WO2020230662A1 - 繊維強化成形材料及びそれを用いた成形品 - Google Patents
繊維強化成形材料及びそれを用いた成形品 Download PDFInfo
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- WO2020230662A1 WO2020230662A1 PCT/JP2020/018378 JP2020018378W WO2020230662A1 WO 2020230662 A1 WO2020230662 A1 WO 2020230662A1 JP 2020018378 W JP2020018378 W JP 2020018378W WO 2020230662 A1 WO2020230662 A1 WO 2020230662A1
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- 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
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- 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
- C08G18/04—Polymeric products of isocyanates or isothiocyanates with vinyl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/144—Polymers containing more than one epoxy group per molecule
-
- 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
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
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- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
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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
- C08J5/04—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
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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
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- 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
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Definitions
- the present invention relates to a fiber reinforced molding material and a molded product thereof.
- a fiber-reinforced resin composite material reinforced with a thermosetting resin such as an epoxy resin or an unsaturated polyester resin using carbon fiber as a reinforced fiber is attracting attention for its light weight and excellent heat resistance and mechanical strength, and is used as a housing for automobiles and aircraft. 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 As a method for molding a material, 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) is known. 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).
- Patent Document 1 since the fluidity of this molding material is insufficiently controlled, there is a problem that efficient press molding is difficult.
- An object to be solved by the present invention is to provide a fiber-reinforced molding material and a molded product thereof, which can obtain a molded product having excellent fluidity and various physical properties such as bending strength.
- the present inventors have found that a fiber-reinforced molding material having a specific thickener and carbon fibers can obtain a molded product having excellent fluidity during molding and excellent various physical properties such as bending strength, and the present invention has been made. Was completed.
- the present invention relates to a characteristic fiber-reinforced molding material and a molded product using the same.
- the maximum value of the viscosity change rate in the temperature region below the temperature Xa showing the minimum melt viscosity A is 100 to 1,500 (Pa ⁇ s / ° C.).
- the maximum value of the viscosity change rate in the temperature range above the temperature Xa is 8,000 to 100,000 (Pa ⁇ s / ° C.).
- the minimum melt viscosity A is 10 to 1,000 Pa ⁇ s, and the temperature Xa is 100 to 140 ° C.
- 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 plastic molding material of the present invention includes a thickener (A) containing a vinyl ester resin (a1), an unsaturated monomer (a2), a polyisocyanate (a3), and a polymerization initiator (a4) as essential raw materials.
- a fiber reinforced plastic material having carbon fibers (B) having a fiber length of 2.5 to 50 mm, and the thickener (A) is measured by a leometer under the following conditions (1) to (3). It satisfies.
- the maximum value of the viscosity change rate in the temperature region below the temperature Xa showing the minimum melt viscosity A is 100 to 1,500 (Pa ⁇ s / ° C.).
- the maximum value of the viscosity change rate in the temperature range above the temperature Xa is 1,000 to 10,000 Pa ⁇ s / ° C.
- the minimum melt viscosity A is 10 to 1,000 Pa ⁇ s, and the temperature Xa is 70 to 140 ° C.
- the thickener (A) is a B-staged composition containing a vinyl ester resin (a1), an unsaturated monomer (a2), a polyisocyanate (a3), and a polymerization initiator (a4) as essential raw materials. It is a thing.
- the vinyl ester resin (a1) is obtained by reacting an epoxy resin with (meth) acrylic acid, and is excellent in a balance between handleability such as film peelability and tackiness during molding and fluidity. It is preferable to react the epoxy group (EP) of the epoxy resin with the molar ratio (COOH / EP) of the carboxyl group (COOH) of the (meth) acrylic acid in the range of 0.6 to 1.1. From this viewpoint, the epoxy equivalent of the epoxy resin is preferably in the range of 180 to 370, and 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.
- epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol fluorene type epoxy resin, bisphenol fluorene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin and the like.
- bifunctional aromatic epoxy resins are preferable because they are superior in strength of molded products, handleability of molding materials, and fluidity during molding of molding materials, and bisphenol A type epoxy resins and bisphenol F type epoxy resins are more preferable. preferable. These epoxy resins may be used alone or in combination of two or more.
- a dibasic acid such as bisphenol A may be used to increase the molecular weight.
