Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4014—Nitrogen containing compounds
  • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
  • C08G59/245—Di-epoxy compounds carbocyclic aromatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/3218—Carbocyclic compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
  • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
  • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
  • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

• the present invention relates to an epoxy resin composition preferably used for a fiber-reinforced composite material such as an aerospace member and an automobile member, and a molding material for a fiber-reinforced composite material and a fiber-reinforced composite material using the same. ..
• Fiber-reinforced composite materials consisting of reinforcing fibers and matrix resins can be designed to take advantage of the advantages of reinforcing fibers and matrix resins, so their applications are expanding to fields such as aerospace, sports, and general industry. ..
• Fiber-reinforced composite materials consisting of reinforcing fibers and matrix resin can be designed to take advantage of the advantages of reinforcing fibers and matrix resin, so their applications are expanding to the aerospace field, automobile field, sports field, general industrial field, etc. is doing.
• the fiber-reinforced composite material is produced by a hand lay-up method, a filament winding method, a pull-fusion method, a resin transfer molding (RTM) method, a prepreg autoclave molding method, a press molding method of a molding material for a fiber-reinforced composite material, or the like.
• molding material for the fiber-reinforced composite material used in the press molding method examples include prepreg, tow preg, bulk molding compound (BMC), sheet molding compound (SMC) and the like. These molding materials for fiber-reinforced composite materials are made by impregnating reinforcing fibers with a matrix resin.
• the reinforcing fiber glass fiber, aramid fiber, carbon fiber, boron fiber, etc. are used.
• the matrix resin both a thermosetting resin and a thermoplastic resin are used, but a thermosetting resin that can be easily impregnated into the reinforcing fibers is often used.
• the thermosetting resin an epoxy resin, an unsaturated polyester resin, a vinyl ester resin, a phenol resin, a bismaleimide resin, a cyanate resin and the like are used.
• epoxy resins are widely used from the viewpoints of adhesiveness to reinforcing fibers, dimensional stability, and mechanical properties such as strength and rigidity of the obtained fiber-reinforced composite material.
• Patent Document 2 a method of uniformly dissolving the solid curing agent in a solvent such as dimethylformamide and using it as a method of uniformly mixing the solid curing agent is disclosed (Patent Document 2).
• any molding material for a thin fiber-reinforced composite material such as prepreg, which can easily remove the solvent, can be applied because the solvent can be easily removed.
• a thick sheet such as SMC it is difficult to remove the solvent, and since the solvent remains inside, voids are generated during molding, and there is a problem that the mechanical properties of the obtained fiber-reinforced composite material become uneven. be.
• the solid curing agent can be uniformly dispersed in the matrix resin by uniformly dissolving the solid curing agent in a solvent such as dimethylformamide in advance.
• a solvent such as dimethylformamide
• an object of the present invention is to improve the drawbacks of the prior art, to provide an epoxy resin composition having excellent dispersibility of the solid curing agent and impregnation property into the reinforcing fibers, and further to provide such an epoxy resin composition.
• An object of the present invention is to provide a fiber-reinforced composite material having excellent properties and less unevenness in physical properties.
• the epoxy resin composition of the present invention is an epoxy resin composition containing all of the following components (A) to (C), and the degree of dispersion of the component (B) in the component (A) is high.
• the glass transition temperature of the epoxy resin cured product at any of 0.1 to 0.8, a viscosity at 25 ° C. of 0.1 to 100 Pa ⁇ s, and a curing degree of 85 to 95% is 110 ° C. or higher.
• B) Solid curing agent
• Component (C) Dispersant compatible with the component (A).
• the molding material for a fiber-reinforced composite material of the present invention is a molding material for a fiber-reinforced composite material composed of a post-thickening resin and a reinforcing fiber, and the post-thickening resin is in a semi-cured state of the epoxy resin composition of the present invention. It is the one. Further, the fiber-reinforced composite material of the present invention is obtained by molding the molding material for the fiber-reinforced composite material of the present invention.
• the epoxy resin composition of the present invention is superior in dispersibility of the solid curing agent and impregnation property into the reinforcing fibers as compared with the conventional epoxy resin composition, the dispersibility of the solid curing agent in the thickened resin is improved. It is possible to provide a molding material for an excellent fiber-reinforced composite material. Further, by using such a molding material for a fiber-reinforced composite material, it is possible to provide a fiber-reinforced composite material having excellent appearance quality and mechanical properties and having less unevenness in physical properties.
• the epoxy resin composition of the present invention contains an epoxy resin having two or more epoxy groups in the component (A): 1 molecule.
• the component (A) is a component necessary for heat resistance and expression of mechanical properties.
• examples of the epoxy resin having two epoxy groups include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, and dicyclopentadiene type epoxy. Examples thereof include resins and epoxy resins obtained by modifying them.
• Examples of the epoxy resin having three or more epoxy groups include an aliphatic epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a cresol type epoxy resin, a tetraglycidyldiaminodiphenylmethane, a triglycidylaminophenol, and a tetraglycidylamine.
• Examples include glycidylamine type epoxy resins, glycidyl ether type epoxy resins such as tetrakis (glycidyloxyphenyl) ethane and tris (glycidyloxymethane), modified epoxy resins thereof, and brominated epoxy resins obtained by bromizing these epoxy resins.
• bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin can be used particularly preferably. It is said that the use of these epoxy resins improves the mechanical properties of the fiber-reinforced composite material as compared with the case of using a highly rigid epoxy resin such as an epoxy resin having a naphthalene skeleton in one molecule. It has a further effect. It is presumed that this is because an epoxy resin with high rigidity is likely to be distorted because the crosslink density increases when it is cured in a short time, whereas it is unlikely that such a problem will occur when the above-mentioned epoxy resin is used. NS.
