formulation described in Example 14 in Table 4, the mixture was poured into a mold at 25 ° C. And cured for 72 hours to obtain a cured resin (cast material) having a thickness of 3 mm.

  The concrete peeling test was conducted in the same manner as in Example 6 except that the amount of the glass flake RCF-140 used for the surface protective layer was changed to 15 parts by mass with respect to 100 parts by mass of the curable resin composition. The test was performed under the same conditions as in Example 1, and other tests were performed under the same conditions as in Example 1. The concrete adhesion strength and concrete peeling strength of the composition with 6% cobalt naphthenate, dimethylaniline and Percure-K added in the composition shown in Table 4 are high, and the concrete has a primer and substrate preparation. The specimens laminated with the material and the surface protective material were completely immersed in warm water at 80 ° C. After 60 days, no abnormality was found between the primer layer, the base material adjusting material layer, and the surface protective layer. Moreover, the hot water (80 degreeC) immersion water absorption showed the low value with 1.2%.

  40 parts by mass of the same aromatic epoxy methacrylate (A) as in Example 14, 20 parts by mass of ethylene oxide 6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Kyoeisha Chemical Co., Ltd. BP-6EM), To 100 parts by mass in total of 30 parts by mass of dicyclopentenyloxyethyl methacrylate (C) and 10 parts by mass of polyol (D) (Asahi Glass Co., Ltd. Excell E1030: number average molecular weight 1000, hydroxyl value 160 mg KOH / g) On the other hand, 20 mass parts of isocyanate compound (E) (Cosmonate LK manufactured by Mitsui Chemicals) was added and dissolved, and then cooled to room temperature to obtain a curable resin composition. 6% cobalt naphthenate, peroxide (Nissan Percure-K) and dimethylaniline were mixed well in the formulation described in the column of Example 15 in Table 4, and then poured into a mold at 25 ° C. It was cured for 72 hours to obtain a cured resin (cast material) having a thickness of 3 mm. For each cured product and composition, in principle, an evaluation test was performed under the same conditions as in Example 1. However, in the same manner as in Example 6, the glass flake RCF-140 used for the surface protective layer was used in the concrete peeling test. Was changed to 15 parts by mass with respect to 100 parts by mass of the curable resin composition, and the other conditions were the same as in Example 1.

  The resin composition of Example 15 having the composition shown in Table 4 and containing 6% cobalt naphthenate, dimethylaniline and Percure-K has high concrete adhesion strength and concrete peeling strength. -Specimens, substrate conditioning material, and surface protective material laminated on the substrate were all immersed in warm water at 80 ° C. After 60 days, there was no abnormality between the primer layer, substrate conditioning material layer, and surface protective layer. There was no. Moreover, the hot water (80 degreeC) immersion water absorption showed the low value with 1.2%.

  40 parts by mass of the same aromatic epoxy methacrylate (A) as in Example 14, 20 parts by mass of ethylene oxide 6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Kyoeisha Chemical Co., Ltd. BP-6EM), 30 parts by mass of dicyclopentenyloxyethyl methacrylate (C), polyol (D) (Asahi Glass Co., Ltd. Excell E240: number average molecular weight 3000, hydroxyl value 56 mg KOH / g, -triol and Excell E2020 : Number average molecular weight 2000, hydroxyl value 56 mg KOH / g molar ratio 0.7 / 0.3, number average molecular weight 2700) Isocyanate compound (E) (Mitsui) for a total of 100 parts by mass Chemical Cosmonate LK) 20 parts by mass was added and dissolved, and then cooled to room temperature to obtain a curable resin composition. After thoroughly mixing 6% cobalt naphthenate, peroxide (NOF Percure-K) and dimethylaniline with the formulation described in Example 16 column of Table 4, the mixture was poured into a mold and 72 hours at 25 ° C. Curing was performed to obtain a cured resin (cast material) having a thickness of 3 mm. The resin concrete was subjected to an evaluation test under the same conditions as in Example 7. In the concrete peeling test, the amount of the glass flake RCF-140 used for the surface protective layer was changed to 15 parts by mass with respect to 100 parts by mass of the curable resin composition in the same manner as in Example 6. 1 and the same conditions. Other evaluation tests were also performed under the same conditions as in Example 1, and the results are shown in Table 4. The composition obtained by adding 6% cobalt naphthenate, dimethylaniline and Percure-K in the composition shown in Table 4 to the resin composition of Example 16 has high concrete adhesion strength and concrete peeling strength. -Specimens, substrate conditioning material, and surface protective material laminated on the substrate were all immersed in warm water at 80 ° C. After 60 days, there was no abnormality between the primer layer, substrate conditioning material layer, and surface protective layer. There was no. Moreover, the hot water (80 degreeC) immersion water absorption showed the low value around 1%.

  Ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Shin-Nakamura Chemical Co., Ltd. BPE-100) to 40 parts by mass of the same aromatic epoxy methacrylate (A) as in Example 14 20 parts by mass, 30 parts by mass of dicyclopentenyloxyethyl methacrylate (C), polyol (D) (Asahi Glass Co., Ltd. Excell E240: number average molecular weight 3000-triol and Excell E2020: number average 10 parts by mass of a molar ratio of 0.5 / 0.5 and a number average molecular weight of 2,500) with a molecular weight of 2000 are added, heated to 70 ° C., and a 20% concentration of 120 degrees F / (FA-512MT) paraffin wax. After dissolving 2.0 parts by mass, the isocyanate compound (E) (Cosmonate manufactured by Mitsui Chemicals) is used with respect to 100 parts by mass in total of (A), (B), (C), and (D). (LK) 20 parts by mass was added and dissolved, and then cooled to room temperature to obtain a curable resin composition. To this resin composition, 6% cobalt naphthenate and Percure-K were added according to the formulation shown in Table 4 to obtain a formulation.

  This compound was poured into a mold, cured at 25 ° C. for 72 hours, and then 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. Example 7 except that the composition of the resin composition containing glass flakes was changed in the same manner as in Example 8 (40 parts by mass of glass flake RCF-140 (manufactured by Nippon Sheet Glass Co., Ltd.)). A resin coat test was conducted under the same conditions. The concrete peeling test was performed in the same manner as in Example 1 except that the composition of the substrate preparation material was changed to the same as in Example 3 (1.0 part by mass of 6% cobalt naphthenate, 2.0 parts by mass of Percure-K). An evaluation test was performed under the same conditions. Other tests were performed under the same conditions as in Example 1, and the results are shown in Table 4.

<Comparative Example 20>
To 400 parts by mass of the same aromatic epoxy methacrylate (A) as in Comparative Example 18, 200 parts by mass of ethylene oxide 6 mol addition ethoxylated bisphenol A dimethacrylate (B) (Kyoeisha Chemical Co., Ltd. BP-6EM) 300 parts by mass of dicyclopentenyloxyethyl methacrylate (C), polyol (D) (Asahi Glass Co., Ltd. Excell E430-triol: number average molecular weight 400, hydroxyl value 400 mg KOH / g, Excell E720- Diol, number average molecular weight 700, hydroxyl value 160 mg KOH / g, molar ratio 0.3 / 0.7, number average molecular weight 610) 100 parts by mass were added and dissolved, and then cooled to room temperature (A), (B ), (C) and (D) are added to 20 parts by mass of an isocyanate compound (Cosmonate LK manufactured by Mitsui Chemicals) with respect to 100 parts by mass in total. A composition was obtained. A 6% cobalt naphthenate, a peroxide (Nissan Percure-K) and dimethylniline were mixed in the composition of Table 4 under the same conditions as in Example 1, and a characteristic value was determined. It was measured. Each evaluation test was performed under the same conditions as in Example 1, and the results are shown in Table 4.

  The curable resin composition of Comparative Example 20 containing 6% cobalt naphthenate, dimethylaniline and Percure-K in the formulation shown in Table 4 has a long surface drying time, a concrete adhesion strength and a concrete content. The initial value of the toe ring strength is low. In addition, the specimen layered with a primer, a base material adjusting material, and a surface protective material on the concrete is fully immersed in warm water at 80 ° C. Swelling was generated between the material layer and the surface protective layer. Moreover, the hot water (80 degreeC) immersion water absorption showed the low value as high as 8%, and the sulfur penetration depth was also large.

