WO2021106588A1 - Composition de résine pour préimprégné, préimprégné et article moulé - Google Patents

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

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Publication number
WO2021106588A1
WO2021106588A1 PCT/JP2020/042181 JP2020042181W WO2021106588A1 WO 2021106588 A1 WO2021106588 A1 WO 2021106588A1 JP 2020042181 W JP2020042181 W JP 2020042181W WO 2021106588 A1 WO2021106588 A1 WO 2021106588A1
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Prior art keywords
prepreg
meth
acrylate
resin composition
mass
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PCT/JP2020/042181
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English (en)
Japanese (ja)
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智昭 新地
隆志 安村
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Dic株式会社
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Publication of WO2021106588A1 publication Critical patent/WO2021106588A1/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
    • 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
    • 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 resin composition for a prepreg, a prepreg, and a molded product thereof.
  • Fiber reinforced resin composite materials reinforced with reinforced fibers such as carbon fiber and glass fiber are attracting attention for their excellent heat resistance and mechanical strength while being lightweight, and they are used in various types of materials such as automobile and aircraft housings and various members. Its use in structural applications is expanding.
  • a method for molding the fiber-reinforced resin composite material for example, a method of curing and molding by autoclave molding or press molding using an intermediate material called prepreg in which the reinforcing fibers are impregnated with a thermosetting resin is used.
  • thermosetting resin such as an epoxy resin composition is often used. I came.
  • the prepreg using the epoxy resin has a problem that it needs to be stored in a refrigerator because the curing proceeds at room temperature.
  • This molding material is composed of a urethane (meth) acrylate compound having a specific structure and reinforcing fibers, but has a problem that the tackiness and moldability required for a prepreg are insufficient.
  • the problem to be solved by the present invention is a resin composition for prepreg, which can obtain a molded product having an appropriate melt viscosity at a high temperature, excellent tackiness and moldability, and excellent various physical properties such as bending strength and interlayer shear strength. , Prepreg and its articles.
  • the present inventors have found that a resin composition for a prepreg containing a specific urethane (meth) acrylate and a polymerization initiator as essential components solves the above-mentioned problems, and has completed the present invention.
  • urethane (meth) acrylate (A) which is a reaction product of polyisocyanate (a1), polyol (a2), and hydroxyalkyl (meth) acrylate (a3), and a polymerization initiator (B) are essential components.
  • a resin composition for prepreg wherein the urethane (meth) acrylate (A) has a viscosity of 0.4 to 900 Pa at 100 ° C. in a dynamic viscoelasticity measurement under the conditions of a temperature rise rate of 15 ° C./min and a frequency of 1 Hz. -Regarding a resin composition for prepreg, which is in the range of s.
  • the resin composition for prepreg and the molded product obtained from the prepreg of the present invention are excellent in bending strength, interlayer shear strength, etc., automobile members, railroad vehicle members, aerospace aircraft members, ship members, housing equipment members, sports It can be suitably used for members, light vehicle members, building civil engineering members, housings for OA equipment, and the like.
  • 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 polymerization initiation.
  • the viscosity of is in the range of 0.4 to 900 Pa ⁇ s.
  • the urethane (meth) acrylate (A) is a reaction product of a polyisocyanate (a1), a polyol (a2), and a hydroxyalkyl (meth) acrylate (a3).
  • the polyisocyanate (a1) is a carbodiimide-modified product of 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, and poly. It preferably contains one or more polyisocyanates selected from methylene polyphenyl polyisocyanates, and more preferably contains polymethylene polyphenyl polyisocyanates. These polyisocyanates (a1) can be used alone or in combination of two or more.
  • polyisocyanates other than the polyisocyanate (a1) can be used in combination.
  • Other polyisocyanates include, for example, a nurate-modified product of diphenylmethane diisocyanate, a bullet-modified product, a urethane imine-modified product, a polyol-modified product modified with a polyol 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), trizine diisocyanate, xylylene diisocyanate, 1,5-naphthalenediocyanate, tetramethylxylene diisocyanate; isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, norbornene diisocyanate, etc.
  • Alicyclic polyisocyanate hexamethylene diisocyanate, nulate-modified product of hexamethylene diisocyanate, burette-modified product, adduct-isocyanate, aliphatic polyisocyanate such as diisocyanate dimerate and the like 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 of the urethane (meth) acrylate (A).
  • the polyol (a2) has an aromatic ring and an oxyalkylene structure, but a hydroxyl group equivalent of 90 to 350 g / eq is preferable because heat resistance is further improved.
