Resin composition and fiber-reinforced resin material using the resin composition.

Abstract

To provide a resin composition that gives a cured article having a high tensile rate and a low boiling water absorption rate and a fiber-reinforced material made of the resin composition.SOLUTION: A resin composition of the invention contains brominated bisphenol A type epoxy methacrylate (A) and n-butyl methacrylate and / or i-butyl methacrylate (B). In a preferable embodiment of the resin composition, the resin composition is used for lining or equipment. In a preferable embodiment of the resin composition, the mass ratio (A) / (B) of the brominated bisphenol A type epoxy methacrylate (A) to the n-butyl methacrylate and / or i-butyl methacrylate (B) is 50-80 / 50-20.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition and a fiber-reinforced resin material using the resin composition, and more particularly to a resin composition that can be used for fiber-reinforced plastics (hereinafter abbreviated as "FRP") and a fiber-reinforced resin material using the resin composition.

Background Art

[0002] The concrete floors of factory facilities that use industrial chemicals, and the liquid contact surfaces of metal chemical tanks or pipes made of steel, stainless steel, etc. are coated with a resin composition or a fiber-reinforced resin material having chemical resistance for the purpose of protection by preventing penetration into the base material. In addition, FRP molded with a fiber-reinforced resin material using a resin composition for the purpose of protecting chemical tanks and pipes themselves from chemical liquids and protecting the environment from the outside is used as a corrosion-resistant device.

[0003] Conventionally, a styrene-diluted epoxy (meth) acrylate resin composition excellent in chemical resistance and impact resistance has been used for the resin composition or fiber-reinforced resin material for the above-mentioned corrosion-resistant lining or corrosion-resistant device applications. Here, epoxy (meth) acrylate is a reaction product of an epoxy resin and acrylic acid or methacrylic acid, and is also called by the alias vinyl ester. In addition to chemical resistance, impact resistance is required for the purpose of preventing cracks in the resin layer due to thermal stress from chemical liquids and peeling from the base material. However, in recent years, styrene volatilized from the resin composition has become a problem in lining construction in a sealed space such as an indoor floor, the inner surface of a tank, or the inner surface of a pipe, and in the production of FRP indoors. This is because styrene is designated as a Class I Specified Chemical Substance under the Chemical Substances Discharge Control Promotion Act and must be managed for its discharge and transfer amounts, and is also designated as a Specified Chemical Substance under the Specified Chemical Substances Injury Prevention Regulations of the Industrial Safety and Health Act. Therefore, a resin composition that does not contain styrene and a fiber-reinforced resin material using the resin composition are required.

[0004] In response to this demand, several styrene-free resin compositions have been proposed, and many of them use an epoxy (meth)acrylate resin composition diluted with a high-boiling (meth)acrylate as a styrene substitute. Here, (meth)acrylate refers to a methacrylic acid ester or an acrylic acid ester. Examples of lining applications include resin compositions composed of aromatic epoxy (meth)acrylate, ethoxylated bisphenol A dimethacrylate, a monofunctional (meth)acrylate-based monomer having a group containing a cyclic hydrocarbon group, and a (meth)acrylate monomer having a phenyl group (Patent Document 1 (Japanese Patent No. 5384715)). Examples of corrosion-resistant equipment applications include vinyl ester resins and vinyl ester resin compositions composed of (meth)acrylate having an aromatic ring group (Patent Document 2 (Japanese Unexamined Patent Application Publication No. 2018-2888)).

[0005] In addition, flexible (meth)acrylates that can increase the tensile elongation rate of the cured product are commercially available, but they generally cannot be selected because they cause the adverse effect of significantly reducing the heat resistance. In response to this problem, there is an example of proposing the use of flexible epoxy (meth)acrylate. That is, a long-chain unsaturated monobasic acid obtained by reacting a monofunctional (meth)acrylate having one hydroxyl group in the molecule and / or an allyl ether compound having one hydroxyl group in the molecule and an unsaturated group at the molecular end with a saturated dibasic acid or its acid anhydride, and a resin composition composed of methacrylic acid and / or a bisphenol-type epoxy compound has been proposed (Patent Document 3 (Japanese Unexamined Patent Application Publication No. 2005-298556)).

