WO2020213414A1 - Matériau de moulage renforcé par des fibres, et article moulé mettant en œuvre celui-ci - Google Patents

Matériau de moulage renforcé par des fibres, et article moulé mettant en œuvre celui-ci Download PDF

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Publication number
WO2020213414A1
WO2020213414A1 PCT/JP2020/015167 JP2020015167W WO2020213414A1 WO 2020213414 A1 WO2020213414 A1 WO 2020213414A1 JP 2020015167 W JP2020015167 W JP 2020015167W WO 2020213414 A1 WO2020213414 A1 WO 2020213414A1
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Prior art keywords
fiber
molding material
resin
mass
members
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PCT/JP2020/015167
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English (en)
Japanese (ja)
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佳浩 安谷
健一 濱田
一迅 人見
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Dic株式会社
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Priority to JP2021509230A priority Critical patent/JPWO2020213414A1/ja
Publication of WO2020213414A1 publication Critical patent/WO2020213414A1/fr

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    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/68—Unsaturated polyesters
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic

Definitions

  • the present invention relates to a fiber reinforced molding material and a molded product thereof.
  • Fiber-reinforced resin composite materials reinforced with thermosetting resins such as epoxy resin and unsaturated polyester resin using carbon fiber as reinforced fibers are attracting attention for their excellent heat resistance and mechanical strength while being lightweight. Its use in various structural applications such as bodies and various members is expanding.
  • a method for molding a material using an epoxy resin in this fiber-reinforced resin composite material an autoclave method in which a material called prepreg is heated and cured by a pressurable autoclave is known, and an unsaturated polyester resin is used.
  • a method for molding a material there is known a method of curing and molding by a method such as press molding or injection molding using an intermediate material called a sheet molding compound (SMC) or a bulk molding compound (BMC). Particularly in recent years, the development of highly productive materials has been actively carried out.
  • SMC sheet molding compound
  • BMC bulk molding compound
  • molding materials include carbon fiber reinforced sheet-like molding containing unsaturated polyester resin, vinyl monomer, thermoplastic polymer, polyisocyanate, filler, conductive carbon black and wide carbon fiber bundle as essential components.
  • the material is known (see, for example, Patent Document 1). Although a molded product having an excellent appearance can be obtained from this molding material, since a highly volatile styrene monomer is used, the odor is strong and there is a problem in the working environment during the molding work.
  • the problem to be solved by the present invention is to obtain a molded product having excellent work environment during molding work, handleability including film peeling property and tackiness of the molding material, flexibility, and various physical properties such as bending strength. It is to provide a fiber-reinforced molding material and a molded product thereof.
  • the present inventors have specified fiber reinforced plastics containing vinyl ester resin, unsaturated monomer having a flammability of 100 ° C. or higher, polyisocyanate, polymerization initiator, and carbon fiber having a fiber length of 2.5 to 50 mm as essential components.
  • the present invention has been completed by finding that a molded product having excellent working environment, handleability and flexibility, and various physical properties such as bending strength can be obtained as a molding material.
  • the present invention relates to a fiber-reinforced molding material having a range of .06 and a molded product using the same.
  • the molded product obtained from the fiber-reinforced molding material of the present invention is excellent in bending strength, flexural modulus, etc., automobile members, railroad vehicle members, aerospace machine members, ship members, housing equipment members, sports members, etc. It can be suitably used for light vehicle members, building civil engineering members, housings for OA equipment, and the like.
  • the fiber-reinforced molding material of the present invention comprises a vinyl ester resin (A), an unsaturated monomer (B) having a flammability of 100 ° C. or higher, a polyisocyanate (C), a polymerization initiator (D), and a fiber length 2.
  • A vinyl ester resin
  • B unsaturated monomer
  • C polyisocyanate
  • D polymerization initiator
  • F fiber length 2
  • E a fiber-reinforced molding material containing, as essential raw materials, the ratio of the transmittance at 3490cm -1 and 3340cm -1 in ATR measurement of FT-IR (3490cm -1 / 3340cm -1 ) (Hereinafter, abbreviated as “transmittance ratio ⁇ ”) is in the range of 1.01 to 1.06.
  • the transmittance of the FT-IR in the ATR measurement of the present invention is obtained from the peak value of the transmission spectrum.
