WO2023199692A1 - Composition de résine pour préimprégnés, préimprégné et article moulé - Google Patents

Composition de résine pour préimprégnés, préimprégné et article moulé Download PDF

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Publication number
WO2023199692A1
WO2023199692A1 PCT/JP2023/010216 JP2023010216W WO2023199692A1 WO 2023199692 A1 WO2023199692 A1 WO 2023199692A1 JP 2023010216 W JP2023010216 W JP 2023010216W WO 2023199692 A1 WO2023199692 A1 WO 2023199692A1
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prepreg
resin
resin composition
meth
acrylate
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PCT/JP2023/010216
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English (en)
Japanese (ja)
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直樹 加藤
智昭 新地
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Dic株式会社
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Priority to JP2023559058A priority Critical patent/JP7480921B2/ja
Publication of WO2023199692A1 publication Critical patent/WO2023199692A1/fr

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    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from 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
    • 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

Definitions

  • the present invention relates to a prepreg and a molded article thereof, from which a molded article with excellent workability and moldability and excellent heat resistance and other various physical properties can be obtained.
  • Fiber-reinforced resin composite materials reinforced with reinforcing fibers such as carbon fibers and glass fibers are attracting attention for their lightweight yet excellent heat resistance and mechanical strength, and are used in a variety of applications, including automobile and aircraft casings and various components. Its use in structural applications is expanding.
  • a method for molding this fiber-reinforced resin composite material for example, a method is used in which an intermediate material called prepreg in which reinforcing fibers are impregnated with a thermosetting resin is cured and molded by autoclave molding or press molding.
  • thermosetting resins such as epoxy resin compositions are often used as resins for prepregs, as they need to be both stable at room temperature and hardenable by heating. It's here.
  • a prepreg using an epoxy resin has the problem of requiring refrigerated storage because it hardens at room temperature.
  • a prepreg resin composition has been proposed that uses a specific urethane (meth)acrylate, a polymerization initiator, and a thermoplastic resin as essential raw materials.
  • a specific urethane (meth)acrylate for example, see Patent Document 2.
  • the prepreg obtained from this resin composition has excellent moldability, and the molded products have excellent physical properties such as impact resistance, but depending on the application, it may be necessary to achieve a higher balance between impact resistance and heat resistance. Ta.
  • the problem to be solved by the present invention is to provide a prepreg resin composition, a prepreg, and a molded product thereof, which can yield a molded product that has both impact resistance and heat resistance in a highly balanced manner.
  • the present inventors have discovered that a prepreg resin composition containing a specific urethane (meth)acrylate, a polymerization initiator, a specific polyester resin, and a thermoplastic resin as essential raw materials, and a prepreg that has excellent impact resistance and heat resistance. They discovered that a molded product could be obtained and completed the present invention.
  • urethane (meth)acrylate (A) which is a reaction product of polyisocyanate (a1), polyol (a2), and hydroxyalkyl (meth)acrylate (a3), a polymerization initiator (B), and a polyester resin (C ) and a thermoplastic resin (D) other than the polyester resin (C) as essential components, wherein the polyisocyanate (a1) is 2,4'-diphenylmethane diisocyanate, 4,4 '-diphenylmethane diisocyanate, a carbodiimide modified product of 4,4'-diphenylmethane diisocyanate, and polymethylene polyphenyl polyisocyanate, and the polyester resin (C) is a lactone (c1) and a polyisocyanate.
  • the present invention relates to a resin composition for prepreg, a prepreg, and a molded article thereof, characterized in that the alkylene ether polyol (c2) is an essential
  • the resin composition for prepreg of the present invention and the molded products obtained from the prepreg have excellent impact resistance and heat resistance, so they can be used for automobile parts, railway vehicle parts, aerospace machine parts, ship parts, housing equipment parts, and sports parts. , light vehicle members, construction civil engineering members, casings of OA equipment, etc.
  • the resin composition for prepreg of the present invention comprises urethane (meth)acrylate (A) which is a reaction product of polyisocyanate (a1), polyol (a2) and hydroxyalkyl (meth)acrylate (a3), and a polymerization initiator.
