Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
  • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
  • B29C70/28—Shaping operations therefor
  • B29C70/40—Shaping or impregnating by compression not applied
  • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
  • B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
• • 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
• • 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
  • C08G59/44—Amides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• • 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

Definitions

• the present invention relates to an epoxy resin composition and a fiber-reinforced composite material molded product to which vibration damping and damping properties are imparted to the epoxy resin drawn-out molded product.
• FRP fiber reinforced plastic
• vibration damping is improved by providing a vibration damping layer such as a rubber layer or an elastomer layer between FRP layers containing fiber fillers such as carbon fiber and glass fiber.
• a vibration damping layer such as a rubber layer or an elastomer layer between FRP layers containing fiber fillers such as carbon fiber and glass fiber.
• methods such as the prepreg method, the hand lay-up method, the filament winding method, the pull-fusion method (pull-out molding method), and the RTM (Resign Transfer Molding) method are applied to the production of the fiber-reinforced composite material.
• the reinforcing fibers are continuously passed through an impregnation tank filled with a liquid thermosetting resin composition, impregnated with the thermosetting resin composition, and passed through a squeeze die and a heating mold by a pulling machine. It is a molding method in which a fiber-reinforced composite material is continuously molded while being continuously drawn out, and has an advantage that a fiber-reinforced composite material can be continuously molded.
• the resin composition needs to have a sufficiently low viscosity so that the reinforcing fibers can be quickly impregnated in the impregnation tank, and the stability of the viscosity is important from the viewpoint of long-term continuous productivity.
• the resin composition needs to have a sufficiently low viscosity so that the reinforcing fibers can be quickly impregnated in the impregnation tank, and the stability of the viscosity is important from the viewpoint of long-term continuous productivity.
• it is necessary to achieve both fast-curing property in which the resin is quickly cured in the mold.
• Patent Document 6 a composition composed of an epoxy resin, an acid anhydride, and imidazole is known (Patent Document 6).
• the epoxy resin used in these products has a high viscosity, the viscosity of the resin composition becomes high and the impregnation property into the reinforcing fibers deteriorates, so that it is difficult to develop mechanical properties and the surface quality of the molded product is poor. There was a drawback that it could become.
• Patent Document 7 there is also known an example in which a low-viscosity epoxy resin is used for drawing molding as an epoxy resin.
• the epoxy resin used since the epoxy resin used has a low viscosity but is polyfunctional, there is a problem that the reactivity is high, the viscosity stability is lowered, and the continuous productivity is lowered.
• the above-mentioned damping property and vibration damping property can be mentioned as an example of imparting properties other than adhesion and mechanical properties to the fiber reinforced composite material.
• an epoxy resin composition the addition of an acrylic elastomer is shown in order to impart damping and vibration damping properties (Patent Document 9).
• Patent Document 9 the addition of an acrylic elastomer is shown in order to impart damping and vibration damping properties.
• these acrylic elastomers are used, the resin viscosity becomes high and the impregnation property into the reinforcing fibers becomes very poor, so that it is difficult to apply to pultrusion.
• Japanese Unexamined Patent Publication No. 2011-183471 Japanese Unexamined Patent Publication No. 2004-352024 WO2012 / 147401 WO2016 / 132655 WO2016 / 104314
• Japanese Unexamined Patent Publication No. 2005-343112 Japanese Patent No. 5-117412 Japanese Patent No. 5028903 Japanese Patent No. 5382258
• the present invention has been made in view of such circumstances, and the epoxy resin composition for pultrusion molding has a viscosity that can be sufficiently impregnated in pultrusion molding, and has excellent quick-curing property, and a change in viscosity during pultrusion molding. It is an object of the present invention to provide a resin composition having a small size, high heat resistance and mechanical strength, and excellent damping and vibration damping properties, and a molded product as a fiber-reinforced composite material obtained from the resin composition.
• the present invention is an epoxy resin composition containing (a) an epoxy resin, (b) an amine-based curing agent, (c) a curing accelerator, (d) an elastomer, and (e) a liquid release agent.
