Epoxy resin compositions, fiber-reinforced composite materials, and molded articles

Abstract

To provide an epoxy resin composition with excellent mechanical properties of moldings while maintaining impregnation into carbon fiber and immediate curing.SOLUTION: An epoxy resin composition comprises an epoxy resin (A), an aromatic epoxy resin (B), an alicyclic amine (C) and a core-shell rubber (D) as essential components, where the aromatic epoxy resin (B) has a structure represented by the general formula (1) in the figure, and has a viscosity of 100 to 5000 mPa s at 25°C.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a fiber-reinforced composite material and an epoxy resin composition used therefor.

Background Art

[0002] Conventionally, fiber-reinforced composite materials composed of reinforcing fibers such as carbon fibers and glass fibers and thermosetting resins such as epoxy resins and phenolic resins are lightweight and have excellent mechanical properties such as strength and rigidity, heat resistance, and corrosion resistance. Therefore, they have been applied to many fields such as aviation and space, automobiles, railway vehicles, ships, civil engineering and construction, and sports goods. In particular, in applications where high performance is required, fiber-reinforced composite materials using continuous reinforcing fibers are used. As the reinforcing fibers, carbon fibers having excellent specific strength and specific modulus are used, and as the matrix resin, thermosetting resins, especially epoxy resins having excellent adhesion to carbon fibers, are widely used.

[0003] Since the epoxy resin composition is used by impregnating the resin into the reinforcing fibers, it is required to have a low viscosity. In addition, when used as a fiber-reinforced resin molded product for structural parts in automobiles and the like or as an electric wire core material, the fiber-reinforced resin molded product is exposed to a harsh use environment, so it is also required to be a resin having excellent heat resistance and mechanical strength.

[0004] In addition to heat resistance and mechanical strength, it is also important that the curing time is short. This is because shortening the curing time makes it possible to improve productivity in limited production facilities.

[0005] Low-viscosity epoxy resin compositions are widely known, including those containing bisphenol-type epoxy resins, acid anhydrides, and imidazole compounds (Patent Document 1). Also known are epoxy resin compositions comprising a glycidyl ether of a divalent phenol and a glycidylamine-type epoxy resin combined with a curing agent (Patent Document 2). Furthermore, epoxy resin compositions containing aliphatic epoxy resins, core-shell type rubber particles, and amine curing agents are also known (Patent Document 3). However, while the epoxy resin compositions provided in Patent Documents 1, 2, and 3 exhibit high impregnation into reinforcing fibers and demonstrate certain performance in terms of heat resistance and mechanical strength in cured products, their viscosity and curing time are long, failing to satisfy the increasingly demanding performance requirements.

[0006] Methods have been explored to improve the mechanical strength of epoxy resins, including the incorporation of rubber components or thermoplastic resins with excellent toughness. For example, the improvement in the toughness of epoxy resins by incorporating rubber components such as acrylonitrile-butadiene rubber containing carboxyl groups has been studied since the 1970s and is generally well known. However, rubber components cause a decrease in heat resistance and elastic modulus, and a large amount of rubber component is required to obtain a sufficient toughness-modifying effect. As a result, viscosity increases, and the inherent heat resistance and mechanical properties of the epoxy resin decrease, making it difficult to obtain composite materials with good physical properties.

[0007] To address this problem, a method has been proposed that uses polymer particles that are substantially insoluble in epoxy resin. In particular, a method has been proposed in which a particulate core portion mainly composed of polymer and core-shell rubber particles in which part or all of the surface of the core portion is covered by a polymer different from the core portion, for example by graft polymerization, is used (Patent Document 4). This method is known to suppress the increase in viscosity of the epoxy resin composition and the decrease in Tg of the cured epoxy resin product.

[0008] However, achieving a sufficient toughness improvement requires the incorporation of a large amount of core-shell rubber particles, which leads to increased viscosity, a decrease in the elastic modulus of the epoxy resin curing product, and ultimately a decline in the mechanical properties of the fiber-reinforced composite material.