  • A urethane (meth)acrylate
  • the polyisocyanate (a1) is 2,4 One or more polyisocyanates selected from '-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, a carbodiimide modified product of 4,4'-diphenylmethane diisocyanate, and polymethylene polyphenyl polyisocyanate, and the polyester resin (C) However, it uses lactone (c1) as an essential raw material.
  • the urethane (meth)acrylate (A) is a reaction product of polyisocyanate (a1), polyol (a2), and hydroxyalkyl (meth)acrylate (a3).
  • the polyisocyanate (a1) is one or more selected from 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, a carbodiimide modified product of 4,4'-diphenylmethane diisocyanate, and polymethylene polyphenyl polyisocyanate. Although it is a polyisocyanate, it is preferable to include polymethylene polyphenyl polyisocyanate because the heat resistance of the molded product is further improved.
  • polyisocyanates other than the polyisocyanate (a1) can be used in combination.
  • Other polyisocyanates include, for example, nurate-modified products of diphenylmethane diisocyanate, biuret-modified products, urethanimine-modified products, polyol-modified products modified with polyols having a number average molecular weight of 1,000 or less such as diethylene glycol and dipropylene glycol, and tolylene diisocyanate.
  • Aromatic polyisocyanates such as isocyanate (TDI), toridine diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, and tetramethylxylylene diisocyanate; isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, norbornene diisocyanate, etc.
  • aliphatic polyisocyanates such as hexamethylene diisocyanate, nurate modified products of hexamethylene diisocyanate, biuret modified products, adduct products, dimer acid diisocyanates, etc. can be used.
  • the polyisocyanate (a1) is preferably 20% by mass or more, more preferably 50% by mass or more in the isocyanate raw material for the urethane (meth)acrylate (A).
  • the polyol (a2) is not particularly limited, but includes, for example, alkylene oxide adducts of bisphenol A, alkylene oxide adducts of aromatic diols, polyester polyols, acrylic polyols, polyether polyols, polycarbonate polyols, polyalkylene polyols, etc. can be used. These polyols (a2) can be used alone or in combination of two or more.
  • the hydroxyl equivalent of the polyol (a2) is preferably in the range of 140 to 250 g/eq.
  • the polyol (a2) is preferably an alkylene oxide adduct of bisphenol A, and one having a hydroxyl equivalent of 140 to 180 g/eq, and one having a hydroxyl equivalent of 180 to 250 g/eq. It is preferable to use them together. At this time, the mass ratio of both is preferably in the range of 40/60 to 60/40.
  • the ratio of the alkylene oxide adduct of bisphenol A to the total mass of the polyol (a2) is preferably 50% by mass or more, more preferably 80% by mass or more.
  • Examples of the hydroxyalkyl (meth)acrylate (a3) include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxy-n-butyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. Examples include meth)acrylate, 2-hydroxy-n-butyl(meth)acrylate, 3-hydroxy-n-butyl(meth)acrylate, and 2-hydroxyethyl(meth)acrylate is preferred. Note that these hydroxyalkyl (meth)acrylates (a3) can be used alone or in combination of two or more.
  • the amount of the hydroxyalkyl (meth)acrylate (a3) in the prepreg resin composition is preferably in the range of 5 to 50% by mass.
  • the molar ratio (NCO/OH) of the isocyanate group (NCO) of the isocyanate compound and the hydroxyl group (OH) of the compound having a hydroxyl group, which is the raw material for the urethane (meth)acrylate (A), is 0.7 to 1.5. is preferable, 0.8 to 1.3 is more preferable, and 0.8 to 1.0 is even more preferable.
  • the content of the urethane (meth)acrylate (A) is preferably 60 to 95% by mass in the prepreg resin composition, and 60 to 95% by mass, since the balance between impact resistance and heat resistance of the molded product is further improved. 90% by mass is more preferred.