  • the polyol (a2) is an alkylene oxide adduct of a bisphenol compound such as an alkylene oxide adduct of bisphenol A, an alkylene oxide adduct of bisphenol S, and an alkylene oxide adduct of bisphenol F; 1,3-bis (2).
  • Alkylene oxide adducts of dihydroxybenzene compounds such as -hydroxyethoxy) benzene and 1,4-bis (2-hydroxyethoxy) benzene; 2'-[(1,1'-biphenyl-4,4'-diyl) bisoxy]
  • Alkylene oxide adducts of biphenol compounds such as bisethanol
  • alkylene oxide adducts of dihydroxynaphthalene compounds, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and the like can be mentioned.
  • an alkylene oxide adduct of bisphenol A and an alkylene oxide adduct of a dihydroxybenzene compound are preferable.
  • These polyols (a2) can be used alone or in combination of two or more.
  • a polyol other than the polyol (a2) can be used in combination as a raw material for the urethane (meth) acrylate (A).
  • a polyester polyol, an acrylic polyol, a polyether polyol, a polycarbonate polyol, a polyalkylene polyol, or the like can be used as the polyol other than the polyol (a2).
  • 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 thereof include meta) acrylate, 2-hydroxy-n-butyl (meth) acrylate, 3-hydroxy-n-butyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate is preferable.
  • These hydroxyalkyl (meth) acrylates (a3) can be used alone or in combination of two or more.
  • the hydroxyalkyl (meth) acrylate (a3) is preferably in the range of 5 to 50% by mass in the resin composition for prepreg.
  • the molar ratio (a2 / a3) of the polyol (a2) to the hydroxyalkyl (meth) acrylate (a3) is preferably 60/40 to 10/90, and 50/50 to 50, because the heat resistance is further improved. 20/80 is more preferable.
  • the molar ratio (NCO / OH) of the isocyanate group (NCO) of the isocyanate compound, which is the raw material of the urethane (meth) acrylate (A), to the hydroxyl group (OH) of the compound having a hydroxyl group is 0.7 to 1.5. Is preferable, 0.8 to 1.3 is more preferable, and 0.8 to 1.0 is further preferable.
  • the viscosity of the urethane (meth) acrylate (A) at 100 ° C. in the dynamic viscoelasticity measurement under the conditions of a temperature rising rate of 15 ° C./min and a frequency of 1 Hz is in the range of 0.4 to 900 Pa ⁇ s, but is 0. If it is less than 4 Pa ⁇ s, resin withering on the surface is likely to occur due to excessive resin flow, and if it is higher than 900 Pa ⁇ s, the resin does not flow easily and voids remain, resulting in deterioration of the appearance and physical properties of the molded product. Occur.
  • the viscosity at 100 ° C. in the dynamic viscoelasticity measurement is preferably in the range of 1 to 450 Pa ⁇ s, and more preferably in the range of 4 to 250 Pa ⁇ s.
  • the gel time of the urethane (meth) acrylate (A) at 150 ° C. is preferably in the range of 10 to 90 seconds because the productivity and the strength of the molded product are further improved.
  • the polymerization initiator (B) 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 per ester compound, and a per. Examples thereof include carbonate compounds and peroxyketal, which can be appropriately selected depending on the molding conditions. These polymerization initiators (B) can be used alone or in combination of two or more.
  • a polymerization initiator having a temperature of 60 ° C. or higher and 100 ° C. or lower for obtaining a 10-hour half-life for the purpose of shortening the molding time. If the temperature is 60 ° C. or higher and 100 ° C. or lower, the life of the prepreg at room temperature is long, and it is preferable that the prepreg can be cured in a short time (within 5 minutes) by heating. 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 (B) is preferably in the range of 0.3 to 3% by mass in the resin composition for prepreg because both the curing characteristics and the storage stability are excellent.
  • the resin composition for prepreg of the present invention preferably contains a radically polymerizable monomer (C) because the tackiness and the fluidity at the time of molding are further improved.
  • Examples of the radically polymerizable monomer (C) include styrene compounds such as styrene, methylstyrene, styrene halide, and divinylbenzene; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl.
  • monofunctional and bifunctional (meth) acrylates having a molecular weight of 150 to 1000 are preferable, and phenoxyethyl (meth) is preferable because the odor in the working environment and the mechanical strength of the molded product are further improved.
  • Acrylate, methylphenoxyethyl (meth) acrylate, benzyl (meth) acrylate, methylbenzyl (meth) acrylate, polytetramethylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate are more preferable, and phenoxyethyl (meth) acrylate. More preferred are meta) acrylates, benzyl (meth) acrylates and ethoxylated bisphenol A di (meth) acrylates.