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, in the prior art including the above-mentioned Patent Documents 1 and 2, many of the (meth)acrylate-diluted epoxy (meth)acrylate resin compositions have a tensile elongation rate of the cured product, which is an index of impact resistance, of less than 3%, and the performance is insufficient compared to 4% or more of the conventional styrene-diluted epoxy (meth)acrylate resin. As a factor, (meth)acrylates with high boiling points generally have large molecular weights, the viscosity of the diluted epoxy (meth)acrylate resin composition increases, and the impregnability to reinforcing fibers decreases, so the (meth)acrylate content increases.

[0008] Further, in Patent Document 3, although the tensile elongation rate can be increased, there is a problem that the boiling water absorption rate, which is an index of the chemical resistance of the cured product, is large, and it is restricted in use for corrosion-resistant linings and corrosion-resistant equipment that come into contact with chemical solutions at normal temperature.

[0009] Therefore, the problem to be solved by the present invention is to provide a resin composition capable of obtaining a cured product having a large tensile elongation rate and a small boiling water absorption rate, and a reinforcing fiber material using the resin composition.

Means for Solving the Problems

[0010] As a result of variously and comprehensively examining the resin composition from various viewpoints, the present inventors have found the resin composition of the present invention.

[0011] That is, the resin composition of the present invention is a resin composition containing brominated bisphenol A type epoxy methacrylate (A) and n-butyl methacrylate and / or i-butyl methacrylate (B). wherein the brominated bisphenol A type epoxy methacrylate (A) is obtained by reacting a brominated bisphenol A type epoxy resin having an epoxy equivalent in the range of 330 to 440 g / eq with methacrylic acid in the range of 0.9 to 1.2 chemical equivalents per 1 chemical equivalent of the epoxy group of the brominated bisphenol A type epoxy resin It is characterized by this.

[0012] In a preferred embodiment of the resin composition of the present invention, the resin composition is for lining or equipment.

[0013] In a preferred embodiment of the resin composition of the present invention, the mass ratio (A) / (B) of the brominated bisphenol A type epoxy methacrylate (A) to the n-butyl methacrylate and / or i-butyl methacrylate (B) is 50 to 80 / 50 to 20.

[0014] In a preferred embodiment of the resin composition of the present invention, the viscosity of the resin composition at 25°C is 15 to 2300 mPa·s or less.

[0015] In a preferred embodiment of the resin composition of the present invention, it contains 0.1 to 5% by mass of an organic peroxide based on 100% by mass in total of (A) and (B).

[0016] The fiber-reinforced resin material of the present invention is characterized by comprising the resin composition of the present invention and reinforcing fibers.

Advantages of the Invention

[0017] According to the resin composition of the present invention, since the tensile elongation rate of the cured product, which is an index of impact resistance, is large and the boiling water absorption rate of the cured product, which is an index of chemical resistance, is small, it has an advantageous effect that it can be used as a corrosion-resistant lining material for contacting with high-temperature chemical solutions and corrosion-resistant machine equipment such as tanks and pipes. Further, according to the resin composition of the present invention, there is an advantageous effect that it is not necessary to contain styrene.

Embodiments for Carrying Out the Invention

[0018] The resin composition of the present invention is characterized by containing brominated bisphenol A type epoxy methacrylate (A) and n-butyl methacrylate and / or i-butyl methacrylate (B). That is, the present inventors have found that a resin composition composed of brominated bisphenol A type epoxy methacrylate, n-butyl methacrylate and / or i-butyl methacrylate has a large tensile elongation rate of the cured product as an index of impact resistance and a small boiling water absorption rate as an index of chemical resistance. Further, in a preferred embodiment of the resin composition of the present invention, from the viewpoint of good corrosion resistance, the resin composition is characterized by being for lining or for equipment. That is, it can be used for corrosion-resistant lining or corrosion-resistant equipment.

[0019] Lining generally means a surface treatment that relatively thickly covers the surface or inner surface of an object with a substance or object that can be fixed, and may refer to the coating itself. According to the present invention, it is also possible to impart corrosion resistance and a protective function.

