WO2018061516A1 - Matériau de moulage de matière plastique renforcée de fibres, son procédé de production, et produit moulé - Google Patents

Matériau de moulage de matière plastique renforcée de fibres, son procédé de production, et produit moulé Download PDF

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Publication number
WO2018061516A1
WO2018061516A1 PCT/JP2017/029710 JP2017029710W WO2018061516A1 WO 2018061516 A1 WO2018061516 A1 WO 2018061516A1 JP 2017029710 W JP2017029710 W JP 2017029710W WO 2018061516 A1 WO2018061516 A1 WO 2018061516A1
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Prior art keywords
fiber
molding material
reinforced plastic
plastic molding
resin composition
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PCT/JP2017/029710
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English (en)
Japanese (ja)
Inventor
晃久 大槻
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新日鉄住金化学株式会社
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Priority to JP2018541985A priority Critical patent/JP6937763B2/ja
Publication of WO2018061516A1 publication Critical patent/WO2018061516A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols

Definitions

  • the present invention relates to a fiber-reinforced plastic molding material that is excellent in handling properties, storage stability, and moldability, and that can significantly reduce molding time, a manufacturing method thereof, and a molded product.
  • Fiber Reinforced Plastics which is a composite of glass fiber and carbon fiber and plastic, has been used for sports / leisure such as tennis rackets, bicycles, fishing rods, etc., taking advantage of its light weight, high strength and high rigidity. It is the material used.
  • fiber reinforced plastic materials has been expanding, and from consumer equipment such as housings for electronic devices such as notebook PCs and tablets, arms for industrial robots, and reinforcing materials for building structures. It has been expanded to industrial equipment.
  • FRP material is produced by impregnating a reinforcing fiber base material with a liquid matrix resin composition and curing it, but as a liquid resin composition impregnating the reinforcing fiber base material, mainly thermosetting epoxy resin etc. Resin is used from the viewpoint of easy impregnation of the resin composition into the fiber substrate.
  • thermosetting resin when a thermosetting resin is used as the matrix resin, it is generally necessary to use a curing agent together. Therefore, the storage load of such a mixture is large, and there is no recyclability like a metal material. Is a problem, and there is a strong need for improvement.
  • thermosetting resin As an FRP molding material, a prepreg in which a thermosetting resin is dissolved in a solvent together with a curing agent, impregnated into a reinforcing fiber base, and kept in a semi-cured (B stage) state is widely used. There was the above-mentioned subject.
  • Patent Document 1 a solid epoxy resin having a softening point of 50 ° C. or higher and a melt viscosity at 150 ° C. of 500 mPa ⁇ s or less by a cone plate viscometer, and a bisphenol type solid epoxy other than the solid epoxy resin
  • An epoxy resin composition is obtained by melt-kneading a resin, tetracarboxylic dianhydride, and a curing accelerator, and then the obtained epoxy resin composition is pulverized into powder, and the powder is reinforced fiber.
  • this method requires the use of two different types of solid epoxy resins in combination, and since a curing agent is used, the curing time is 1 even when a curing accelerator is used as seen in the examples. Since the Tg of the cured matrix resin is also 150 ° C. or less, the heat resistance is insufficient.
  • Patent Document 2 proposes an FRP prepreg impregnated with a low molecular weight non-changeable polyamide resin in contact with a reinforced substrate in a powder state.
  • the polyamide resin used has a low molecular weight, the mechanical properties of FRP are slightly low, and the molding temperature is as high as 290 ° C. Therefore, it takes time to raise and lower the temperature, and the FRP molded product has high productivity. Not suitable for manufacturing.
  • Patent Document 3 discloses a novel high-heat-resistant phenoxy resin having high moldability, impregnating a reinforcing fiber base material with a hot melt method or a solvent method, and applying an FRP prepreg for molding processing. Manufacturing is described.
  • this method requires a special condensed ring structure-containing phenoxy resin, and this condensed ring structure-containing phenoxy resin has a maximum glass transition temperature (Tg) of about 150 ° C. This is insufficient for application to a member used in a difficult environment.
  • Tg maximum glass transition temperature
  • the FRP molding material is required to have a material that can be melted at a relatively low temperature and can greatly reduce the molding time (high moldability and high productivity). It is also required to have high properties (high toughness, high heat resistance, long life) that can be used in harsh environments.
  • Patent Document 4 discloses a phenoxy resin composition capable of causing a crosslinking reaction and improving heat resistance by adding a crosslinking agent to a phenoxy resin or epoxy resin which is a thermoplastic resin and applying heat.