  • the polymerization initiator (B) is not particularly limited, but organic peroxides are preferred, such as diacyl peroxide compounds, peroxy ester compounds, hydroperoxide compounds, ketone peroxide compounds, alkyl perester compounds, and peroxide compounds. Examples include carbonate compounds, peroxyketals, etc., and can be appropriately selected depending on molding conditions. In addition, these polymerization initiators (B) can be used alone or in combination of two or more.
  • a polymerization initiator whose temperature is 70° C. or higher and 100° C. or lower in order to obtain a half-life of 10 hours for the purpose of shortening the molding time.
  • a temperature of 70°C or higher and 100°C or lower is preferable because the prepreg has a long life at room temperature and can be cured in a short time (within 5 minutes) by heating, and when combined with the prepreg of the present invention, curability and moldability are improved. Excellent.
  • polymerization initiators examples include 1,6-bis(t-butylperoxycarbonyloxy)hexane, 1,1-bis(t-butylperoxy)cyclohexane, and 1,1-bis(t-butylperoxy)hexane.
  • amylperoxy)cyclohexane 1,1-bis(t-hexylperoxy)cyclohexane, t-butylperoxydiethyl acetate, t-butylperoxyisopropyl carbonate, t-amylperoxyisopropyl carbonate, t-hexylperoxyisopropyl carbonate, di-tert-butylperoxyhexahydroterephthalate, t-amylperoxytrimethylhexanoate, t-hexylperoxy-2-ethylhexanoate, and the like.
  • the content of the polymerization initiator (B) is preferably in the range of 0.3 to 3% by mass in the prepreg resin composition since both curing properties and storage stability are excellent.
  • the polyester resin (C) is obtained by reacting the lactone (c1) and the polyalkylene ether polyol (c2) as essential raw materials.
  • polyester resin (C) Since the polyester resin (C) has a lactone-derived polyester structure and a polyalkylene ether structure at the end, a molded article with an excellent balance of impact resistance and heat resistance can be obtained.
  • the lactone (c1) includes, for example, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, etc., but ⁇ -caprolactone is preferable because molded products with a better balance of impact resistance and heat resistance can be obtained. is more preferable.
  • the polyalkylene ether polyol (c2) is a polyol having oxyalkylene units as repeating units, but polyethylene glycol, polypropylene glycol, polybutylene can be used because molded products with a better balance of impact resistance and heat resistance can be obtained. Those having an oxyalkylene unit having 2 to 4 carbon atoms, such as glycol, are preferred.
  • the number average molecular weight of the polyalkylene ether polyol (c2) is preferably 700 to 4,000, and 1,000 to 3,500, since a molded product with a better balance of impact resistance and heat resistance can be obtained. preferable.
  • the average molecular weight of the present invention is a value converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as "GPC") measurement.
  • Raw materials other than the lactone (c1) and the polyalkylene ether polyol (c2) can also be used for the polyester resin (C).
  • the ratio of the total mass of the lactone (c1) and the polyalkylene ether polyol (c2) to the raw materials of the polyester resin (C) is preferably 70% by mass or more, more preferably 90% by mass or more.
  • the number average molecular weight of the polyester resin (C) is preferably 3,000 to 15,000, more preferably 5,000 to 12,000, since the balance between impact resistance and heat resistance of the molded product is further improved. .
  • the hydroxyl value of the polyester resin (C) is preferably 5 to 30 mgKOH/g, more preferably 10 to 20 mgKOH/g, since the balance between impact resistance and heat resistance of the molded product is further improved.
  • the content of the polyester resin (C) is preferably 2.5 to 8% by mass in the prepreg resin composition, since the balance between impact resistance and heat resistance of the molded product obtained is improved. .5 to 6% by weight is more preferable, and 4 to 6% by weight is particularly preferable.
  • thermoplastic resin (D) examples include polyurethane resin, polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, polypropylene resin, polyethylene resin, polystyrene resin, acrylic resin, polybutadiene resin, polyisoprene resin, and these.
  • thermoplastic polyurethane resins are preferred because they improve the balance between impact resistance and heat resistance of molded products, and polyalkylene ether polyols are essential.