• aliphatic epoxy resins include “Denacol®” EX-313, EX-314, EX-321, EX-411, EX-421, EX-512, EX-521, EX-611, EX.
• Examples of commercially available bisphenol A type epoxy resins such as -612, EX-614, EX-614B, and EX-622 (all manufactured by Nagase ChemteX Corporation) include "jER (registered trademark)” 825, "JER (registered trademark)” 826, “jER (registered trademark)” 827, “jER (registered trademark)” 828, “jER (registered trademark)” 834, "jER (registered trademark)” 1001, "jER (registered trademark)” ) "1002,” jER (registered trademark) “1003 (manufactured by Mitsubishi Chemical Co., Ltd.),” Epicron (registered trademark) "850 (manufactured by DIC Co., Ltd
• bisphenol F-type epoxy resins include “jER (registered trademark)” 806, “jER (registered trademark)” 807, “jER (registered trademark)” 1750, and “Epicron (registered trademark)” 830 (DIC Corporation).
• "Epototo (registered trademark)” YDF-170, “Epototo (registered trademark)” YDF2001 and the like are exemplified.
• Examples of commercially available products of the tetramethylbisphenol F type epoxy resin which is an alkyl substituent include “Epototo (registered trademark)” YSLV-80Y / X (Nippon Steel & Sumikin Chemical Co., Ltd.).
• Examples of the bisphenol S type epoxy resin include "Epiclon (registered trademark)" EXA-1515 (manufactured by DIC Corporation).
• phenol novolac type epoxy resins include "jER (registered trademark)” 152, “jER (registered trademark)” 154 (manufactured by Mitsubishi Chemical Corporation), “Epicron (registered trademark)” N-740, “Epicron. Examples thereof include (registered trademark) "N-770,” Epicron (registered trademark) “N-775 (all manufactured by DIC Co., Ltd.).
• cresol novolac type epoxy resins include "Epiclon®” N-660, “Epiclon®” N-665, “Epiclon®” N-670, and “Epiclon®”. Examples thereof include “N-673,” Epicron (registered trademark) "N-695 (manufactured by DIC Co., Ltd.), EOCN-1020, EOCN-102S, EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.), and the like. ..
• the epoxy resin composition of the present invention contains a component (B): a solid curing agent.
• the component (B) is a curing agent of the component (A) and is a curing agent in a solid state at 25 ° C.
• the component (B) is not particularly limited as long as it is a curing agent in a solid state at 25 ° C., but is preferably an aromatic amine curing agent, dicyandiamide or a derivative thereof.
• the aromatic amine curing agent is not particularly limited as long as it is an aromatic amine used as an epoxy resin curing agent, but specifically, 3,3'-diaminodiphenylsulfone (3,3'-.
• DDS 4,4'-diaminodiphenylsulfone (4,4'-DDS), diaminodiphenylmethane (DDM), 3,3'-diisopropyl-4,4'-diaminodiphenylmethane, 3,3'-di-t- Butyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5,5'-dimethyl-4,4' -Diaminodiphenylmethane, 3,3'-di-t-butyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5
• aromatic amine curing agents include Seika Cure S (manufactured by Wakayama Seika Kogyo Co., Ltd.), MDA-220 (manufactured by Mitsui Chemicals Co., Ltd.), and "jER Cure (registered trademark)" W (Japan Epoxy Resin (Japan Epoxy Resin).
• the content of the component (B) is preferably 1 to 50 parts by mass, more preferably 2 to 50 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of heat resistance and mechanical properties. It is more preferably 3 to 25 parts by mass.
• the content of the component (B) is 1 part by mass or more, a sufficient effect of improving the curability can be easily obtained. Further, when the content of the component (B) is 50 parts by mass or less, the epoxy resin cured product obtained by curing the epoxy resin composition tends to have higher heat resistance.
• the average particle size of the component (B) is preferably 0.5 to 50 ⁇ m.
• the upper limit of the average particle size is more preferably 25 ⁇ m, further preferably 10 ⁇ m, and most preferably 3 ⁇ m.
• the average particle size of the component (B) in the present invention is an arithmetic mean value of the average particle size of each particle extracted in an observation image observed by an observation means such as an optical microscope or an electron microscope.
• the average particle size of each particle is calculated by connecting two points on the outer circumference of each particle and averaging the diameters passing through the center of gravity.
• the average particle size of each particle and its average value are obtained by using the image processing software "Image Pro Premier 3D 64-bit Ver 9.2" manufactured by Media Cybernetics to obtain a dispersed image acquired by an observation means such as an optical microscope or an electron microscope. From (B), the average particle size is calculated.
• the average particle size of the component (B) is 50 ⁇ m or less, for example, when used in a prepreg application, the component (B) gets into the carbon fiber bundle when the carbon fiber bundle is impregnated with the resin composition by heating and pressurizing. It is easy to be left behind on the surface layer of the carbon fiber bundle.
• the component (B) is preferably dicyandiamide or a derivative thereof.
• curing agent other than the curing agent described above examples include amines such as alicyclic amines, phenol compounds, acid anhydrides, polyaminoamides, organic acid hydrazides, and isocyanates. These curing agents may be used in combination with an aromatic amine curing agent, dicyandiamide or a derivative thereof.
• the epoxy resin composition of the present invention contains a dispersant compatible with component (C): component (A).
• the component (C) has the effect of uniformly dispersing the component (B) in the component (A).
• Specific examples of the component (C) include a surfactant, a high molecular weight dispersant, and an ionic liquid.
• the component (C) is preferably a liquid at 25 ° C. from the viewpoint of compatibility with the component (A), and the viscosity at 25 ° C. measured by a rheometer is in the range of 0.01 to 50 Pa ⁇ s. Is preferable.
• the upper limit of the viscosity is more preferably 25 Pa ⁇ s, further preferably 5 Pa ⁇ s, and most preferably 3 Pa ⁇ s.
