WO2011034040A1 - バインダー組成物、強化繊維基材、プリフォームおよび繊維強化複合材料とその製造方法 - Google Patents
バインダー組成物、強化繊維基材、プリフォームおよび繊維強化複合材料とその製造方法 Download PDFInfo
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- WO2011034040A1 WO2011034040A1 PCT/JP2010/065790 JP2010065790W WO2011034040A1 WO 2011034040 A1 WO2011034040 A1 WO 2011034040A1 JP 2010065790 W JP2010065790 W JP 2010065790W WO 2011034040 A1 WO2011034040 A1 WO 2011034040A1
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- reinforced composite
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- preform
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- 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
- C08J5/248—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using pre-treated fibres
-
- 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
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
-
- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
- C08K5/435—Sulfonamides
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
- B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
- B29C70/48—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs and impregnating the reinforcements in the closed mould, e.g. resin transfer moulding [RTM], e.g. by vacuum
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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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/31728—Next to second layer of polyamide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/30—Woven fabric [i.e., woven strand or strip material]
- Y10T442/3179—Woven fabric is characterized by a particular or differential weave other than fabric in which the strand denier or warp/weft pick count is specified
- Y10T442/3195—Three-dimensional weave [e.g., x-y-z planes, multi-planar warps and/or wefts, etc.]
Definitions
- the present invention relates to a fiber reinforced composite material and a method for producing the same, and a preform, a reinforced fiber base material, and a binder composition used for the fiber reinforced composite material.
- Fiber reinforced composite materials consisting of carbon fiber, glass fiber and other reinforcing fibers and epoxy resins, phenolic resins and other thermosetting resins are lightweight, but have excellent mechanical properties such as strength and rigidity, heat resistance and corrosion resistance. Therefore, it has been used in many fields such as aircraft, spacecraft, automobiles, railway vehicles, ships, civil engineering and construction equipment. In particular, in applications that require high performance, a fiber-reinforced composite material using continuous reinforcing fibers is used. Carbon fibers excellent in specific strength and specific elastic modulus are used as reinforcing fibers, and epoxy resins excellent in mechanical properties and adhesion to carbon fibers are often used as matrix resins.
- Fiber reinforced composite materials are manufactured by various methods, but a resin, a transfer resin, and a fiber reinforced composite material are obtained by injecting a liquid thermosetting resin composition into a reinforced fiber base placed in a mold and heat curing. Molding (Resin Transfer Molding, hereinafter abbreviated as RTM) has recently attracted attention as a low-cost molding method with excellent productivity.
- RTM Resin Transfer Molding
- a preform is prepared by processing the reinforcing fiber base into a shape close to the desired composite material, and after the preform is placed in the mold, a liquid thermosetting resin is placed in the mold. Is often injected.
- a method of creating a three-dimensional braid from reinforcing fibers and a method of stacking and stitching reinforcing fiber fabrics.
- a method of laminating and shaping a sheet-like substrate such as a reinforced fiber fabric using a hot-melt binder (also called a tackifier) is known.
- thermoplastic resin As the hot-melt binder, a resin composition that does not have tackiness at room temperature but softens at high temperature and has adhesiveness is used.
- thermosetting resin As the hot-melt binder, as described in Patent Document 1, both a thermoplastic resin and a thermosetting resin can be applied.
- thermoplastic resin When a thermoplastic resin is used as a hot-melt binder, the glass transition temperature or melting point of the thermoplastic resin is relatively high, so a very high temperature is required to heat-bond the reinforcing fiber substrates together. Sex is inferior.
- thermosetting resin When a thermosetting resin is used as a hot-melt binder, there are a type in which the binder alone is curable (Patent Documents 2 to 4) and a type in which the binder alone is not curable (Patent Documents 5 to 6). is there.
- the former is excellent in that it can be cured without depending on the liquid thermosetting resin, and the latter is excellent in storage stability.
- a fiber reinforced composite material using a thermosetting resin such as an epoxy resin as a matrix resin generally has a lower fracture toughness than a thermoplastic resin.
- a thermosetting resin such as an epoxy resin as a matrix resin
- improvement in impact resistance has been a major issue because excellent impact resistance is required against tool dropping during assembly and impact of a kite during operation.
- Fiber reinforced composite materials generally have a laminated structure, and when an impact is applied thereto, high stress is generated between the layers, and cracks are generated. In order to suppress the generation of cracks, it is effective to increase the plastic deformation ability of the thermosetting resin, and as a means for that, it is effective to blend a thermoplastic resin having an excellent plastic deformation ability.
- thermoplastic resin As a method of blending a thermoplastic resin, various studies have been made in the prepreg method, which is one of the molding methods of fiber-reinforced composite materials. For example, there is a method of using a high toughness thermosetting resin obtained by dissolving a thermoplastic resin in a thermosetting resin as a matrix resin (see Patent Documents 7 to 8). However, when the thermoplastic resin is blended with the thermosetting resin, the viscosity is remarkably increased. Therefore, the content of the thermoplastic resin is limited, and is not particularly suitable for an RTM having a limitation on the viscosity of the matrix resin.
- thermoplastic resin or an elastomer exists between layers where cracks easily occur.
- This technique can also be applied to RTM by applying the binder technology described above.
- the binder component exists between the layers.
- thermoplastic resin has a problem that the glass transition temperature or melting point is high and the processing temperature is high. Therefore, a thermosetting resin can be blended with the thermoplastic resin to adjust the processing temperature (Patent Documents 9 to 10).
- a thermosetting resin can be blended with the thermoplastic resin to adjust the processing temperature (Patent Documents 9 to 10).
- the solubility of the binder may change due to variations in molding conditions, particularly temperature and heating rate, and it is difficult to stably develop the same toughness.
- An object of the present invention is a binder composition that is excellent in impact resistance, exhibits stable physical properties against fluctuations in molding conditions, and can produce a fiber-reinforced composite material suitable for a member such as an aircraft primary structure by RTM. It is to provide an article, a reinforcing fiber base and a preform.
- the present invention is a binder composition
- a binder composition comprising the following components [A] and [B]; [A] an amorphous polyamide having a dicyclohexylmethane skeleton in the molecule and a glass transition temperature of 140 ° C. or higher; [B] A sulfonamide compound.
- a preferred embodiment of the binder composition is to satisfy the following conditions (I) and (II); Condition (I) The glass transition temperature of the binder composition is 40 to 90 ° C .; Condition (II) 10 parts by mass of the binder composition is blended with 100 parts by mass of an epoxy resin containing 40% by mass or more of N, N, N ′, N′-tetraglycidyl-4,4′-methylenedianiline, After stirring at a temperature of 1 ° C. for 1 hour, when using a transmission observation type optical microscope and observing at a magnification of 5 times, a solid content with a particle size of 10 ⁇ m or more was observed, and the solid content was filtered off. Is less than 5 times the viscosity of the epoxy resin.
- a more preferred embodiment is a binder composition containing 40 to 80% by mass of component [A] and 10 to 40% by mass of component [B].
- component [A] a polyamide containing 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane units is most preferable.
- component [B] toluenesulfonamide is most preferable.
- the binder composition is a particle having a volume average particle diameter of 30 to 200 ⁇ m.
- the reinforcing fiber substrate of the present invention includes the binder composition of the present invention and reinforcing fibers.
- the reinforcing fiber is a warp composed of a carbon fiber bundle, an auxiliary warp of a fiber bundle composed of glass fibers or chemical fibers arranged in parallel to the warp, and glass fibers or chemical fibers arranged so as to be orthogonal thereto.
- the reinforcing fiber base material is laminated, and the binder composition is present between layers of the reinforcing fiber base material.
- the fiber-reinforced composite material of the present invention includes the preform and a cured product of an epoxy resin.
- the preform is placed in a cavity formed by a rigid open mold and a flexible film, the cavity is sucked with a vacuum pump, and atmospheric pressure is used.
- the method includes a step of injecting a liquid thermosetting resin composition from the inlet into the cavity and impregnating the preform, and then heat-curing the liquid thermosetting resin composition.
- the binder composition of the present invention is insoluble in a thermosetting resin, particularly an epoxy resin, which is a matrix resin of a fiber reinforced composite material, and therefore, changes in mechanical properties due to changes in molding conditions, particularly temperature and heating rate, are small. Productivity of the fiber reinforced composite material can be improved.
- the fiber reinforced composite material using the binder composition of the present invention has excellent impact resistance against external impact and has high post-impact compressive strength (CAI), it is an aircraft member, spacecraft member, automobile member and ship. It can use suitably for structural members, such as a member.
- CAI post-impact compressive strength
- the binder composition of the present invention contains at least the following components [A] and [B].
- the heat of crystal fusion is 5 cal / g or less.
- the heat of crystal melting is preferably 1 cal / g or less.
- a polyamide containing a diamine unit having a dicyclohexylmethane skeleton as an essential component is used.
- diamines include 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and 4,4'-diaminodicyclohexylmethane.
- diamine in particular, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane can be preferably used because a polyamide having an excellent balance of physical properties can be obtained. It is also possible to copolymerize a small amount of a diamine having one cyclohexane ring in the molecule, such as 1,3-bisaminomethylcyclohexane and 1,4-bisaminomethylcyclohexane.
- An amorphous polyamide can be obtained by polymerizing such diamine and dicarboxylic acid.
- Preferred dicarboxylic acids include adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid and the like. Polymerization is preferably performed at a ratio of 95 to 30% by mass of diamine and 5 to 70% by mass of dicarboxylic acid.
- Such amorphous polyamide is required to have a glass transition temperature of 140 ° C. or higher measured by a differential scanning calorimeter (DSC) in accordance with JIS K7121 (1987).
- the glass transition temperature is preferably 150 ° C. or higher.
- the amorphous polyamide can be synthesized using the diamine, or a commercially available polyamide can be used.