  • 3490 cm -1 is the peak derived from the OH bond
  • 3340 cm -1 is derived from the NH bond. Is the peak of.
  • the transmittance ratio ⁇ is in the range of 1.01 to 1.06 from the viewpoint of film peelability and the balance between tackiness and flexibility, but the film peelability and tackiness are further improved. Therefore, it is preferably 1.02 or more, and more preferably 1.05 or less because the flexibility is further improved.
  • the vinyl ester resin (A) can be obtained by reacting the epoxy resin (a1) with the (meth) acrylic acid (a2), and has the handleability and fluidity such as film peelability and tackiness during molding.
  • the molar ratio (COOH / EP) of the epoxy group (EP) of the epoxy resin (a1) to the carboxyl group (COOH) of the (meth) acrylic acid (a2) is 0.6 to 1 because of its excellent balance. It is preferable to react in the range of 1.
  • the epoxy equivalent of the epoxy resin (a1) is preferably in the range of 180 to 370, more preferably in the range of 180 to 250.
  • (meth) acrylic acid means one or both of acrylic acid and methacrylic acid
  • (meth) acrylate means one or both of acrylate and methacrylate.
  • Examples of the epoxy resin (a1) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol fluorene type epoxy resin, biscresol fluorene type and other bisphenol type epoxy resins, phenol novolac type epoxy resin, and cresol novolac type epoxy.
  • Novolak type epoxy resin such as resin, oxodoridone modified epoxy resin, phenolic glycidyl ether such as brominated epoxy resin of these resins, dipropylene glycol diglycidyl ether, trimethylpropan triglycidyl ether, alkylene oxide adduct of bisphenol A Diglycidyl ether, glycidyl ether of polyhydric alcohols such as diglycidyl ether of bisphenol A hydride, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 1-epociethyl- Alicyclic epoxy resin such as 3,4-epoxycyclohexane, phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, diglycidyl-p-oxybenzoic acid, glycidyl ester such as dimer acid glycidyl ester,
  • Examples include resin.
  • bifunctional aromatic epoxy resins are preferable, and bisphenol A type epoxy resins and bisphenol F type epoxy resins are more preferable because they are superior in the strength of the molded product, the handleability of the molding material, and the fluidity during molding of the molding material. preferable.
  • These epoxy resins may be used alone or in combination of two or more.
  • the epoxy resin (a1) may be used by increasing the molecular weight with a dibasic acid such as bisphenol A in order to adjust the epoxy equivalent.
  • the reaction between the epoxy resin and (meth) acrylic acid described above is preferably carried out at 60 to 140 ° C. using an esterification catalyst. Further, a polymerization inhibitor or the like can also be used.
  • the unsaturated monomer (B) has a flash point of 100 ° C. or higher. As a result, the odor during the molding work can be suppressed, and the work environment is excellent. Further, since the unsaturated monomer has a high boiling point, it has excellent moldability during high-temperature molding, enables high-temperature single-hour molding, and improves productivity.
  • the flash point in the present invention is the flash point measured by the Cleveland opening method specified in JIS K2265-4: 2007.
  • Examples of the unsaturated monomer (B) include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate alkyl ether, and polypropylene glycol (meth) acrylate.
  • unsaturated monomers having an aromatic are preferable because a molding material having higher strength can be obtained, and benzyl methacrylate. , Phenoxyethyl methacrylate is more preferred.
  • these unsaturated monomers can be used alone or in combination of two or more.
  • the mass ratio ((A) / (B)) of the vinyl ester resin (A) to the unsaturated monomer (B) is determined by the resin impregnation property, handleability (tack property) and curability of the carbon fibers.
  • the range of 40/60 to 85/15 is preferable, and the range of 50/50 to 70/30 is more preferable, because the balance is further improved.
  • the viscosity of the mixture of the vinyl ester resin (A) and the unsaturated monomer (B) is The range of 200 to 8,000 mPa ⁇ s (25 ° C.) is preferable because the resin impregnation property of the carbon fiber is further improved.
  • the polyisocyanate (C) is, for example, a diphenylmethane diisocyanate (4,4'-form, 2,4'-form, or 2,2'-form, or a mixture thereof), a carbodiimide-modified product of diphenylmethane diisocyanate, or a nurate-modified product.