• the epoxy resin composition has a viscosity of 5000 mPa ⁇ s or less at 40 ° C., (a) the epoxy resin is a bifunctional bisphenol A type epoxy resin, and (d) the elastomer is a triblock having an MBM structure. It is an epoxy resin composition characterized by being a copolymer.
• M is a block composed of a homopolymer of methyl methacrylate or a copolymer containing at least 50 wt% of methyl methacrylate
• B is a block incompatible with the epoxy resin and block M
• B and M are used.
• Each block represented is directly linked or linked via a linking group.
• the curing agent is dicyandiamide or a derivative thereof.
• the elastomer is 5 wt% or more and 13 wt% or less of the entire resin composition.
• the ratio of methyl methacrylate is preferably 3 wt% or more and 25 wt% or less of the total elastomer.
• the elastomer is a copolymer of methyl methacrylate and n-butyl acrylate. It is preferable that the gelation time at 150 ° C. is 100 seconds or less, and the rate of increase in resin viscosity after 8 hours at 50 ° C. is 100% or less.
• the present invention is a draw-molded product obtained by using the epoxy resin composition as a matrix resin and curing a composite material containing reinforcing fibers.
• the reinforcing fiber is carbon fiber. It is preferable that the loss coefficient (tan ⁇ ) measured in the temperature range of ⁇ 20 ° C. to 20 ° C. is 0.04 or more.
• the epoxy resin composition for pultrusion molding of the present invention has a viscosity that can be sufficiently impregnated in the pultrusion molding method, has excellent quick-curing property, has a small change in viscosity during pultrusion molding, and has mechanical properties and storage stability. It is possible to obtain a molded product that is not only excellent in vibration damping property and damping property when cured. That is, in the present invention, by incorporating an acrylic block copolymer having high vibration damping properties into an epoxy resin composition and combining reinforcing fibers, the epoxy resin composition has high heat resistance and high loss coefficient. It is possible to provide a molded product having excellent vibration and damping properties, and it can be used for applications requiring damping and damping properties such as automobile parts, industrial parts, and sports parts.
• the epoxy resin composition used in the present invention is an epoxy resin composition for pultrusion including (a) epoxy resin, (b) curing agent, (c) curing accelerator, (d) elastomer, and (e) liquid release agent. It is a thing. Hereinafter, it is also simply referred to as a component (a), a component (b), a component (c), and a component (d). The same applies to other components such as the component (e). Further, a cured product obtained by curing and molding a resin composition is referred to as a molded product, which is also a reinforcing fiber base material or FRP.
• the epoxy resin (a) used in the present invention is an epoxy resin that is liquid at 25 ° C. and preferably has a low viscosity.
• the viscosity at 25 ° C. is 50,000 mPa ⁇ s or less because the viscosity of the final epoxy resin composition at 40 ° C. is 5000 mPa ⁇ s or less.
• the viscosity of the epoxy resin is raised at a frequency of 1 Hz and 2 ° C./min, and a rheometer (rotary dynamic viscoelasticity measuring device) such as DSR-200 (Leometrics) is used. It is obtained by measuring the viscosity at 25 ° C.
• the molecular weight (Mw) of this liquid epoxy resin varies depending on the structure of the liquid epoxy resin. For example, in the case of a bisphenol type bifunctional epoxy resin, it is preferably 200 or more and less than 600, and more preferably 500 or less.
• the epoxy resin is a bisphenol A type epoxy resin from the viewpoint of dissolution with an elastomer, which will be described later, and compatibility during kneading.
• a bisphenol A type epoxy resin having a viscosity at 25 ° C. of 50,000 mPa ⁇ s or less and a molecular weight (Mw) of 200 or more and less than 600
• YD-127 manufactured by Nittetsu Chemical & Materials Co., Ltd.
• the curing agent may include other epoxy resin curing agents in addition to the amine-based curing agent.
• epoxy resin curing agents for example, imidazoles, acid anhydrides, boron chloride amine complexes and the like can be used.
• imidazoles include 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole.
• acid anhydride include hydrogenated methylnadic acid anhydride and methylhexahydrophthalic acid anhydride.
• an imidazole-based curing aid is suitably used to satisfy the heat resistance at the time of curing, in addition to the impregnation property of the reinforcing fibers at the time of mixing and the suppression of the increase in viscosity.