• the weight average molecular weight of the component (C) is preferably in the range of 1.5 to 100,000.
• the upper limit of the weight average molecular weight is more preferably 50,000 and even more preferably 10,000.
• the component (C) is not limited to one type of dispersant, and two or more types of dispersants such as a surfactant and a high molecular weight dispersant and a surfactant and an ionic liquid can be used in combination. ..
• Surfactants are mainly classified into anionic, cationic, nonionic, and amphoteric, and suitable types and blending amounts can be appropriately selected and used according to the required characteristics.
• the anionic surfactant is not particularly limited, and specifically, a fatty acid salt, a polysulfonate, a polycarboxylate, an alkyl sulfate, an alkylaryl sulfonate, an alkylnaphthalene sulfonate, and a dialkyl.
• Examples of the cationic surfactant include alkylamine salts and quaternary ammonium salts. Specifically, ammonium stearate, stearyl amine acetate, trimethyl palm ammonium chloride, trimethyl beef ammonium chloride, dimethyldiolyl ammonium chloride, methyloleyl diethanol chloride, tetramethylammonium chloride, laurylpyridinium chloride, laurylpyridinium bromide, laurylpyridinium disulfate.
• Cetylpyridinium bromide cetylpyridinium bromide, 4-alkyl mercaptopyridine, poly (vinylpyridine) -dodecyl bromide, dodecylbenzyltriethylammonium chloride, tetradecyldimethylbenzyl-ammonium chloride, distearyldimethylammonium chloride and the like.
• Commercially available cationic surfactants "Nissan cation (R)" M 2 -100R (NOF Corporation), lipoic card 2HP flakes (manufactured by Lion Corporation), and the like.
• amphoteric surfactants include aminocarboxylic acid salts.
• nonionic surfactant examples include polyoxyethylene alkyl ether, polyoxyalkylene derivative, polyoxyethylene phenyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, alkyl allyl ether, and the like, and specifically, polyoxy.
• examples thereof include ethylene lauryl ether, sorbitan fatty acid ester, polyoxyethylene octylphenyl ether and the like.
• the selection of the surfactant is not limited to one type, and it is also possible to use two or more types of surfactants in combination.
• the high molecular weight dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts.
• polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts.
• Oily dispersants such as amides and salts thereof, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone
• water-soluble resins such as, water-soluble polymer compounds, polyester-based resins, modified polyacrylate-based resins, ethylene oxide / propylene oxide-added compounds, and phosphoric acid ester-based resins. These can be used alone or in combination of two or more, but are not necessarily limited to these.
• High molecular weight dispersants include DISPERBYK-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171 and 174, 180.
• the ionic liquid is an organic compound salt such as an imidazolium salt, a pyridinium salt, an ammonium salt, or a phosphonium salt that is liquid at room temperature.
• Examples of the ionic liquid which is an imidazolium salt include 1,3-dimethylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium bis (pentafluoroethylsulfonyl) imide, and 1-ethyl-3-.
• Examples of the ionic liquid that is a pyridinium salt include 3-methyl-1-propylpyridinium bis (trifluoromethylsulfonyl) imide, 1-butyl-3-methylpyridinium bis (trifluoromethylsulfonyl) imide, and 1-.
• Ionic liquids that are ammonium salts include, for example, tetrabutylammonium heptadecafluorooctane sulfonate, tetrabutylammonium nonafluorobutane sulfonate, tetrapentylammonium methanesulfonate, tetrapentylammonium thiocyanate, and methyl-. Examples thereof include tri-n-butylammonium and methylsulfate.
• Examples of the ionic liquid which is a phosphonium salt include tetrabutylphosphonium / methanesulfonate, tetrabutylphosphonium / p-toluenesulfonate, trihexyltetradecylphosphonium / bis (trifluoroethylsulfonyl) imide, and trihexyltetradecyl.
• Phosphonium bis (2,4,4-trimethylpentyl) phosphinate trihexyltetradecylphosphonium bromide, trihexyl tetradecylphosphonium chloride, trihexyl tetradecylphosphonium decanoate, trihexyl tetradecylphosphonium hexafluorophosphinate , Triethyltetradecylphosphonium / tetrafluoroborate, tributylmethylphosphonium / tosylate and the like. These can be used alone or in admixture of two or more, but are not necessarily limited to these.
• ionic liquid a commercially available product can be used as it is.
• 3M ionic liquid type antistatic agent FC4400 manufactured by 3M Japan Ltd.
• CIL-313, CIL-312 above, Japan Carlit Co., Ltd.
• IL-A2 IL-A5, IL-A12, IL-AP1, IL-AP3, IL-C1, IL-C3, IL-C5, IL-C6, IL-IM1, IL-IM4, IL-
• MA1, IL-MA2, IL-MA3, IL-P14, IL-P18, and IL-OH9 all manufactured by Koei Chemical Industry Co., Ltd.).
• the content of the component (C) is preferably 0.1 to 10 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of heat resistance and mechanical properties. More preferably, it is more preferably 1 to 3 parts by mass.
• the content of the component (C) is 0.1 parts by mass or more, the component (B) can be dispersed more efficiently.
• the content of the component (C) is 10 parts by mass or less, the epoxy resin cured product obtained by curing the epoxy resin composition tends to have higher heat resistance.
• the total content of (A) to (C) in the entire epoxy resin composition is preferably 30 to 95% by mass, preferably 50 to 85. It is more preferably by mass, more preferably 60 to 80% by mass.
• the total content of (A) to (C) is 30% by mass or more, the mechanical properties are further improved. If it is 95% by mass or less, the effect of sufficiently improving the bending strength can be easily obtained.