  • Diphenylmethane diisocyanate modified product such as body, bullet modified product, urethane imine modified product, polyol modified product modified with polyol having a number average molecular weight of 1,000 or less such as diethylene glycol and dipropylene glycol, tolylene diisocyanate, trizine diisocyanate, polymethylene poly Aromatic polyisocyanates such as phenyl polyisocyanate, xylylene diisocyanate, 1,5-naphthalenediocyanate, tetramethylxylene diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, norbornene diisocyanate; Hexamethylene diisocyanate, a nurate-modified product of hexamethylene diisocyanate, a bullet-modified product, an adduct-isocyanate, an
  • the molar ratio (NCO / OH) of the isocyanate group (NCO) of the polyisocyanate (C) to the hydroxyl group (OH) of the vinyl ester resin (A) has a transmittance ratio ⁇ of 1.01 to 1.06. Since the range can be easily controlled, the range of 0.5 to 0.95 is preferable, and further, the balance between handleability (film peeling property and tackiness) and flexibility is more excellent, so 0.55 to 0. 85 is more preferable.
  • the polymerization initiator (D) is not particularly limited, but an organic peroxide is preferable, and for example, a diacyl peroxide compound, a peroxy ester compound, a hydroperoxide compound, a ketone peroxide compound, an alkyl perester compound, and a par. Examples thereof include carbonate compounds and peroxyketal, which can be appropriately selected depending on the molding conditions.
  • these polymerization initiators (D) can be used alone or in combination of two or more.
  • a polymerization initiator having a temperature of 70 ° C. or higher and 110 ° C. or lower for obtaining a 10-hour half-life for the purpose of shortening the molding time.
  • the temperature is 70 ° C. or higher and 110 ° C. or lower, the life of the fiber-reinforced molding material at room temperature is long, and it can be cured in a short time by heating, which is preferable, and the balance between curability and moldability is more excellent.
  • Examples of such a polymerization initiator include 1,6-bis (t-butylperoxycarbonyloxy) hexane, 1,1-bis (t-butylperoxy) cyclohexane, and 1,1-bis (t-).
  • the content of the polymerization initiator (D) is 0 with respect to the total amount of the vinyl ester resin (A) and the unsaturated monomer (B) because both the curing characteristics and the storage stability are excellent.
  • the range of 3 to 3% by mass is preferable.
  • the carbon fiber (E) As the carbon fiber (E), a carbon fiber cut to a length of 2.5 to 50 mm is used, but since the fluidity in the mold at the time of molding, the appearance of the molded product and the mechanical properties are further improved. Carbon fibers cut to 5 to 40 mm are more preferable.
  • carbon fiber (E) various types such as polyacrylonitrile-based, pitch-based, rayon-based, etc. can be used, but among these, polyacrylonitrile-based ones because high-strength carbon fibers can be easily obtained. Is preferable.
  • the number of filaments of the fiber bundle used as the carbon fiber (E) is preferably 1,000 to 60,000 because the resin impregnation property and the mechanical physical properties of the molded product are further improved.
  • the content of the carbon fiber (E) in the components of the fiber-reinforced molded material of the present invention is preferably in the range of 20 to 80% by mass, preferably 40 to 80%, because the mechanical properties of the obtained molded product are further improved.
  • the range of 70% by mass is more preferable. If the carbon fiber content is low, a high-strength molded product may not be obtained, and if the carbon fiber content is high, the resin impregnation property of the fibers is insufficient, causing swelling of the molded product, which is also high. There is a possibility that a strong molded product cannot be obtained.
  • the carbon fiber (E) in the fiber-reinforced molding material of the present invention is impregnated with the resin in a state where the fiber direction is random.
  • the components of the fiber-reinforced molding material of the present invention include the vinyl ester resin (A), the unsaturated monomer (B), the polyisocyanate (C), the polymerization initiator (D), and the carbon fiber (E).
  • a thermosetting resin other than the vinyl ester resin (A) a thermoplastic resin, a polymerization inhibitor, a curing accelerator, a filler, a low shrinkage agent, a mold release agent, etc. It can contain a thickener, a thickener, a pigment, an antioxidant, a plasticizer, a flame retardant, an antibacterial agent, an ultraviolet stabilizer, a reinforcing material, a photocuring agent and the like.