- Commercially available products are “Novamid” (registered trademark) (manufactured by Mitsubishi Engineering Plastics), “Gramide” (registered trademark) (manufactured by Toyobo Co., Ltd.), “Grillamide” (registered trademark) TR (MS Chemie Japan) And “Trogamide” (registered trademark) T (manufactured by Daicel-Evonik Co., Ltd.).
- the binder composition of the present invention satisfies the above condition (I), that is, the glass transition temperature of 40 to 90 ° C. so that the shape of the preform can be fixed at a relatively low temperature, for example, in the range of 60 to 100 ° C. It is preferable.
- the glass transition temperature of the binder composition was measured according to JIS K7121 (1987).
- the glass transition temperature of the binder composition is preferably in the range of 45 to 85 ° C, more preferably in the range of 50 to 80 ° C.
- transportation or storage at room temperature causes the binder compositions to be fused together, so that temperature control is required and costs are increased.
- the glass transition temperature of the binder composition exceeds 90 ° C., it is not preferable because the shape of the preform cannot be fixed at a relatively low temperature, the workability is lowered, and the cost is increased.
- the glass transition temperature of the binder composition can be adjusted to 40 to 90 ° C. by blending the sulfonamide compound of component [B].
- Preferred sulfonamide compounds include, for example, o-toluenesulfonamide, p-toluenesulfonamide, N-ethyl-o / p-toluenesulfonamide, N-cyclohexyl-p-toluenesulfonamide, p-ethylbenzenesulfonamide, N- Examples thereof include n-butylbenzenesulfonamide.
- Such sulfonamide compounds can be used alone or in combination of two or more.
- toluenesulfonamides typified by o-toluenesulfonamide, p-toluenesulfonamide, and mixtures thereof are preferably used because they have excellent compatibility with the amorphous polyamide as the constituent element [A]. Can do.
- the content of the component [A] is preferably 40 to 80% by mass, more preferably 45 to 75% by mass.
- the content of component [B] is preferably 10 to 40% by mass, more preferably 15 to 35% by mass.
- Fiber reinforced composite materials generally have a laminated structure, and when an impact is applied thereto, high stress is generated between the layers, resulting in peeling damage. Therefore, when improving the impact resistance against an external impact, the toughness of the resin layer forming the interlayer of the fiber reinforced composite material may be improved.
- a thermosetting resin particularly an epoxy resin, which is a brittle material is often used.
- a technique for blending a thermoplastic resin is known.
- RTM since the matrix resin is desired to have a low viscosity, it is not preferable to previously dissolve a thermoplastic resin that significantly increases the viscosity in the matrix resin.
- thermoplastic resin when the thermoplastic resin is dissolved in the matrix resin, it is preferably dissolved during molding.
- solubility of the thermoplastic resin changes due to variations in molding conditions, particularly temperature and temperature rise rate, it is difficult to stably develop toughness.
- aircraft members and the like are often large and have complicated shapes, and when such members are molded, the molding conditions are likely to vary.
- thermoplastic resin soluble in the matrix resin in RTM, the thermoplastic resin may be dissolved in the matrix resin during the resin injection process. In that case, the viscosity of the matrix resin increases, and impregnation failure may occur.
- the binder composition is required to be difficult to dissolve in the epoxy resin that is frequently used as the main component of the matrix resin.
- the binder composition of the present invention satisfies the condition (II). That is, 10 parts by mass of the binder composition of the present invention is blended with 100 parts by mass of the epoxy resin, and after stirring for 1 hour at a temperature of 180 ° C., the solid content as the binder composition remains and remains.
- the viscosity of the filtrate obtained by filtering the solid content to be filtered is preferably 5 times or less than the viscosity of the epoxy resin before blending.
- the solid content of the binder composition having a particle size of 10 ⁇ m or more is observed when the mixture after stirring is observed with a transmission optical microscope at a magnification of 5 times.
- the particle size is obtained by measuring and averaging the particle size of at least 20 solids from an optical microscope image.
- the shape of solid content is non-spherical, let the length of the part with the longest diameter be the particle size of the solid content.
- the epoxy resin used for a measurement is an epoxy resin used as a matrix resin.
- N, N, N ′, N′-tetraglycidyl-4,4′-methylene is used as the epoxy resin. Measure with dianiline. It should be noted that other preferable epoxy resin, which will be described later, may be mixed. In that case, 40 mass of N, N, N ′, N′-tetraglycidyl-4,4′-methylenedianiline is contained in the epoxy resin mixture. % Or more is necessary. In addition, no epoxy resin curing agent is added during the measurement.
- the viscosity of the filtrate is not more than 5 times the viscosity of the epoxy resin before blending, the viscosity of the epoxy resin after mixing with the binder composition is much less than before mixing with the binder composition It means not rising.
- the solid content of the binder composition remains and the viscosity of the epoxy resin does not increase means that the binder composition is hardly dissolved in the epoxy resin. .
- the molding conditions vary depending on the degree of dissolution, and thereby the mechanical properties of the resulting fiber-reinforced composite material. May change.
- the viscosity of the filtrate is higher than 5 times the viscosity of the epoxy resin before blending, poor resin impregnation may occur during the RTM resin injection process.
- the amorphous polyamide of the constituent element [A] of the present invention has very poor compatibility with the epoxy resin and is insoluble in the epoxy resin alone, so the content of the constituent element [B] is 40% by mass or less. Therefore, the binder composition can satisfy the condition (II).
- the component [A] is a polyamide containing 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane units, this tendency becomes remarkable, which is preferable.
- the binder composition of the present invention has a poor compatibility with the epoxy resin and is compatible with the epoxy resin by mixing the component [B] with the component [A] having a high glass transition temperature. And that the glass transition temperature of the binder composition can be adjusted to an appropriate range.
- thermoplastic elastomer in the binder composition, can be further blended as the component [C] within a range not impairing the effects of the present invention.
- the thermoplastic elastomer is a block copolymer having a hard segment component and a soft segment component in the molecule, has a glass transition temperature below room temperature and a melting point above room temperature, and flows when heated above the melting point. It is a polymer that exhibits rubber elasticity when cooled to a temperature between the glass transition temperature and the melting point.
- thermoplastic elastomer By blending a thermoplastic elastomer into the binder composition, the deformability of the binder composition and the adhesion to the reinforcing fibers at the temperature at which the shape of the preform is fixed, for example, in the range of 60 to 100 ° C., is improved. In addition, there is an advantage that the compression strength after impact (CAI) of the obtained fiber-reinforced composite material is improved.
- CAI compression strength after impact
- thermoplastic elastomer one or more selected from thermoplastic elastomers such as urethane elastomer, polyester elastomer, and polyamide elastomer can be used.
- thermoplastic elastomers such as urethane elastomer, polyester elastomer, and polyamide elastomer
- polyamide-based thermoplastic elastomers are excellent in compatibility with the constituent elements [A] and [B], and are excellent in the balance of physical properties such as heat resistance and toughness, and thus can be suitably used.
- the polyamide-based thermoplastic elastomer is a block copolymer having polyamide such as polyamide 6 and polyamide 12 as a hard segment component and polyester or polyol as a soft segment component.
- polyamide elastomer having a hard segment component of a polyamide based on a polymerized fatty acid or dimer acid is preferably used because of its excellent balance of hydrolyzability, heat resistance and toughness.
- thermoplastic elastomer can be synthesized or commercially available.
- Commercially available products include, for example, “Hytrel” (registered trademark) (manufactured by Toray DuPont), which is a polyester elastomer, “Belprene” (registered trademark) (manufactured by Toyobo), and “PANDEX” (which is a urethane elastomer) ( (Registered trademark) (manufactured by DIC Bayer Polymer Co., Ltd.), "Milactolan” (registered trademark) (manufactured by Nippon Milactolan Co., Ltd.), polyamide elastomer "UBESTA XPA” (registered trademark) (manufactured by Ube Industries) "GRILFLEX” (registered trademark) (manufactured by Ms.
- the TPAE series (made by Fuji Kasei Kogyo Co., Ltd.), which is a polyamide elastomer based on polymerized fatty acid or dimer acid, can be preferably used for the above reasons.
- the content of the thermoplastic elastomer as the constituent element [C] is preferably 5 to 25% by mass, more preferably 7 to 20% by mass.
- the binder composition of the present invention further includes components other than the constituent elements [A], [B] and [C] within a range not impairing the effects of the present invention, for example, antioxidants such as hindered phenol and hindered amine; salicylic acid UV absorbers such as those based on benzophenone and triazine; rubber particles, core-shell type polymer particles; inorganic particles and the like can be appropriately blended.
- antioxidants such as hindered phenol and hindered amine
- salicylic acid UV absorbers such as those based on benzophenone and triazine
- rubber particles, core-shell type polymer particles; inorganic particles and the like can be appropriately blended.
- the form of the binder composition of the present invention a film having a through hole, a tape, a long fiber, a short fiber, a spun yarn, a woven fabric, a knit, a non-woven fabric, a net, a particle and the like can be employed.
- the reinforcing fiber substrate is shaped into a complicated shape. In that case, since it is a particle
- the volume average particle size measured with a laser diffraction / scattering particle size distribution analyzer according to JIS Z8825-1 (2001) is preferably 30 to 200 ⁇ m. More preferably, it is 35 to 180 ⁇ m.
- Partica LA-950V2 manufactured by Horiba, Ltd.
- the resulting particle size distribution assumes that the particles to be measured are spherical.
- the actual shape of the particles is non-spherical (indefinite particles), the resulting particle size distribution is broad.
- the minor axis signal is usually difficult to read, and the obtained particle size distribution is that of the major axis.
- the volume average particle size is set to 30 ⁇ m or more, the particles do not excessively enter the reinforcing fiber base, and the effect of binding the reinforcing fiber base can be efficiently expressed even with a small amount of the binder composition. Further, the fluidity of the particles can be made sufficient, and the handling of the binder composition can be facilitated.
- the volume average particle size to 200 ⁇ m or less, it is possible to prevent waviness when the preform is formed and adversely affect the physical properties of the fiber-reinforced composite material.