• imidazole-based curing aids examples include 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, It is preferable to use 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4', 5'-dihydroxymethylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole and the like.
• the elastomer includes a triblock copolymer having an MBM structure (hereinafter, also referred to as a triblock copolymer).
• the component (d) improves toughness and vibration damping while maintaining the excellent heat resistance of the epoxy resin composition.
• the blocks represented by B and M are directly linked or linked via a linking group.
• block M is a block made of a homopolymer of polymethyl methacrylate or a copolymer containing at least 50% by mass of methyl methacrylate.
• the block B is incompatible with the block M and its glass transition temperature Tg is 20 ° C. or lower.
• the elastomer (d) include poly (methyl methacrylate) / poly (butyl acrylate) / poly (methyl methacrylate) triblock copolymers.
• the block B as a soft block and a polymer block incompatible with the epoxy resin
• the block M as a hard block and a polymer that is easily compatible with the epoxy resin
• the blocks are well micro-dispersed in the epoxy resin matrix. ..
• micro-dispersing the triblock copolymer in the epoxy resin it is possible to increase the loss coefficient of the resin itself while suppressing the deterioration of the mechanical properties of the cured product of the epoxy resin composition, and improve the vibration damping property. be able to.
• the poly (methyl methacrylate) / poly (butyl acrylate) / poly (methyl methacrylate) triblock copolymer having a hard block that is easily compatible with the epoxy resin has good dispersion in the epoxy resin and is an epoxy resin composition. It is more preferable because it can suppress the deterioration of the mechanical properties of the cured product.
• the block B in addition to butyl acrylate, 1,4-polybutadiene, ethyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, 2-ethylhexyl methacrylate and the like can be used.
• Examples of the block M include glycidyl methacrylate, tert-butyl methacrylate and the like in addition to methyl methacrylate, and it is preferable that at least 50 wt% or more is composed of methyl methacrylate. More preferably 70 wt% or more, still more preferably 90 wt% or more is block M composed of methyl methacrylate.
• the proportion of methyl methacrylate is preferably 5 wt% or more and 25 wt% or less of the total elastomer. It is more preferably 5 wt% or more and 20 wt% or less, and further preferably 5 wt% or more and 15 wt% or less. If the block M is less than 5 wt% of the whole, the compatibility with the epoxy resin is low, so that the resin composition becomes cloudy and phase-separated, and the mechanical properties and the like are greatly deteriorated.
• the block M when the block M exceeds 25 wt% of the whole, the block M has high compatibility with the epoxy resin, so that the block M is compatible with the epoxy resin and the viscosity of the resin is greatly increased.
• the ratio of the block M when the ratio of the block M is in the above range, it shows suitable compatibility with the epoxy resin (bisphenol A type epoxy resin), shows high compatibility at high temperature, forms a transparent resin composition, does not increase the viscosity, and has a low temperature. Then, since the compatibility is slightly lowered, the compatibility is slightly clouded and the viscosity is also not high. High heat resistance and mechanical strength can be exhibited by rapid curing in a state showing high compatibility in a high-temperature mold at the time of pultrusion.
• the liquid release agent may be a liquid at room temperature (10 to 30 ° C.) so that even a low-viscosity composition can be mixed uniformly. Further, by mixing the liquid release agent in the resin, the pultrusion moldability is improved. As a result, the orientation of the fibers in the molded product is improved, so that the mechanical properties such as the compressive strength of the molded product and the adhesion to the adhesive are increased due to the smooth surface.
• the blending amount of the liquid release agent is preferably 0.1 to 6 parts by mass with respect to 100 parts by mass of the total epoxy resin. More preferably, it is 0.1 to 4 parts by mass. If it is less than 0.1 parts by mass, sufficient releasability may not be obtained. Further, if it is added in an amount of more than 6 parts by mass, the strength of the molded product may be lowered, and the adhesiveness and adhesiveness may be lowered.
• Such a liquid release agent is not particularly limited as long as it does not phase-separate from the epoxy resin composition and does not evaporate or decompose at the temperature of the mold.