  • thermosetting resin examples include vinyl urethane resin, unsaturated polyester resin, acrylic resin, epoxy resin, phenol resin, melamine resin, furan resin and the like. In addition, these thermosetting resins can be used alone or in combination of two or more.
  • thermoplastic resin examples include polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, urethane resin, polypropylene resin, polyethylene resin, polystyrene resin, acrylic resin, polybutadiene resin, polyisoprene resin, and copolymerization thereof. Examples thereof include those modified by the above. In addition, these thermoplastic resins can be used alone or in combination of two or more.
  • polymerization inhibitor examples include hydroquinone, trimethylhydroquinone, pt-butylcatechol, t-butylhydroquinone, toluhydroquinone, p-benzoquinone, naphthoquinone, hydroquinone monomethyl ether, phenothiazine, copper naphthenate, copper chloride and the like. Be done. These polymerization inhibitors may be used alone or in combination of two or more.
  • curing accelerator examples include metal soaps such as cobalt naphthenate, cobalt octate, vanazyl octate, copper naphthenate, and barium naphthenate, and metal chelates such as vanadylacetyl acetate, cobalt acetylacetate, and iron acetylacetonate. Examples include compounds.
  • These curing accelerators can be used alone or in combination of two or more.
  • the filler includes inorganic compounds and organic compounds, which can be used to adjust physical properties such as strength, elastic modulus, impact strength, and fatigue durability of molded products.
  • examples of the inorganic compound include calcium carbonate, magnesium carbonate, barium sulfate, mica, talc, kaolin, clay, celite, asbestos, burlite, baryta, silica, silica sand, dolomite limestone, gypsum, aluminum fine powder, hollow balloon, and the like.
  • examples thereof include alumina, glass powder, aluminum hydroxide, cold water stone, zirconium oxide, antimony trioxide, titanium oxide, molybdenum dioxide, and iron powder.
  • organic compound examples include natural polysaccharide powders such as cellulose and chitin, synthetic resin powders, and the like, and synthetic resin powders are composed of hard resins, soft rubbers, elastomers, polymers (copolymers), and the like.
  • Particles having a multilayer structure such as organic powder or core-shell type can be used. Specific examples thereof include particles made of butadiene rubber and / or acrylic rubber, urethane rubber, silicon rubber and the like, polyimide resin powder, fluororesin powder, phenol resin powder and the like. These fillers can be used alone or in combination of two or more.
  • release agent examples include zinc stearate, calcium stearate, paraffin wax, polyethylene wax, carnauba wax and the like.
  • paraffin wax, polyethylene wax, carnauba wax and the like can be mentioned.
  • These release agents may be used alone or in combination of two or more.
  • thickener examples include metal oxides such as magnesium oxide, magnesium hydroxide, calcium oxide and calcium hydroxide, acrylic resin-based fine particles such as metal hydroxides, and the fiber-reinforced molding material of the present invention. It can be selected as appropriate depending on the handleability of. These thickeners can be used alone or in combination of two or more.
  • the fiber-reinforced molding material of the present invention is a sheet molding compound (hereinafter abbreviated as "SMC") or a bulk molding compound (hereinafter, “BMC”) from the viewpoint of excellent productivity and moldability having design diversity. It is abbreviated as).
  • SMC sheet molding compound
  • BMC bulk molding compound
  • the vinyl ester resin (A) and the unsaturated monomer (B) are produced by using a mixer such as an ordinary mixer, an intermixer, a planetary mixer, a roll, a kneader, or an extruder.
  • a mixer such as an ordinary mixer, an intermixer, a planetary mixer, a roll, a kneader, or an extruder.
  • the polyisocyanate (C), the polymerization initiator (D) and the like are mixed and dispersed, and the obtained resin composition is applied to the carrier films placed on the upper and lower sides so as to have a uniform thickness.
  • the carbon fiber (E) is sandwiched between the resin compositions on the carrier films installed above and below, and then the whole is passed between the impregnated rolls and pressure is applied to the carbon fiber (E).
  • the aging step it is important to control the reaction between the vinyl ester resin (A) and the polyisocyanate (C). For example, by sealing the molding material with a metal-deposited film or the like, moisture or the like can be obtained. The side reaction of the above can be suppressed, and the transmittance ratio ⁇ of the molded material after aging can be controlled in the range of 1.01 to 1.06.