- the preparation method is not particularly limited, and various known methods can be used.
- the most economical method is a method of kneading each component at about 150 to 220 ° C. using an extruder, a kneader or the like.
- the obtained binder composition can be pulverized into particles, or processed into a fiber or film form by melt extrusion from a die.
- a method is also possible in which the binder composition is once dissolved in a solvent to prepare a solution, and then the solvent is removed.
- an organic solvent solution is dispersed in water to form an emulsion, the emulsion is heated to volatilize the solvent to form a dispersion, and then filtered to extract the particles.
- the binder composition of the present invention is used as a reinforcing fiber substrate containing the binder composition and reinforcing fibers.
- carbon fiber is preferably used as the reinforcing fiber.
- carbon fibers include acrylic carbon fibers, pitch carbon fibers, and rayon carbon fibers.
- acrylic carbon fibers having high tensile strength are preferably used.
- form of the carbon fiber twisted yarn, untwisted yarn, untwisted yarn and the like can be used, but untwisted yarn or untwisted yarn is preferably used because the balance between moldability and strength characteristics of the fiber reinforced composite material is good.
- the tensile elastic modulus of the carbon fiber is preferably in the range of 200 to 400 GPa from the viewpoint of the characteristics and weight of the molded structural member. When the elastic modulus is lower than this range, the rigidity of the structural member may be insufficient. Conversely, if the elastic modulus is higher than this range, the strength of the carbon fiber tends to decrease.
- a more preferable elastic modulus is in a range of 250 to 370 GPa, and further preferably in a range of 290 to 350 GPa.
- the tensile elastic modulus of the carbon fiber is measured in accordance with JIS R7601-2006.
- the reinforcing fiber substrate is preferably in the form of a sheet.
- the sheet-like fiber substrate is made of carbon fiber alone or a combination of carbon fiber and other inorganic fiber or chemical fiber.
- a unidirectional sheet, a woven fabric, a knit, a braid, a mat, and the like can be used.
- a so-called unidirectional woven fabric is preferably used in that a fiber-reinforced composite material having high mechanical properties and a high volume content of reinforcing fibers can be obtained.
- a unidirectional woven fabric for example, carbon fiber bundles are arranged parallel to each other in one direction as warps, and fiber bundles made of glass fibers or chemical fibers orthogonal to the carbon fibers are used as wefts.
- the fineness means the weight (g) per 1000 m of the fiber bundle, and is expressed by the unit tex.
- the carbon fiber bundle is composed of 6,000 to 70,000 filaments, and the fineness is preferably in the range of 400 to 5,000 tex, more preferably composed of 12,000 to 25,000 filaments, The fineness is 800 to 1,800 tex. If the number and fineness of the carbon fiber filaments are smaller than the above ranges, there are too many intersection points in the woven fabric, and the mechanical properties may be lowered. Conversely, if the number of carbon fiber filaments and the fineness are larger than the above ranges, the number of crossing points in the woven fabric is too small, and the morphological stability and handleability of the woven fabric may be lowered.
- the carbon fiber bundle and the weft are orthogonal, so the carbon fiber bundle is bent.
- the orthogonal warp and glass fiber made of glass fiber or chemical fiber are orthogonal.
- a carbon fiber bundle becomes difficult to bend.
- the fineness of the fiber bundle of glass fiber or chemical fiber forming the auxiliary warp is preferably 20% or less, more preferably 10% or less of the fineness of the carbon fiber bundle.
- the auxiliary warp By setting the fineness of the auxiliary warp to 20% or less of the fineness of the carbon fiber bundle, the auxiliary warp is more easily deformed than the carbon fiber bundle, and a woven fabric can be formed without bending the carbon fiber bundle.
- the lower limit of the fineness of the auxiliary warp is not particularly limited. The smaller the better, the better. However, from the viewpoint of the form stability and production stability of the fabric, it is preferably 0.05% or more of the fineness of the carbon fiber bundle. In addition, if the fineness of the weft forming the woven structure is too large, bending of the carbon fiber bundle may be promoted.
- the fineness of the fiber bundle of glass fiber or chemical fiber forming the weft is preferably 10% or less, more preferably 5% or less of the fineness of the carbon fiber bundle.
- the fineness of the weft is preferably 0.05% or more of the fineness of the carbon fiber bundle from the viewpoint of the form stability and production stability of the fabric.
- the content of the binder composition in the reinforcing fiber base is preferably 5 to 50 g / m 2 , more preferably 7 to 40 g / m 2 in terms of basis weight.
- the content is less than 5 g / m 2, the effect of improving toughness is reduced between layers of the obtained fiber-reinforced composite material.
- the content is more than 50 g / m 2 , only the interlayer is thick, and the volume content of the carbon fiber in the obtained fiber-reinforced composite material is lowered, so that it is thick to express the physical properties necessary for the member.
- a fiber reinforced composite material may be required, and as a result, the weight of the member may increase.
- the binder composition of the present invention may be fused to one side of the reinforcing fiber base or may be fused to both sides, and can be appropriately used.
- a preferred method for fusing the binder composition to the surface of the reinforcing fiber base for example, while the binder composition is measured with an embossing roll and a doctor blade, the binder composition is naturally dropped on the surface of the reinforcing fiber base to form a vibration net.
- the binder composition is supplied to the spray nozzle with a quantitative feeder, and the binder composition is sprayed onto the surface of the reinforcing fiber base using air spray, and then heated by passing through a far-infrared heater.
- a method of fusing the substrate and the reinforcing fiber base is also a method of fusing the substrate and the reinforcing fiber base.
- the binder composition fused on the reinforcing fiber substrate by such a method is scattered in the form of dots, and preferably 80% by volume or more of the binder composition is exposed on the reinforcing fiber substrate. State.
- the binder composition is scattered in the form of dots, it is possible to suppress a decrease in resin injection property in RTM.
- the binder composition works as a spacer to form an appropriate interlayer thickness, and externally Is preferable because it can efficiently absorb the impact from the interlayer.
- the reinforcing fiber base material is laminated and used as a preform.
- a preform in which the binder composition is present between the layers of the reinforcing fiber base by laminating the reinforcing fiber base to which the binder composition of the present invention is applied on at least one surface is preferable.
- reinforcement fiber base materials can be adhere
- this aspect can be processed into a desired shape freely and easily, and can be laminated at any fiber axis angle in order to develop strength, structural materials such as spacecraft, aircraft, railway vehicles, automobiles, ships, etc. It can be particularly preferably used.
- a preform for example, when the shape of the reinforcing fiber base is a three-dimensional blade, it can be used as it is as a preform.
- the shape of a reinforced fiber base material is a strand, after winding a reinforced fiber base material on a mandrel, it can be heated to bond the reinforced fiber strands together to form a preform.
- a preform can be obtained by cutting a sheet-like reinforcing fiber base to which a binder composition has been applied in advance into a predetermined shape, laminating on a mold, and applying appropriate heat and pressure.
- a method of applying appropriate heat and pressure after alternately laminating the sheet-like reinforcing fiber fabric and applying the binder composition of the present invention is adopted. You may do it.
- a press When a preform is produced by applying pressure, a press can be used as a pressurizing means, or a method of pressurizing by atmospheric pressure by bagging and sucking the inside with a vacuum pump can be used.
- the heating temperature when producing the preform is preferably 60 to 150 ° C. When the heating temperature is less than 60 ° C., the layers forming the preform may not be sufficiently fixed. When the heating temperature exceeds 150 ° C., the binder composition may be crushed too much to block the flow path of the thermosetting resin, and an unimpregnated portion may be generated in the resulting fiber reinforced composite material.
- the preform may include a foam core, a honeycomb core, a metal part, and the like.
- the preform of the present invention is suitably used for RTM. After the preform is placed in the mold, a liquid thermosetting resin composition is injected into the mold, the preform is impregnated with the thermosetting resin composition, and cured to obtain a fiber-reinforced composite material. Obtainable.
- the mold used for RTM may be a closed mold made of a rigid body, or may be a rigid open mold and a flexible film (bag). In the latter case, the preform can be placed between the rigid open mold and the flexible film.
- the rigid material various existing materials such as metals such as steel and aluminum, fiber reinforced plastic (FRP), wood and plaster are used. Nylon, fluorine resin, silicone resin, or the like is used as the material for the flexible film.
- thermosetting resin composition In the case of using a rigid closed mold, a preform is placed in a cavity formed by a rigid mold, the mold is pressurized and clamped, and then a liquid thermosetting resin composition is injected from the injection port into the cavity. Inject the object under pressure.
- a suction port may be provided separately from the injection port, and the suction port may be connected to a vacuum pump to suck the cavity.
- the degree of vacuum is preferably ⁇ 90 kPa or less. When the degree of vacuum is higher than ⁇ 90 kPa, voids are generated in the obtained fiber-reinforced composite material, and the mechanical properties may be lowered.
- the degree of vacuum is preferably ⁇ 90 kPa or less. When the degree of vacuum is higher than ⁇ 90 kPa, voids are generated in the obtained fiber-reinforced composite material, and the mechanical properties may be lowered.
- the liquid thermosetting resin composition is composed of a liquid resin mainly composed of a monomer component and a curing agent having a function of curing the monomer component by three-dimensional crosslinking.
- Such a liquid resin is preferably an epoxy resin because of its excellent mechanical properties and adhesiveness with reinforcing fibers.
- Epoxy resins include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, tetrabromobisphenol A diglycidyl ether, bisphenol AD diglycidyl ether, 2,2 ′, 6,6′-tetramethyl-4,4′-biphenol Diglycidyl ether, N, N, O-triglycidyl-m-aminophenol, N, N, O-triglycidyl-p-aminophenol, N, N, O-triglycidyl-4-amino-3-methylphenol, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, N, N, N ′, N′-tetraglycidyl-4,4′-methylenedianiline, N, N, N ′, N′- Tetraglycidyl-2,
- N, N, N ′, N′-tetraglycidyl-4,4′-methylenedianiline is preferably used because it has a high effect of increasing heat resistance and is excellent in chemical resistance of a cured product.