[0020] In addition, the equipment to which the resin composition of the present invention can be applied is not particularly limited, and examples thereof include chemical tanks, hot and cold water tanks, pipes, reaction vessels, scrubbers, chimneys, etc. By applying the present invention, it is possible to improve the corrosion resistance of the equipment.

[0021] The brominated bisphenol A type epoxy methacrylate (A) of the present invention has a function of reducing the boiling water absorption rate, which is an index of the chemical resistance of the cured product of the resin composition.

[0022] As the brominated bisphenol A type epoxy methacrylate (A), it can be obtained by reacting a brominated bisphenol A type epoxy resin having 3 or 4 bromine atoms in one molecule and 2 epoxy groups in one molecule with methacrylic acid.

[0023] As the brominated bisphenol A type epoxy resin, it can be obtained by reacting brominated bisphenol A and epichlorohydrin under a basic catalyst such as known caustic soda, or a commercially available brominated bisphenol A type epoxy resin can be used.

[0024] The epoxy equivalent of the brominated bisphenol A type epoxy resin is preferably in the range of 330 to 440 g / eq., more preferably in the range of 390 to 410 g / eq. When it is less than 330 g / eq., depending on the conditions, the bromine content may be low and the boiling water absorption of the cured product of the resin composition may increase. When it exceeds 410 g / eq., depending on the conditions, the molecular weight of the epoxy resin is large, the viscosity of the brominated bisphenol A type epoxy methacrylate (A) is high, the mass ratio of (A) in the resin composition is small, and the boiling water absorption of the cured product of the resin composition may increase.

[0025] The commercially available brominated bisphenol A type epoxy is not particularly limited, and examples include "EPICLON152" and "EPICLON153" manufactured by DIC Corporation, "NPEB-340" and "NPEB-400" with the trade name of Nan Ya Plastics Corporation, and "BEB350" and "BEB400" with the trade name of Changchun Artificial Resin Factory. These can be used alone or in combination of two or more.

[0026] The brominated bisphenol A type epoxy resin and methacrylic acid can be reacted in the temperature range of 80 to 140 °C, preferably 100 to 130 °C, in the presence of a known esterification catalyst and a known polymerization inhibitor.

[0027] The known esterification catalysts are not particularly limited. From the perspective of smoothly advancing the esterification reaction without gelation, triphenylphosphine having a tertiary phosphorus in the molecule, triethylamine having a tertiary nitrogen in the molecule, 2-methylimidazole, N,N-dimethylaniline, 2,4,6-tris(dimethylaminomethyl)phenol, dimethylaminoethyl methacrylate, etc. can be mentioned, and these can be used alone or in combination of two or more. Among these esterification catalysts, triphenylphosphine and 2-methylimidazole are particularly preferred.

[0028] The addition amount of these esterification catalysts can be in the range of 0.01 to 5% by mass, preferably 0.05 to 2% by mass, based on 100% by mass of the total of brominated bisphenol A type epoxy resin and methacrylic acid. If the addition amount is less than 0.01% by mass, the esterification reaction will be extremely slow, and if it exceeds 5% by mass, the esterification reaction will be extremely fast and temperature control may become difficult due to rapid heat generation. Also, if the reaction temperature is less than 80°C, the esterification reaction will be extremely slow, and if the temperature exceeds 140°C, there is a risk of gelation, so it is not practical.

[0029] The methacrylic acid is preferably used in the range of 0.9 to 1.2 chemical equivalents, preferably 1.0 to 1.1 chemical equivalents, of methacrylic acid with respect to 1 chemical equivalent of the epoxy group of the brominated bisphenol A type epoxy resin. If it is less than 0.9 chemical equivalent, the storage stability after the reaction may deteriorate, and if it exceeds 1.2 chemical equivalents, the boiling water absorption rate of the cured product may increase.