  • polyethylene film polyethylene film, polypropylene film, polyethylene and polypropylene laminated film, polyethylene terephthalate, nylon and the like can be used.
  • the vinyl ester resin (A) can be produced by using a mixer such as a normal mixer, an intermixer, a planetary mixer, a roll, a kneader, or an extruder, as in the method for producing the SMC.
  • a mixer such as a normal mixer, an intermixer, a planetary mixer, a roll, a kneader, or an extruder, as in the method for producing the SMC.
  • a mixer such as a normal mixer, an intermixer, a planetary mixer, a roll, a kneader, or an extruder, as in the method for producing the SMC.
  • a mixer such as a normal mixer, an intermixer, a planetary mixer, a roll, a kneader, or an extruder, as in the method for producing the SMC.
  • Each component such as the unsaturated monomer (B), the polyisocyanate (C), and the polymerization initiator (D) is
  • the molded product of the present invention can be obtained from the fiber-reinforced molding material, but from the viewpoint of excellent productivity and excellent design diversity, heat compression molding of SMC or BMC is preferable as the molding method.
  • a predetermined amount of a molding material such as SMC or BMC is weighed, put into a mold preheated to 110 to 180 ° C., molded by a compression molding machine, and the molding material is applied.
  • a manufacturing method is used in which a molding material is cured by molding and holding a molding pressure of 0.1 to 30 MPa, and then the molded product is taken out to obtain a molded product.
  • molding conditions in which the molding pressure of 1 to 15 MPa is maintained in the mold at a mold temperature of 120 to 160 ° C. for 1 to 5 minutes per 1 mm of thickness of the molded product is preferable, and the productivity is good. It is more preferable that the molding conditions are such that the molding pressure of 1 to 15 MPa is maintained for 1 to 3 minutes per 1 mm of the thickness of the molded product at a mold temperature of 140 to 160 ° C.
  • the molded product obtained from the fiber-reinforced molded material of the present invention is excellent in appearance, bending strength, flexural modulus, etc., it is an automobile member, a railroad vehicle member, an aerospace machine member, a ship member, a housing equipment member, a sports member. , Light vehicle members, building civil engineering members, housings for OA equipment, etc. can be suitably used.
  • the present invention will be described in more detail below with specific examples.
  • the number of milligrams (mgKOH / g) was measured.
  • Example 1 Preparation and evaluation of fiber-reinforced molding material (1)
  • Polyisocyanate (“Luplanate MI” manufactured by BASF, aromatic polyisocyanate) was added to 100 parts by mass of a resin solution prepared by dissolving 55 parts by mass of the vinyl ester resin (A-1) obtained in Synthesis Example 1 in 45 parts by mass of phenoxyethyl methacrylate.
  • polyisocyanate (C-1) (Hereinafter abbreviated as “polyisocyanate (C-1)") 22.0 parts by mass, and polymerization initiator ("Kayacarboxylic AIC-75” manufactured by Chemical Axo Co., Ltd., organic peroxide; hereinafter, “polymerization” Initiator (D-1) “is abbreviated.) 1.2 parts by mass and 0.035 parts by mass of a polymerization inhibitor (parabenzoquinone; hereinafter abbreviated as polymerization inhibitor (1)) are mixed to form a resin.
  • the composition (X-1) was obtained.
  • the molar ratio (NCO / OH) in this resin composition (X-1) was 0.83.
  • the resin composition (X-1) obtained above is applied onto a polyethylene and polypropylene laminated film so that the average coating amount is 0.5 kg / m 2, and carbon fiber roving (Toray Co., Ltd.) is applied thereto.
  • a carbon fiber (hereinafter abbreviated as carbon fiber (E-1)) obtained by cutting a product "T700SC-12000-50C”) to 25 mm has a uniform thickness and a carbon fiber content of 50% by mass without fiber directionality.
  • the resin composition (X-1) is similarly dropped from the air so as to be uniform, sandwiched between films coated at 0.5 kg / m 2 , carbon fibers are impregnated with resin, and then packed and sealed with an aluminum vapor-deposited film.
  • this sheet-shaped fiber-reinforced molding material (1) was 2 kg / m 2 .