- 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.
- Examples of the unsaturated monomer (a2) 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.
- Benzyl methacrylate and phenoxyethyl methacrylate are more preferable.
- These unsaturated monomers may be used alone or in combination of two or more.
- the mass ratio ((A) / (B)) of the vinyl ester resin (a1) and the unsaturated monomer (a2) further improves the balance between resin impregnation property, handleability and curability of carbon fibers. Therefore, the range of 40/60 to 85/15 is preferable, and the range of 50/50 to 70/30 is more preferable.
- the viscosity of the mixture of the vinyl ester resin (A) and the unsaturated monomer (B) is 200 to 8,000 mPa ⁇ s (25 ° C.) because the resin impregnation property into the carbon fibers is further improved. ) Is preferable.
- 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) is 0.5 to 0 because the melt viscosity can be easily controlled.
- the polymerization initiator (a4) 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 (a4) can be used alone or in combination of two or more.
- a polymerization initiator having a temperature of 70 to 110 ° C. for obtaining a 10-hour half-life for the purpose of shortening the molding time.
- the temperature is 70 to 100 ° C.
- 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 (a4) is 0 with respect to the total amount of the vinyl ester resin (a1) and the unsaturated monomer (a2) because both the curing characteristics and the storage stability are excellent.
- the range of 3 to 3% by mass is preferable.
- thermosetting resin other than the vinyl ester resin (a1), a thermoplastic resin, a polymerization inhibitor, a curing accelerator, a filler, a low shrinkage agent, a mold release agent, a thickener, and a thickener may be used. It can contain agents, pigments, antioxidants, plasticizers, flame retardants, antibacterial agents, ultraviolet stabilizers, reinforcing materials, photocuring agents 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.
- amines, m-toluidine, diethylenetriamine, pyridine, phenylmorpholin, piperidine, diethanolaniline and the like 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 thickener (A) contains the vinyl ester resin (a1), the unsaturated monomer (a2), the polyisocyanate (a3), the polymerization initiator (a4), and if necessary, other formulations. It can be obtained by mixing and aging the product, for example, by aging at a temperature of 10 to 60 ° C. for 2 to 48 hours.
- the thickener (A) is less than the temperature Xa when the temperature showing the minimum melt viscosity A is set to the temperature Xa when measured with a rheometer in order for the fiber reinforced molding material to exhibit excellent fluidity. It is important that the maximum value of the viscosity change rate in the temperature range is 100 to 1,500 Pa ⁇ s / ° C, and preferably 100 to 1,300 Pa ⁇ s / ° C. Further, it is important that the maximum value of the viscosity change rate in the temperature range above the temperature Xa is 1,000 to 10,000 Pa ⁇ s / ° C, and that it is 2,000 to 9,000 Pa ⁇ s / ° C. preferable.
- the minimum melt viscosity A of the thickener (A) is 10 to 1,000 Pa ⁇ s in order for the fiber-reinforced molding material to exhibit excellent fluidity, and 10 to 900 Pa ⁇ s. Is preferable.
- the temperature Xa of the thickener (A) is 70 to 140 ° C., and preferably 80 to 130 ° C., in order for the fiber-reinforced molding material to exhibit excellent fluidity.
- the maximum value of the loss tangent (Tan ⁇ ) in the temperature region below the temperature Xa is 0.9 to 10 in order for the fiber-reinforced molding material to exhibit excellent fluidity. Is preferable, and 1 to 5 is more preferable.
- the value of viscoelasticity such as the minimum melt viscosity in the present invention was measured by a rheometer under the condition of a heating rate of 2 ° C./min. More specifically, it was measured with a rheometer (“MCR302” manufactured by AntonioPaar) under the following conditions. Parallel plate 30 mm ⁇ , angular frequency 10 rad / s, swing angle 10%, heating rate 2 ° C / min, gap 1.5 mm.
- carbon fiber (B) 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 (B) for example, various types such as polyacrylonitrile-based, pitch-based, rayon-based, etc. can be used, and among these, polyacrylonitrile-based carbon fibers can be easily obtained because high-strength carbon fibers can be easily obtained. Is preferable.
- the number of filaments of the fiber bundle used as the carbon fiber (B) is preferably 1,000 to 60,000 because the resin impregnation property and the mechanical properties of the molded product are further improved.