  • a crosslinked phenoxy resin molded body is obtained using this material, no investigation as a material for FRP molding has been made.
  • This phenoxy resin composition also requires a heat treatment of 30 to 60 minutes for the crosslinking reaction for improving Tg, and therefore requires a heat treatment of 30 to 60 minutes.
  • the kneading of the material before the molding There is a problem of how to impregnate the reinforcing fiber base material because the reaction with the inherent crosslinking agent proceeds and gelation easily occurs.
  • JP 2006-232915 A Special table 2012-503893 JP 2010-126694 A WO2014 / 157132
  • An object of the present invention is an FRP molding material that has good moldability, which is a characteristic of phenoxy resin, and can suppress a change in mechanical properties under a high temperature environment, which has been a problem due to a crosslinking reaction.
  • an object of the present invention is to provide an FRP molding material capable of obtaining an FRP molded body having high heat resistance that can be used and excellent mechanical strength at normal temperature and hot temperature, and a method for producing the same.
  • the present inventor has, as a component constituting the matrix resin composition, a phenoxy resin which is a reactive thermoplastic resin as a main component, and an epoxy resin and a compatible resin.
  • a fiber reinforced plastic molding material that uses an aromatic acid anhydride cross-linking agent having high ether groups and ester groups in the molecule, and then pulverizes and blends these matrix resin composition powders onto the reinforcing fiber substrate FRP having a high heat resistance of 160 ° C. or higher at a Tg that can withstand harsh usage environments while maintaining good moldability and storage stability It has been found that a molded body can be obtained.
  • the present invention is a fiber reinforced plastic molding material comprising a matrix resin composition and a reinforced fiber base material, the matrix resin composition comprising a phenoxy resin (A), an epoxy resin (B), and a crosslinking agent (C).
  • the epoxy resin (B) is contained in an amount of 9 to 85 parts by weight with respect to 100 parts by weight of the phenoxy resin (A)
  • the crosslinking agent (C) is at least represented by the following general formulas (1) to (3).
  • One kind of tetracarboxylic dianhydride so that the amount of acid anhydride group of the crosslinking agent (C) is in the range of 0.6 to 1.3 mol with respect to 1 mol of the secondary hydroxyl group of the phenoxy resin (A).
  • the matrix resin composition is solid at room temperature and has a melt viscosity of 3000 Pa ⁇ s or less in any temperature range of 160 ° C. to 220 ° C., and a fiber-reinforced plastic molding material is a matrix.
  • the resin composition containing 20 ⁇ 50 wt%, and a fiber reinforced plastic molding material, wherein the fine powder of the matrix resin composition is adhered to the surface of the reinforcing fiber substrate.
  • X represents O, —CH 2 — or —C (CH 3 ) —.
  • Y represents — (CH 2 ) m —, — (Ph) m —, —Ph—CH 2 —Ph—, or —Ph—C (CH 3 ) 2 —.
  • Ph— represents a phenylene group, and m represents an integer of 1 to 4.
  • the fiber-reinforced plastic molding material preferably satisfies any one or more of the following.
  • the crosslinking agent (C) is soluble in the molten phenoxy resin (A) and the epoxy resin (B).
  • the glass transition temperature (Tg) of the crosslinked cured product of the matrix resin composition that has been crosslinked or cured is 160 ° C. or higher.
  • the glass transition temperature (Tg) of the phenoxy resin (A) is 65 ° C. to 150 ° C.
  • the phenoxy resin (A), the epoxy resin (B) and the cross-linking agent (C) are present in powder form, and the average particle diameter (D50) of the phenoxy resin (A) and the epoxy resin (B) is 10 to 150 ⁇ m. And 1 to 1.5 times the average particle size of the powder of the crosslinking agent (C).
  • the reinforcing fiber base is one or more selected from the group consisting of carbon fiber, boron fiber, silicon carbide fiber, glass fiber and aramid fiber.
  • Another aspect of the present invention is a crosslinked cured product of the above-mentioned fiber-reinforced plastic molding material. It is preferable that it is a crosslinked hardened
  • the present invention also relates to a method for producing a fiber reinforced plastic molding material, wherein the phenoxy resin (A), the epoxy resin (B), and the crosslinking agent (C) are separately pulverized into powders, The powder was mixed to obtain a normal temperature solid matrix resin composition fine powder, which was adhered to the reinforcing fiber substrate by powder coating so that the ratio of the matrix resin composition was in the range of 20 to 50 wt%.
  • the powder coating is preferably powder coating using an electrostatic field.
  • the present invention is a method for producing a fiber-reinforced plastic molded product, characterized in that the fiber-reinforced plastic molding material is molded by heating and pressing.