  • the sheet-shaped fiber-reinforced molding material (1) obtained above was peeled from the film, three pieces cut into 265 cm ⁇ 265 cm were stacked, and set in the center of a 30 ⁇ 30 cm 2 flat plate mold, and pressed. Molding was performed at a mold temperature of 150 ° C., a pressing time of 5 minutes, and a pressing pressure of 12 MPa to obtain a flat molded product (1) having a thickness of 3 mm.
  • Example 2 Preparation and evaluation of fiber-reinforced molding material (2)
  • Polyisocyanate (“Lupranate M5S” manufactured by BASF, aromatic polyisocyanate) was added to 100 parts by mass of a resin solution prepared by dissolving 55 parts by mass of the vinyl ester resin (A-1) obtained in Synthesis Example 1 in 45 parts by mass of phenoxyethyl methacrylate.
  • polyisocyanate (C-2) 17.5 parts by mass, 1.2 parts by mass of polymerization initiator (D-1), and 0.035 parts by mass of polymerization inhibitor (E-1).
  • the parts were mixed to obtain a resin composition (X-2).
  • the molar ratio (NCO / OH) in this resin composition (X-2) was 0.63.
  • Example 3 Preparation and evaluation of fiber-reinforced molding material (3)
  • Polyisocyanate (“Cosmonate LL” manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.) was added to 100 parts by mass of a resin solution prepared by dissolving 55 parts by mass of the vinyl ester resin (A-1) obtained in Synthesis Example 1 in 45 parts by mass of phenoxyethyl methacrylate.
  • the molar ratio (NCO / OH) in this resin composition (X-3) was 0.68.
  • Example 4 Preparation and evaluation of fiber-reinforced molding material (4)
  • a resin solution prepared by dissolving 55 parts by mass of the vinyl ester resin (A-1) obtained in Synthesis Example 1 in 45 parts by mass of phenoxyethyl methacrylate, 24 parts by mass of polyisocyanate (C-1) and a polymerization initiator ( D-1) 1.2 parts by mass and 0.035 parts by mass of the polymerization inhibitor (E-1) were mixed to obtain a resin composition (X-4).
  • the molar ratio (NCO / OH) in this resin composition (X-4) was 0.90.
  • Example 5 Preparation and evaluation of fiber-reinforced molding material (5)
  • a resin solution prepared by dissolving 55 parts by mass of the vinyl ester resin (A-1) obtained in Synthesis Example 1 in 45 parts by mass of phenoxyethyl methacrylate, 16 parts by mass of polyisocyanate (C-2) and a polymerization initiator ( D-1) 1.2 parts by mass and 0.035 parts by mass of the polymerization inhibitor (E-1) were mixed to obtain a resin composition (X-5).
  • the molar ratio (NCO / OH) in this resin composition (X-5) was 0.57.
  • Example 6 Preparation and evaluation of fiber-reinforced molding material (6)
  • Polymerization of polyisocyanate (C-2) was started in 100 parts by mass of a resin solution prepared by dissolving 58 parts by mass of the vinyl ester resin (A-2) obtained in Synthesis Example 2 in 42 parts by mass of phenoxyethyl methacrylate.
  • 1.2 parts by mass of the agent (D-1) and 0.035 parts by mass of the polymerization inhibitor (E-1) were mixed to obtain a resin composition (X-6).
  • the molar ratio (NCO / OH) in this resin composition (X-6) was 0.73.
  • Example 7 Preparation and evaluation of fiber-reinforced molding material (7)
  • D-1) 1.2 parts by mass and 0.035 parts by mass of the polymerization inhibitor (E-1) were mixed to obtain a resin composition (X-7).
  • the molar ratio (NCO / OH) in this resin composition (X-7) was 0.61.
  • Example 2 The same operation as in Example 1 was performed except that the resin composition (X-1) used in Example 1 was changed to the resin compositions (X-2) to (X-7), and the fiber reinforced molding material (2) was operated. )-(7) were prepared and each evaluation was performed.
  • Example 2 The same operation as in Example 1 was performed except that the resin composition (X-1) used in Example 1 was changed to the resin composition (RX-1) or (RX-2), and the fiber reinforced molding material (R1) was operated. ) Or (R2) was prepared and each evaluation was performed. Since the handleability was poor, the bending strength and flexural modulus of the molded product were not evaluated.