[0009] Therefore, there was a need for an epoxy resin composition that has low viscosity, good impregnation properties into fibers, and even better Tg, elastic modulus, and rapid curing properties. [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] Japanese Patent Publication No. 2010-163573 [Patent Document 2] International Publication No. 2016 / 148175 [Patent Document 3] International Publication No. 2020 / 022950 [Patent Document 4] Japanese Patent Application Publication No. 5-65391 [Overview of the Initiative] [Problems that the invention aims to solve]

[0011] The present invention provides an epoxy resin composition that maintains impregnation properties into carbon fibers and rapid curing properties while exhibiting excellent mechanical properties in molded products. [Means for solving the problem]

[0012] In other words, the present invention relates to an epoxy resin composition comprising an epoxy resin (A), an aromatic epoxy resin (B), an alicyclic amine (C), and a core-shell rubber (D) as essential components, wherein the aromatic epoxy resin (B) has a structure represented by general formula (1) and a viscosity of 100 to 5000 mPa·s at 25°C. [ka] (wherein n is an integer between 0 and 4, and Rm consists of 0 to 4 substituents, each independently representing either a hydrogen atom or an aliphatic hydrocarbon group with 4 or fewer carbon atoms.)

[0013] Another aspect of the present invention is a fiber-reinforced composite material characterized by being compounded with reinforcing fibers in the epoxy resin composition described above. Preferably, the volume content of the reinforcing fibers is 30 to 75%. [Effects of the Invention]

[0014] The epoxy resin composition of the present invention has low viscosity, good impregnation properties into fibers, and is fast-curing, and the resulting cured product exhibits excellent heat resistance and mechanical properties. [Modes for carrying out the invention]

[0015] The embodiments of the present invention will be described in detail below. The epoxy resin composition of the present invention comprises an epoxy resin (A), an aromatic epoxy resin (B), an alicyclic amine (C), and a core-shell rubber (D) as essential components. Hereinafter, the epoxy resin (A), aromatic epoxy resin (B), alicyclic amine (C), and core-shell rubber (D) will also be referred to as component (A), component (B), component (C), and component (D), respectively.

[0016] The amount of epoxy resin (A) used in the present invention is 45 to 85 parts by mass, preferably 45 to 80 parts by mass, and more preferably 55 to 75 parts by mass, out of a total of 100 parts by mass of components (A) to (D). The epoxy resin (A) includes bisphenol-type epoxy resins such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol E-type epoxy resin, bisphenol S-type epoxy resin, bisphenol Z-type epoxy resin, isophorone-bisphenol-type epoxy resin, etc., which have two epoxy groups in one molecule, as well as high molecular weight products having multiple repeating units, glycidyl ethers of alkylene oxide adducts, phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, bisphenol A novolac-type epoxy resin, etc., and 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexyl Alicyclic epoxy resins such as carboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 1-epoxyethyl-3,4-epoxycyclohexane; aliphatic epoxy resins such as trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, and polyoxyalkylene diglycidyl ether; glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, and glycidyl dimer acid; and glycidylamines such as tetraglycidyldiaminodiphenylmethane, tetraglycidyldiaminodiphenylsulfone, triglycidylaminophenol, triglycidylaminocresol, and tetraglycidylxylylenediamine can be used. These may be used individually or in combination of two or more. Preferably, it is a liquid bisphenol-type epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, or bisphenol Z type epoxy resin.

[0017] The epoxy equivalent of epoxy resin (A) is preferably 130 to 220 g / eq., more preferably 140 to 200 g / eq. The epoxy resin (A) is preferably liquid, and the viscosity at 25°C is preferably selected from the range of 1000 to 20000 mPa·s, more preferably 1000 to 15000 mPa·s.

[0018] The aromatic epoxy resin (B) is an epoxy resin represented by the general formula (1), and it is necessary that the viscosity at 25°C is 100 to 5000 mPa·s. [Chemical formula] (However, n is an integer of 0 or more and 4 or less, and Rm is 0 to 4 substituents, each independently representing a hydrogen atom or an aliphatic hydrocarbon group having 4 or less carbon atoms) Specifically, depending on the position (ortho, meta, para) at which the glycidyl ether group is bonded to the benzene ring with respect to the ether oxygen atoms at both ends of the aliphatic chain connecting the two benzene ring units, there are catechol type having a glycidyl ether group at the ortho position, resorcinol type having a glycidyl ether group at the meta position, and hydroquinone type having a glycidyl ether group at the para position isomers. Even in the case of a dimer (n = 1), from the viewpoint of the effect of improving the elastic modulus due to the reduction of the free volume of the cured product utilizing the flexibility of the molecular chain, the catechol type and the resorcinol type are preferable. Further, since the dimer has a hydroxyl group at the inter-unit connecting portion, the intermolecular chain interaction is strong, and it is more preferable for improving the elastic modulus of the cured product. Furthermore, regarding the substituent Rm of the aromatic ring of each unit, it is either a hydrogen atom or an aliphatic hydrocarbon group. In the case of an aliphatic hydrocarbon group, in order to maintain compatibility with other components and obtain high mechanical properties, the number of carbon atoms is 4 or less, more preferably 2 or less.