• the component (C) is compatible with the component (A) when mixed. 2 parts by mass of the component (C) is mixed with 100 parts by mass of the component (A) at room temperature, that is, 25 ° C., and the area ratio of the phase formed by the component (C) to the total area of the observed image of the mixture is 0 to 1. When it becomes 5%, it is regarded as a compatible state.
• the area ratio of the phase formed by the component (C) is preferably 0 to 1%, more preferably 0 to 0.7%.
• the component (C) By setting the area ratio of the phase formed by the component (C) to 1.5% or less, the component (C) can be uniformly present in the component (A), and the dispersion effect can be efficiently exhibited. be able to.
• the compatibility of the component (C) with respect to the component (A) is evaluated by the method described later.
• the epoxy resin composition of the present invention has a viscosity at 25 ° C. of 0.1 to 100 Pa ⁇ s.
• the upper limit of the viscosity is preferably 50 Pa ⁇ s, more preferably 25 Pa ⁇ s, and even more preferably 20 Pa ⁇ s.
• the viscosity shall be measured by mixing each component and measuring the epoxy resin composition after stirring for 1 minute. In the present invention, the viscosity of the epoxy resin composition is measured by the method described later. As a means for satisfying the above viscosity range, for example, reducing the content of the solid component in the epoxy resin composition or using the component (A) having a lower viscosity can be mentioned.
• the dispersity of the component (B) in the component (A) is 0.1 to 0.8, preferably 0.1 to 0.7, and more preferably 0.1 to 0.5. ..
• the dispersity of the component (B) is 0.1 to 0.8, preferably 0.1 to 0.7, and more preferably 0.1 to 0.5. ..
• the epoxy resin composition of the present invention preferably has a large amount of non-volatile components from the viewpoint of suppressing the generation of gas. Specifically, it is preferably 95% by mass or more, particularly preferably 97% by mass or more, further preferably 98% by mass or more, and particularly preferably 98.5% by mass or more. preferable.
• the upper limit is about 100% by mass.
• the non-volatile component referred to here represents the remaining amount ratio when vacuum dried for 24 hours at a pressure of 25 ° C. and a gauge pressure of ⁇ 0.1 MPa.
• the gauge pressure indicates the pressure when the atmospheric pressure is set to zero, and the lower the pressure, the higher the degree of vacuum and the higher the ability to remove volatile components.
• the heat resistance of the fiber-reinforced composite material using the epoxy resin composition of the present invention depends on the glass transition temperature (Tg) of the epoxy resin cured product obtained by curing the epoxy resin composition.
• Tg glass transition temperature
• the glass transition temperature of the epoxy resin cured product at a curing degree of any one of 85 to 95% (for example, 90%) is 110 ° C. or higher.
• curing conditions for the epoxy resin composition include heating at a temperature of 180 ° C. for 3 hours.
• the degree of curing of the epoxy resin cured product is determined by the method described later.
• the upper limit of the glass transition temperature is not particularly limited, but is preferably 250 ° C. or lower. It is more preferable that the glass transition temperature is 120 ° C. or higher and 220 ° C. or lower. When the glass transition temperature is 110 ° C. or higher, high heat resistance is likely to be imparted to the epoxy resin cured product obtained by curing the epoxy resin composition. When the glass transition temperature is 250 ° C. or lower, the crosslink density of the three-dimensional crosslinked structure of the epoxy resin cured product obtained by curing the epoxy resin composition does not become too high, and high mechanical properties are likely to be exhibited.
• the glass transition temperature of the cured epoxy resin composition obtained by curing the epoxy resin composition is determined by measurement using a dynamic viscoelasticity measuring device (DMA). That is, using a rectangular test piece cut out from a resin cured plate, DMA measurement is performed under temperature rise, and the temperature of the inflection point of the obtained storage elastic modulus G'is defined as Tg. The measurement conditions are as described in the examples.
• the molding material for a fiber-reinforced composite material of the present invention is a molding material for a fiber-reinforced composite material composed of a post-thickening resin and a reinforcing fiber, and the post-thickening resin puts the epoxy resin composition of the present invention in a semi-cured state. It is a thing. The definition of the thickened resin and the like will be described later.
• the dispersibility of the component (B) in the thickened resin is preferably 0.1 to 1.0, and preferably 0.1 to 0.9. More preferably, it is more preferably 0.1 to 0.8, and most preferably 0.1 to 0.7.
• the dispersity of the component (B) is measured by the method described later.
• the epoxy resin composition of the present invention is used, especially for reinforcing fibers.
• the dispersity of the component (B) in the component (A) may be within the above range.
• the molding material for a fiber-reinforced composite material of the present invention is excellent in dispersibility of the solid curing agent in the epoxy resin composition and impregnation property into the reinforcing fiber, so that there is little unevenness in physical properties after curing and the fiber has excellent mechanical properties. It is excellent in that it provides a reinforced composite material.
• the uneven physical properties of the fiber-reinforced composite material of the present invention preferably have a variation in bending strength (CV value) of 15% or less, and more preferably 10% or less.
• the CV value of the bending strength is obtained by calculating the average value of the bending strength from 10 arbitrarily selected test pieces and dividing the difference between this average value and the bending strength of each test piece by the average value. Is a percentage and averaged value.
• the type and length of the reinforcing fiber, the content ratio of the reinforcing fiber and the resin, etc. are not particularly limited, but glass fiber, carbon fiber, graphite fiber, aramid fiber, boron fiber, etc. Alumina fiber, silicon carbide fiber and the like are exemplified. Two or more of these reinforcing fibers may be mixed and used. It is preferable to use carbon fiber or graphite fiber in order to obtain a molded product that is lighter and has higher durability. In particular, in applications where there is a high demand for weight reduction and high strength of the material, it is preferable that the reinforcing fiber is carbon fiber because of its excellent specific elastic modulus and specific strength.