- N, N, O-triglycidyl-p-aminophenol has an extremely low viscosity among epoxy resins having an effect of improving heat resistance, and has an effect of reducing the viscosity of the thermosetting resin composition. It can be preferably used.
- the trifunctional or higher functional epoxy resin is preferably contained in an amount of 40 to 85% by mass, more preferably 45 to 75% by mass in 100% by mass of the total epoxy resin.
- a bifunctional epoxy resin such as N, N-diglycidylaniline or N, N-diglycidyl-o-toluidine having a diglycidylaniline skeleton has a low viscosity.
- the content of the bifunctional epoxy resin is preferably 10 to 55% by mass, more preferably 15 to 50% by mass in 100% by mass of the total epoxy resin.
- the content of the bifunctional epoxy resin By setting the content of the bifunctional epoxy resin to 10% by mass or more, the viscosity of the obtained thermosetting resin composition is lowered, the elastic modulus of the obtained cured product is increased, and the obtained fiber-reinforced composite material Compression characteristics can be improved.
- the content of the bifunctional epoxy resin is 55% by mass or less, the heat resistance and fracture toughness of the obtained cured product can be improved.
- Curing agents that can cure these epoxy resins include aliphatic polyamines, aromatic polyamines, dicyandiamides, polycarboxylic acids, polycarboxylic acid hydrazides, acid anhydrides, polymercaptans, polyphenols, and the like compounds that undergo a quantitative reaction. , Imidazole, Lewis acid complex, and onium salts. When a compound that undergoes a stoichiometric reaction is used, a curing accelerator such as imidazole, Lewis acid complex, onium salt, phosphine, and the like may be blended.
- aliphatic polyamines When molding fiber reinforced composite materials by RTM, aliphatic polyamines, aromatic polyamines, acid anhydrides or imidazoles are suitable as curing agents.
- aromatic polyamines are most suitable, and liquid ones are preferably used.
- liquid aromatic polyamine examples include diethyltoluenediamine (a mixture containing 2,4-diethyl-6-methyl-m-phenylenediamine and 4,6-diethyl-2-methyl-m-phenylenediamine as main components), 2,2'-diethyl-4,4'-methylenedianiline, 2,2'-isopropyl-6,6'-dimethyl-4,4'-methylenedianiline, 2,2 ', 6,6'tetraisopropyl Examples thereof include alkyl group derivatives of diaminodiphenylmethane such as -4,4'-methylenedianiline and polyoxytetramethylene bis (p-aminobenzoate). Of these, diethyltoluenediamine having low viscosity and excellent physical properties such as glass transition temperature of the obtained cured product can be preferably used.
- the liquid aromatic polyamine can be mixed with a solid aromatic polyamine as long as no crystals are precipitated.
- Solid aromatic polyamines such as 3,3'-diaminodiphenylsulfone and 4,4'-diaminodiphenylsulfone can provide cured products with excellent heat resistance and elastic modulus. Furthermore, they have linear expansion coefficient and heat resistance due to moisture absorption. Can be preferably used since the decrease in the resistance is small.
- diaminodiphenyl sulfone has a strong crystallinity, and even if it is mixed with liquid aromatic polyamine at a high temperature to form a liquid, it tends to precipitate as a crystal in the cooling process.
- diaminodiphenyl sulfone two isomers of diaminodiphenyl sulfone and liquid aromatic polyamine are used.
- the content of diaminodiphenylsulfone is preferably 10 to 40% by mass and more preferably 20 to 35% by mass in 100% by mass of the wholly aromatic amine.
- the content is 10% by mass or more, the effect of the cured product as described above can be easily obtained, and if the content is 40% by mass or less, it is preferable to suppress the precipitation of crystals.
- the mass ratio of the two is preferably 10:90 to 90:10, The closer the ratio between the two, the higher the effect of suppressing crystal precipitation.
- the compounding amount of the epoxy resin and the curing agent is within the range of 0.7 to 1.3 active hydrogen in the curing agent with respect to one epoxy group contained in all epoxy resins.
- the amount is preferably in the range of 0.8 to 1.2.
- active hydrogen refers to a highly reactive hydrogen atom bonded to nitrogen, oxygen or sulfur in an organic compound.
- the aromatic polyamine When an aromatic polyamine is used as the curing agent, the aromatic polyamine is generally known to have a slow crosslinking reaction, and therefore a curing accelerator may be added to accelerate the reaction.
- a curing accelerator such as a tertiary amine, a Lewis acid complex, an onium salt, an imidazole, or a phenol compound can be used.
- t-Butylcatechol is suitable for RTM because it has a small curing acceleration effect at the temperature (50 to 80 ° C.) when the resin composition is injected, and the curing acceleration effect increases in a temperature range of 100 ° C. or higher.
- the content when the curing accelerator is blended is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and still more preferably 1 to 1 part by mass with respect to 100 parts by mass of the total epoxy resin. 2.5 parts by mass. If the content of the curing accelerator is out of this range, it is not preferable because the balance between the uncured handling time and the reaction rate at high temperature is lost.
- the viscosity of the liquid thermosetting resin composition is measured at 70 ° C.
- the viscosity within 5 minutes from the start of the measurement is preferably 300 mPa ⁇ s or less, more preferably 200 mPa ⁇ s or less.
- the viscosity was measured according to the “cone-plate rotational viscometer viscosity measurement method” in JIS Z8803 (1991), an E-type viscometer equipped with a standard cone rotor (1 ° 34 ′ ⁇ R24) (Toki Sangyo ( Using a TVE-30H), the measurement is performed at a rotation speed of 50 rotations / minute.
- the impregnation property of the thermosetting resin composition may be insufficient.
- the lower limit of the viscosity at 70 ° C. is not particularly limited, and the lower the viscosity, the easier the injection and impregnation of the thermosetting resin composition in RTM.
- thermosetting resin composition After the liquid thermosetting resin composition is injected and impregnated, heat curing is performed at a temperature in the range of 50 to 200 ° C. for a time in the range of 0.5 to 10 hours.
- the heating condition may be one stage or may be a multistage condition in which a plurality of heating conditions are combined.
- the initial curing is performed at a temperature in the range of 50 to 140 ° C., preferably around 130 ° C., and after the molded product is removed from the mold, the final curing is performed at a higher temperature using an apparatus such as an oven. preferable.
- the final curing condition is, for example, to obtain a desired fiber-reinforced composite material by curing at a temperature in the range of 160 to 180 ° C. for a time in the range of 1 to 10 hours. Can do.
- the fiber-reinforced composite material preferably has a volume content (Vf) of reinforcing fibers of 50 to 65%, more preferably 53 to 60%.
- Vf volume content of reinforcing fibers
- the weight of the fiber-reinforced composite material is reduced, and can be suitably used for aircraft members and the like. Further, stress concentration is less likely to occur and the strength is increased. Further, it is preferable because a non-impregnated portion or a defective portion such as a void hardly occurs in the fiber reinforced composite material having a volume content of the reinforcing fiber of 65% or less.
- the fiber reinforced composite material in which the binder composition of the present invention is present between the layers is excellent in impact resistance against external impact, and particularly has high compressive strength after impact (CAI).
- CAI compressive strength after impact
- the CAI is preferably 230 MPa or more, more preferably 240 MPa or more.
- the CAI measurement of the fiber reinforced composite material was performed according to JIS K 7089 (1996), after applying a drop weight impact of 6.76 J per 1 mm thickness of the test piece to the test piece, and then measuring the CAI according to JIS K 7089 (1996). I do.
- the CAI is lower than 230 MPa, the laminate thickness increases for use as a structural member, and the weight increases accordingly. An increase in weight is not preferable because the fuel efficiency of the aircraft deteriorates.
- the present invention is particularly suitable for RTM, but molding methods other than RTM can also be suitably used.
- the shape of the reinforcing fiber substrate of the present invention is a strand or a tape, it is suitable for a filament winding method, a pultrusion method, a prepreg method, and the like.
- the shape of the reinforcing fiber substrate of the present invention is a sheet, it is also suitable for hand lay-up method, prepreg method and the like.
- the binder composition of the present invention is insoluble in a thermosetting resin, particularly an epoxy resin, which is a matrix resin of a fiber reinforced composite material, so there is no change in mechanical properties due to fluctuations in molding conditions, particularly temperature and heating rate, Productivity of the fiber reinforced composite material can be improved.
- the fiber-reinforced composite material produced using the binder composition of the present invention can be lightened and has excellent resistance to external impacts, so that the fuselage, main wing, tail, Aircraft members such as wings, fairings, cowls, doors, seats and interior materials; spacecraft members such as motor cases and main wings; satellite members such as structures and antennas; automotive members such as skins, chassis, aerodynamic members and seats It can be suitably used for many structural materials such as railway vehicle members such as structures and seats; ship members such as hulls and seats.
- the unit “part” of the composition ratio means part by mass unless otherwise specified.
- the reinforcing fiber fabric used in the examples was produced as follows. Carbon fiber bundle “Torayca” (registered trademark) T800S-24K-10E (manufactured by Toray Industries, Inc., PAN-based carbon fiber, number of filaments: 24,000, fineness: 1,033 tex, tensile elastic modulus: 294 GPa) as warp Glass fiber bundle ECDE-75-1 / 0-1.0Z (manufactured by Nittobo Co., Ltd., number of filaments) as auxiliary warp yarns arranged at a density of 1.8 yarns / cm, parallel and alternately arranged therewith
- the unidirectional sheet-like reinforcing fiber bundle group was formed by aligning 800 pieces and fineness: 67.5 tex) at a density of 1.8 pieces / cm.
- Glass fiber bundle E-glass yarn ECE-225-1 / 0-1.0Z (manufactured by Nittobo Co., Ltd., number of filaments: 200, fineness: 22.5 tex) is used as the weft to reinforce the unidirectional sheet.
