WO2017104445A1 - プリフォーム用バインダー樹脂組成物、バインダー粒子、強化繊維基材、プリフォームおよび繊維強化複合材料 - Google Patents
プリフォーム用バインダー樹脂組成物、バインダー粒子、強化繊維基材、プリフォームおよび繊維強化複合材料 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/046—Reinforcing macromolecular compounds with loose or coherent fibrous material with synthetic macromolecular fibrous material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
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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
- C08L101/00—Compositions of unspecified macromolecular compounds
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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
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- 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
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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
- 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
- C08L71/12—Polyphenylene oxides
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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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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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
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
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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
- C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2439/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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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
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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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
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Definitions
- the present invention relates to a binder resin composition used in the production of preforms of reinforcing fibers, and binder particles, reinforcing fiber substrates, preforms, and fiber-reinforced composite materials using the same.
- Fiber reinforced composite materials consisting of reinforced fibers and matrix resins can be designed using the advantages of reinforced fibers and matrix resins, so the application has been expanded to aerospace, sports and general industrial fields. .
- the reinforcing fiber glass fiber, aramid fiber, carbon fiber, boron fiber, etc. are used.
- the matrix resin either a thermosetting resin or a thermoplastic resin is used, but a thermosetting resin that can be easily impregnated into the reinforcing fiber is often used.
- the thermosetting resin a resin composition obtained by adding a curing agent or a curing catalyst to an epoxy resin, an unsaturated polyester resin, a vinyl ester resin, a phenol resin, a bismaleimide resin, a cyanate resin, or the like is used.
- Fiber reinforced composite materials are manufactured by various methods.
- RTM Resin Transfer Molding
- the method is attracting attention as a method with excellent low-cost productivity.
- a preform in which a reinforcing fiber substrate is processed into a shape close to the desired product is prepared in advance, and this preform is placed in a mold and a liquid thermosetting resin is injected. Often to do.
- the binder a general-purpose high molecular weight epoxy resin can be used.
- the temperature applied to the binder varies depending on the position in the mold. There was a problem that a portion having insufficient adhesiveness occurred in the reform.
- Patent Document 1 discloses a binder resin composition excellent in adhesion between a thermoplastic resin and a reinforcing fiber made of an epoxy resin.
- Patent Document 2 uses a mold at a constant temperature by using a binder resin composition having a curing reactivity in which a curing catalyst such as imidazole is combined with an epoxy resin such as liquid bisphenol A type epoxy resin and a thermoplastic resin.
- a binder resin composition excellent in high cycle performance of a preform is disclosed.
- Patent Documents 3 and 4 disclose those in which the viscosity characteristics of a composition comprising a thermosetting resin and a thermoplastic resin are controlled.
- Patent Document 1 When producing a preform using the binder disclosed in Patent Document 1, it is possible to eliminate unevenness in adhesion by heating the mold to a high temperature. It was necessary to heat, and it was inferior in terms of high cycle performance and energy cost.
- the binder resin composition shown in the above-mentioned Patent Document 2 cannot solve the unevenness of adhesion in the preform of a large member, and the reaction of the binder may proceed at the time of storage, resulting in storage stability. It was inferior.
- the binder composition disclosed in Patent Document 3 had a low Tg of the binder and was inferior in storage stability at room temperature.
- the binder composition disclosed in Patent Document 4 had a low Tg of the binder composition, poor storage stability at room temperature, and poor adhesion.
- the purpose of the present invention is to improve the disadvantages of the prior art, have excellent storage stability at room temperature and excellent preform interlayer adhesion at low temperature, and can exhibit stable adhesion even when the preform temperature is uneven.
- Another object of the present invention is to provide a binder resin composition, a reinforced fiber substrate, a preform and a fiber reinforced composite material using the binder resin composition.
- the present invention for solving the above problems is as follows.
- Tg of 50 ° C. ⁇ 100 ° C., a 10 kPa ⁇ 500 kPa complex modulus G * is at Tg + 30 ° C. by dynamic viscoelasticity measurement, be it 10 ⁇ 300 (G * at G * / Tg + 80 ° C. in Tg + 30 ° C.)
- the present invention includes binder particles made of the above-described preform binder resin composition.
- the present invention includes a reinforcing fiber substrate with a binder having the preform binder resin composition on at least one surface of the reinforcing fiber substrate.
- the present invention includes a preform on which the above-mentioned reinforcing fiber substrate with a binder is laminated.
- the present invention includes a fiber-reinforced composite material composed of a cured product of the above preform and a thermosetting resin.
- the present invention it is possible to obtain a preform binder resin composition having excellent stability during storage at room temperature, to produce a preform having excellent adhesion at low temperatures, and Even when the molding temperature is uneven, stable adhesiveness can be expressed.
- the binder resin composition for preforms according to the present invention has a Tg of 50 ° C. to 100 ° C., a complex elastic modulus G * by dynamic viscoelasticity measurement of 10 kPa to 500 kPa at Tg + 30 ° C., and (G * at Tg + 30 ° C.) .
- G * ) at / Tg + 80 ° C. is 10 to 300, and G * monotonously decreases as the temperature rises in the range of 0 to 200 ° C.