[0019] For the aromatic epoxy resin (B), n is preferably an integer of 0 or more and 4 or less, more preferably 0 or more and 3 or less. When n is 5 or more, the viscosity increases significantly, so it is not suitable for this study.

[0020] The epoxy equivalent of aromatic epoxy resin (B) is preferably 100 to 170 g / eq., more preferably 110 to 150 g / eq. The aromatic epoxy resin (B) must have a viscosity of 100 to 5000 mPa·s at 25°C. Preferably, it is 100 to 1000 mPa·s, and more preferably, 200 to 700 mPa·s.

[0021] Aromatic epoxy resin (B) can be obtained, for example, by the following method. First, epichlorohydrin and isopropyl alcohol are dissolved in dihydroxybenzene, heated, and an aqueous sodium hydroxide solution is added dropwise. Next, the saline solution is separated and removed, and the excess epichlorohydrin, isopropyl alcohol, and water are recovered by distillation to obtain crude resin. This is then dissolved in toluene, an aqueous basic solution is added, and the mixture is heated and stirred. After that, the salts and alkalis generated by washing with water are removed by oil-water separation, and toluene can be recovered by distillation after dehydration and filtration.

[0022] The amount of aromatic epoxy resin (B) used in the present invention is 5 to 30 parts by mass, preferably 5 to 25 parts by mass, and more preferably 5 to 20 parts by mass, out of a total of 100 parts by mass of components (A) to (D).

[0023] The alicyclic amine (C) is a curing agent for epoxy resins, and a low viscosity type can be used. The viscosity at 25°C is preferably 1 to 100 mPa·s, more preferably 3 to 50 mPa·s, and even more preferably 5 to 30 mPa·s. Examples of alicyclic amines (C) include 4,4'-methylenebiscyclohexylamine, diaminodicyclohexylmethane, bis(4-amino-3-methylcyclohexyl)methane, bis(aminomethyl)cyclohexane, isophoronediamine, norbornenedimethylamine, N-aminoethylpiperazine, and epoxy adducts of these cyclic aliphatic amines. Among these, 1,3-bis(aminomethyl)cyclohexane is preferred due to its high reactivity and low viscosity.

[0024] The ratio of active hydrogen equivalents of the alicyclic amine (C) to the epoxy equivalents in the epoxy resin composition is 0.7 to 1.2, preferably 0.8 to 1.2, and more preferably 0.8 to 1.1. If the active hydrogen equivalent ratio is lower than 0.7, the Tg of the cured product decreases significantly, and if it is higher than 1.2, the heat resistance is greatly impaired.

[0025] Core-shell rubber (D) is a particulate core component whose main component is a cross-linked rubber-like polymer or elastomer, and the surface of the core component is coated with a shell component by graft polymerization of a shell component polymer of a different type from the core component.

[0026] When a core-shell polymer is applied to the epoxy resin composition of the present invention, the core-shell polymer preferably has an average particle diameter of 1 to 500 nm in volume average particle diameter, and more preferably 3 to 300 nm. The volume average particle diameter can be measured using a NanoTrac particle size distribution analyzer (manufactured by Nikkiso Co., Ltd.). If the volume average particle diameter of the core-shell polymer used in the present invention is 1 nm or less, it is difficult to manufacture or becomes extremely expensive and practically unusable. If the volume average particle diameter is 500 nm or more, in the manufacturing process of the tow prepreg, the reinforcing fibers are bundles of fibers of about 1 μm, which form a mesh-like structure that prevents core-shell polymers of the same size from passing through, resulting in an uneven dispersion state of the core-shell polymer, which is undesirable.

[0027] The amount of core-shell rubber (D) blended is preferably 0.5 to 15 parts by mass per 100 parts by mass of the epoxy resin composition, and more preferably 1 to 10 parts by mass. If the blending amount is 0.5 parts by mass or more, the fracture toughness required for the fiber-reinforced composite material after molding is easily obtained, and if the blending amount is 15 parts by mass or less, the viscosity of the resulting epoxy resin composition for fiber-reinforced composite material is suppressed, and the reinforcing fibers can be impregnated without difficulty, making it more suitable for fiber-reinforced composite materials.