  • Thermoplastic polyurethane used as a raw material is more preferred.
  • These thermoplastic resins can be used alone or in combination of two or more.
  • thermoplastic resin (D) may be added in the form of particles or may be melted and mixed.
  • the particle size is preferably 30 ⁇ m or less, more preferably 20 ⁇ m, from the viewpoint of dispersibility into fibers.
  • the weight average molecular weight of the thermoplastic resin (D) is preferably 5,000 to 500,000, more preferably 10,000 to 100,000, since the balance between impact resistance and heat resistance of the molded product is further improved. It is preferably 30,000 to 80,000, more preferably 40,000 to 65,000.
  • the content of the thermoplastic resin (D) in the prepreg resin composition is preferably 1 to 25% by mass, and 5 to 15% by mass is more preferred.
  • the mass ratio (C/D) of the polyester resin (C) and the thermoplastic resin (D) is from 3/2 to 3/2 to improve the balance between impact resistance and heat resistance of the molded product obtained. 1/3 is preferable, and 1/1 to 1/2 is more preferable.
  • an ethylenically unsaturated monomer may be used as necessary.
  • these ethylenically unsaturated monomers include styrene compounds such as styrene, methylstyrene, halogenated styrene, and divinylbenzene; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl ( meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, methylbenzyl (meth)acrylate, phenoxyethyl (meth)acrylate, methylphenoxy Ethyl (meth)acrylate, Morpholine (meth)acrylate, Phenylphenoxyethyl acrylate
  • dimethacrylate an ethylene oxide adduct of bisphenol A, tricyclodecane dimethanol dimethacrylate, and 1,12 dodecane diol are used because of the odor in the work environment, the handling of hazardous materials, the mechanical strength and heat resistance of the molded product
  • Dimethacrylate hydrogenated bisphenol A dimethacrylate, polytetramethylene glycol dimethacrylate, 9,9-bis[4-(2-methacryloyloxyethoxy)phenyl]fluorene, dimethacrylate of ethylene oxide adduct of isosorbide, hydrogenated bisphenol A
  • dimethacrylate of ethylene oxide adduct of trimethylolpropane trimethacrylate of ethylene oxide adduct of trimethylolpropane
  • tetramethacrylate of ethylene oxide adduct of pentaerythritol and hexamethacrylate of ethylene oxide adduct of dipent
  • the molecular weight is preferably 320 to 2,000, and the (meth)acrylic equivalent weight is preferably 150 to 1,000, more preferably 150 to 500.
  • the number of functional groups is preferably 2 to 4, more preferably 2.
  • the content of the ethylenically unsaturated monomer in the resin composition for prepreg of the present invention is preferably 50% by mass or less, and 30% by mass or less from the balance of workability (tackiness), heat resistance, and curability. is more preferable.
  • Components of the prepreg resin composition of the present invention may include those other than those listed above, such as a thermosetting resin, a polymerization inhibitor, a curing accelerator, a filler, a low shrinkage agent, and a mold release agent. , thickeners, thinners, pigments, antioxidants, plasticizers, flame retardants, antibacterial agents, ultraviolet stabilizers, reinforcing materials, photocuring agents, and the like.
  • thermosetting resin examples include vinyl ester resin, unsaturated polyester resin, phenol resin, melamine resin, furan resin, and the like. Moreover, these thermosetting resins can be used alone or in combination of two or more kinds.
  • 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. It will be done. These polymerization inhibitors can be used alone or in combination of two or more.
  • curing accelerator examples include metal soaps such as cobalt naphthenate, cobalt octenoate, vanadyl octenoate, copper naphthenate, and barium naphthenate, and metal chelates such as vanadyl acetylacetate, cobalt acetylacetate, and iron acetylacetonate. Examples include compounds.
  • amines N,N-dimethylamino-p-benzaldehyde, N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, N-ethyl-m-toluidine, triethanol
  • amines N,N-dimethylamino-p-benzaldehyde, N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, N-ethyl-m-toluidine, triethanol
  • amines amine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, diethanolaniline, and the like.