  • Tables 1 and 2 show the evaluation results of the fiber-reinforced molding materials (1) to (7), (R1) and (R2) obtained above.
  • the fiber-reinforced molding materials of the present invention of Examples 1 to 7 are excellent in handleability such as film peelability and tackiness, and flexibility, and the obtained molded product is excellent in bending strength and flexural modulus. It was.
  • Comparative Example 1 although the ratio of the transmittance at 3490cm -1 and 3340cm -1 in ATR measurement of FT-IR (transmittance ratio alpha) is 1.06 greater example, that flexibility is inferior confirmed.
  • Comparative Example 2 is an example in which the transmittance ratio ⁇ is smaller than 1.01, but it was confirmed that the film peelability and tackiness were inferior.

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  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention fournit un matériau de moulage renforcé par des fibres qui a pour matières de départ essentielles une résine vinylester (A), un monomère insaturé (B) de point d'éclair supérieur ou égal à 100°C, un polyisocyanate (C), un initiateur de polymérisation (D), et des fibres de carbone (E) de longueur de fibres comprise entre ２,５ et ５０ｍｍ. Ce matériau de moulage renforcé par des fibres est caractéristique en ce que le rapport （３４９０ｃｍ－１／３３４０ｃｍ－１） de la transmission à ３４９０ｃｍ－１ et ３３４０ｃｍ－１ dans le cadre d'une mesure ATR de IRTF, est compris dans une plage de １,０１ à １,０６. Ce matériau de moulage renforcé par des fibres se révèle excellent en termes d'environnement de travail lors d'une opération de moulage, et de souplesse ainsi que de maniabilité, ceci incluant des propriétés de pelage de film et d'adhérence de matériau de moulage, et permet d'obtenir un article moulé excellent du point de vue de diverses propriétés physiques dont la résistance à la flexion, ou similaire. Par conséquent, ce matériau de moulage renforcé par des fibres peut être mis en œuvre de manière adéquate dans une enveloppe, ou similaire, pour élément automobile, élément de véhicule ferroviaire, élément d'avion spatial, élément de navire, élément d'appareil ménager, élément pour le sport, élément de véhicule léger, élément de construction et génie civil, équipement de bureautique, ou similaire.
PCT/JP2020/015167 2019-04-16 2020-04-02 Matériau de moulage renforcé par des fibres, et article moulé mettant en œuvre celui-ci WO2020213414A1 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
EP3971232A4 (fr) * 2019-05-16 2022-12-07 DIC Corporation Matériau à mouler renforcé par fibres et article moulé l'utilisant
WO2023089999A1 (fr) * 2021-11-18 2023-05-25 Dic株式会社 Composition de résine durcissable par voie radiculaire, matériau de moulage renforcé par des fibres et article moulé les utilisant

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018070076A1 (fr) * 2016-10-11 2018-04-19 Dic株式会社 Matériau à mouler renforcé par fibres et article moulé l'utilisant
JP2019085508A (ja) * 2017-11-08 2019-06-06 Dic株式会社 繊維強化成形材料及びそれを用いた成形品
JP2019099609A (ja) * 2017-11-29 2019-06-24 Dic株式会社 繊維強化成形材料及びそれを用いた成形品

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
WO2018070076A1 (fr) * 2016-10-11 2018-04-19 Dic株式会社 Matériau à mouler renforcé par fibres et article moulé l'utilisant
JP2019085508A (ja) * 2017-11-08 2019-06-06 Dic株式会社 繊維強化成形材料及びそれを用いた成形品
JP2019099609A (ja) * 2017-11-29 2019-06-24 Dic株式会社 繊維強化成形材料及びそれを用いた成形品

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3971232A4 (fr) * 2019-05-16 2022-12-07 DIC Corporation Matériau à mouler renforcé par fibres et article moulé l'utilisant
WO2023089999A1 (fr) * 2021-11-18 2023-05-25 Dic株式会社 Composition de résine durcissable par voie radiculaire, matériau de moulage renforcé par des fibres et article moulé les utilisant
JP7298800B1 (ja) * 2021-11-18 2023-06-27 Dic株式会社 ラジカル硬化性樹脂組成物、繊維強化成形材料、及びそれを用いた成形品

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