  • the mass ratio (A / C) of the urethane (meth) acrylate (A) to the radically polymerizable monomer (C) further improves the handleability in a working environment and the mechanical strength of the molded product. It is preferably 95/5 to 50/50, more preferably 95/5 to 70/30.
  • thermosetting resin e.g., a thermosetting resin
  • thermoplastic resin e.g., a thermoplastic resin
  • polymerization inhibitor e.g., a curing accelerator
  • filler e.g., a filler
  • low shrinkage agent e.g., a low shrinkage agent
  • Mold release agent, thickener, thickener, pigment, antioxidant, plasticizer, flame retardant, antibacterial agent, ultraviolet stabilizer, reinforcing material, photocuring agent and the like can be contained.
  • thermosetting resin examples include vinyl ester resin, unsaturated polyester resin, phenol resin, melamine resin, furan resin and the like. Further, 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. Among these, polyamide resin and urethane resin are preferable. In addition, these thermoplastic resins can be used alone or in combination of two or more. Further, the thermoplastic resin can be used by adding it in the form of particles, or by melting and mixing it. When a particulate thermoplastic resin is used, the particle system is preferably 30 ⁇ m or less, more preferably 20 ⁇ m, from the viewpoint of dispersibility in fibers.
  • 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, phenylmorpholine, 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.
  • Alumina, glass powder, aluminum hydroxide, cold water stone, zirconium oxide, antimony trioxide, titanium oxide, molybdenum dioxide, iron powder and the like can be mentioned.
  • 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 acrylic particles, polyamide particles, butadiene rubber and / or particles composed of 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, and acrylic resin-based fine particles such as metal hydroxides, and the prepreg of the present invention can be handled easily. 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 (C), and the reinforcing fiber (C) includes carbon fiber, glass fiber, silicon carbide fiber, alumina fiber, and boron. Examples thereof include organic fibers such as fibers, metal fibers, aramid fibers, vinylon fibers, and tetron fibers. However, carbon fibers or glass fibers are preferable, and carbon fibers are more preferable because a molded product having higher strength and higher elasticity can be obtained. preferable. These reinforcing fibers (C) can be used alone or in combination of two or more.
  • carbon fibers various types such as polyacrylonitrile-based, pitch-based, and rayon-based ones can be used, but among these, polyacrylonitrile-based ones are preferable because high-strength carbon fibers can be easily obtained.
  • the shape of the reinforcing fiber (C) is not particularly limited, and is a reinforcing fiber toe in which the reinforcing fiber filament is converged, a unidirectional material in which the reinforcing fiber toe is aligned in one direction, a woven fabric, or a shortly cut reinforcing fiber.
  • a non-woven fabric or paper made of reinforcing fibers cut into short pieces can be mentioned, but it is preferable to use a unidirectional material as the reinforcing fibers and laminate and mold the fibers because high mechanical properties can be obtained.
  • stitches are made so that sheets such as plain weave, twill weave, satin weave, or non-crimped fabric, in which fiber bundles are aligned in one direction or sheets that are laminated at different angles, are not unraveled. Examples include stitching sheets.
  • the basis weight 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 the fiber width is less uneven and the mechanical properties are improved.
  • a basis weight of 650 g / m 2 or less is preferable because the impregnation of the resin is good.
  • the basis weight is more and more preferably 50 ⁇ 500g / m 2, particularly preferably 50 ⁇ 300g / m 2.
  • the content of the reinforcing fiber (C) in the prepreg of the present invention is preferably in the range of 20 to 85% by mass, preferably in the range of 40 to 80% by mass, because the mechanical strength of the obtained molded product is further improved. More preferable.
  • the prepreg of the present invention uses, for example, a known mixer such as a planetary mixer or a kneader to obtain the polyisocyanate (a1), the polyol (a2), the hydroxyalkyl (meth) acrylate (a3), and a polymerization initiator.
  • Step 1 in which the reinforcing fiber (C) is impregnated with the resin solution mixed with (B), further sandwiched from the upper surface with a release PET film and rolled by a rolling mill to obtain a sheet, which is allowed to stand at room temperature to 50 ° C.
  • step 2 in which the isocyanate group of the polyisocyanate (a1) is reacted with the hydroxyl group of the polyol (a2) and the hydroxyalkyl (meth) acrylate (a3). Further, in step 1, the polyisocyanate (a1), the polyol (a2), and the hydroxyalkyl (meth) acrylate (a3) are partially reacted in advance within a range that does not impair the impregnation property of the fiber. 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 preferable because it is easy to handle for laminating, and a thickness of 1 mm or less is preferable because impregnation of the resin is good. Further, 0.05 to 0.5 mm is more preferable.