  • the present invention compared with a fiber reinforced plastic (FRP) molding material using a conventional thermosetting resin, it has excellent storage stability at room temperature and good workability without tackiness.
  • FRP fiber reinforced plastic
  • the FRP molding material of the present invention does not cure and cure the phenoxy resin and the epoxy resin separately by pressure molding by hot press, but simultaneously performs the shaping and the crosslinking and curing of the matrix resin composition at the same time.
  • the resin softening point of the cured product of the matrix resin composition can be within ⁇ 25 ° C. of Tg, it can be demolded at a high temperature of 100 ° C.
  • the process can be greatly shortened and the productivity can be greatly improved.
  • the FRP molded body obtained by thermoforming the FRP molding material of the present invention can be used for curing the matrix resin composition even when disposal is necessary after being used for various applications.
  • the ester bond of the cross-linking agent (C) it is possible to separate the FRP molded product into reinforcing fiber and matrix resin composition by using hydrolysis reaction and recycle without discarding. is there.
  • the mechanism of the crosslinking reaction of the present invention is not clear, but is considered to be the following two-stage reaction.
  • the secondary hydroxyl group of the phenoxy resin reacts with the acid anhydride of the crosslinking agent, and then as the second step, the carboxylic acid group generated by the first step reaction and the epoxy of the phenoxy resin or epoxy resin
  • an esterification reaction of a group or a secondary hydroxyl group occurs and the excellent effect of the present invention is expressed.
  • most of the crosslinking reaction by the secondary hydroxyl group of the phenoxy resin, which is the main component is a small proportion of the epoxy resin being cured by acid anhydride.
  • the matrix resin of the FRP molding material of the present invention is a solvent-free room temperature solid phenoxy resin composition comprising phenoxy resin (A), epoxy resin (B), and crosslinking agent (C) as essential components. , (A), (B), and (C) are adhered to the reinforcing fiber substrate while maintaining the reactivity.
  • the phenoxy resin (A) used as an essential component in the matrix resin composition is solid at room temperature and has a melt viscosity of 1 ⁇ 10 4 Pa ⁇ s or less at 200 ° C. Things are suitable.
  • the melt viscosity is preferably 1 ⁇ 10 2 to 6 ⁇ 10 3 Pa ⁇ s, more preferably 2 ⁇ 10 2 to 3 ⁇ 10 3 Pa ⁇ s. If the melt viscosity exceeds 1 ⁇ 10 4 Pa ⁇ s, the resin fluidity due to heat during the molding process is poor, so the resin does not spread sufficiently in the fiber base material, causing voids, and the mechanical properties of the molded product It will decline.
  • the phenoxy resin (A) is a thermoplastic resin obtained from a condensation reaction of a dihydric phenol compound and an epihalohydrin or a polyaddition reaction of a dihydric phenol compound and a bifunctional epoxy resin. It can be obtained by a known method.
  • the average molecular weight is usually 10,000 to 200,000 as a mass average molecular weight (Mw), preferably 20,000 to 100,000, more preferably 30,000 to 80,000. When Mw is too low, the strength of the molded article is inferior, and when it is too high, the workability and workability tend to be inferior.
  • Mw represents a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.
  • the hydroxyl equivalent (g / eq) of the phenoxy resin (A) is usually 50 to 1000, preferably 100 to 750, particularly preferably 200 to 500. If the hydroxyl equivalent is too low, the water absorption increases due to the increase of hydroxyl groups, which is not preferable because there is a concern that the mechanical properties are lowered. If it is too high, the crosslinking density is insufficient and the heat resistance is lowered.
  • the glass transition point (Tg) of the phenoxy resin (A) is suitably from 65 ° C. to 150 ° C., preferably from 70 ° C. to 100 ° C., more preferably from 80 ° C. to 100 ° C. If the glass transition point is lower than 65 ° C., the moldability is improved, but there is a problem in the storage stability of the powder and the tackiness of the FRP molding material. When the temperature is higher than 150 ° C., the melt viscosity is also increased, and the moldability and the filling property into the fiber are inferior.
  • the glass transition temperature of the phenoxy resin was measured in the range of 20 to 280 ° C. under a temperature rising condition of 10 ° C./min using a differential scanning calorimeter (DSC), and calculated from the peak value of the second scan. It is a numerical value.
  • the phenoxy resin (A) is not particularly limited as long as it satisfies the above physical properties.