• any kind of carbon fiber can be used depending on the application, but from the viewpoint of impact resistance, a carbon fiber having a tensile elastic modulus of at most 400 GPa is preferable. Further, from the viewpoint of strength, since a composite material having high rigidity and mechanical strength can be obtained, carbon fibers having a tensile strength of 4.4 to 6.5 GPa are preferably used. In addition, tensile elongation is also an important factor, and it is preferable that the carbon fiber has a high strength and high elongation of 1.7 to 2.3%. Therefore, carbon fibers having the characteristics of a tensile elastic modulus of at least 230 GPa, a tensile strength of at least 4.4 GPa, and a tensile elongation of at least 1.7% are most suitable.
• the reinforcing fiber in the present invention either continuous fiber or discontinuous fiber can be used.
• the reinforcing fiber is a continuous fiber
• examples of the form of the reinforcing fiber include fiber structures such as long fibers aligned in one direction, tow, woven fabric, mat, knit, and braid.
• reinforcing fibers are continuous fibers
• reinforcing fibers having an average fiber diameter of 3 ⁇ m or more and 12 ⁇ m or less and a reinforcing fiber mass fraction in the range of 40% or more and 90% or less are preferably used.
• the reinforcing fiber mass fraction is 40% or more, the mass of the obtained fiber-reinforced composite material does not become excessive, and the advantages of the fiber-reinforced composite material having excellent specific strength and specific elastic coefficient can be fully exhibited, and the reinforcing fiber is reinforced.
• the fiber mass fraction is 90% or less
• the reinforcing fibers of the epoxy resin composition are excellently impregnated.
• the fiber-reinforced composite material obtained by using such continuous fibers include prepregs and towpregs.
• a reinforcing fiber having a fiber length in the range of 5 mm or more and 100 mm or less, an average fiber diameter of 3 ⁇ m or more and 12 ⁇ m or less, and a reinforcing fiber mass fraction in the range of 40% or more and 90% or less is preferably used.
• the reinforcing fiber mass fraction is 40% or more, the mass of the obtained fiber-reinforced composite material does not become excessive, and the advantages of the fiber-reinforced composite material having excellent specific strength and specific elastic coefficient can be fully exhibited, and the reinforcing fiber is reinforced.
• the fiber mass fraction is 90% or less, the reinforcing fibers of the epoxy resin composition are excellently impregnated.
• molding materials for fiber-reinforced composite materials obtained by using such discontinuous fibers include BMC and SMC. Of these, SMC is particularly preferably used from the viewpoint of productivity and the degree of freedom in the shape of the molded product.
• the form of the bundled aggregate of such discontinuous fibers is not particularly limited, and a known technique can be applied.
• the bundle-shaped aggregate has both ends of the reinforcing fibers in the bundle-shaped aggregate with respect to the arrangement direction of the reinforcing fibers on the surface where the width in the direction perpendicular to the arrangement direction of the reinforcing fibers is maximized.
• the angles of the acute angles taken by the sides formed by the arrangement of are angles a and b, respectively, it is preferable that each of the angles a and b is 2 ° or more and 30 ° or less.
• the effect of improving the surface quality and strength is great in the fiber-reinforced composite material formed by using this.
• the angle a and the angle b are 30 ° or less, the effect is remarkable.
• the smaller the angle a and the angle b the lower the handleability of the bundled aggregate itself.
• the smaller the angle between the arrangement direction of the reinforcing fibers and the cutting blade the lower the stability in the cutting process.
• the angle a and the angle b are preferably 2 ° or more.
• the angle a and the angle b are more preferably 3 ° or more and 25 ° or less.
• the angles a and b are more preferably 5 ° or more and 15 ° or less in view of the balance between the surface quality and strength improving effect of the fiber-reinforced composite material and the processability in the manufacturing process of the bundled aggregate.
• Examples of cutting means for continuously reinforcing fiber bundles for producing bundled aggregates of discontinuous fibers include rotary cutters such as a guillotine cutter and a roving cutter.
• the continuous reinforcing fiber bundle is inserted into the cutting means and cut in a state where the longitudinal direction of the continuous reinforcing fiber bundle and the direction of the cutting blade equipped in the cutting means are relatively oblique.
• the method for producing the molding material for the fiber-reinforced composite material of the present invention is not particularly limited.
• the epoxy resin composition of the present invention is used as a component (D): a compound that thickens and reacts with the epoxy resin (hereinafter, In the presence of the component (D)), the reinforcing fiber is impregnated by a known method suitable for the form of the reinforcing fiber, and then kept at a temperature of about room temperature to 80 ° C. for several hours to several days.
• the molding material for the fiber-reinforced composite material of the present invention can be obtained by bringing the epoxy resin composition into a semi-cured state in which the increase in viscosity is saturated.
• a resin in which the increase in viscosity of the epoxy resin composition is saturated and is in a semi-cured state is referred to as a thickened resin.
• the thickening reaction means that the epoxy resin composition is in a semi-cured state.
• the component (D) is not particularly limited as long as it is a component that thickens the epoxy resin composition by covalently bonding with the epoxy resin, but is preferably an aliphatic amine, an acid anhydride, an isocyanate compound or a derivative thereof.
• the aliphatic amine is an amine that does not have an aromatic ring, and is not particularly limited as long as it has one or more amino groups in the molecule. Specific examples thereof include polyalkylene polyamines, isophorone diamines, and 3,3'-.
• the amino group is preferably bonded to a primary, secondary, or tertiary carbon atom, and is primary or secondary in order to easily thicken the epoxy resin composition. It is more preferable that it is bonded to a carbon atom.
• Acid anhydride is a compound having one or more acid anhydride groups in the molecule.
• the acid anhydride include methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, maleic anhydride, succinic anhydride and the like.