- the fineness ratio of the weft to the carbon fiber bundle fineness of the obtained reinforcing fiber fabric was 2.2%
- the fineness ratio of the auxiliary warp was 6.5%
- the basis weight of the carbon fiber was 192 g / m 2 .
- thermosetting resin composition used in the examples is a two-component amine curable epoxy resin, and was prepared as follows.
- “Araldite” (registered trademark) MY721 (manufactured by Huntsman Japan K.K., component: N, N, N ′, N′-tetraglycidyl-4,4′-methylenedianiline) 50 parts and GAN (Nippon Kayaku ( Co., Ltd., component: N, N-diglycidylaniline) 50 parts were mixed at a temperature of 70 ° C. to obtain a main agent.
- the viscosity of the main agent at 70 ° C. was 61 mPa ⁇ s.
- DIC-TBC DIC Corporation, component: 4-t-butylcatechol
- the mixture was further mixed with stirring at a temperature of 70 ° C. until no solids existed to obtain a curing agent.
- the viscosity of the curing agent at 70 ° C. was 81 mPa ⁇ s.
- the liquid curing resin composition was obtained by mixing 43.4 parts of the curing agent with 100 parts of the main agent.
- the viscosity measured at 70 ° C. after 5 minutes from the start of mixing was 68 mPa ⁇ s.
- T mg the midpoint glass transition The temperature (T mg ) was measured.
- a differential scanning calorimeter DSC Q2000 manufactured by TA Instruments Inc. was used, the number of samples was 2, and an average value was obtained.
- Vf volume content of reinforcing fiber in fiber-reinforced composite material
- binder composition 1 Preparation of binder composition 1 70 parts of “Grillamide” (registered trademark) TR55 (manufactured by Emschemy Japan, glass transition temperature 160 ° C.), which is an amorphous polyamide having a 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane skeleton And 30 parts of “Topsizer” (registered trademark) No. 5 (manufactured by Fujiamide Chemical Co., Ltd., component: o / p-toluenesulfonamide) are kneaded at a temperature of 180 ° C. using a twin screw extruder, and pellets Got.
- “Grillamide” registered trademark
- TR55 manufactured by Emschemy Japan, glass transition temperature 160 ° C.
- Topsizer registered trademark
- No. 5 manufactured by Fujiamide Chemical Co., Ltd., component: o / p-toluenesulfonamide
- the obtained pellets were freeze-pulverized with liquid nitrogen using a hammer mill (PULVERIZER, manufactured by Hosokawa Micron Co., Ltd., and the following examples and comparative examples) to obtain a particulate binder composition 1.
- the obtained binder composition 1 had a volume average particle diameter of 86 ⁇ m and a glass transition temperature of 70 ° C.
- Preparation of Preform 1 After cutting the obtained reinforcing fiber base 1 into a predetermined size, the longitudinal direction of the carbon fiber of the four-layer reinforcing fiber base 1 is [+ 45 ° / 0 ° / ⁇ 45 ° / 90 °]. The adjacent layers were laminated so as to be shifted by 45 degrees, and this was repeated three times to obtain a total of 12 layers. Next, the two 12-layer laminates were laminated symmetrically so that the 90-degree layers face each other to obtain a total of 24 laminates. The obtained laminate was placed on the surface of an aluminum flat mold, and the top was sealed with a bag material (polyamide film) and a sealant.
- a bag material polyamide film
- the mold After the cavity formed by the mold and the bag material is evacuated, the mold is transferred to a hot air dryer, the temperature is raised from room temperature to 80 ° C. by 3 ° C. per minute, and then at a temperature of 80 ° C. Heated for 1 hour. Then, after cooling to 60 degrees C or less in air
- Example 1 (Molding of fiber reinforced composite material 1a: Example 1-1)
- the obtained preform 1 is placed on the surface of an aluminum flat mold, a polyester fabric subjected to a release treatment as a peel ply, and a polypropylene knit as a resin diffusion medium are arranged in order, Using a bag material and a sealant, a cavity was formed by sealing, except for providing a resin injection port and a vacuum suction port. Then, the inside of the cavity was sucked from the vacuum suction port by a vacuum pump to adjust the degree of vacuum to ⁇ 90 kPa or less, and then the temperature of the mold and the preform was adjusted to 70 ° C. A hot air dryer was used for temperature adjustment.
- the liquid thermosetting resin composition was prepared by mixing the main component and the curing agent of the liquid thermosetting resin composition in a ratio of 43.4 parts of the curing agent to 100 parts of the main component.
- the liquid thermosetting resin composition was preheated at a temperature of 70 ° C. for 30 minutes to perform vacuum deaeration treatment.
- thermosetting resin composition By setting the liquid thermosetting resin composition that has been preheated and degassed in the resin inlet of the mold, and utilizing the pressure difference between the pressure in the cavity and the atmospheric pressure in the vacuumed cavity A thermosetting resin composition was injected and impregnated into the preform 1. When the liquid thermosetting resin composition reached the vacuum suction port, the resin injection port was closed, and the vacuum suction port was closed after holding for another hour while continuing the suction from the vacuum suction port.
- the temperature was raised to 140 ° C. at 1.5 ° C. per minute, and then pre-cured at 140 ° C. for 2 hours.
- the temperature is raised to 180 ° C. in a hot air dryer at a rate of 1.5 ° C. per minute, and then at a temperature of 180 ° C.
- Time hardening was performed to obtain a fiber reinforced composite material 1a.
- the obtained fiber reinforced composite material 1a had a carbon fiber volume content of 56%.
- thermosetting resin composition was injected by the same procedure as described above (molding of the fiber-reinforced composite material 1a).
- the resin injection port was closed, and the vacuum suction port was closed after holding for another hour while continuing the suction from the vacuum suction port.
- the temperature was raised to 180 ° C. at a rate of 1.5 ° C. per minute and then cured at a temperature of 180 ° C. for 2 hours.
- the cured product was taken out of the mold and each auxiliary material such as peel ply was removed to obtain a fiber reinforced composite material 1b.
- the obtained fiber reinforced composite material 1b had a carbon fiber volume content of 58%.
- CAI Compressive strength after impact
- Example 2> (Preparation of binder composition 2) 70 parts of “Grillamide” (registered trademark) TR90 (manufactured by Emschemy Japan, glass transition temperature 155 ° C.), which is an amorphous polyamide having a 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane skeleton And “Topsizer” (registered trademark) No. 1 S (manufactured by Fujiamide Chemical Co., Ltd., component: p-toluenesulfonamide) were kneaded and freeze-ground by the same procedure as in Example 1. A binder composition 2 was obtained. The obtained binder composition 2 had a volume average particle diameter of 92 ⁇ m and a glass transition temperature of 64 ° C.
- a reinforcing fiber substrate 2 provided with the binder composition 2 was obtained by the same procedure as in Example 1 except that the obtained binder composition 2 was used.
- Preparation of preform 2 A preform 2 was obtained by the same procedure as in Example 1 except that the obtained reinforcing fiber substrate 2 was used.
- a fiber reinforced composite material 2 was obtained by the same procedure as in Example 1 (Molding of fiber reinforced composite material 1a) except that the obtained preform 2 was used.
- the obtained fiber reinforced composite material 2 had a carbon fiber volume content of 57%.
- Example 3> (Preparation of binder composition 3) 60 parts of “grill amide” (registered trademark) TR90 (manufactured by Emschemie Japan, glass transition temperature 155 ° C.), which is an amorphous polyamide having a 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane skeleton And EBSA (manufactured by Fujiamide Chemical Co., Ltd., component: p-ethylbenzenesulfonamide) were kneaded and freeze-ground by the same procedure as in Example 1 to obtain a binder composition 3.
- the obtained binder composition 3 had a volume average particle diameter of 88 ⁇ m and a glass transition temperature of 65 ° C.
- a reinforcing fiber substrate 3 provided with the binder composition 3 was obtained by the same procedure as in Example 1 except that the obtained binder composition 3 was used.
- Preparation of Preform 3 A preform 3 was obtained by the same procedure as in Example 1 except that the obtained reinforcing fiber substrate 3 was used.
- a fiber-reinforced composite material 3 was obtained by the same procedure as in Example 1 (molding of the fiber-reinforced composite material 1a) except that the obtained preform 3 was used.
- the volume content of carbon fibers of the obtained fiber reinforced composite material 3 was 57%.
- Example 4> (Preparation of binder composition 4) 55 parts of “Grillamide” (registered trademark) TR90 (manufactured by Emschemie Japan KK, glass transition temperature 155 ° C.) which is an amorphous polyamide having a 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane skeleton , "Topsizer” (registered trademark) No.
- binder composition 4 had a volume average particle diameter of 85 ⁇ m and a glass transition temperature of 67 ° C.
- a reinforcing fiber substrate 4 provided with the binder composition 4 was obtained by the same procedure as in Example 1 except that the obtained binder composition 4 was used.
- Preparation of preform 4 A preform 4 was obtained by the same procedure as in Example 1 except that the obtained reinforcing fiber substrate 4 was used.
- a fiber-reinforced composite material 4 was obtained by the same procedure as in Example 1 (molding of the fiber-reinforced composite material 1a) except that the obtained preform 4 was used.
- the obtained fiber reinforced composite material 3 had a carbon fiber volume content of 57%.
- Example 5> Preparation of binder composition 4 70 parts of “Grillamide” (registered trademark) TR90 (manufactured by Emschemy Japan, glass transition temperature 155 ° C.), which is an amorphous polyamide having a 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane skeleton , “Topsizer” (registered trademark) No.
- binder composition 5 (manufactured by Fujiamide Chemical Co., Ltd., component: p-toluenesulfonamide) and “PANDEX” (registered trademark) (manufactured by DIC Bayer Polymer Co., Ltd., component) : Urethane elastomer) 5 parts was used and kneaded and freeze-ground by the same procedure as in Example 1 to obtain a binder composition 5.