  • a bisphenol A type phenoxy resin for example, phenototo YP-50, phenototo YP-50S, phenototo, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) Tote YP-55U
  • bisphenol F type phenoxy resin for example, phenototox FX-316 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • a copolymer type phenoxy resin of bisphenol A and bisphenol F for example, YP manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • other special phenoxy resins for example, YPB-43C, FX-293 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • the epoxy resin (B) is blended together with the phenoxy resin (A).
  • the melt viscosity of the matrix resin composition can be reduced to improve the impregnation property to the reinforcing fiber base, and the strength physical properties of the cured molded product can be improved.
  • the melt viscosity of the matrix resin composition basically depends on the melt viscosity of the phenoxy resin, but is affected by the amount of the epoxy resin and the type of the crosslinking agent.
  • the epoxy resin (B) is preferably a bifunctional or higher functional epoxy resin, such as a bisphenol A type epoxy resin (for example, Epototo YD-011, Epototo YD-7011, Epototo YD-900 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), bisphenol F type Epoxy resin (for example, Nippon Steel & Sumikin Chemical Co., Ltd.
  • a bisphenol A type epoxy resin for example, Epototo YD-011, Epototo YD-7011, Epototo YD-900 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • bisphenol F type Epoxy resin for example, Nippon Steel & Sumikin Chemical Co., Ltd.
  • Epototo YDF-2001 diphenyl ether type epoxy resin (for example, Nippon Steel & Sumikin Chemical Co., Ltd. YSLV-80DE), tetramethylbisphenol F type epoxy resin (for example, Nippon Steel & Sumikin Chemical Co., Ltd.) YSLV-80XY), bisphenol sulfide type epoxy resin (for example, YSLV-120TE manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), hydroquinone type epoxy resin (for example, EPO manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) YDC-1312), phenol novolac type epoxy resin (for example, Epoto YDPN-638 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), orthocresol novolac type epoxy resin (for example, Epoto YDCN-701 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Epoto YDCN) -702, Epot
  • the epoxy resin (B) is more preferably a solid at room temperature, a melting point of 75 ° C. to 145 ° C., and a melt viscosity at 160 ° C. of 1.
  • a crystalline epoxy resin having a viscosity of 0 Pa ⁇ s or less is preferable. If it exceeds 1.0 Pa ⁇ s, the filling property of the matrix resin composition into the reinforcing fiber base is inferior, and the homogeneity of the resulting molded article is inferior. Since the crystalline epoxy resin has a melt viscosity much lower than that of the solid epoxy resin, the impregnation property of the matrix resin can be improved by blending the crystalline epoxy resin. Therefore, a high melt viscosity phenoxy resin can be used.
  • the crosslinking agent (C) used in the present invention has two or more functional groups that react with the secondary hydroxyl group of the phenoxy resin and the epoxy group of the epoxy resin, and is represented by the above general formulas (1) to (3).
  • Acid anhydride One acid anhydride group is understood to have two of the above functional groups because it yields two carboxy groups upon hydrolysis.
  • the acid anhydride as a cross-linking agent forms an ester bond with the secondary hydroxyl group of the phenoxy resin, thereby cross-linking the phenoxy resin three-dimensionally. Therefore, unlike the strong crosslinking such as curing of the thermosetting resin, the crosslinking can be released by a hydrolysis reaction, so that the recyclability is not hindered.
  • the acid anhydride can be used as a crosslinking agent (C) if it is solid at room temperature and has low sublimation properties.
  • C crosslinking agent
  • the heat resistance is imparted to the molded product and the crosslinking density is increased. From this point of view, it is an aromatic tetracarboxylic dianhydride and is at least one aromatic tetracarboxylic dianhydride represented by the general formulas (1) to (3).
  • X is O, —CH 2 —, —C (CH 3 ) —, — (Ph) m —, —Ph—CH 2 —Ph—, or —Ph—C (CH 3 ) 2 —Ph -
  • Ph is a phenylene group
  • m is an integer from 1 to 4.
  • Y represents — (CH 2 ) m —, — (Ph) m —, —Ph—CH 2 —Ph—, or —Ph—C (CH 3 ) 2 —Ph—
  • Ph represents a phenylene group
  • m is an integer from 1 to 4.
  • aromatic tetracarboxylic dianhydrides represented by the general formulas (1) to (3) are compatible with the phenoxy resin and epoxy resin, which are the main components of the matrix resin composition, until the crosslinking agent itself is melted by heat. Since there are many things which are hard to do, the melt viscosity does not increase due to the crosslinking reaction starting from a low temperature.