• Specific controlled products include MOLDWIZ INT-1836, 1846, 1850, 1854, 1882 manufactured by Tomoe Kogyo Co., Ltd., which are polycondensed with an organic acid or glycede.
• the initial viscosity at 40 ° C. immediately after mixing the epoxy resin composition of the present invention is preferably 50 to 5000 mPa ⁇ s in order to sufficiently impregnate the reinforcing fibers. It is more preferably 100 to 4000 mPa ⁇ s, and even more preferably 200 to 3000 mPa ⁇ s. If it is less than 50 mPa ⁇ s, the amount of resin impregnated into the reinforcing fibers may decrease. Further, if the viscosity is higher than 5000 mPa ⁇ s, it becomes difficult to enter the reinforcing fiber, the impregnation property is insufficient, and voids may occur.
• the environment until it enters the mold such as a resin bath at the time of pultrusion and a paper pass, may be heated to 40 to 50 ° C.
• the viscosity increase rate with respect to the initial viscosity after leaving the epoxy resin composition at 25 ° C. for 8 hours is preferably 100% or less.
• the resin viscosity increase rate is preferably 100% or less, more preferably 50% or less after being left at 50 ° C. for 8 hours.
• the gel time of the epoxy resin composition at 150 ° C. is preferably 100 seconds or less. A more preferable gel time is 90 seconds or less. The gel time is greatly affected by the amount of imidazole blended, and can be changed by appropriately changing the blending amount.
• the content of the elastomer component (d) is preferably 3 to 13 parts by mass, particularly preferably 5 to 13 parts by mass, and more preferably 6 to 11 parts by mass.
• the amount of the component (d) is 3 parts by mass or more with respect to 100 parts by mass of all the epoxy resins in total, the damping and vibration damping properties of the cured product of the epoxy resin composition and the composite material with carbon fibers are high. It is also preferable from the viewpoint of compatibility with the component (a). On the other hand, it is preferably 13 parts by mass or less because of the impregnation property of the resin and the mechanical properties of the cured product.
• the content of the component (b) varies depending on the type, but in the case of dicyandiamide, for example, it is usually 1 to 10 parts by mass with respect to 100 parts by mass in total of all the epoxy resins. More preferably, the number of moles of active hydrogen of dicyandiamide is 0.6 to 1.0 times the total number of moles of epoxy groups contained in the epoxy resin contained in the epoxy resin composition. By setting the value to 0.6 times or more, a cured product having good heat resistance and good mechanical properties (that is, high strength) can be obtained. Further, by setting the value to 1.0 times or less, a cured product having good mechanical properties can be obtained. More preferably, it is 0.6 to 0.8 times. The total number of moles of epoxy groups contained in the epoxy resin contained in the epoxy resin composition may be calculated from the charged amount.
• the epoxy resin composition may contain various additives (component (f)) such as a thermoplastic resin, an antifoaming agent, and a leveling agent as arbitrary components.
• component (f) such as a thermoplastic resin, an antifoaming agent, and a leveling agent as arbitrary components.
• the component (f) has a role of changing the viscoelasticity of the thermoplastic resin epoxy resin composition to optimize the viscosity, the storage elastic modulus and the thixotropic property, as well as the cured product of the epoxy resin composition. Improves breaking toughness.
• the thermoplastic resin may be used alone or in combination of two or more. These additives can be blended in an amount of 1 to 15 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of the entire resin composition.
• the thermoplastic resin may be dissolved in the components of the epoxy resin composition, and may be contained in the epoxy resin composition in the form of fine particles, long fibers, short fibers, textiles, non-woven fabrics, meshes, pulps and the like. good.
• the thermoplastic resin is a group consisting of a carbon-carbon bond, an amide bond, an imide bond, an ester bond, an ether bond, a carbonate bond, a urethane bond, a urea bond, a thioether bond, a sulfone bond, an imidazole bond and a carbonyl bond in the main chain.
• a thermoplastic resin having at least one bond selected from the above is preferably used. More specifically, examples thereof include thermoplastic resins belonging to engineering plastics such as polyacrylate, polyamide, polyaramid, polyester, polycarbonate, polyphenylene sulfide, polybenzimidazole, polyimide, polyetherimide, polysulfone and polyethersulfone. ..