- the content of the carbon fiber (B) 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 (B) 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 fiber-reinforced molding material of the present invention has the thickener (A) and the carbon fibers (B), but from the viewpoint of excellent productivity and moldability having design diversity, the sheet It is preferably a molding compound (hereinafter abbreviated as “SMC”) or a bulk molding compound (hereinafter abbreviated as “BMC”).
- SMC molding compound
- BMC bulk molding compound
- the vinyl ester resin (a1) and the unsaturated monomer (a2) 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 (a3), the polymerization initiator (a4) and other components are mixed and dispersed, and the obtained resin composition is applied to carrier films placed on the upper and lower sides so as to have a uniform thickness.
- the carbon fiber (B) is sandwiched between the resin compositions on the carrier films placed above and below, and then the whole is passed between the impregnated rolls and pressure is applied to the carbon fiber (B).
- polyethylene film polyethylene film, polypropylene film, polyethylene and polypropylene laminated film, polyethylene terephthalate, nylon and the like can be used.
- the vinyl ester resin (a1) 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 (a2), the polyisocyanate (a3), and the polymerization initiator (a
- 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 of resin composition] Polyisocyanate ("Cosmonate LL” manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd. "in a resin solution prepared by dissolving 52.1 parts by mass of the vinyl ester resin (a1-2) obtained in Synthesis Example 2 in 35.0 parts by mass of phenoxyethyl methacrylate.
- Aromatic polyisocyanate hereinafter abbreviated as “polyisocyanate (a3-1)) 22.0 parts by mass
- polymerization initiator (“Kayacarboxylic AIC-75” manufactured by Chemical Axo Co., Ltd., organic peroxide ;
- polymerization initiator (a4-1)) 1.2 parts by mass and 0.035 parts by mass of a polymerization inhibitor (parabenzoquinone; hereinafter abbreviated as polymerization inhibitor (1)) was mixed to obtain a resin composition (A'-1).
- the resin composition (A'-1) obtained above was applied onto a polyethylene and polypropylene laminated film so that the average coating amount was 0.5 kg / m 2, and carbon fiber roving (Toray Co., Ltd.) was applied thereto.
- a carbon fiber (hereinafter abbreviated as carbon fiber (B-1)) obtained by cutting a product "T700SC-12000-50C”) to 25 mm has no fiber directionality, a uniform thickness, and a carbon fiber content of 50% by mass.
- the resin composition (A'-1) was similarly dropped from the air so as to be uniform, sandwiched between films coated at 0.5 kg / m 2, and the carbon fibers were impregnated with the resin, and then placed in a thermostat at 40 ° C.
- a sheet-shaped fiber-reinforced molding material (1) having a thickener (A-1) and carbon fibers (B-1) was obtained.
- the basis weight of this sheet-shaped fiber-reinforced molding material (1) was 2 kg / m 2 .
- the enlargement ratio is 3 or more and the separation between the resin and the carbon fiber is 5 mm or more or the enlargement ratio is 2 or more and less than 3. Yes, the separation between the resin and the carbon fiber is less than 10 mm ⁇ : The enlargement ratio is 2 or more and less than 3, and the separation between the resin and the carbon fiber is 10 mm or more or the enlargement ratio is less than 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 Resin compositions (A'-2) to (A'-4) and sheet-shaped fiber-reinforced molding material (2) in the same manner as in Example 1 except that the compounding composition was changed as shown in Table 1. -(4) and molded products (2)-(4) were prepared and evaluated.
- Table 1 shows the composition and evaluation results of the fiber-reinforced molding materials (1) to (4) and (R1) to (R2) obtained above.
- Comparative Example 1 is an example in which the maximum value of the viscosity change rate in the temperature region below the temperature Xa showing the minimum melt viscosity A is smaller than the lower limit of 100 Pa ⁇ s / ° C. of the present invention, but the fluidity is inferior. It was confirmed that.
- Comparative Example 2 is an example in which the maximum value of the viscosity change rate in the temperature region above the temperature Xa showing the minimum melt viscosity A is larger than the upper limit of the present invention of 10,000 Pa ⁇ s / ° C, but the fluidity is inferior. It was confirmed that.