  • the matrix resin composition melts at the time of molding and becomes sufficiently low in viscosity to start the crosslinking reaction, the matrix fiber impregnation into the reinforcing fiber base material is good and the crosslinking reaction Since it is carried out promptly without excess or deficiency, it does not remain as a foreign substance in the matrix resin in an unreacted state, and the mechanical strength of the molded product starting from the residual crosslinking agent (C) or a decrease in hot mechanical strength, etc. Does not cause a problem.
  • the matrix resin composition which is these mixtures is melt
  • aromatic tetracarboxylic dianhydrides include 4,4'-oxydiphthalic anhydride, 4,5'-oxydiphthalic anhydride, 5,5'-methylenebis (isobenzofuran-1,3-dione) 5,5′-isopropylidenebis (isobenzofuran-1,3-dione), ethylene glycol bisanhydro trimellitate, bis (1,3-dioxoisobenzofuran-5-carboxylic acid) tetramethylene, 4, 5 ′-[1,4-phenylenebis (oxy)] bis (isobenzofuran-1,3-dione), 4,4 ′-(m-phenylenebisoxy) bis (isobenzofuran-1,3-dione), 5,5 ′-[1,3-phenylenebis (oxy)] bis (isobenzofuran-1,3-dione), 3,3 ′-(p-phenylenedioxy) diphthalic anhydride, 5,5- [
  • the reaction of the phenoxy resin (A), the epoxy resin (B) and the cross-linking agent (C) includes an esterification reaction between the secondary hydroxyl group in the phenoxy resin (A) and the acid anhydride group of the cross-linking agent (C). It is crosslinked and cured by the reaction between the carboxyl group generated by this esterification reaction and the epoxy group of the epoxy resin (B).
  • a cross-linked phenoxy resin can be obtained by the reaction of the phenoxy resin (A) and the cross-linking agent (C), but the melt viscosity of the matrix resin composition is reduced by the coexistence of the epoxy resin (B) to provide a reinforcing fiber substrate.
  • the epoxy resin (B) coexists, but the main component is the phenoxy resin (A) which is a thermoplastic resin, and an acid anhydride of the secondary hydroxyl group and the crosslinking agent (C).
  • the esterification reaction with the group is considered to have priority.
  • the FRP molding material of the present invention maintains the moldability and physical properties of the FRP molded product even after long-term storage at room temperature, unlike ordinary FRP molding materials mainly composed of an epoxy resin that is a thermosetting resin. And excellent in storage stability.
  • the phenoxy resin composition of the present invention can also contain a curing accelerator (D).
  • the curing accelerator (D) is not particularly limited as long as it is solid at room temperature and has no sublimation property.
  • a tertiary amine such as triethylenediamine, 2-methylimidazole, 2-phenylimidazole.
  • Imidazoles such as 2-phenyl-4-methylimidazole, organic phosphines such as triphenylphosphine, and tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate.
  • These curing accelerators (D) may be used alone or in combination of two or more. From the viewpoint of the production process of the present invention, it is preferable to use a curing accelerator that is a latent catalyst of imidazoles that is solid at room temperature and has a catalyst activation temperature of 130 ° C. or higher.
  • thermoplastic resin powders such as polyvinyl chloride resin, as long as the good adhesion to the reinforcing fiber base and the physical properties of the molded FRP molded article are not impaired.
  • Powders such as polyvinylidene chloride resin, natural rubber, and synthetic rubber, and other additives such as various inorganic fillers, extender pigments, colorants, antioxidants, and ultraviolet inhibitors can also be blended.
  • the matrix resin composition of the FRP molding material of the present invention comprises phenoxy resin (A), epoxy resin (B) and crosslinking agent (C), which are essential components, and further a curing accelerator (D) and a moisture resistant pigment as necessary.
  • the colorant and other additives are pulverized to a predetermined size, mixed at a predetermined blending ratio, and the fine powder of the matrix resin composition is adhered to the reinforcing fiber substrate in a powder state. can get.
  • the epoxy resin (B) is blended in an amount of 5 to 85 parts by weight with respect to 100 parts by weight of the phenoxy resin (A).
  • the amount is preferably 9 to 83 parts by weight, more preferably 10 to 70 parts by weight. If the compounding amount of the epoxy resin (B) exceeds 85 parts by weight, it takes time to cure the epoxy resin, so that it is difficult to obtain the strength necessary for demolding in a short time, and the recyclability of FRP is lowered.
  • the matrix resin composition is solid at room temperature, and its melt viscosity is 3000 Pa ⁇ s or less in any temperature range of 160 to 220 ° C.
  • the temperature range of 160 to 220 ° C. is a temperature range for performing normal hot press molding.
  • the pressure is preferably 2900 Pa ⁇ s or less, more preferably 2800 Pa ⁇ s.