• thermoplastic resins have a reactive functional group with the epoxy resin from the viewpoint of improving the fracture toughness of the cured product of the epoxy resin composition of the present invention and maintaining the environmental resistance.
• the functional group having a preferable reactivity with the epoxy resin include a carboxyl group, an amino group and a hydroxyl group.
• component (f) it is possible to add an antifoaming agent and a leveling agent for the purpose of improving surface smoothness.
• additives can be blended in an amount of 0.01 to 3 parts by mass, preferably 0.01 to 1 part by mass, based on 100 parts by mass of the entire epoxy resin composition. If the blending amount is less than 0.01 parts by mass, the effect of smoothing the surface does not appear, and if it exceeds 3 parts by mass, the additive causes bleed-out on the surface, which is not preferable because it causes a factor of impairing smoothness. .. It is also possible to add pigments and other additives if necessary.
• the method for producing the epoxy resin composition of the present invention is not particularly limited, and the epoxy resin composition may be produced by a known method.
• the epoxy resin composition of the present invention can be used to perform a general pultrusion molding method, and can be heat-cured in parallel with the pultrusion or after the pultrusion to obtain a pultrusion product.
• a general pultrusion method the reinforcing fibers are continuously passed through an impregnation tank of an epoxy resin composition, and are cured while being continuously pultruded by a pulling machine through a squeeze die and a heating die. Furthermore, it is completely cured in an aftercure oven.
• the above is only an example of the pultrusion molding method, and is not limited to the above.
• the impregnation tank is generally preferably maintained at 10 to 40 ° C., but may be maintained at 40 to 50 ° C. depending on the viscosity and viscosity stability of the resin. If the temperature of the impregnation tank is 10 ° C. or lower, the impregnation of the fibers may be poor.
• the temperature of the mold is preferably 100 to 250 ° C. More preferably, it is 120 to 220 ° C. If the temperature is lower than 100 ° C., curing failure may occur in the mold, and if the temperature exceeds 250 ° C., a runaway reaction of the epoxy resin composition may occur or the resin may be thermally deteriorated.
• Aftercure may be performed to increase heat resistance or complete the reaction of epoxy groups.
• After-cure may be performed online by installing an after-cure oven after passing through the mold and before winding, or may be placed in the oven after winding to cure.
• the temperature of the aftercure is preferably 130 to 220 ° C. from the viewpoint of heat resistance and physical properties. More preferably, it is 140 to 200 ° C. If the temperature is lower than 130 ° C., the glass transition temperature of the resin is not exceeded, so that the reaction may be difficult to proceed, and aftercure may take a long time to reduce the productivity. On the other hand, if it exceeds 220 ° C., it may be deformed by heat.
• the after-cure time is preferably 5 minutes to 1 hour, although it depends on the cure temperature. Cures shorter than 5 minutes may be too short to complete the reaction. Also, if it is longer than one hour, for example, when used online, there is a concern that it will be too long and productivity will drop.
• reinforcing fibers that make up the reinforcing fiber base material
• carbon fiber, graphite fiber, glass fiber, organic fiber, boron fiber, steel fiber, etc. can be used.
• carbon fibers and graphite fibers have a good specific elastic modulus and are found to have a great effect on weight reduction of molded products containing the fibers. Therefore, they are suitably used for pultrusion molding using the epoxy resin composition of the present invention. be able to.
• any kind of carbon fiber or graphite fiber can be used depending on the application.
• the reinforcing fiber used in the epoxy resin composition of the present invention preferably has an elastic modulus of 100 GPa or more and 900 GPa or less.
• the resin content of the fiber-reinforced composite material is preferably 25 to 50% by mass.
• the damping effect can be exhibited even at the interface, and a suitable loss coefficient for the entire molded product can be obtained. It is thought that it can be expressed.
• the loss coefficient (tan ⁇ ) measured in the temperature range of ⁇ 20 ° C. to 20 ° C. is 0.04 or more. More preferably, it expresses 0.05 or more, more preferably 0.06 or more.
• the molded cured product preferably has a high bending strength of 50 MPa or more.