- the obtained binder composition 5 had a volume average particle diameter of 82 ⁇ m and a glass transition temperature of 74 ° C.
- a reinforcing fiber substrate 5 provided with the binder composition 5 was obtained by the same procedure as in Example 1 except that the obtained binder composition 5 was used.
- Preparation of preform 5 A preform 5 was obtained by the same procedure as in Example 1 except that the obtained reinforcing fiber substrate 5 was used.
- a fiber reinforced composite material 5 was obtained by the same procedure as in Example 1 (molding of the fiber reinforced composite material 1a) except that the obtained preform 5 was used.
- the obtained fiber reinforced composite material 3 had a carbon fiber volume content of 56%.
- ⁇ Comparative Example 1> (Preparation of binder composition 6) 60 parts of “SUMIKA EXCEL” (registered trademark) PES5003P (manufactured by Sumitomo Chemical Co., Ltd., glass transition temperature 277 ° C.), which is soluble in epoxy resin and is an amorphous polyethersulfone, and AK-601 (Nipponization) 40 parts of Yaku Co., Ltd. product, component: hexahydrophthalic acid diglycidyl ester) was kneaded at a temperature of 210 ° C. using a twin screw extruder to obtain pellets. The obtained pellets were freeze pulverized in the same procedure as in Example 1 to obtain a particulate binder composition 6. The obtained binder composition 6 had a volume average particle diameter of 90 ⁇ m and a glass transition temperature of 68 ° C.
- a reinforcing fiber substrate 6 provided with the binder composition 6 was obtained by the same procedure as in Example 1 except that the obtained binder composition 6 was used.
- Preparation of preform 6 A preform 6 was obtained by the same procedure as in Example 1 except that the obtained reinforcing fiber base 6 was used.
- a fiber reinforced composite material 6a was obtained by the same procedure as in Example 1 (Molding of fiber reinforced composite material 1a: Example 1-1) except that the obtained preform 6 was used.
- the obtained fiber reinforced composite material 6a had a carbon fiber volume content of 56%.
- a fiber reinforced composite material 6b was obtained by the same procedure as in Example 1 (Molding of fiber reinforced composite material 1b: Example 1-2) except that the obtained preform 6 was used.
- the obtained fiber reinforced composite material 6b had a carbon fiber volume content of 61%.
- CAI Compressive strength after impact
- a fiber-reinforced composite material 7 is obtained by the same procedure as in Example 1 (forming of fiber-reinforced composite material 1a). It was.
- the obtained fiber reinforced composite material 7 had a carbon fiber volume content of 53%.
- Example 6> (Preparation of binder composition 8) 35 parts of “Grillamide” (registered trademark) TR55 (manufactured by Emschemie Japan, glass transition temperature 160 ° C.), which is an amorphous polyamide having a 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane skeleton And “Topsizer” (registered trademark) No. 1 S (manufactured by Fujiamide Chemical Co., Ltd., component: p-toluenesulfonamide) were kneaded and freeze-ground by the same procedure as in Example 1. A binder composition 8 was obtained. The obtained binder composition 8 had a volume average particle size of 112 ⁇ m and a glass transition temperature of 52 ° C.
- a reinforcing fiber substrate 8 provided with the binder composition 8 was obtained by the same procedure as in Example 1 except that the obtained binder composition 8 was used.
- Preparation of preform 8 A preform 8 was obtained by the same procedure as in Example 1 except that the obtained reinforcing fiber substrate 8 was used.
- a fiber-reinforced composite material 8 was obtained by the same procedure as in Example 1 (Molding of fiber-reinforced composite material 1a) except that the obtained preform 8 was used.
- the obtained fiber reinforced composite material 8 had a carbon fiber volume content of 53%.
- Example 7> (Preparation of binder composition 9) 10 parts “grill amide” (registered trademark) TR90 (manufactured by Emschemie Japan, glass transition temperature 155 ° C.), which is an amorphous polyamide having a 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane skeleton "Topsizer” (registered trademark) No.
- Example 1 S (manufactured by Fujiamide Chemical Co., Ltd., component: p-toluenesulfonamide) and TPAE-8 (manufactured by Fuji Kasei Kogyo Co., Ltd., component: polymerized fatty acid polyamide) (Elastomer) 40 parts were kneaded and freeze-ground by the same procedure as in Example 1 to obtain a binder composition 9.
- the obtained binder composition 9 had a volume average particle size of 120 ⁇ m, but the glass transition temperature was a low value of 38 ° C.
- a reinforcing fiber substrate 9 provided with the binder composition 9 was obtained by the same procedure as in Example 1 except that the obtained binder composition 9 was used.
- Preparation of preform 9 A preform 9 was obtained by the same procedure as in Example 1 except that the obtained reinforcing fiber substrate 9 was used.
- a fiber-reinforced composite material 9 was obtained by the same procedure as in Example 1 (Molding of the fiber-reinforced composite material 1a) except that the obtained preform 9 was used.
- the obtained fiber reinforced composite material 9 had a carbon fiber volume content of 53%.
- “Grillamide” registered trademark
- TR90 manufactured by Emschemy Japan, glass transition temperature 155 ° C.
- AK-601 manufactured by Nippon Kayaku Co., Ltd., component: hexahydrophthalic acid diglycidyl ester
- the obtained binder composition 10 had a volume average particle diameter of 79 ⁇ m and a glass transition temperature of 82 ° C.
- a reinforcing fiber substrate 10 provided with the binder composition 10 was obtained by the same procedure as in Example 1 except that the obtained binder composition 10 was used.