  • the melt viscosity exceeds 3000 Pa ⁇ s, impregnation of the matrix resin composition into the reinforcing fiber base becomes insufficient during molding by hot pressing, resulting in defects such as internal voids, and the mechanical properties of the FRP are lowered.
  • the melt viscosity increases rapidly when the phenoxy resin (A) and epoxy resin (B) in the matrix resin composition react with the crosslinking agent (C). Therefore, if the reaction with the crosslinking agent (C) is started before the phenoxy resin (A) and the epoxy resin (B) are sufficiently melted, the melt viscosity does not become 3000 Pa ⁇ s or less, and the reinforcing fiber base material is obtained. This results in poor impregnation of the matrix resin and voids in the molded body. Therefore, the melting point of the crosslinking agent (C) is preferably 150 ° C. or higher, and preferably in the range of the molding temperature (160 to 220 ° C.).
  • the blending amount of the crosslinking agent (C) is usually an amount in the range of 0.6 to 1.3 moles of acid anhydride groups with respect to 1 mole of secondary hydroxyl groups of the phenoxy resin (A), preferably 0.9.
  • the amount is in the range of -1.3 mol, more preferably in the range of 0.9-1.1 mol. If the amount of the acid anhydride group is too small, the acid anhydride group reactive to the secondary hydroxyl group of the phenoxy resin (A) is insufficient, so that the crosslink density is low and the rigidity is inferior.
  • the phenoxy resin (A) The acid anhydride becomes excessive with respect to the secondary hydroxyl group of the above, and the unreacted acid anhydride adversely affects the curing characteristics and the crosslinking density.
  • the blending amount of (D) is the sum of the phenoxy resin (A), the epoxy resin (B) and the crosslinking agent (C).
  • the amount is 0.1 to 5 parts by weight per 100 parts by weight.
  • another additive it adjusts suitably so that it may become in the range which does not impair the adhesion
  • a flame retardant is added to the FRP molding material of the present invention.
  • the flame retardant is not particularly limited as long as it is solid at room temperature and has no sublimation property.
  • a non-halogen flame retardant is preferable from the viewpoint of environment and health.
  • an inorganic flame retardant such as calcium hydroxide, And organic and inorganic phosphorus flame retardants such as ammonium phosphates and phosphate ester compounds, nitrogen-containing flame retardants such as triazine compounds, and bromine-containing flame retardants such as brominated phenoxy resins.
  • brominated phenoxy resins and phosphorus-containing phenoxy resins can be preferably used because they can be used as flame retardant / matrix resins.
  • the blending amount of the flame retardant is appropriately selected depending on the type of flame retardant and the desired degree of flame retardancy, but is generally within the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the matrix resin composition. It is preferable to blend in such an extent that the adhesion of the matrix resin composition and the physical properties of FRP are not impaired.
  • each component constituting the matrix resin composition is made into a fine powder and adhered to the reinforcing fiber substrate. Therefore, each component is pulverized into a fine powder.
  • the pulverization is preferably performed by a pulverizing mixer such as a low temperature drying pulverizer (centridry mill), but is not limited thereto.
  • the components may be pulverized and then mixed, or the components may be mixed in advance and then pulverized, but the former is preferred. In this case, the pulverization conditions may be set so that each fine powder has an average particle diameter described later.
  • the powder thus obtained has an average particle size of 10 to 100 ⁇ m, preferably 40 to 80 ⁇ m, more preferably 40 to 50 ⁇ m.
  • the average particle diameter exceeds 100 ⁇ m, the energy when the resin collides with the fiber increases in the adhesion to the reinforcing fiber substrate by powder coating in an electrostatic field, and the adhesion rate to the reinforcing fiber substrate decreases. End up. If the thickness is less than 10 ⁇ m, particles are scattered by the accompanying air flow and the adhesion efficiency is lowered, and fine powder resin floating in the atmosphere may cause deterioration of the working environment.
  • the average particle diameter of the phenoxy resin (A) and the epoxy resin (B) powder is preferably 1 to 1.5 times the average particle diameter of the crosslinking agent (C).
  • the powder of the matrix resin composition is adhered to the reinforcing fiber substrate by a powder coating method, whereby the FRP molding material of the present invention is obtained.
  • a powder coating method There are two types of powder coating methods: fluid coating using a fluidized bed and electrostatic coating using an electrostatic field. Both methods can be used in the present invention. From the viewpoint of uniformity, an electrostatic coating method using an electrostatic field is suitable.