• the isocyanate compound is not particularly limited as long as it has one or more isocyanate groups on average in one molecule, and examples thereof include aliphatic isocyanates and aromatic isocyanates.
• examples of the aliphatic isocyanate include ethylene diisocyanate, trimethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, propylene-1,2-diisocyanate, 2,3-dimethyltetramethylene diisocyanate, butylene-1.
• aromatic isocyanate examples include p-phenylenediocyanate, 1-methylphenylene-2,4-diisocyanate, naphthalene-1,4-diisocyanate, tolylene diisocyanate, diphenyl-4,4-diisocyanate, benzene-1,2, 4-Triisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate (MDI), diphenylpropane diisocyanate, tetramethylene xylene diisocyanate, polymethylene polyphenyl polyisocyanate, and those having a structure in which these aromatic isocyanates are linked by a methylene group or the like Can be mentioned.
• MDI diphenylmethane diisocyanate
• MDI diphenylpropane diisocyanate
• tetramethylene xylene diisocyanate polymethylene polyphenyl polyisocyanate
• the viscosity of the component (D) at 25 ° C. is preferably 1 mPa ⁇ s or more and 10000 mPa ⁇ s or less, and more preferably 10 mPa ⁇ s or more and 10000 mPa ⁇ s or less.
• the viscosity of the component (D) is in the above range, the viscosity of the epoxy resin composition is likely to be sufficiently lowered.
• the fiber-reinforced composite material of the present invention is formed by molding the molding material for the fiber-reinforced composite material of the present invention.
• the method for producing the fiber-reinforced composite material of the present invention is not particularly limited, but is limited to a hand lay-up method, a filament winding method, a pull-fusion method, a resin transfer molding (RTM) method, a prepreg autoclave molding method, and the like. Further, a press molding method for a molding material for a fiber-reinforced composite material such as a prepreg, a tow preg, a bulk molding compound (BMC), and a sheet molding compound (SMC) is preferably used.
• fiber-reinforced composite materials especially fiber-reinforced composite materials used in the automobile field
• mechanical properties such as high heat resistance and bending strength are required.
• the fiber-reinforced composite material of the present invention has excellent heat resistance and mechanical properties, it is also suitably used in the field of automobiles.
• the molding material for a fiber-reinforced composite material of the present invention exhibits excellent fluidity regardless of the molding temperature without the resin alone flowing in advance during press molding, and the homogeneity of the fiber and the resin is very high. High fiber reinforced composites are obtained.
• the epoxy resin composition of the present invention the molding material for the fiber-reinforced composite material, and the fiber-reinforced composite material will be described in more detail by way of examples, but the present invention is not limited to these examples.
• Ingredient (D) Compound that thickens with epoxy resin, 1,4-butanediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) -"Luplanate (registered trademark)" M20S (manufactured by BASF INOC Polyurethane Co., Ltd.): Polymeric MDI (polymethylene polyphenyl polyisocyanate).
• a mixture of the component (A) and the component (C) was prepared by mixing 2 parts by mass of the component (C) with respect to 100 parts by mass of the component (A) at room temperature (25 ° C.), and placed on a cover glass placed on a slide glass. 0.5 mg of a mixture of the above-mentioned components (A) and (C) is applied, covered with a cover glass, and the epoxy resin composition is spread over the cover glass.
• Nikon optical microscope "OPTIPHOT”, Zeiss camera " Observation was performed using "AxioCam MRc", and a dispersed image was acquired.
• the particles of the component (C) were extracted from the acquired dispersed image using the image processing software "Image Pro Premier 3D” manufactured by Media Cybernetics, and the area of the phase formed by the component (C) / the area of the entire observed image ⁇ 100 was calculated. ..
• ⁇ Measurement of dispersion of component (B) in component (A)> 0.5 mg of the epoxy resin composition prepared in the above ⁇ Preparation of epoxy resin composition> and ⁇ Preparation of epoxy resin composition for molding material (SMC) for fiber-reinforced composite material> was placed on a cover glass placed on a slide glass.
• the epoxy resin composition is spread over the cover glass, covered with a cover glass, and observed with a Nikon optical microscope "OPTIPHOT” and a Zeiss camera "AxioCam MRc" at an observation magnification of 200 times to obtain a dispersed image. Obtained.
• the acquired dispersed image is extracted from the particles of the component (B) using the image processing software "Image Pro Premier 3D” manufactured by Media Cybernetics, and the average area and the standard deviation of the boronoy-divided region with respect to the particles of the component (B) are calculated. Then, the value obtained by dividing the standard deviation by the average area was taken as the degree of dispersion.
• Tg of glass transition temperature Tg of cured epoxy resin> A test piece having a width of 12.7 mm and a length of 40 mm was cut out from the epoxy resin cured product having a curing degree measured in the above ⁇ Measurement of curing degree> obtained in the above ⁇ Preparation of an epoxy resin cured product>, and DMA (TA Instruments). Tg measurement was performed using ARES) manufactured by the company. The measurement conditions are a heating rate of 5 ° C./min. The temperature at the inflection point of the storage elastic modulus G'obtained by the measurement was defined as Tg.
• ⁇ Making SMC> As the carbon fiber, "Trading Card (registered trademark)" T700S-12K (manufactured by Toray Industries, Inc.) was used. By cutting the continuous carbon fiber strands at a desired angle and spraying them so as to uniformly disperse the bundled aggregates of carbon fibers, a discontinuous carbon fiber non-woven fabric having an isotropic fiber orientation was obtained. A rotary cutter was used as the cutting device. The distance between the blades was 30 mm. The basis weight of the discontinuous carbon fiber non-woven fabric was 1 kg / m 2 .
• the epoxy resin composition obtained from the discontinuous carbon fiber non-woven fabric in the above ⁇ Preparation of Epoxy Resin Composition for Molding Material for Fiber Reinforced Composite Material (SMC)> so that the carbon fiber weight content of the obtained SMC is 40%.