  • the prepreg is peeled from the mold release PET film, 8 to 16 prepregs are laminated, and then the mold is preheated to 110 ° C to 160 ° C.
  • a method is used in which the prepreg is cured by charging, molding is performed with a compression molding machine, the prepreg is molded, and the molding pressure of 0.1 to 10 MPa is maintained, and then the molded product is taken out to obtain a molded product. Be done.
  • the molding pressure of 1 to 8 MPa is maintained for a specified time of 1 to 2 minutes per 1 mm of the thickness of the molded product at a mold temperature of 120 ° C. to 160 ° C., and heat compression molding is performed.
  • the manufacturing method is preferable.
  • the molded product obtained from the prepreg of the present invention is excellent in bending strength, interlayer shear strength, etc., automobile members, railroad vehicle members, aerospace aircraft members, ship members, housing equipment members, sports members, light vehicle members, construction It can be suitably used for civil engineering members, housings for OA equipment, and the like.
  • Example 1 Production and evaluation of resin composition for prepreg (1)
  • the resin composition (1) for prepreg obtained above is placed in a polyethylene bag and aged at 45 ° C. for 24 hours, and then a viscoelasticity measuring device (MCR302 manufactured by Anton Pearl Japan Co., Ltd., measuring jig diameter 25 mm).
  • the melt viscoelasticity at 100 ° C. was measured under the conditions of a temperature rising rate of 15 ° C./min and a frequency of 1 Hz.
  • [Making prepreg] After applying the above-mentioned resin composition for prepreg (1) to one side of a release PET film, carbon fibers (“TRK979PQRW” manufactured by Mitsubishi Rayon Co., Ltd.) have a carbon fiber content of 50% by a hand lay-up method.
  • a prepreg (1) was prepared by impregnating the fibers so as to be the same as above, covering with the same release PET film, and then aging under the conditions of 45 ° C. for 24 hours.
  • the molar ratio (NCO / OH) in the raw material excluding carbon fiber in this prepreg (1) was 1.00.
  • the thickness was 0.25 mm.
  • Example 2 Production and evaluation of resin composition for prepreg (2)
  • Additive, hydroxyl equivalent; 164 g / eq) 24 parts by mass, New Pole BPE-40 manufactured by Sanyo Kasei Co., Ltd .: EO adduct of bisphenol A, hydroxyl equivalent; 204 g / eq) 31 parts by mass, phenoxyethyl methacrylate 11 A part and 2.3 parts by mass of a polymerization initiator (“Trigonox 122-C80” manufactured by Chemical Axo Co., Ltd., organic peroxide) are mixed, placed in a
  • Example 3 Production and evaluation of resin composition for prepreg (3)
  • Additive, hydroxyl equivalent; 164 g / eq) 24 parts by mass, New Pole BPE-40 manufactured by Sanyo Kasei Co., Ltd .: EO adduct of bisphenol A, hydroxyl equivalent; 204 g / eq) 31 parts by mass, phenoxyethyl methacrylate 38 A part and 2.5 parts by mass of a polymerization initiator (“Trigonox 122-C80” manufactured by Chemical Axo Co., Ltd., organic peroxide) are mixed, placed in a polymerization initiator (“Tri
  • Example 4 Production and evaluation of resin composition for prepreg (4)
  • Additive, hydroxyl equivalent; 164 g / eq) 24 parts by mass, New Pole BPE-40 manufactured by Sanyo Kasei Co., Ltd .: EO adduct of bisphenol A, hydroxyl equivalent; 204 g / eq) 31 parts by mass, phenoxyethyl methacrylate 71 2.9 parts by mass of the polymerization initiator (“Trigonox 122-C80” manufactured by Chemical Axo Co., Ltd., organic peroxide) is mixed, placed in a polyethylene
  • Example 5 Production and evaluation of resin composition for prepreg (5)
  • Additive, hydroxyl equivalent; 164 g / eq) 24 parts by mass, New Pole BPE-40 manufactured by Sanyo Kasei Co., Ltd .: EO adduct of bisphenol A, hydroxyl equivalent; 204 g / eq) 31 parts by mass, phenoxyethyl methacrylate 92 A part and 3.1 parts by mass of a polymerization initiator (“Trigonox 122-C80” manufactured by Chemical Axo Co., Ltd., organic peroxide) are mixed, placed in
  • Example 6 Production and evaluation of resin composition for prepreg (6)