  • the resin adhesion amount of the matrix resin composition powder to the reinforcing fiber base is applied such that the resin ratio (RC) is 20 to 50 wt%, preferably 25% to 40%, more preferably 25% to 30%. If the resin adhesion rate exceeds 50%, mechanical properties such as the tensile and bending elastic modulus of FRP will decrease. If the resin adhesion rate is less than 10%, the amount of resin adhesion will be extremely small. It becomes insufficient, and both the thermophysical property and the mechanical property are lowered.
  • the powder of the matrix resin composition coated with powder is fixed to the reinforcing fiber base by heating and melting, and it is applied to cold coating that heat-fuses after coating the powder and reinforcing fiber that has been heated in advance. Either hot coating or powder coating may be used. By this heating and melting, the matrix resin on the surface of the reinforcing fiber base is melted, thereby improving the adhesion to the base and preventing the coated resin powder from falling off.
  • the matrix resin is concentrated on the surface of the reinforcing fiber base, and does not reach the inside of the reinforcing fiber base like the molded body after the heat and pressure molding.
  • the heating time after the powder coating is not particularly limited as long as the matrix resin composition of the FRP molding material can maintain fluidity and reactivity, but is preferably 1 to 2 minutes. In other words, heat treatment is performed in a much shorter time than during molding, so that phenoxy resin, epoxy resin, etc. are fixed to the reinforced fiber base by thermal fusion without reacting the cross-linking agent and resin, thus preventing powder falling.
  • the melting temperature is 150 to 240 ° C., preferably 160 to 220 ° C., and more preferably 180 to 200 ° C. If the melting temperature exceeds the upper limit, the curing reaction may proceed, and if the melting temperature is lower than the lower limit, thermal fusion will be insufficient, causing matrix resin to fall off or fall off when handling FRP molding materials. To do.
  • Carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, mineral fiber, silicon carbide fiber, etc. can be used as the reinforced fiber base material, but it is necessary to have conductivity when using the electrostatic coating method. Therefore, carbon fiber is preferable.
  • the form of the reinforcing fiber base is not particularly limited, and for example, a unidirectional material, a cloth such as a plain weave or twill, a three-dimensional cloth, a chopped strand mat, a tow composed of several thousand or more filaments, or a nonwoven fabric Etc. can be used. These reinforcing fiber bases can be used alone or in combination of two or more.
  • the FRP molded product of the present invention produced as described above can be easily produced by single or laminating, heating and pressurizing.
  • a metal foil such as aluminum or stainless steel can be laminated between the layers and the outermost layer.
  • the FRP molding material of the present invention can simultaneously perform shaping and cross-linking and curing of the matrix resin by pressure molding by hot pressing.
  • various molding methods such as autoclave molding and hot press molding using a mold are appropriately selected according to the size and shape of the target molding as long as it is heat-pressure molding. Can be implemented.
  • the molding temperature is 150 to 240 ° C, preferably 160 ° C to 220 ° C, more preferably 180 ° C to 200 ° C.
  • the molding temperature exceeds the upper limit temperature in the above range, excessive heat may be applied to cause decomposition of the resin. If the molding temperature is lower than the lower limit temperature, the melt viscosity of the matrix resin composition is high. Adhesive impregnation property becomes worse.
  • the molding time is usually 30 to 60 minutes, but even with a short time of about 10 minutes, the crosslinking agent (C) using the secondary hydroxyl group of the phenoxy resin (A) as the main component is used. By the reaction, strength capable of demolding can be obtained.
  • post-curing at 200 to 250 ° C. for about 30 to 60 minutes is preferable.
  • the heat resistance of the matrix resin composition is greatly increased as compared with that before molding due to the crosslinking reaction utilizing the secondary hydroxyl group of the phenoxy resin, and a molded product having a Tg of 160 ° C. or higher can be obtained.
  • the softening point of the cured product of the matrix resin composition is generally within ⁇ 25 ° C. from Tg, for example, in the hot press molding using a mold, the demolding temperature of the molded product from the mold is the matrix resin composition It is possible to be in the range of ⁇ 30 ° C. or lower from the Tg of the cured product, preferably from ⁇ 35 ° C. or lower, more preferably from Tg to ⁇ 40 ° C.
  • a softening point shows the temperature of the inflexion point where the storage elastic modulus (E ') measured by DMA of a matrix resin hardened
  • the cured product of the fiber-reinforced plastic molding material of the present invention is obtained by heat-curing the FRP molding material, and has developed the above-mentioned crosslinking.
  • the cured product includes a cured product of a matrix resin in the upper fiber reinforced plastic molding material and a reinforced fiber base material, which are firmly bonded to give characteristics such as a predetermined strength. And it is good that the glass transition temperature of the crosslinked hardened
  • the method for producing a fiber-reinforced plastic molding of the present invention is to cure and mold the above-mentioned fiber-reinforced plastic molding material by heating and pressing.