  • These curing accelerators can be used alone or in combination of two or more.
  • the filler includes inorganic compounds and organic compounds, and can be used to adjust the physical properties of the molded product, such as strength, elastic modulus, impact strength, and fatigue durability.
  • examples of the inorganic compounds include calcium carbonate, magnesium carbonate, barium sulfate, mica, talc, kaolin, clay, celite, asbestos, barite, baryta, silica, silica sand, dolomite limestone, gypsum, fine aluminum powder, hollow balloons,
  • examples include alumina, glass powder, aluminum hydroxide, agarite, zirconium oxide, antimony trioxide, titanium oxide, molybdenum dioxide, iron powder, and the like.
  • organic compounds examples include natural polysaccharide powders such as cellulose and chitin, synthetic resin powders, etc., and synthetic resin powders include hard resins, soft rubbers, elastomers, polymers (copolymers), etc. Particles having a multilayer structure such as organic powder or core-shell type particles can be used. Specific examples include acrylic particles, polyamide particles, particles made of butadiene rubber and/or acrylic rubber, urethane rubber, silicone rubber, etc., polyimide resin powder, fluororesin powder, phenol resin powder, and the like. These fillers can be used alone or in combination of two or more.
  • mold release agent examples include zinc stearate, calcium stearate, paraffin wax, polyethylene wax, and carnauba wax. Preferred examples include paraffin wax, polyethylene wax, carnauba wax, and the like. These mold release agents can be used alone or in combination of two or more.
  • thickener examples include metal oxides and metal hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide, and calcium hydroxide, and acrylic resin-based fine particles, which improve the handling properties of the prepreg of the present invention. can be selected as appropriate. These thickeners can be used alone or in combination of two or more.
  • the prepreg of the present invention contains the resin composition for prepreg and the reinforcing fiber (E), and the reinforcing fiber (E) includes carbon fiber, glass fiber, silicon carbide fiber, alumina fiber, and boron fiber. Fibers, metal fibers, organic fibers such as aramid fibers, vinylon fibers, Tetron fibers, natural fibers such as basalt fibers and flax fibers, etc., but carbon fibers can be used because they can produce molded products with higher strength and higher elasticity. Alternatively, glass fiber is preferable, and carbon fiber is more preferable. These reinforcing fibers (E) can be used alone or in combination of two or more.
  • carbon fiber various types such as polyacrylonitrile type, pitch type, rayon type, etc. can be used, but among these, polyacrylonitrile type is preferable because high strength carbon fiber can be easily obtained.
  • the shape of the reinforcing fiber (E) is not particularly limited, and may be a reinforcing fiber tow in which reinforcing fiber filaments are converged, a unidirectional material in which reinforcing fiber tows are aligned in one direction, a woven fabric, or a reinforcing fiber cut into short pieces.
  • a non-woven fabric or paper made of reinforcing fibers cut into short lengths may be used, but it is preferable to use a unidirectional material as the reinforcing fibers, since high mechanical properties can be obtained by laminating and forming the reinforcing fibers.
  • sheets made of fiber bundles aligned in one direction such as plain weave, twill weave, satin weave, or non-crimped fabrics, or sheets laminated at different angles, are stitched to prevent them from unraveling. Examples include stitching sheets, etc.
  • the basis weight (weight per m 2 of fiber) of the reinforcing fibers is not particularly limited, but is preferably 10 g/m 2 to 650 g/m 2 .
  • a basis weight of 10 g/m 2 or more is preferable because it reduces unevenness in fiber width and improves mechanical properties.
  • a basis weight of 650 g/m 2 or less is preferable because it improves resin impregnation.
  • This basis weight is more preferably 50 to 500 g/m 2 , particularly preferably 50 to 300 g/m 2 .
  • the content of the reinforcing fiber (E) in the prepreg of the present invention is preferably in the range of 20 to 85% by mass, and preferably in the range of 40 to 80% by mass, since the mechanical strength of the obtained molded product is further improved. More preferred.