[0030] The known polymerization inhibitors are not particularly limited. From the perspective of preventing gelation during synthesis without inhibiting the esterification reaction, hydroquinones such as hydroquinone, monomethyl ether hydroquinone, and methyl hydroquinone, quinones such as benzoquinone and naphthoquinone, phenols such as 2,6 tertiary butyl 4-methylphenol, phenothiazine, copper salts, etc. can be mentioned. These can be used alone or in combination of two or more.

[0031] Regarding the addition amount of the aforementioned known polymerization inhibitor, it can be preferably used in the range of 0.0001 to 1% by mass, more preferably in the range of 0.001 to 0.5% by mass, based on 100% by mass of the combination of brominated bisphenol A type epoxy resin and methacrylic acid. If it is less than 0.0001% by mass, gelation will occur during synthesis, and if it exceeds 1% by mass, the curing of the resin composition containing the obtained brominated bisphenol A type epoxy methacrylate will be extremely slow and may become impractical. Also, these polymerization inhibitors can be added for the purpose of adjusting the gelation time of the resin composition.

[0032] n-Butyl methacrylate and / or i-butyl methacrylate (B) used in the resin composition of the present invention has a function of increasing the tensile elongation rate, which is an index of the impact resistance of the cured product of the resin composition. In particular, n-butyl methacrylate can increase the tensile elongation rate. Also, n-butyl methacrylate and / or i-butyl methacrylate (B) has a function of reducing the boiling water absorption rate, which is an index of the chemical resistance of the cured product of the resin composition. In particular, i-butyl methacrylate can reduce the boiling water absorption rate. n-Butyl methacrylate and i-butyl methacrylate can be used alone or mixed in any ratio to obtain a desired tensile elongation rate and boiling water absorption rate.

[0033] The aforementioned n-butyl methacrylate and / or i-butyl methacrylate (B) can be obtained by a known production method through a condensation reaction of n-butyl alcohol or i-butyl alcohol with methacrylic acid respectively, or by a transesterification reaction with methyl methacrylate, or commercially available products can be used.

[0034] The n-butyl methacrylate of the commercially available n-butyl methacrylate and / or i-butyl methacrylate (B) is not particularly limited, and examples thereof include the product name "n-butyl methacrylate" of Mitsubishi Gas Chemical Company, the product name "butyl methacrylate" of Nippon Shokubai Co., Ltd., and the product name "Acryester B" of Mitsubishi Chemical Corporation. Further, the i-butyl methacrylate is not particularly limited, and examples thereof include the product name "i-butyl methacrylate" of Mitsubishi Gas Chemical Company, the product name "i-butyl methacrylate" of Nippon Shokubai Co., Ltd., and the product name "Acryester IB" of Mitsubishi Chemical Corporation.

[0035] Further, in a preferred embodiment of the resin composition of the present invention, the mass ratio (A) / (B) of the brominated bisphenol A type epoxy methacrylate (A) to the n-butyl methacrylate and / or i-butyl methacrylate (B) is 50 to 80 / 50 to 20 from the viewpoint of achieving both a lower boiling water absorption rate and a higher tensile elongation rate of the cured product, and good impregnability to the reinforcing fiber.

[0036] Further, in a preferred embodiment of the resin composition of the present invention, the viscosity of the resin composition at 25°C is in the range of 15 to 2300 mPa·s. That is, the viscosity at 25°C is preferably 15 to 2300 mPa·s, more preferably 20 to 2000 mPa·s. A resin composition having a viscosity at 25°C of 15 to 100 mPa·s is a suitable material as a primer in lining, a resin composition having a viscosity of 100 to 1000 mPa·s is a suitable material as a fiber-reinforced resin material impregnated with reinforcing fibers, and a resin composition having a viscosity of 1000 to 2300 mPa·s is a suitable material as a coating material in lining.

[0037] The resin composition of the present invention has the following function: an organic peroxide is added and dissolved, and when used at room temperature, a known organic cobalt compound or amine compound is added to form a redox reaction with the organic peroxide to decompose the organic peroxide and generate radicals. These radicals react with the carbon-carbon double bonds of the methacrylic groups of brominated bisphenol A type epoxy methacrylate (A), n-butyl methacrylate and / or i-butyl methacrylate (B) contained in the resin composition, and a copolymerization reaction proceeds to form a crosslinked structure, thereby obtaining a cured product.