  • C-2) 4,4′-oxydiphthalic anhydride (acid anhydride equivalent: 153, melting point: 225 ° C., OPDA)
  • melt viscosity The melt viscosity of the matrix resin composition, etc. was measured using a rheometer (manufactured by Anton Paar), with a sample size of 4.3 cm3 sandwiched between parallel plates and a temperature of 50 ° C / min. : The melt viscosity at 160 ° C. was measured under the condition of 5%.
  • Average particle diameter The average particle diameter of the matrix resin composition powder, etc. is measured on a volume basis with a laser diffraction / scattering particle diameter distribution measuring device (Microtrack MT3300EX, manufactured by Nikkiso Co., Ltd.). It was.
  • the tack sheet of the preform sheet The surface of the obtained FRP molding material was touched with a finger.
  • Resin ratio (RC:%) (W2-W1) / W2 ⁇ 100
  • W1 Reinforcing fiber weight before adhesion of matrix resin composition
  • W2 Weight of FRP molding material after adhesion of matrix resin composition
  • the resin softening temperature was the temperature at the inflection point at which the storage elastic modulus (E ′) measured by DMA of a similar test piece of the molded cured product was attenuated. The temperature at which demolding is possible after molding and curing is shown.
  • Example 1 (A-1) as the phenoxy resin (A), (B-1) as the epoxy resin (B), and (C-1) as the crosslinking agent (C) were pulverized and classified to obtain an average particle diameter D50 of 80 ⁇ m (A , B, and C have the same average particle size) and are dry blended in the proportions (parts by weight) shown in Table 1 and carbon fiber (STANDARD Modulus type HTS40 3K, manufactured by Toho Tenax Co., Ltd.).
  • the resulting plain-woven reinforced fiber base material was subjected to powder coating in an electrostatic field under conditions of an electric charge of 70 kV and a spraying air pressure of 0.32 MPa. Thereafter, the resin was heat-fused by heating at 170 ° C. for 1 minute in an oven to obtain an FRP molding material.
  • the resin ratio (RC) of the obtained FRP molding material was 27%.
  • Various physical properties of the FRP molding material and FRP cured product thus obtained were measured. These results are shown in Table 1.
  • the fiber reinforced plastic molding material of the present invention is a fiber reinforced plastic (FRP) material, such as the body and body of a transport device such as an automobile or an aircraft device, the housing of an electronic device such as a notebook PC or tablet, an industrial robot, etc. It can be used in a wide range of fields, such as sports and leisure fields such as armrests, reinforcing materials for building structures, and fishing rods and road bike bodies.
  • FRP fiber reinforced plastic

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  • Inorganic Chemistry (AREA)
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Abstract

La présente invention concerne un matériau de moulage de matière plastique renforcée de fibres (FRP) qui fait preuve d'une bonne aptitude au moulage, qui est caractéristique des résines phénoxy, tout en étant apte à supprimer les changements dans les caractéristiques mécaniques dans les environnements de température élevée, qui était un problème causé par les réactions de réticulation. Le matériau de moulage de matière plastique renforcée de fibres est caractérisé en ce que : une composition de résine formant matrice contient une résine phénoxy (A), une résine époxy (B) et un agent de réticulation (C) comme constituants essentiels, l'agent de réticulation (C) est un dianhydride d'acide tétracarboxylique spécifique et est contenu sous une quantité telle que la quantité des groupes anhydrides d'acide dans l'agent de réticulation (C) se situe dans la plage de 0,6 à 1,3 mole par rapport à 1 mole des groupes hydroxyle secondaires dans la résine phénoxy (A) ; la composition de résine formant matrice est solide à la température normale et présente une viscosité à l'état fondu de 3 000 Pa•s ou moins à n'importe quelle température située dans la plage de 160 à 220 °C ; et une fine poudre de la composition de résine formant matrice adhère à la surface d'un substrat de fibre de renfort.
PCT/JP2017/029710 2016-09-28 2017-08-21 Matériau de moulage de matière plastique renforcée de fibres, son procédé de production, et produit moulé WO2018061516A1 (fr)

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JP2022022762A (ja) * 2020-07-06 2022-02-07 株式会社イノアックコーポレーション 繊維強化樹脂成形体とその製造方法

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WO2004060981A1 (fr) * 2002-12-27 2004-07-22 Nitto Boseki Co., Ltd. Procede de production de plastique thermoplastique renforce par des fibres et plastique thermoplastique renforce par des fibres
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