  • the prepreg of the present invention can be prepared by mixing polyisocyanate (a1), polyol (a2), hydroxyalkyl (meth)acrylate (a3), and polymerization initiator (B) using a known mixer such as a planetary mixer or a kneader.
  • the reinforcing fibers (E) are impregnated in a resin solution containing a mixture of , polyester resin (C), and thermoplastic resin (D), and further sandwiched between a release PET film from the top and rolled with a rolling machine to obtain a sheet.
  • Step 1 a step of allowing this to stand at room temperature to 50°C and reacting the isocyanate groups of the polyisocyanate (a1) with the hydroxyl groups of the polyol (a2) and the hydroxyalkyl (meth)acrylate (a3). 2.
  • the polyisocyanate (a1), the polyol (a2), and the hydroxyalkyl (meth)acrylate (a3) may be partially reacted in advance within a range that does not impair impregnating properties into the fibers. It can also be used.
  • the thickness of the prepreg of the present invention is preferably 0.02 to 1.0 mm.
  • a thickness of 0.02 mm or more is preferred because it facilitates handling for lamination, and a thickness of 1 mm or less is preferred because resin impregnation becomes good.
  • 0.05 to 0.5 mm is more preferable.
  • a method for obtaining a molded product from the prepreg obtained above is, for example, by peeling the prepreg from the release PET film, laminating 8 to 16 sheets of prepreg, and then inserting the prepreg into a mold preheated to 110°C to 160°C.
  • a method is used in which the prepreg is put into a mold, the mold is clamped in a compression molding machine, the prepreg is shaped, the prepreg is cured by maintaining a molding pressure of 0.1 to 10 MPa, and then the molded product is taken out to obtain a molded product. It will be done.
  • a molding pressure of 1 to 8 MPa is maintained in a mold with a shear edge at a mold temperature of 120°C to 160°C for a specified time of 1 to 2 minutes per 1 mm of thickness of the molded product, and the heat compression molding is performed.
  • a manufacturing method is preferred.
  • Molded products obtained from the prepreg of the present invention have excellent interlaminar shear strength, heat resistance, etc., so they can be used in automobile parts, railway vehicle parts, aerospace machine parts, ship parts, housing equipment parts, sports parts, light vehicle parts, construction materials, etc. It can be suitably used for civil engineering members, casings of OA equipment, etc.
  • the hydroxyl value is the amount of potassium hydroxide required to neutralize acetic acid produced when 1 g of a resin sample is reacted with an acetylating agent at the specified temperature and time according to the specified method of JIS K-0070.
  • the number of milligrams (mgKOH/g) is measured.
  • the average molecular weight was measured under the following GPC measurement conditions.
  • Measuring device High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were used by connecting them in series. "TSKgel G5000” (7.8mm I.D. x 30cm) x 1 "TSKgel G4000” (7.8mm I.D. x 30cm) x 1 "TSKgel G3000” (7.8mm I.D. x 30cm) x 1 Book “TSKgel G2000" (7.8mm I.D.
  • polyester resin (C-1) 300 parts by mass of polytetramethylene glycol (PTMG3000, manufactured by Mitsubishi Chemical Corporation) and 600 parts by mass of ⁇ -caprolactone ("Plaxel M", manufactured by Daicel Corporation) were placed in a reaction apparatus, and heating and stirring were started. Next, after raising the internal temperature to 190°C, 0.009 parts by mass of isopropyl titanate (TiPT) was charged and reacted at 190°C for 10 hours to synthesize polyester resin (C-1). This polyester resin (C-1) had a hydroxyl value of 13.8 and a number average molecular weight of 8,130.
  • PTMG3000 polytetramethylene glycol
  • ⁇ -caprolactone manufactured by Daicel Corporation
  • thermoplastic resin (D-1) (Synthesis Example 2: Synthesis of thermoplastic resin (D-1)) 71 parts of polytetramethylene ether glycol ("PTMG1000" manufactured by Mitsubishi Chemical Corporation), 3 parts by mass of 1,4-butanediol, and 26 parts by mass of 4,4'-diphenylmethane diisocyanate were mixed and cast in a vat, A thermoplastic resin (D-1) was produced by reacting at 90° C. for 24 hours. The weight average molecular weight of this thermoplastic resin (D-1) was 50,000.