[0038] Examples of the organic peroxide include ketone peroxide-based such as methyl ethyl ketone peroxide and acetoacetic acid ester peroxide; hydroperoxide-based such as cumene hydroperoxide; peroxycarbonate-based such as bis-(4-t-butylcyclohexyl) peroxycarbonate; peroxyketal-based such as 1,1-di-t-butylperoxy 3,3,5-trimethylcyclohexanone and 1,1-di-t-butylperoxycyclohexanone; diacyl peroxide-based such as t-butylperoxy-2-ethylhexanoate and benzoyl peroxide; and peroxyester-based such as t-butylperoxybenzoate and t-butylperoxy-2-ethylhexanoate. In addition, organic peroxides commercially available as dedicated curing agents for epoxy (meth)acrylate or vinyl ester can also be used. Examples of such dedicated curing agents include "Perkure K" and "Perkure VS" manufactured by NOF Corporation, and "328E" and "328EM" manufactured by KAC Chemical Nuon Co., Ltd. These can be used alone or in combination of two or more.

[0039] Further, in a preferred embodiment of the resin composition of the present invention, it is characterized in that it contains 0.1 to 5% by mass of an organic peroxide based on 100% by mass in total of (A) and (B).

[0040] Commercially available organic peroxides have various purities. However, the amount of the organic peroxide used is preferably in the range of 0.1 to 5% by mass based on the total 100% by mass of (A) and (B), when converted to a purity of 100%. If it is less than 0.1% by mass, there is a risk that curing will be extremely slow and it will not be practical. If it exceeds 5% by mass, there is a risk that the heat resistance, water resistance, and various physical properties of the cured product will deteriorate. Among these, the use of the product named "Perkure K" manufactured by NOF Corporation is most effective when curing the resin composition of the present invention.

[0041] Examples of the organic cobalt compound include cobalt naphthenate, cobalt 2-ethylhexanoate, etc. Commercially available organic cobalt compounds have various cobalt concentrations of 6 to 24%. However, the amount of the organic cobalt compound used in the resin composition of the present invention is preferably in the range of 0.1 to 3% by mass based on the total 100% by mass of (A) and (B) for any cobalt concentration, and more preferably 0.8 to 2% by mass. If it is less than 0.1% by mass, the amount forming a redox with the organic peroxide is small, and there is a risk that curing will be extremely slow and it will not be practical. If it exceeds 3% by mass, the molecular weight of the copolymerized cured product will be small, and there is a risk that the heat resistance and heat water resistance will deteriorate.

[0042] Examples of the amine compound include N,N-dimethylaniline, N,N-diethanolaniline, N,N-dimethyl-p-toluidine, N,N-dihydroxyethyl-p-toluidine, etc. The amount of the amine compound used in the resin composition of the present invention is preferably in the range of 0.001 to 2% by mass based on the total 100% by mass of (A) and (B). If it is less than 0.001% by mass, there is a risk that curing will be extremely slow and it will not be practical. If it exceeds 2 parts by mass, there is a risk that curing will occur rapidly and deformation or warping will occur due to heat generation.

[0043] In the resin composition of the present invention, paraffin waxes with different melting points and commercially available waxes can be added as needed for the purpose of improving the surface drying property during curing. Examples of commercially available waxes include products named "BYK-S740" and "BYK-S782" manufactured by BYK Chemie Japan Co., Ltd., and products named "NPS-8070" manufactured by Nippon Seiro Co., Ltd.

[0044] In addition, the resin composition of the present invention can contain a thixotropic agent such as fumed silica for the purpose of preventing resin sagging. Furthermore, a commercially available thixotropy aid can be contained as needed for the purpose of efficiently dispersing the thixotropic agent. Examples of commercially available thixotropy aids include a product named "BYK-R605" manufactured by BYK Chemie Japan Co., Ltd.

[0045] In addition, in the resin composition of the present invention, known polymerization inhibitors, chain transfer agents, mold release agents, metal adhesion promoters, pigments, defoaming agents, low shrinkage agents, inorganic fillers, flake glass, pigments, etc. can be appropriately selected and added as needed.