• a sheet-shaped SMC precursor was obtained by sandwiching the material between the coated polyethylene films, pressing with a roller, and impregnating with the epoxy resin composition. The SMC precursor was held at 40 ° C. for 24 hours to thicken the resin to obtain SMC.
• ⁇ Measurement of dispersion of component (B) in resin after thickening of molding material for fiber-reinforced composite material> Image analysis software for observing the epoxy resin composition portion on the surface of the SMC obtained in the above ⁇ Preparation of SMC> using a digital microscope VHX-7000 (manufactured by KEYENCE CORPORATION) at a magnification of 1000 times.
• the particles of the component (B) are extracted by Image Pro Premier 3D (manufactured by Media Cybernetics Co., Ltd.), the average area of the boronoy-divided region with respect to the particles of the component (B) and the standard deviation thereof are calculated, and the standard deviation is calculated.
• the value divided by the average area is defined as the degree of dispersion.
• ⁇ SMC impregnation evaluation> The front and back surfaces of the SMC obtained in the above ⁇ Preparation of SMC> are divided into two pieces, and the impregnation property is good when the resin is impregnated to the center in the thickness direction, and the impregnation property is poor when the resin is not impregnated. And said.
• a flat fiber-reinforced composite material having a thickness of 300 ⁇ 400 mm and a thickness of 1.6 mm was obtained by curing under the conditions of 150 ° C. ⁇ 30 minutes under a pressure of 10 MPa with a pressure press using the above SMC.
• the surface of the obtained fiber-reinforced composite material was evenly divided into 9 points, and the glossiness of each point was measured at an incident angle of 60 ° using a digital variable angle gloss meter UGV-5D (manufactured by Suga Test Instruments Co., Ltd.). ..
• the average value of each point was calculated, the difference between the average value and the glossiness of each point divided by the average value was divided into percentages, and the CV value was calculated from the averaged value. Those with a CV value of less than 5% were considered good, and those with a CV value of 5% or more were considered defective.
• Examples 1 to 8 A resin composition was prepared by changing the type of the component (C) according to the above-mentioned preparation method of the resin composition at the content shown in Table 1-1, and the viscosity and dispersion of the epoxy resin composition immediately after the preparation were obtained. The impregnation property was measured. In addition, an epoxy resin cured product of each epoxy resin composition was prepared. The viscosity of the epoxy resin composition immediately after preparation at 25 ° C. was in the range of 0.1 to 100 Pa ⁇ s. The dispersity of the component (B) in the component (A) was in the range of 0.1 to 0.8. The impregnation time was shorter than that of Comparative Example 1 in which the component (C) was not added, and it was confirmed that the impregnation property was improved.
• Example 11 to 16 The procedure was carried out in the same manner as in Example 1 except that the types and contents of the component (B) and the component (C) were changed.
• the viscosity, dispersity, and impregnation property of the epoxy resin composition immediately after preparation were measured.
• an epoxy resin cured product of each epoxy resin composition was prepared.
• the viscosity of the epoxy resin composition immediately after preparation at 25 ° C. was in the range of 0.1 to 100 Pa ⁇ s.
• the dispersity of the component (B) in the component (A) was in the range of 0.1 to 0.8.
• the impregnation time was shorter than that of Comparative Example 1 in which the component (C) was not added, and it was confirmed that the impregnation property was improved.
• a resin composition was prepared according to the above-mentioned method for preparing a resin composition with the contents of the component (A) and the component (B) shown in Table 2, and the viscosity and impregnation property of the epoxy resin composition immediately after the preparation were measured. did.
• an epoxy resin cured product of each epoxy resin composition was prepared.
• the viscosity of the epoxy resin composition immediately after preparation at 25 ° C. was in the range of 0.1 to 100 Pa ⁇ s.
• the dispersity of the component (B) in the component (A) was 1.0, and the impregnation time was 680 seconds, which were inferior in impregnation property.
• Example 9 The procedure was carried out in the same manner as in Example 1 except that the content of the component (B) was changed.
• the viscosity of the epoxy resin composition immediately after preparation at 25 ° C. was in the range of 0.1 to 100 Pa ⁇ s.
• the dispersity of the component (B) in the component (A) was in the range of 0.1 to 0.8.
• the impregnation time was shorter than that of Comparative Example 3 in which the component (C) was not added, and it was confirmed that the impregnation property was improved.
• Example 10 The procedure was carried out in the same manner as in Example 9 except that the type and content of the component (A) were changed.
• the viscosity of the epoxy resin composition immediately after preparation at 25 ° C. was in the range of 0.1 to 100 Pa ⁇ s.
• the dispersity of the component (B) in the component (A) was in the range of 0.1 to 0.8.
• the impregnation time was shorter than that of Comparative Example 3 in which the component (C) was not added, and it was confirmed that the impregnation property was improved.
• Example 3 The procedure was carried out in the same manner as in Example 9 except that the component (C) was removed.
• the viscosity of the epoxy resin composition immediately after preparation at 25 ° C. was in the range of 0.1 to 100 Pa ⁇ s. Further, the dispersity of the component (B) in the component (A) was 1.0, and the impregnation time was 564 seconds, which were inferior in impregnation property as compared with Examples 9 and 10.
• Example 17 The procedure was carried out in the same manner as in Example 1 except that the content of the component (B) was changed.
• the viscosity of the epoxy resin composition immediately after preparation at 25 ° C. was in the range of 0.1 to 100 Pa ⁇ s.
• the dispersity of the component (B) in the component (A) was in the range of 0.1 to 0.8.
• the impregnation time was shorter than that of Comparative Example 5 in which the component (C) was not added, and it was confirmed that the impregnation property was improved.