  • thermoplastic resin (D-2) (Synthesis Example 3: Synthesis of thermoplastic resin (D-2)) 74 parts of polytetramethylene ether glycol ("PTMG1000" manufactured by Mitsubishi Chemical Corporation), 2 parts by mass of 1,4-butanediol, and 24 parts by mass of 4,4'-diphenylmethane diisocyanate were mixed and cast in a vat, A thermoplastic resin (D-2) was produced by reacting at 90° C. for 24 hours. The weight average molecular weight of this thermoplastic resin (D-2) was 100,000.
  • Example 1 Production and evaluation of resin composition for prepreg (1)
  • 10 parts by mass of Newpol BPE-20 manufactured by Sanyo Chemical Co., Ltd.: EO adduct of bisphenol A, hydroxyl equivalent; 164 g/eq)
  • Newpol BPE-40 manufactured by Sanyo Chemical Co., Ltd.
  • Company-made 12 parts by mass of EO adduct of bisphenol A, hydroxyl equivalent: 204 g/eq)
  • 1 part by mass of polymerization initiator Kerayaku Nourion Co., Ltd. "Trigonox 122-C
  • the prepreg resin composition (1) was poured into a casting mold with a 4 mm thick spacer inserted between two glass plates coated with a mold release agent, and aged at 45°C for 48 hours to increase the thickness.
  • a B-staged resin composition (1) with a diameter of 4 mm was obtained.
  • the obtained B-staged resin composition (1) with a thickness of 4 mm was cured at 150° C. for 30 minutes to obtain a cured product (1).
  • a test piece with a width of 8.4 mm and a length of 40 mm was cut from the obtained cured product (1).
  • a test piece with a width of 10 mm and a length of 56 mm was cut from the obtained cured product, and this test piece was measured using a DMA ("RSA-G2" manufactured by TA Instruments Japan Co., Ltd.) at a measurement frequency of 1 Hz.
  • the dynamic viscoelasticity of the cured product was measured by bending the cured product on both sides at a heating rate of 3° C./min.
  • the intersection of the approximate straight line of the glass region of the obtained storage modulus chart and the tangent of the transition region was defined as the glass transition temperature, and the heat resistance was evaluated according to the following criteria.
  • ⁇ Glass transition temperature is 120°C or higher
  • ⁇ Glass transition temperature is lower than 120°C
  • prepreg After coating the prepreg resin composition (1) on one side of a polyethylene terephthalate film that had been subjected to mold release treatment, carbon fiber (Toray Industries, Ltd. "T-700-12K-50C") was coated with a carbon fiber content of 50% by mass.
  • a prepreg (1) was produced by impregnating the prepreg so as to have the same properties, covering it with the same film, and aging it at 45° C. for 48 hours.
  • a molded article (1) was obtained by laminating 12 prepregs (1) and molding them under heat and pressure using a plate-shaped mold.
  • the heating and pressurizing conditions were as follows: the mold temperature was 140° C., the mold closing pressure was held at 4 MPa for 5 minutes, and after the mold was opened, the mold was taken out and left to cool at room temperature.
  • Example 2 Production and evaluation of resin composition for prepreg (2)
  • a prepreg resin composition (2) was obtained in the same manner as in Example 1, except that 4 parts by mass of the polyester resin (C-1) used in Example 1 was changed to 6 parts by mass, and each evaluation was performed. did.
  • Example 2 Production and evaluation of resin composition for prepreg (R2)
  • a prepreg resin was produced in the same manner as in Example 1, except that the polyester resin (C-1) used in Example 1 was not used and the thermoplastic resin (D-1) was changed from 6 parts by mass to 10 parts by mass.
  • a composition (R2) was obtained and various evaluations were performed.
  • Example 3 Production and evaluation of resin composition for prepreg (R3)) Example 1 except that the polyester resin (C-1) used in Example 1 was not used and 6 parts by mass of thermoplastic resin (D-1) was changed to 6 parts by mass of thermoplastic resin (D-2).