<Comparative Example 21>
400 parts by mass of the same aromatic epoxy (meth) acrylate (A) as in Comparative Example 18 and 2.6 parts by mass of ethylene oxide 2.6 mol addition ethoxylated bisphenol A dimethacrylate (B) as in Example 1 and Dissolve by adding 300 parts by weight of dicyclopentenyloxyethyl methacrylate (C) and 100 parts by weight of polyol (D) (Asahi Glass Co., Ltd. Excell E837: number average molecular weight 6,000, hydroxyl value 28 mg KOH / g). Then, 20 parts by mass of an isocyanate compound (Cosmonate LK manufactured by Mitsui Chemicals) is added to 100 parts by mass of the above (A), (B), (C) and (D) cooled to room temperature. A curable resin composition was obtained. Using this composition, a laminate was prepared by the method described in Example 14. About this laminated board and resin composition, the evaluation test was done on the same conditions as Example 1, and the result was described in Table 4.

  The formulation obtained by adding 6% cobalt naphthenate, dimethylaniline and percure-K to the curable resin composition of Comparative Example 21 in the formulation shown in Table 4 has a long surface drying time, and tack is eliminated even after 24 hours. could not. In addition, the initial values of the concrete adhesion strength and concrete peeling strength are low, and a specimen in which a primer, a base material adjusting material and a surface protective material are laminated on the concrete is immersed in hot water at 80 ° C. 60 In all days, swelling occurred between the primer layer, the base material adjusting material layer, and the surface protective layer. Moreover, the hot water (80 degreeC) immersion water absorption showed the low value as high as 6%, and sulfur penetration depth was also large.

Claims (10)

(A) an epoxy (meth) acrylate containing a reaction product of an aromatic epoxy resin and (meth) acrylic acid, having a number average molecular weight in the range of 500 to 1100 and an acid value of 10 KOH mg / g or less; ,
(B) an ethoxylated bisphenol A dimethacrylate of a bifunctional (meth) acrylate monomer having 2 to 10 moles of alkylene oxide addition,
(C) a number average molecular weight of 300 or less, alcohol - as Le residues, one carbon-carbon double bond in the ring, or a group containing a cyclic hydrocarbon group having one ChissoHara child in the ring A monofunctional (meth) acrylate monomer having
(D) a polyol having a hydroxyl value (KOHmg / g) of 160 or less and a number average molecular weight of 1,000 or more;
Including
A curable resin composition comprising 1 to 30 parts by mass of (E) polyisocyanate with respect to 100 parts by mass in total of components (A), (B), (C) and (D).
(A) 10-25 parts by mass of epoxy (meth) acrylate,
(B) 5 to 15 parts by mass of ethoxylated bisphenol A dimethacrylate;
(C) 50 to 70 parts by mass of a monofunctional (meth) acrylate monomer;
(D) 5 to 15 parts by mass of polyol,
The curable resin composition according to claim 1, which is used as a primer for concrete anticorrosion coating. (A) 30-60 parts by mass of epoxy (meth) acrylate,
(B) 10-30 parts by mass of ethoxylated bisphenol A dimethacrylate;
(C) monofunctional (meth) acrylate monomer-20 to 40 parts by mass;
(D) 5 to 15 parts by mass of polyol,
The curable resin composition according to claim 1, which is used for a concrete anticorrosion coating. The components (A), (B), (C), (D) and (E) are the main component containing the components (A), (B), (C) and (D), and the component (E). Is distinguished from secondary agents containing
The curable resin composition according to any one of claims 1 to 3, wherein the main agent and the auxiliary main agent are mixed in use.   The polyisocyanate (E) contains at least one MDI derivative selected from the group consisting of a carpositimide form of diphenylmethane diisocyanate (MDI), a uretonimine form of MDI, and an isocyanurate form of MDI. The curable resin composition of any one of Claims 1-4 characterized by these.   The organic peroxide is further contained in an amount of 0.5 to 10 parts by mass with respect to 100 parts by mass in total of (A), (B), (C) and (D). The curable resin composition according to any one of 1 to 5.   The concrete coating composition containing the curable resin composition of any one of Claims 1-6.   (A), (B), (C), and 100 parts by mass of (D), and further, an inert fine particle and / or powdery inorganic aggregate material having an average particle size of 0.02 to 10 mm. The concrete coating composition according to claim 7, comprising 30 to 600 parts by mass.   The lining material containing the curable resin composition of any one of Claims 1-6.   It contains 5-50 mass parts of scale-like inorganic fillers with respect to a total of 100 mass parts of (A), (B), (C), and (D), It is characterized by the above-mentioned. Lining material.