- Preparation of preform 10 A preform 10 was obtained by the same procedure as in Example 1 except that the obtained reinforcing fiber substrate 10 was used.
- a fiber-reinforced composite material 10 was obtained by the same procedure as in Example 1 (Molding of fiber-reinforced composite material 1a) except that the obtained preform 10 was used.
- the obtained fiber reinforced composite material 10 had a carbon fiber volume content of 56%.
- the binder composition of the present invention it is possible to fix the form of a preform in which reinforcing fiber substrates are laminated.
- the fiber reinforced composite material molded by RTM using the preform has excellent impact resistance against external impacts and has high post-impact compressive strength (CAI). Therefore, aircraft members, spacecraft members, automobile members It can be suitably used for structural members such as ship members.
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Abstract
Description
[A]分子内にジシクロヘキシルメタン骨格を有し、ガラス転移温度が140℃以上である非晶性のポリアミド;
[B]スルホンアミド化合物。
条件(I)該バインダー組成物のガラス転移温度が40~90℃である;
条件(II)N,N,N’,N’-テトラグリシジル-4,4’-メチレンジアニリンを40質量%以上含むエポキシ樹脂100質量部に、該バインダー組成物を10質量部配合し、180℃の温度下で1時間攪拌した後、透過観察型の光学顕微鏡を使用し、倍率5倍で観察したとき、粒径10μm以上の固形分が観察され、かつ、固形分をろ別したろ液の粘度が、該エポキシ樹脂の粘度の5倍以下である。
[A]分子内にジシクロヘキシルメタン骨格を有し、ガラス転移温度が140℃以上である非晶性のポリアミド
[B]スルホンアミド化合物。
実施例で用いた強化繊維織物は以下のように作製した。炭素繊維束“トレカ”(登録商標)T800S-24K-10E(東レ(株)製、PAN系炭素繊維、フィラメント数:24,000本、繊度:1,033tex、引張弾性率:294GPa)を経糸として1.8本/cmの密度で引き揃え、これに平行、かつ交互に配列された補助経糸としてガラス繊維束ECDE-75-1/0-1.0Z(日東紡(株)製、フィラメント数:800本、繊度:67.5tex)を1.8本/cmの密度で引き揃えて一方向性シート状強化繊維束群を形成した。緯糸としてガラス繊維束E-glassヤーンECE-225-1/0-1.0Z(日東紡(株)製、フィラメント数:200本、繊度:22.5tex)を用い、前記一方向性シート状強化繊維束群に直交する方向に3本/cmの密度で配列し、織機を用いて該補助経糸と該緯糸が互いに交差するように織り込み、実質的に炭素繊維が一方向に配列されクリンプがない、一方向性ノンクリンプ織物を作製した。なお、得られた強化繊維織物の炭素繊維束繊度に対する緯糸の繊度割合は2.2%、補助経糸の繊度割合は6.5%であり、炭素繊維の目付は192g/m2であった。
実施例で用いた熱硬化性樹脂組成物は、二液型のアミン硬化型エポキシ樹脂であり、以下のように調製した。
JIS Z8803(1991)における「円すい-板形回転粘度計による粘度測定方法」に従い、標準コーンローター(1°34’×R24)を装備したE型粘度計(東機産業(株)、TVE-30H)を使用して、回転速度50回転/分にて所定温度における粘度を測定した。
各実施例で得られたバインダー組成物を、JIS Z8825-1(2001)に従い、レーザー回析・散乱式粒度分布測定装置Partica LA-950V2((株)堀場製作所製)を用い、取込回数15回にて測定した。
各実施例で使用した構成要素[A]である非晶性のポリアミド、および各実施例で得られたバインダー組成物をそれぞれ5~10mgを採取し、JIS K7121(1987)に従い、中間点ガラス転移温度(Tmg)を測定した。測定には示差走査熱量計DSC Q2000(ティー・エイ・インスツルメント社製)を用い、サンプル数は2とし、平均値を求めた。
得られた繊維強化複合材料から、試験片の長手方向を炭素繊維配向角0度として縦150mm、横100mmの矩形試験片を切り出し、その矩形試験片の中心に、JIS K 7089(1996)に従って、試験片の厚さ1mmあたり6.76Jの落錘衝撃を与えた後、JIS K 7089(1996)に従い残存圧縮強度(CAI)を測定した。サンプル数は5とし、平均値を求めた。
各実施例で得られた繊維強化複合材料から質量0.2~0.5gのサンプルを切り出し、JIS K7075(1991)に記載された硝酸分解法にてVfを測定した。サンプル数は5とし、平均値を求めた。
(バインダー組成物1の調製)
3,3’-ジメチル-4,4’-ジアミノジシクロヘキシルメタン骨格を有する非晶性のポリアミドである“グリルアミド”(登録商標)TR55(エムスケミー・ジャパン(株)製、ガラス転移温度160℃)70部と“トップサイザー”(登録商標)5号(富士アミドケミカル(株)製、成分:o/p-トルエンスルホンアミド)30部を二軸押出機を用いて180℃の温度で混練して、ペレットを得た。得られたペレットを、液体窒素を用いてハンマーミル(PULVERIZER、ホソカワミクロン(株)製、以下の実施例および比較例も同様)にて凍結粉砕し、粒子状のバインダー組成物1を得た。得られたバインダー組成物1の体積平均粒子径は86μm、ガラス転移温度は70℃であった。
得られたバインダー組成物1を、前記の炭素繊維からなる強化繊維織物の片面にエンボスロールとドクターブレードにて計量しながら自然落下させ、振動ネットを介して均一分散させながら、25g/m2の目付で散布した。その後、その強化繊維織物を温度160℃、速度0.3m/分の条件にて遠赤外線ヒーターを通過させてバインダー組成物1を融着させ、片側表面にバインダー組成物1が付与された強化繊維基材1を得た。
得られた強化繊維基材1を所定の大きさにカットした後、4層の強化繊維基材1を、炭素繊維の長手方向が、[+45°/0°/-45°/90°]と、隣り合う層同士で45度ずつずれるように積層し、それを3回繰り返して、合計12層の積層体を得た。次に該12層の積層体2つを90度層同士が向かい合うように対称に積層し、合計24層の積層体を得た。得られた積層体をアルミニウム製の平面状成形型の面上に配置し、その上をバッグ材(ポリアミドフィルム)とシーラントにて密閉した。成形型とバッグ材により形成されたキャビティを真空にした後、成形型を熱風乾燥機に移し、室温から80℃の温度まで、1分間に3℃ずつ昇温した後、80℃の温度下で1時間加熱した。その後、キャビティの真空状態を保ちながら大気中にて60℃以下に冷却した後、キャビティを大気解放してプリフォーム1を得た。
得られたプリフォーム1をアルミニウム製の平面状成形型の面上に配置し、その上にピールプライとして離型処理を施したポリエステル布帛、樹脂拡散媒体としてポリプロピレン製ニットを順に配置し、その上をバッグ材とシーラントを用いて、樹脂注入口と減圧吸引口を設けた以外は密閉してキャビティを形成した。そして、減圧吸引口から真空ポンプによってキャビティ内を吸引して、真空度を-90kPa以下になるよう調整した後、成形型およびプリフォームを70℃に温度調節した。温度調整には熱風乾燥機を使用した。
樹脂拡散媒体としてアルミ製金網を使用した以外は、前記(繊維強化複合材料1aの成形)と同手順により液状熱硬化性樹脂組成物の注入まで行った。液状熱硬化性樹脂組成物が減圧吸引口に到達したら樹脂注入口を閉じ、減圧吸引口から吸引を継続したままさらに1時間保持した後、減圧吸引口を閉じた。
得られた繊維強化複合材料から、前記した方法にて試験片を作製し、CAIを測定した結果、繊維強化複合材料1aは275MPa、繊維強化複合材料1bは290MPaと共に高く、かつ成形温度が異なるにもかかわらず、両者とも高いCAIを有しており、高い力学物性と品質が要求される航空機用構造部材に適していた。
(バインダー組成物2の調製)
3,3’-ジメチル-4,4’-ジアミノジシクロヘキシルメタン骨格を有する非晶性のポリアミドである“グリルアミド”(登録商標)TR90(エムスケミー・ジャパン(株)製、ガラス転移温度155℃)70部と“トップサイザー”(登録商標)1号S(富士アミドケミカル(株)製、成分:p-トルエンスルホンアミド)30部を使用して、実施例1と同手順により混練および凍結粉砕を行って、バインダー組成物2を得た。得られたバインダー組成物2の体積平均粒子径は92μm、ガラス転移温度は64℃であった。
得られたバインダー組成物2を使用した以外は、実施例1と同手順により、バインダー組成物2を付与した強化繊維基材2を得た。
得られた強化繊維基材2を使用した以外は、実施例1と同手順により、プリフォーム2を得た。
得られたプリフォーム2を使用した以外は、実施例1の(繊維強化複合材料1aの成形)と同手順により繊維強化複合材料2を得た。得られた繊維強化複合材料2の炭素繊維の体積含有率は57%であった。実施例1と同様にしてCAIを測定した結果、276MPaと高い値であり、航空機用構造部材に適していた。
(バインダー組成物3の調製)
3,3’-ジメチル-4,4’-ジアミノジシクロヘキシルメタン骨格を有する非晶性のポリアミドである“グリルアミド”(登録商標)TR90(エムスケミー・ジャパン(株)製、ガラス転移温度155℃)60部とEBSA(富士アミドケミカル(株)製、成分:p-エチルベンゼンスルホンアミド)40部を使用して、実施例1と同手順により混練および凍結粉砕を行って、バインダー組成物3を得た。得られたバインダー組成物3の体積平均粒子径は88μm、ガラス転移温度は65℃であった。
得られたバインダー組成物3を使用した以外は、実施例1と同手順により、バインダー組成物3を付与した強化繊維基材3を得た。
得られた強化繊維基材3を使用した以外は、実施例1と同手順により、プリフォーム3を得た。
得られたプリフォーム3を使用した以外は、実施例1の(繊維強化複合材料1aの成形)と同手順により繊維強化複合材料3を得た。
(バインダー組成物4の調製)
3,3’-ジメチル-4,4’-ジアミノジシクロヘキシルメタン骨格を有する非晶性のポリアミドである“グリルアミド”(登録商標)TR90(エムスケミー・ジャパン(株)製、ガラス転移温度155℃)55部、“トップサイザー”(登録商標)1号S(富士アミドケミカル(株)製、成分:p-トルエンスルホンアミド)30部およびTPAE-8(富士化成工業(株)製、成分:重合脂肪酸系ポリアミドエラストマー)15部を使用して、実施例1と同手順により混練、凍結粉砕を行って、バインダー組成物4を得た。得られたバインダー組成物4の体積平均粒子径は85μm、ガラス転移温度は67℃であった。
得られたバインダー組成物4を使用した以外は、実施例1と同手順により、バインダー組成物4を付与した強化繊維基材4を得た。
得られた強化繊維基材4を使用した以外は、実施例1と同手順により、プリフォーム4を得た。
得られたプリフォーム4を使用した以外は、実施例1の(繊維強化複合材料1aの成形)と同手順により繊維強化複合材料4を得た。得られた繊維強化複合材料3の炭素繊維の体積含有率は57%であった。実施例1と同様にしてCAIを測定した結果、281MPaと高い値であり、航空機用構造部材に適していた。
(バインダー組成物4の調製)
3,3’-ジメチル-4,4’-ジアミノジシクロヘキシルメタン骨格を有する非晶性のポリアミドである“グリルアミド”(登録商標)TR90(エムスケミー・ジャパン(株)製、ガラス転移温度155℃)70部、“トップサイザー”(登録商標)1号S(富士アミドケミカル(株)製、成分:p-トルエンスルホンアミド)25部および“PANDEX”(登録商標)(ディーアイシーバイエルポリマー(株)製、成分:ウレタン系エラストマー)5部を使用して、実施例1と同手順により混練および凍結粉砕を行って、バインダー組成物5を得た。得られたバインダー組成物5の体積平均粒子径は82μm、ガラス転移温度は74℃であった。