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Abstract
Description
(1)最低溶融粘度Aを示す温度Xa未満の温度領域における粘度変化率の最大値が、100~1,500(Pa・s/℃)である。
(2)前記温度Xa以上の温度領域における粘度変化率の最大値が、8,000~100,000(Pa・s/℃)である。
(3)前記最低溶融粘度Aが10~1,000Pa・sであり、前記温度Xaが100~140℃である。
(1)最低溶融粘度Aを示す温度Xa未満の温度領域における粘度変化率の最大値が、100~1,500(Pa・s/℃)である。
(2)前記温度Xa以上の温度領域における粘度変化率の最大値が、1,000~10,000Pa・s/℃である。
(3)前記最低溶融粘度Aが10~1,000Pa・sであり、前記温度Xaが70~140℃である。
温度計、窒素導入管、撹拌機を設けた2Lフラスコに、エポキシ樹脂(DIC株式会社製「エピクロン860」、ビスフェノールA型エポキシ樹脂、エポキシ当量 220) 725質量部、メタクリル酸 284質量部、及びt-ブチルハイドロキノン 0.28質量部を仕込み、窒素と空気とを1対1で混合したガス流通下で、90℃まで昇温した。ここに2-メチルイミダゾール 0.60質量部を入れ、110℃に昇温して10時間反応させると、酸価が6以下になったので、反応を終了した。60℃付近まで冷却した後、反応容器より取り出し、水酸基価215mgKOH/gのビニルエステル樹脂(a1-1)を得た。
温度計、窒素導入管、撹拌機を設けた2Lフラスコに、エポキシ樹脂(DIC株式会社製「エピクロン850」、ビスフェノールA型エポキシ樹脂、エポキシ当量 188) 677質量部、メタクリル酸 310質量部、及びt-ブチルハイドロキノン 0.29質量部を仕込み、窒素と空気とを1対1で混合したガス流通下で、90℃まで昇温した。ここに2-メチルイミダゾール 0.60質量部を入れ、110℃に昇温して10時間反応させると、酸価が6以下になったので、反応を終了した。60℃付近まで冷却した後、反応容器より取り出し、水酸基価217mgKOH/gのビニルエステル樹脂(a1-2)を得た。
温度計、窒素導入管、撹拌機を設けた2Lフラスコに、エポキシ樹脂(DIC株式会社製「エピクロン850」、ビスフェノールA型エポキシ樹脂、エポキシ当量188)656質量部、ビスフェノールA 147質量部、及び2-メチルイミダゾール0.4質量部を仕込み、120℃に昇温して3時間反応させ、エポキシ当量を測定した。エポキシ当量が設定通り365になったことを確認後、60℃付近まで冷却した後、メタクリル酸185質量部、及びt-ブチルハイドロキノン0.29質量部を仕込み、窒素と空気とを1対1で混合したガス流通下で、90℃まで昇温した。ここに2-メチルイミダゾール0.18質量部を入れ、110℃に昇温して10時間反応させると、酸価が6以下になったので、反応を終了した。60℃付近まで冷却した後、反応容器より取り出し、水酸基価209mgKOH/gのビニルエステル樹脂(a1-3)を得た。
[樹脂組成物の調製]
合成例2で得たビニルエステル樹脂(a1-2)52.1質量部をフェノキシエチルメタクリレート35.0質量部に溶解させた樹脂溶液に、ポリイソシアネート(三井化学SKCポリウレタン社製「コスモネートLL」、芳香族ポリイソシアネート;以下、「ポリイソシアネート(a3-1)」と略記する。)22.0質量部、及び重合開始剤(化薬アクゾ株式会社製「カヤカルボンAIC-75」、有機過酸化物;以下、「重合開始剤(a4-1)」と略記する。)1.2質量部、及び重合禁止剤(パラベンゾキノン;以下、重合禁止剤(1)と略記する。)0.035質量部を混合し、樹脂組成物(A’-1)を得た。
上記で得た樹脂組成物(A’-1)を、厚み3mmのガラス板の間にスペーサー1.5mmを用いて挟みこみ、40℃恒温機中に20時間放置し、シート状の増粘物を得た。このシート状の増粘物を30mmφにカットしたものを、AntonPaar社製MCRレオメータ「MCR302」を用いて、パラレルプレート30mmφ、角周波数10rad/s、振り角10%、昇温速度2℃/min、ギャップ1.5mmの条件にて粘弾性を測定した。得られた測定結果から、貯蔵弾性率、損失弾性率、複素粘度、損失正接を得た。