[0046] The fiber-reinforced resin material of the present invention is characterized by comprising the resin composition of the present invention and reinforcing fibers. Regarding the resin composition of the present invention, the above description can be directly referred to.

[0047] As the reinforcing fibers used in the fiber-reinforced resin material of the present invention, glass fibers, carbon fibers, aramid fibers, and natural fibers can be used. The shape of the fibers can be chopped strands or those made into mats, or rovings or roving cloths woven from rovings, or those with fibers aligned in one direction, etc. In addition, hybrid-type fiber-reinforcing materials combining carbon fibers, glass fibers, and aramid fibers can also be used. These reinforcing fibers can be used alone or in combination of two or more. Also, as a method for further enhancing corrosion resistance, a surfacing mat such as glass fibers, polyester fibers, or carbon fibers can be used on the contact surface as needed.

[0048] As a method for molding the fiber-reinforced resin material of the present invention, lining on concrete, steel, stainless steel, etc., open mold methods such as hand lay-up and spray-up, filament winding method, etc. can be used.

Example

[0049] Hereinafter, the present invention will be described with reference to the following examples and comparative examples, but the present invention is not limited to these examples.

[0050] Synthesis Example 1 Into a four-necked flask equipped with a stirring device, a thermometer, and a gas introduction tube, 4000 g of brominated bisphenol A type epoxy resin "EPICLON 153" with an epoxy equivalent of 400 g / eq. manufactured by DIC was charged into the flask, heated to 100 °C and dissolved. Then, while blowing air, 861 g of methacrylic acid (1 chemical equivalent relative to 1 chemical equivalent of epoxy group), 5 g of 2-methylimidazole, and 5 g of monomethyl ether hydroquinone were charged, and reacted at 120 °C for 3 hours to obtain brominated bisphenol A type epoxy methacrylate (A-1) with an acid value of 2 mgKOH / g and a softening point of 60 °C.

[0051] Synthesis Example 2 Into a four-necked flask equipped with a stirring device, a thermometer, a cooling tower, and a gas introduction tube, 2582 g of bisphenol A type epoxy resin "EPICLON 850" with an epoxy equivalent of 189 g / eq. manufactured by DIC, 418 g of bisphenol A, and 1.5 g of triethylamine were charged, and reacted at 150 °C for 1 hour while blowing air under stirring to obtain a bisphenol A type epoxy resin with an epoxy equivalent of 300 g / eq. Next, 861 g of methacrylic acid (1.03 chemical equivalents relative to 1 chemical equivalent of epoxy group), 2 g of hydroquinone, and 12 g of 2,4,6-tris(dimethylaminomethyl)phenol were charged, and reacted at 130 °C for 4 hours while blowing air under stirring to obtain bisphenol A type epoxy methacrylate (A-2) with an acid value of 7 mgKOH / g.

[0052] Examples 1 to 8, Comparative Examples 1 to 4 For the brominated bisphenol A type epoxy methacrylate (A-1) obtained in Synthesis Example 1 and the bisphenol A type epoxy methacrylate (A-2) obtained in Synthesis Example 2, resin compositions were prepared with the formulations shown in Tables 1 and 2. The liquid properties and cast plate properties of the obtained resin compositions were measured, and the chemical resistance evaluation of FRP (fiber reinforced plastic) using glass fibers was carried out.

[0053] (1) Liquid properties Viscosity Weighed 180 g of the resin composition into a 225 mL cylindrical glass bottle, immersed it in a water bath thermostatically controlled at 25 °C for 30 minutes or more, and after confirming with a thermometer that the temperature of the resin composition was 25 °C, measured it with a single cylindrical rotational viscometer. The measurement method conformed to JIS K6901 "Viscosity".

[0054] Room temperature curing characteristics Weighed 50 g of the resin composition into a 100 mL beaker, immersed it in a water bath thermostatically controlled at 25 °C for 30 minutes or more, and after confirming with a thermometer that the temperature of the resin composition was 25 °C, measured the gelation time in accordance with JIS K6901 "Room temperature curing characteristics (exothermic method)".