[0028] The epoxy resin composition of the present invention may further contain other stabilizers, modifiers, etc. Preferred stabilizers are boric acid compounds represented by B(OR)3 (where R represents a hydrogen atom, an alkyl group, or an aryl group). The amount of boric acid compound added is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the total resin composition. Adding less than 0.01 parts by mass does not ensure stability during storage, and adding more than 10 parts by mass results in a greater effect of inhibiting the curing reaction, leading to curing failure.

[0029] The epoxy resin composition of the present invention may contain defoaming agents and leveling agents as additives to improve surface smoothness. These additives can be blended in an amount of preferably 0.01 to 3 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the total resin composition. If the blending amount is less than 0.01 parts by mass, the effect of smoothing the surface will not be observed, and if it exceeds 3 parts by mass, the additive will bleed out to the surface, which will conversely impair the smoothness.

[0030] The epoxy resin composition of the present invention may also contain other curable resins. Examples of such curable resins include, but are not limited to, unsaturated polyester resins, curable acrylic resins, curable amino resins, curable melamine resins, curable urea resins, curable cyanate ester resins, curable urethane resins, curable oxetane resins, and curable epoxy / oxetane composite resins.

[0031] The epoxy resin composition of the present invention has a viscosity at 25°C measured using an E-type viscometer, preferably 1 to 80 Pa·s, more preferably 1 to 50 Pa·s, and particularly preferably 1 to 10 Pa·s, for components (A), (B), and (D) excluding the alicyclic amine (C). If the viscosity is too high, the impregnation into carbon fibers deteriorates, and if the viscosity is too low, the resin flows, resulting in a low RC of the cured product and insufficient performance.

[0032] The reinforcing fibers used in the epoxy resin composition of the present invention can be selected from glass fibers, aramid fibers, carbon fibers, boron fibers, etc., but carbon fibers are preferred to obtain a fiber-reinforced composite material with excellent strength.

[0033] In the molded article composed of the epoxy resin composition and reinforcing fibers of the present invention, the volume content of the reinforcing fibers is preferably 30 to 75%, more preferably 45 to 75%. Within this range, a molded article with few voids and a high volume content of reinforcing fibers can be obtained, thus providing a molded material with excellent strength.

[0034] The epoxy resin composition of the present invention can be heated at any temperature between 80 and 180°C for any duration between 20 minutes and 1 hour to allow the crosslinking reaction to proceed and obtain a cured product. The heating conditions may be a single stage or a multi-stage combination of multiple heating conditions. In particular, when considering high-pressure vessels filled with hydrogen gas, such as those used in fuel cells, the desired properties of the cured product can be obtained by heating and curing at any temperature between 80 and 150°C for any duration between 20 minutes and 1 hour. [Examples]

[0035] The present invention will be described in more detail below with reference to examples. The following resin raw materials were used to obtain the resin compositions of each example.

[0036] (A) Epoxy resin • Liquid bisphenol F type epoxy resin: YDF-170 (manufactured by Nippon Steel Chemical & Material Co., Ltd.) Epoxy equivalent weight 160-180 g / eq., viscosity 3000 mPa·s • Liquid bisphenol A type epoxy resin: YD-128 (manufactured by Nippon Steel Chemical & Material Co., Ltd.) Epoxy equivalent weight 184-194 g / eq., viscosity 13000 mPa·s (B) Aromatic epoxy resin Resorcinol diglycidyl ether: DE-703 (Kokuto Chemical Co., Ltd.) Epoxy equivalent 115-135 g / eq., viscosity 360 mPa·s (B') Epoxy resin for comparison Trimethylolpropane triglycidyl ether: YH-300 (Nippon Steel Chemical & Material Co., Ltd.) Epoxy equivalent 140-155 g / eq., viscosity 145 mPa·s (C) Alicyclic amine • 1,3-Bis(aminomethyl)cyclohexane: 1,3-BAC (manufactured by Mitsubishi Gas Chemical Co., Ltd.) Viscosity 9 mPa·s Norbornenediamine: NBDA (Mitsui Fine Chemical Industries, Ltd.) Viscosity 20 mPa·s (D) Core Shell Rubber (CSR) • Masterbatch "MX-154" consisting of bisphenol A epoxy resin dispersed with core-shell rubber (CSR): Core-shell rubber (CSR) content 40 wt%, BPA-type epoxy resin content 60 wt%, average particle size 200 nm (manufactured by Kaneka Corporation), viscosity 30,000 mPa·s (50℃)