• Example 5 The procedure was carried out in the same manner as in Example 17 except that the component (C) was removed.
• the viscosity of the epoxy resin composition immediately after preparation at 25 ° C. was in the range of 0.1 to 100 Pa ⁇ s. Further, the dispersity of the component (B) in the component (A) was 1.3, and the impregnation time was 823 seconds, which were inferior in impregnation property as compared with Example 17.
• Example 2 The procedure was carried out in the same manner as in Example 1 except that the type of component (C) was changed.
• the viscosity of the epoxy resin composition immediately after preparation at 25 ° C. was in the range of 0.1 to 100. Further, the dispersity of the component (B) in the component (A) was 1.2, and the impregnation time was 1070 seconds, which were inferior in impregnation property.
• Example 4 The procedure was carried out in the same manner as in Example 1 except that the type of the component (A) and the content of the component (B) were changed.
• the viscosity of the epoxy resin composition immediately after preparation at 25 ° C. was higher than 100 Pa ⁇ s. Further, the dispersity of the component (B) in the component (A) was 0.8, and the impregnation time was 2951 seconds, which were inferior in impregnation property.
• Example 6 The procedure was carried out in the same manner as in Example 1 except that the content of the component (B) was changed.
• the viscosity of the epoxy resin composition immediately after preparation at 25 ° C. was higher than 100 Pa ⁇ s. Further, the dispersity of the component (B) in the component (A) was 1.4, and the impregnation time was 4100 seconds, which were inferior in impregnation property.
• Example 7 The procedure was carried out in the same manner as in Example 1 except that the content of the component (C) was changed.
• the viscosity of the epoxy resin composition immediately after preparation at 25 ° C. was in the range of 0.1 to 100 Pa ⁇ s. Further, the dispersity of the component (B) in the component (A) was 1.2, and the impregnation time was 930 seconds, which were inferior in impregnation property.
• Example 18 and 19 The type of the component (C) was changed to prepare an epoxy resin composition at the content shown in Table 3 according to the above-mentioned method for preparing an epoxy resin composition for SMC, and the viscosity of the epoxy resin composition immediately after preparation was prepared. , Dispersibility and impregnation were measured. In addition, an epoxy resin cured product of each epoxy resin composition was prepared. The viscosity of the epoxy resin composition immediately after preparation at 25 ° C. was in the range of 0.1 to 100 Pa ⁇ s. The dispersity of the component (B) in the component (A) was in the range of 0.1 to 0.8.
• the impregnation time was shorter than that of Comparative Example 8 in which the component (C) was not added, and it was confirmed that the impregnation property was improved.
• each SMC was prepared, and the dispersity and SMC impregnation property of the component (B) in the thickened resin of the molding material for the fiber-reinforced composite material were evaluated.
• the degree of dispersion was in the range of 0.1 to 1.0, and the SMC impregnation property and appearance quality were good.
• Example 8 The procedure was carried out in the same manner as in Examples 18 and 19 except that the component (C) was removed.
• the viscosity of the epoxy resin composition immediately after preparation at 25 ° C. was in the range of 0.1 to 100 Pa ⁇ s.
• the dispersity of the component (B) in the component (A) was 1.1 and the impregnation time was 421 seconds, which were inferior in impregnation property as compared with Examples 9 and 10.
• the dispersity of the component (B) in the thickened resin of the molding material for the fiber-reinforced composite material was 1.1, and the SMC impregnation property and the appearance quality were poor.
• Example 20 The same procedure as in Examples 18 and 19 was carried out except that the types and contents of the components (A) to (D) were changed.
• the viscosity of the epoxy resin composition immediately after preparation at 25 ° C. was in the range of 0.1 to 100 Pa ⁇ s.
• the dispersity of the component (B) in the component (A) was in the range of 0.1 to 0.8.
• the impregnation time was shorter than that of Comparative Examples 9 and 10 in which the component (C) was not added, and it was confirmed that the impregnation property was improved.
• each SMC was prepared, and the dispersity of the component (B) in the thickened resin of the molding material for the fiber-reinforced composite material was measured.
• the degree of dispersion was in the range of 0.1 to 1.0, and the SMC impregnation property and appearance quality were good.
• Example 9 It was carried out in the same manner as in Example 20 except that the component (C) was removed.
• the viscosity of the epoxy resin composition immediately after preparation at 25 ° C. was in the range of 0.1 to 100 Pa ⁇ s.
• the dispersity of the component (B) in the component (A) was 1.2, and the impregnation time was 540 seconds, which were inferior in impregnation property as compared with Example 20.
• the dispersity of the component (B) in the thickened resin of the molding material for the fiber-reinforced composite material was 1.3, and the SMC impregnation property and the appearance quality were poor.
• Example 10 The procedure was carried out in the same manner as in Example 20 except that the type of component (C) was changed.
• the viscosity of the epoxy resin composition immediately after preparation at 25 ° C. was in the range of 0.1 to 100 Pa ⁇ s.
• the dispersity of the component (B) in the component (A) was 1.3, and the impregnation time was 793 seconds, which were inferior in impregnation property as compared with Example 20.
• the dispersity of the component (B) in the thickened resin of the molding material for the fiber-reinforced composite material was 1.5, and the SMC impregnation property and the appearance quality were poor.
• the epoxy resin composition of the present invention is excellent in dispersibility of the solid curing agent and impregnation property into the reinforcing fibers, so that there is little unevenness in the physical properties after curing and the appearance quality is good. Further, by providing a molding material for a fiber-reinforced composite material, and further, by using such a molding material for a fiber-reinforced composite material, it is excellent in that a fiber-reinforced composite material having excellent appearance quality and mechanical properties is provided. As a result, it is suitably used for textiles and the like in general sports and industrial applications as well as aerospace applications and automobile applications.

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• 2021
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