  • Additive, hydroxyl equivalent; 164 g / eq) 24 parts by mass, New Pole BPE-40 manufactured by Sanyo Kasei Co., Ltd .: EO adduct of bisphenol A, hydroxyl equivalent; 204 g / eq) 31 parts by mass, phenoxyethyl methacrylate 214 A part and 4.3 parts by mass of a polymerization initiator (“Trigonox 122-C80” manufactured by Chemical Axo Co., Ltd., organic peroxide) are mixed, placed in
  • Example 7 Production and evaluation of resin composition for prepreg (7)
  • Additive, hydroxyl equivalent; 164 g / eq) 24 parts by mass, New Pole BPE-40 manufactured by Sanyo Kasei Co., Ltd .: EO adduct of bisphenol A, hydroxyl equivalent; 204 g / eq) 31 parts by mass, NK ester BPE- 41 parts of 100 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd .: ethoxylated bisphenol A dimethacrylate) and 2.5 parts by mass of a polymerization initi
  • Example 8 Production and evaluation of resin composition for prepreg (8)
  • Additive, hydroxyl equivalent; 164 g / eq) 24 parts by mass, New Pole BPE-40 manufactured by Sanyo Kasei Co., Ltd .: EO adduct of bisphenol A, hydroxyl equivalent; 204 g / eq) 31 parts by mass, NK ester BPE- 78 parts of 100 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd .: ethoxylated bisphenol A dimethacrylate) and 2.9 parts by mass of a polymer
  • Example 9 Production and evaluation of resin composition for prepreg (9)
  • New Pole BPE-40 manufactured by Sanyo Kasei Co., Ltd .: EO adduct of bisphenol A, hydroxyl equivalent; 204 g / eq) 14 parts by mass, phenoxyethyl methacrylate 10 2.
  • Example 10 Production and evaluation of resin composition (10) for prepreg
  • Trigonox 122-C80 organic peroxide 2.1 parts by mass is mixed, placed in a polyethylene bag, and aged at 45 ° C. for 24 hours to form a resin composition for prepreg (prepreg resin composition). 10) was obtained.
  • Each of the prepreg resin compositions (1) used in Example 1 was changed to prepreg resin compositions (2) to (10) and (R1) to (R2) in the same manner as in Example 1. Evaluation was performed.
  • Comparative Example 1 is an example in which the melt viscosity at 100 ° C. is lower than the lower limit of 0.4 Pa ⁇ s of the present invention, but it was confirmed that the moldability, the bending strength of the molded product, and the interlayer shear strength are inferior. ..
  • Comparative Example 2 is an example in which the melt viscosity at 100 ° C. is higher than the upper limit of 900 Pa ⁇ s of the present invention, but it was confirmed that the tackability and moldability are inferior.

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Abstract

L'invention concerne une composition de résine pour un préimprégné, comprenant essentiellement de l'uréthane (méth)acrylate (A) qui est un produit de réaction de polyisocyanate (a1), de polyol (a2) et de (méth)acrylate d'hydroxyalkyle (a3), ainsi qu'un initiateur de polymérisation (B), caractérisée en ce que la viscosité à 100 °C de l'uréthane (meth)acrylate (A), lors de la mesure de viscoélasticité dynamique dans des conditions de vitesse d'augmentation de la température de 15 °C/minute et de fréquence de 1 Hz, est dans la plage de 0,4 à 900 Pa·s. La composition de résine pour un préimprégné présente une viscosité à l'état fondu appropriée aux températures élevées et un excellent caractère poisseux et une excellente aptitude au moulage, ce qui permet la production d'un article moulé doté de diverses excellentes propriétés telles que la résistance à la flexion et la résistance au cisaillement intercouches.
PCT/JP2020/042181 2019-11-27 2020-11-12 Composition de résine pour préimprégné, préimprégné et article moulé WO2021106588A1 (fr)

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CN115286947A (zh) * 2022-08-19 2022-11-04 华容县恒兴建材有限公司 一种高固体份、高耐水性抗菌水性聚氨酯涂料及其制备方法
WO2022260093A1 (fr) * 2021-06-08 2022-12-15 日鉄ケミカル＆マテリアル株式会社 Préimprégné de fibres de renforcement unidirectionnelles, feuille de plastique renforcé par des fibres utilisant ce dernier, procédé de production de plastique renforcé par des fibres et plastique renforcé par des fibres

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CN113605595A (zh) * 2021-07-05 2021-11-05 王婧 一种耐火隔热型混凝土砖体

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