  • a prepreg resin composition (R3) was obtained in the same manner as above, and various evaluations were performed.
  • Table 1 shows the compositions and evaluation results of the prepreg resin compositions (1) to (2) and (R1) to (R3) obtained above.
  • the cured product of the resin composition for prepreg of the present invention has excellent impact resistance and heat resistance, and the prepreg using this composition has excellent moldability.
  • Comparative Examples 1 to 3 are examples in which the polyester resin (C), which is an essential component of the present invention, was not used, but it was confirmed that the impact resistance was insufficient.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

La présente invention concerne : une composition de résine pour préimprégnés, la composition de résine permettant d'obtenir un article moulé qui présente à la fois une résistance aux chocs et une résistance à la chaleur d'une manière hautement équilibrée ; un préimprégné ; et un article moulé à base du préimprégné. La présente invention utilise une composition de résine pour préimprégnés, la composition de résine contenant essentiellement (A) un (méth)acrylate d'uréthane qui est un produit de réaction d'un polyisocyanate (a1), d'un polyol (a2) et d'un (méth)acrylate d'hydroxyalkyle (a3), (B) un amorceur de polymérisation, (C) une résine de polyester et (D) une résine thermoplastique autre que la résine de polyester (C).
PCT/JP2023/010216 2022-04-14 2023-03-16 Composition de résine pour préimprégnés, préimprégné et article moulé WO2023199692A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09169862A (ja) * 1995-08-11 1997-06-30 Takeda Chem Ind Ltd プリプレグシートおよびそれを用いた成形体
JP2004231848A (ja) * 2003-01-31 2004-08-19 Dainippon Ink & Chem Inc プリプレグ及びそれを用いたｆｒｐ成形品
JP2004238755A (ja) * 2003-02-05 2004-08-26 Asahi Schwebel Co Ltd 樹脂組成物及びガラス繊維織布
WO2019065210A1 (fr) * 2017-09-27 2019-04-04 Dic株式会社 Composition de résine pour préimprégné, préimprégné et article moulé
JP2020139000A (ja) * 2019-02-27 2020-09-03 三菱ケミカル株式会社 硬化性樹脂組成物、並びにこれを用いたフィルム、成形品、プリプレグ及び繊維強化プラスチック
WO2021006163A1 (fr) * 2019-07-08 2021-01-14 Dic株式会社 Composition de résine, préimprégné, plaque stratifiée, carte de circuit imprimé multicouche et boîtier de semi-conducteur
WO2021131566A1 (fr) * 2019-12-25 2021-07-01 Dic株式会社 Pré-imprégné et article moulé

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09169862A (ja) * 1995-08-11 1997-06-30 Takeda Chem Ind Ltd プリプレグシートおよびそれを用いた成形体
JP2004231848A (ja) * 2003-01-31 2004-08-19 Dainippon Ink & Chem Inc プリプレグ及びそれを用いたｆｒｐ成形品
JP2004238755A (ja) * 2003-02-05 2004-08-26 Asahi Schwebel Co Ltd 樹脂組成物及びガラス繊維織布
WO2019065210A1 (fr) * 2017-09-27 2019-04-04 Dic株式会社 Composition de résine pour préimprégné, préimprégné et article moulé
JP2020139000A (ja) * 2019-02-27 2020-09-03 三菱ケミカル株式会社 硬化性樹脂組成物、並びにこれを用いたフィルム、成形品、プリプレグ及び繊維強化プラスチック
WO2021006163A1 (fr) * 2019-07-08 2021-01-14 Dic株式会社 Composition de résine, préimprégné, plaque stratifiée, carte de circuit imprimé multicouche et boîtier de semi-conducteur
WO2021131566A1 (fr) * 2019-12-25 2021-07-01 Dic株式会社 Pré-imprégné et article moulé

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JP7480921B2 (ja) 2024-05-10
JPWO2023199692A1 (fr) 2023-10-19

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