[0055] (2) Cast plate (cured product) properties To 100% by mass of the resin compositions prepared in the above Examples and Comparative Examples, an appropriate amount of hydroquinone was added as a polymerization inhibitor so that the gelation time at 25 °C was about 30 minutes, and 0.5% by mass of "Nickel Octix Cobalt (8%)" manufactured by Nippon Chemical Industry Co., Ltd. was added and dissolved as a curing accelerator. Then, 1% by mass of the product named "Perkure K" manufactured by NOF Corporation was added and dissolved as an organic peroxide. The resin composition was poured into a cell made of tempered glass of a 3 mm thick flat plate with cellophane for release attached, cured at room temperature for 16 hours, and further post-cured at 120 °C for 2 hours to prepare cast plates respectively. For these cast plates, the boiling water absorption rate and tensile elongation rate were measured.

[0056] Boiling water absorption rate The casting plate was processed into 50 mm × 50 mm, immersed in pure water at 100 °C for two weeks, the mass before and after immersion was measured, and the boiling water absorption rate was calculated. The evaluation criteria for the water heat resistance were ○ when the boiling water absorption rate was less than 1.7% and × when it was 1.7% or more.

[0057] Tensile test The casting plate was processed in accordance with JIS K7164 Type IB System B, and a tensile test was conducted in a room at a temperature of 23 °C at a test speed of 1 mm / min. The tensile elongation rate was calculated by attaching an extensometer conforming to JIS K7161. The evaluation criteria for the tensile elongation rate were ○ when the elongation rate was 3.9% or more and × when it was less than 3.9%.

[0058] (3) Evaluation of the moldability of FRP Impregnability To 100% by mass of the resin compositions prepared in the above Examples and Comparative Examples, an appropriate amount of hydroquinone was added as a polymerization inhibitor so that the gelation time at 25 °C was 20 to 40 minutes, and 0.5% by mass of "Nick Octix Cobalt (8%)" manufactured by Nippon Chemical Industry Co., Ltd. was added and dissolved as a curing accelerator. Then, 1% by mass of a product named "Perkure K" manufactured by NOF Corporation was added and dissolved as an organic peroxide. A resin composition in which the content of glass fiber in the fiber-reinforced resin material was 30% by mass was poured from above a three-layered 300 mm × 300 mm glass chopped strand mat (450 g / m2), and impregnated while squeezing with a defoaming roller for 5 minutes. The evaluation criteria were ○ when all three layers were uniformly impregnated with the resin composition during the 20 to 40 minutes when the gelation of the resin composition started, and × when even one layer was not impregnated or was non-uniformly impregnated. The evaluation was conducted in a room at a temperature of 23 °C.

[0059]

Table 1

[0060]

Table 2

Claims

1. A resin composition containing brominated bisphenol A type epoxy methacrylate (A) and n-butyl methacrylate and / or i-butyl methacrylate (B), wherein the brominated bisphenol A type epoxy methacrylate (A) is obtained by reacting a brominated bisphenol A type epoxy resin in the range of epoxy equivalent of 330 to 440 g / eq with methacrylic acid in the range of 0.9 to 1.2 chemical equivalents per 1 chemical equivalent of the epoxy group of the brominated bisphenol A type epoxy resin. The resin composition is characterized by this.

2. The resin composition according to Claim 1, which is for lining or for equipment.

3. The resin composition according to Claim 1 or 2, wherein the mass ratio (A) / (B) of the brominated bisphenol A type epoxy methacrylate (A) to the n-butyl methacrylate and / or i-butyl methacrylate (B) is 50 to 80 / 50 to 20.

4. The resin composition according to any one of Claims 1 to 3, wherein the viscosity of the resin composition at 25°C is 15 to 2300 mPa·s.

5. The resin composition according to any one of Claims 1 to 4, which contains 0.1 to 5% by mass of an organic peroxide based on 100% by mass in total of (A) and (B).

6. A fiber-reinforced resin material comprising the resin composition according to any one of Claims 1 to 5 and a reinforcing fiber.

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