• the bending strength is more preferably 80 MPa or more, still more preferably 90 MPa or more.
• the epoxy resin composition of the present invention is also very excellent in pultrusion moldability when a fiber-reinforced composite material is molded by pultrusion molding.
• the ratio of the elastic modulus of the cured resin to the elastic modulus of the reinforcing fiber in the molded product containing the reinforcing fiber is preferably 1: 150 to 1: 900.
• the elastic modulus of the resin is preferably 1.0 to 2.5 GPa, more preferably 1.0 to 2.0 GPa.
• a pitch-based carbon fiber having a high elastic modulus is more preferable than a glass fiber or a PAN-based carbon fiber having a low elastic modulus because a larger elastic modulus ratio between the resin and the fiber exhibits higher vibration damping properties.
• Some pitch-based carbon fibers exhibit a high elastic modulus of 600 to 900 GPa, and the elastic modulus ratio of the resin and the reinforcing fiber is more preferably 1: 300 to 1: 900, still more preferably 1: 600 to 1: 1. It is in the range of 900.
• the elastic modulus is the flexural modulus.
• the molded product of the present invention comprises a cured product of the epoxy resin composition described above and reinforcing fibers.
• this molded product can be used for structural materials for aircraft, automobiles, ships, sports, and other general industrial applications such as wind power generation and rolls.
• Suitable for transportation equipment applications such as automobile applications that require vibration damping.
• M has an MBM structure of poly (methyl methacrylate) and B of poly (butyl acrylate).
• M has an MBM structure of poly (methyl methacrylate) and B of poly (butyl acrylate).
• -Acrylic diblock copolymer Nanostrength D51N, manufactured by Arkema Co., Ltd.
• M has a poly (methyl methacrylate) and B has a poly (butyl acrylate) BM structure.
• Table 1 shows the formulations of the epoxy resin compositions for Examples and Comparative Examples.
• the procedure for blending these epoxy resin compositions is as follows.
• a resin composition 1 was prepared by uniformly dispersing a part (18 parts) of YD-128 and the total amount of DICYANEX1400F and 2MZA-PW with a three-roll mill.
• the obtained epoxy resin composition was poured into a mold having a thickness of 4 mm, a width of 10 mm, and a length of 150 mm while heating at 60 to 80 ° C.
• a cured resin plate was obtained by curing at 150 ° C. for 5 minutes.
• ⁇ Viscosity measurement method The resin composition was measured at 1 Hz and 1000 dyn / cm 2 using a rheometer (HAAKE Rheo Win manufactured by Thermo) to obtain viscosities at each temperature.
• ⁇ Measurement method of tan ⁇ > The cured resin plate is processed into a test piece (length 50 mm ⁇ width 10 mm), and a bending load of 4 N, a frequency of 1 Hz, and a frequency of -40 to 200 ° C. are used using a dynamic viscoelasticity measuring device (DMS6100 manufactured by Seiko Electronics Co., Ltd.). Dynamic viscoelasticity was measured in the range. The obtained tan ⁇ was used as the loss coefficient at each temperature.
• DMS6100 dynamic viscoelasticity measuring device manufactured by Seiko Electronics Co., Ltd.
• ⁇ Measurement method of bending characteristics of cured resin plate The bending characteristics of the cured resin plate were measured using a universal testing machine (manufactured by Shimadzu Corporation, product name: AGS-X) equipped with a 1000N load cell. The bending strength, flexural modulus, and bending strain of the test piece were measured in accordance with JIS K7074 using a three-point bending jig in an environment of a temperature of 23 ° C. and a humidity of 50% RH.
• the molded product obtained by drawing and molding the epoxy resin composition of the present invention can obtain a high loss coefficient, and can obtain excellent vibration damping and damping properties while having high heat resistance and mechanical properties. Can be done.
• fiber-reinforced plastic molded bodies that are low-cost, high-productivity, high heat resistance, and have excellent vibration damping and damping properties due to drawing molding, such as automobile / industrial vibration damping agents, aircraft applications, and sports / leisure applications. Can be provided widely.

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• 2020
  • 2020-12-23 JP JP2021567514A patent/JPWO2021132300A1/ja active Pending
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