得られたバインダー組成物5を使用した以外は、実施例1と同手順により、バインダー組成物5を付与した強化繊維基材5を得た。
得られた強化繊維基材5を使用した以外は、実施例1と同手順により、プリフォーム5を得た。
得られたプリフォーム5を使用した以外は、実施例1の(繊維強化複合材料1aの成形)と同手順により繊維強化複合材料5を得た。得られた繊維強化複合材料3の炭素繊維の体積含有率は56%であった。実施例1と同様にしてCAIを測定した結果、277MPaと高い値であり、航空機用構造部材に適していた。
(バインダー組成物6の調製)
エポキシ樹脂に可溶であり、非晶性ポリエーテルスルホンである“スミカエクセル”(登録商標)PES5003P(住友化学工業(株)製、ガラス転移温度277℃)60部と、AK-601(日本化薬(株)製、成分:ヘキサヒドロフタル酸ジグリシジルエステル)40部を二軸押出機を用いて210℃の温度で混練して、ペレットを得た。得られたペレットを、実施例1と同手順にて凍結粉砕し、粒子状のバインダー組成物6を得た。得られたバインダー組成物6の体積平均粒子径は90μm、ガラス転移温度は68℃であった。
得られたバインダー組成物6を使用した以外は、実施例1と同手順により、バインダー組成物6を付与した強化繊維基材6を得た。
得られた強化繊維基材6を使用した以外は、実施例1と同手順により、プリフォーム6を得た。
得られたプリフォーム6を使用した以外は、実施例1の(繊維強化複合材料1aの成形:実施例1-1)と同手順により繊維強化複合材料6aを得た。得られた繊維強化複合材料6aの炭素繊維の体積含有率は56%であった。
得られたプリフォーム6を使用した以外は、実施例1の(繊維強化複合材料1bの成形:実施例1-2)と同手順により繊維強化複合材料6bを得た。得られた繊維強化複合材料6bの炭素繊維の体積含有率は61%であった。
実施例1と同様にしてCAIを測定した結果、繊維強化複合材料6aは250MPaと高い値であったが、繊維強化複合材料6bは195MPaと低く、成形温度が変化したことにより、バインダー組成物の溶解性が変わったため、CAIが変動した。よって、高い力学物性と品質が要求される航空機用構造部材には不適であった。
(バインダー組成物7)
結晶性のポリアミドであるナイロン12(融点:176℃、ガラス転移温度:50℃)の不織布を使用した。使用したナイロン12不織布の目付は10g/m2であった。
前記した強化繊維織物とナイロン12不織布を所定の大きさにカットした後、強化繊維織物とナイロン12不織布の各1枚を1セットとし、4セットを、炭素繊維の長手方向が、[+45°/0°/-45°/90°]と、隣り合う層同士で45度ずつずれるように積層し、それを3回繰り返して、強化繊維織物の合計が12層で、各層間にナイロン12不織布が配置された積層体を得た。次に該12層の積層体2つを90度層同士が向かい合うように対称に積層し、強化繊維織物の合計が24層で、各層間にナイロン12不織布が配置された積層体7を得た。
得られた積層体7を崩れないようにアルミニウム製の平面状成形型の面上に配置した後、実施例1の(繊維強化複合材料1aの成形)と同手順により繊維強化複合材料7を得た。得られた繊維強化複合材料7の炭素繊維の体積含有率は53%であった。実施例1と同様にしてCAIを測定した結果、190MPaと低く、高い力学物性と品質が要求される航空機用構造部材には不適であった。
(バインダー組成物8の調製)
3,3’-ジメチル-4,4’-ジアミノジシクロヘキシルメタン骨格を有する非晶性のポリアミドである“グリルアミド”(登録商標)TR55(エムスケミー・ジャパン(株)製、ガラス転移温度160℃)35部と“トップサイザー”(登録商標)1号S(富士アミドケミカル(株)製、成分:p-トルエンスルホンアミド)65部を使用して、実施例1と同手順により混練および凍結粉砕を行って、バインダー組成物8を得た。得られたバインダー組成物8の体積平均粒子径は112μm、ガラス転移温度は52℃であった。
得られたバインダー組成物8を使用した以外は、実施例1と同手順により、バインダー組成物8を付与した強化繊維基材8を得た。
得られた強化繊維基材8を使用した以外は、実施例1と同手順により、プリフォーム8を得た。
得られたプリフォーム8を使用した以外は、実施例1の(繊維強化複合材料1aの成形)と同手順により繊維強化複合材料8を得た。得られた繊維強化複合材料8の炭素繊維の体積含有率は53%であった。実施例1と同様にしてCAIを測定した結果、221MPaであった。
(バインダー組成物9の調製)
3,3’-ジメチル-4,4’-ジアミノジシクロヘキシルメタン骨格を有する非晶性のポリアミドである“グリルアミド”(登録商標)TR90(エムスケミー・ジャパン(株)製、ガラス転移温度155℃)10部、“トップサイザー”(登録商標)1号S(富士アミドケミカル(株)製、成分:p-トルエンスルホンアミド)50部およびTPAE-8(富士化成工業(株)製、成分:重合脂肪酸系ポリアミドエラストマー)40部を使用して、実施例1と同手順により混練および凍結粉砕を行って、バインダー組成物9を得た。得られたバインダー組成物9の体積平均粒子径は120μmであったが、ガラス転移温度は38℃と低い値であった。
得られたバインダー組成物9を使用した以外は、実施例1と同手順により、バインダー組成物9を付与した強化繊維基材9を得た。
得られた強化繊維基材9を使用した以外は、実施例1と同手順により、プリフォーム9を得た。
得られたプリフォーム9を使用した以外は、実施例1の(繊維強化複合材料1aの成形)と同手順により繊維強化複合材料9を得た。得られた繊維強化複合材料9の炭素繊維の体積含有率は53%であった。実施例1と同様にしてCAIを測定した結果、228MPaであった。
3,3’-ジメチル-4,4’-ジアミノジシクロヘキシルメタン骨格を有する非晶性のポリアミドである“グリルアミド”(登録商標)TR90(エムスケミー・ジャパン(株)製、ガラス転移温度155℃)70部と、AK-601(日本化薬(株)製、成分:ヘキサヒドロフタル酸ジグリシジルエステル)30部を実施例1と同手順により混練を行った。しかしながら、各原料が相溶することなく分離して吐出され、バインダー組成物を得ることができなかった。
比較例1で使用した非晶性ポリエーテルスルホンで“スミカエクセル”(登録商標)PES5003P(住友化学工業(株)製、ガラス転移温度277℃)65部と、“トップサイザー”(登録商標)1号S(富士アミドケミカル(株)製、成分:p-トルエンスルホンアミド)35部を使用して、比較例1と同手順により混練および凍結粉砕を行って、バインダー組成物10を得た。得られたバインダー組成物10の体積平均粒子径は79μm、ガラス転移温度は82℃であった。
得られたバインダー組成物10を使用した以外は、実施例1と同手順により、バインダー組成物10を付与した強化繊維基材10を得た。
得られた強化繊維基材10を使用した以外は、実施例1と同手順により、プリフォーム10を得た。
得られたプリフォーム10を使用した以外は、実施例1の(繊維強化複合材料1aの成形)と同手順により繊維強化複合材料10を得た。得られた繊維強化複合材料10の炭素繊維の体積含有率は56%であった。実施例1と同様にしてCAIを測定した結果、248MPaであった。
Claims (13)
- 次の構成要素[A]および[B]を含むバインダー組成物;
[A]分子内にジシクロヘキシルメタン骨格を有し、ガラス転移温度が140℃以上である非晶性のポリアミド;
[B]スルホンアミド化合物。 - 次の条件(I)および(II)を満たす、請求項1に記載のバインダー組成物;
条件(I)該バインダー組成物のガラス転移温度が40~90℃である;
条件(II)N,N,N’,N’-テトラグリシジル-4,4’-メチレンジアニリンを40質量%以上含むエポキシ樹脂100質量部に、該バインダー組成物を10質量部配合し、180℃の温度下で1時間攪拌した後、透過観察型の光学顕微鏡を使用し、倍率5倍で観察したとき、粒径10μm以上の固形分が観察され、かつ、固形分をろ別したろ液の粘度が、該エポキシ樹脂の粘度の5倍以下である。 - 構成要素[A]が3,3’-ジメチル-4,4’-ジアミノジシクロヘキシルメタン単位を含むポリアミドである、請求項1または2に記載のバインダー組成物。
- 構成要素[A]を40~80質量%、構成要素[B]を10~40質量%含有する請求項1~3のいずれかに記載のバインダー組成物。
- 構成要素[B]がトルエンスルホンアミドである、請求項1~4のいずれかに記載のバインダー組成物。
- 構成要素[C]として、熱可塑性エラストマーをさらに含む、請求項1~5のいずれかに記載のバインダー組成物。
- 構成要素[C]がポリアミドエラストマーである、請求項6に記載のバインダー組成物。
- バインダー組成物の形状が、体積平均粒子径30~200μmの粒子である請求項1~7のいずれかに記載のバインダー組成物。
- 請求項1~8のいずれかに記載のバインダー組成物および強化繊維を含む強化繊維基材。
- 強化繊維が炭素繊維束からなる経糸とこれに平行に配列されたガラス繊維または化学繊維からなる繊維束の補助経糸と、これらと直交するように配列されたガラス繊維または化学繊維からなる緯糸からなり、該補助経糸と該緯糸が互いに交差することにより、炭素繊維束が一体に保持されて織物が形成されているノンクリンプ構造の織物であり、前記バインダー組成物の含有量が目付で5~50g/m2である、請求項9に記載の強化繊維基材。
- 請求項9または10に記載の強化繊維基材を積層してなり、該強化繊維基材の層間に前記バインダー組成物を存在させたプリフォーム。
- 請求項11に記載のプリフォームおよび、エポキシ樹脂の硬化物を含む繊維強化複合材料。
- 請求項11に記載のプリフォームを、剛体オープンモールドと可撓性フィルムによって形成されたキャビティ内に設置し、該キャビティを真空ポンプにて吸引し、大気圧を用いて注入口からキャビティ内に液状熱硬化性樹脂組成物を注入してプリフォームに含浸させた後、該液状熱硬化性樹脂組成物を加熱硬化させる工程を含む、繊維強化複合材料の製造方法。
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EP10817153.9A EP2479217B1 (en) | 2009-09-16 | 2010-09-14 | Binder composition, reinforcing-fiber base material, preform, fiber-reinforced composite material, and manufacturing method therefor |
JP2010537177A JP5672006B2 (ja) | 2009-09-16 | 2010-09-14 | バインダー組成物、強化繊維基材、プリフォームおよび繊維強化複合材料とその製造方法 |
CA2770587A CA2770587A1 (en) | 2009-09-16 | 2010-09-14 | Binder composition, reinforcing-fiber base material, preform, fiber-reinforced composite material, and manufacturing method therefor |
CN201080041592.1A CN102498173B (zh) | 2009-09-16 | 2010-09-14 | 粘合剂组合物、增强纤维基材、预成型体及纤维增强复合材料及其制造方法 |
US13/496,759 US9062203B2 (en) | 2009-09-16 | 2010-09-14 | Binder composition, reinforcing-fiber base material, preform, fiber-reinforced composite material, and manufacturing method therefor |
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JP2019511617A (ja) * | 2016-04-05 | 2019-04-25 | アルケマ フランス | 補強剤を含む複合材料から作製された部品を製造するための方法 |
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CN102498173A (zh) | 2012-06-13 |
EP2479217A1 (en) | 2012-07-25 |
US20120178329A1 (en) | 2012-07-12 |
JPWO2011034040A1 (ja) | 2013-02-14 |
EP2479217B1 (en) | 2019-08-28 |
JP5672006B2 (ja) | 2015-02-18 |
EP2479217A4 (en) | 2015-08-26 |
CN102498173B (zh) | 2014-04-23 |
US9062203B2 (en) | 2015-06-23 |
CA2770587A1 (en) | 2011-03-24 |
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