上記で得た樹脂組成物(A’-1)を、ポリエチレンとポリプロピレンのラミネートフィルム上に塗布量が平均0.5kg/m2となるよう塗布し、この上に、炭素繊維ロービング(東レ株式会社製「T700SC-12000-50C」)を25mmにカットした炭素繊維(以下、炭素繊維(B-1)と略記する。)を繊維方向性が無く厚みが均一で炭素繊維含有率が50質量%になるよう空中から均一落下させ、同様に樹脂組成物(A’-1)を0.5kg/m2となるよう塗布したフィルムで挟み込み炭素繊維に樹脂を含浸させた後、40℃恒温機中に20時間放置し、増粘物(A-1)と炭素繊維(B-1)を有するシート状の繊維強化成形材料(1)を得た。このシート状の繊維強化成形材料(1)の目付け量は、2kg/m2であった。
上記で得られたシート状の繊維強化成形材料(1)をフィルムから剥離し、直径150mmφに切り出したものを3枚積層し、金型温度150/140 ℃、加圧保持300秒、成形圧力13MPa、型締め速度5.5mm/secの条件にてプレスし、面積を測定し、初期からの拡大比率を計算し、以下の基準により流動性を評価した。
○:拡大比率が3以上であり、樹脂と炭素繊維との分離が5mm未満
△:拡大比率が3以上であり、樹脂と炭素繊維との分離が5mm以上
又は、拡大比率が2以上3未満であり、樹脂と炭素繊維との分離が10mm未満
×:拡大比率が2以上3未満であり、樹脂と炭素繊維との分離が10mm以上
又は、拡大比率が2未満
上記で得られたシート状の繊維強化成形材料(1)をフィルムから剥離し、265cm×265cmにカットしたものを3枚重ね、30×30cm2の平板金型の中央部にセットし、プレス金型温度150℃、プレス時間5分間、プレス圧力12MPaで成形し、厚み3mmの平板状の成形品(1)を得た。
上記で得られた成形品(1)から水平方向及び垂直方向にサンプル5本ずつ切り出し、JIS K7074に準拠し、3点曲げ試験を行い、次の基準により、曲げ強さ・曲げ弾性率を評価した。曲げ強さについては、300MPa以上のものを「○」とし、300MPa未満のものを「×」とした。また、曲げ弾性率については、20GPa以上のものを「○」とし、20GPa未満のものを「×」とした。
配合組成を表1に示した通りに変更した以外は、実施例1と同様にして、樹脂組成物(A’-2)~(A’-4)、シート状の繊維強化成形材料(2)~(4)及び成形品(2)~(4)を作製し、各評価を行った。
配合組成を表1に示した通りに変更した以外は、実施例1と同様にして、樹脂組成物(RA’-1)~(RA’-2)、シート状の繊維強化成形材料(R1)~(R2)及び成形品(R1)~(R2)を作製し、各評価を行った。
Claims (3)
- ビニルエステル樹脂(a1)、不飽和単量体(a2)、ポリイソシアネート(a3)、及び重合開始剤(a4)を必須原料とする増粘物(A)と、繊維長2.5~50mmの炭素繊維(B)とを有する繊維強化成形材料であって、前記増粘物(A)が、レオメータで測定した際、下記(1)~(3)の条件を満たすものであることを特徴とする繊維強化成形材料。
(1)最低溶融粘度Aを示す温度Xa未満の温度領域における粘度変化率の最大値が、100~1,500Pa・s/℃である。
(2)前記温度Xa以上の温度領域における粘度変化率の最大値が、1,000~10,000Pa・s/℃である。
(3)前記最低溶融粘度Aが10~1,000Pa・sであり、前記温度Xaが70~140℃である。 - 前記増粘物(A)の前記温度Xa未満の温度領域における損失正接(Tanδ)の最大値が、0.9~10の範囲である請求項1記載の繊維強化成形材料。
- 請求項1又は2記載の繊維強化成形材料を用いた成形品。
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