[0037] The measurement method is as follows. (1) Epoxy equivalent: The measurements were performed in accordance with JIS K 7236 standard. Specifically, a potentiometric titrator was used, tetrahydrofuran was used as the solvent, tetraethylammonium brominated acetate solution was added, and a 0.1 mol / L perchloric acid-acetic acid solution was used. (2) Viscosity: The procedure conformed to JIS K7117-1. Specifically, the viscosity of the pre-curing resin composition, excluding the aliphatic amine curing agent, at 25°C was measured using an E-type viscometer. (3) Gel time: Using an Anton Paar MCR-102 rheometer, time dispersion measurements were performed in vibration mode at a temperature of 90°C, a strain of 0.1%, and a frequency of 1 Hz. The time at the intersection of the storage modulus G' and the loss modulus G'' was defined as the gel time. (3) Glass transition temperature (Tg): The temperature is expressed as the DSC extrapolated value obtained when measurements were taken using a differential scanning calorimetry system (EXSTAR6000 DSC6200, manufactured by SII Nanotechnology Co., Ltd.) under a heating condition of 20°C / min. (4) Fracture toughness (K1c): The measurements were performed in accordance with ASTM E399. Specifically, test specimens with a width of 10 mm, a thickness of 2 mm, and a length of 50 mm were prepared and measured at room temperature (23°C) with a crosshead speed of 0.5 mm / min. (5) Tensile modulus, tensile strength, tensile elongation: The test conformed to JIS K7161. Specifically, a universal material testing machine (Autograph AGS-H, manufactured by Shimadzu Science Corporation) was used. At room temperature, a dumbbell test specimen with a total length of 215 mm (including the gripping part), a width of 10 mm, and a thickness of 2 mm was subjected to a tensile test at a distance of 114 mm between the chucks and a speed of 50 mm / min. Tensile strength, tensile modulus, and tensile elongation were determined from the resulting stress-strain diagram.

[0038] Examples 1-3, Comparative Examples 1-5 (1) Preparation of epoxy resin composition Epoxy resin (A), aromatic epoxy resin (B), and core-shell rubber (D) were placed in a container in the proportions shown in Table 1 and kneaded for 2 minutes at 2000 rpm and 4.0 mmHg using a THINKY PLANETARY VACUUM MIXER (manufactured by THINKY Co., Ltd.). Then, alicyclic amine (C) was added and kneaded for 20 seconds at 2000 rpm and 4.0 mmHg to prepare epoxy resin compositions with the compositions shown in Table 1. (2) Preparation of test specimens The epoxy resin composition prepared in (1) above was poured into a mold heated to 90°C, cured in an oven at 90°C for 8 minutes, and then in an oven at 150°C for 20 minutes to produce a 2 mm thick plate-shaped cured resin product. Next, the obtained plate-shaped cured resin product was cut out and used for test analysis. The results are shown in Table 1.

[0039] [Table 1]

Claims

1. An epoxy resin composition comprising a bisphenol-type epoxy resin (A), an aromatic epoxy resin (B), an alicyclic amine (C), and a core-shell rubber (D) as essential components, wherein the aromatic epoxy resin (B) is a resorcinol diglycidyl ether having a structure represented by the following general formula (1), and having a viscosity of 100 to 5000 mPa·s at 25°C. 【Chemistry 1】 (However, n is an integer between 0 and 4, and Rm consists of 0 to 4 substituents, each independently representing either a hydrogen atom or an aliphatic hydrocarbon group with 4 or fewer carbon atoms.)

2. The epoxy resin composition according to claim 1, wherein the active hydrogen equivalent ratio of the alicyclic amine (C) is in the range of 0.7 to 1.2 with respect to the epoxy equivalent in the epoxy resin composition.

3. The epoxy resin composition according to claim 1, wherein the viscosity of the resin composition excluding the alicyclic amine (C) at 25°C is 5 to 80 Pa·s.

4. The epoxy resin composition according to claim 1, wherein the fracture toughness is 1.3 or higher, the glass transition temperature is 130°C or higher, and the tensile modulus is 2 GPa or higher.

5. A fiber-reinforced composite material characterized by being obtained by blending reinforcing fibers into the epoxy resin composition according to claim 1.

6. The fiber-reinforced composite material according to claim 5, wherein the volume content of reinforcing fibers is 30 to 75%.

7. A molded article obtained by curing the fiber-reinforced composite material described in claim 5.

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