- the binder resin composition has the above-mentioned Tg and rheological properties, a preform having excellent stability at room temperature storage and excellent adhesion at low temperatures can be produced, and the molding temperature of the preform is uneven. Even if it is a case, stable adhesiveness can be expressed.
- the preform binder resin composition according to the present invention has a Tg of 50 to 100 ° C., preferably 50 to 80 ° C.
- the Tg of the binder resin composition is an important value for storage stability when the resin composition is used as a binder, and when Tg is less than 50 ° C., the storage resin stability at room temperature of the preform binder resin composition is insufficient. To do.
- Tg exceeds 100 ° C., heating at a high temperature is required to melt the binder resin composition, which is inferior in terms of high cycle performance and energy cost.
- the glass transition temperature Tg of the binder resin composition can be determined by dynamic viscoelasticity measurement.
- a dynamic viscoelasticity measuring apparatus for example, ARES-G2 (manufactured by TA Instruments) can be used.
- the resin sample is set on an 8 mm parallel plate, and the complex elastic modulus G * is measured by raising the temperature at 5 ° C./min while applying a traction period of 0.5 Hz at a temperature of 0 to 200 ° C.
- the temperature at the intersection of the tangent of the glass region and the tangent at the inflection point of the glass transition region is defined as Tg.
- the inflection point on the lowest temperature side is adopted.
- the binder resin composition for preforms according to the present invention needs to have a complex elastic modulus G * by dynamic viscoelasticity measurement of 10 kPa to 500 kPa at Tg + 30 ° C., and preferably 10 kPa to 300 kPa.
- the temperature of Tg + 30 ° C. is a temperature assuming that the binder resin composition is melted at a relatively low temperature
- the value of G * is appropriately determined when the binder resin composition is molded at that temperature. It is a value that serves as an indicator of whether or not it is possible to melt and bond between preform layers, that is, between the reinforcing fiber substrate and the reinforcing fiber substrate.
- the preform binder resin composition of the present invention (G * at G * / Tg + 80 ° C. in Tg + 30 ° C.) ratio of G * at Tg + 30 ° C. for G * at Tg + 80 ° C. is required to be 10 to 300, More preferably, it is 10 to 200.
- the ratio of G * at Tg + 30 ° C. to G * at Tg + 80 ° C. is a value representing the magnitude of the influence of G * in the molten binder resin composition for preforms due to temperature changes. When the ratio is less than 10, the binder resin composition tends to be in a rubber state, and sufficient adhesion to the reinforcing fiber base cannot be obtained. On the other hand, when the ratio is greater than 300, there is a large influence on temperature unevenness when the preform is molded, and there are places where sufficient adhesiveness cannot be obtained depending on the position in the preform.
- G * monotonously decreases as the temperature rises in the range of 0 to 200 ° C. This indicates that the binder resin composition has substantially no curing reactivity by itself. If G * does not decrease monotonously when the temperature is raised in the range of 0 to 200 ° C., the storage stability of the binder is insufficient.
- G * monotonously decreases as the temperature rises in the range of 0 to 200 ° C. means that when the temperature is raised from 0 ° C. to 200 ° C., there is a region where G * increases or a region where G * is constant. It means not existing. Note that the monotonously decreasing, not always at the same rate G * is meant to have decreased, the speed whatever, reduced G * when heated from 0 °C to 200 ° C. Means to keep doing.
- the preform binder resin composition has the above Tg and rheological properties
- the preform binder resin composition according to the present invention preferably includes the following components [A] and [B].
- Component [A] Epoxy resin
- Component [B] Thermoplastic resin soluble in component [A]
- Component [A] is preferably an epoxy resin having a Tg of 30 to 80 ° C.
- Component [A] epoxy resin adjusts the Tg of the binder resin composition for preforms in addition to the adhesiveness to the reinforcing fiber substrate and the affinity with the matrix resin when making the fiber-reinforced composite material, It is preferably used for controlling the Tg of the preform binder resin composition to 50 to 100 ° C.
- the epoxy resin is an aromatic glycidyl ether obtained from a phenol having a plurality of hydroxyl groups, an aliphatic glycidyl ether obtained from an alcohol having a plurality of hydroxyl groups, a glycidyl amine obtained from an amine, a glycidyl ester obtained from a carboxylic acid having a plurality of carboxyl groups, Any of alicyclic epoxy resins obtained from the oxidation of olefins can be used.
- the epoxy resin it is preferable to use a solid epoxy resin having a Tg of preferably 30 to 80 ° C., more preferably 40 to 80 ° C.
- a liquid or semi-solid epoxy resin it is necessary to add a large amount of thermoplastic resin in order to ensure the storage stability of the binder resin composition, and the binder resin composition will melt when molding a preform at a low temperature. In some cases, the adhesiveness may decrease.
- the liquid or semi-solid epoxy resin means an epoxy resin having a Tg lower than 30 ° C. and having a liquid or semi-solid form at room temperature.
- an epoxy resin having a Tg higher than 80 ° C. is used, the Tg of the binder resin composition tends to be high, and the adhesiveness may be lowered when the preform is molded at a low temperature.
- the Tg of the epoxy resin can be determined by dynamic viscoelasticity measurement in the same manner as the Tg of the binder resin composition for preform described above.
- the component [A] epoxy resin in the binder resin composition is composed of plural types of epoxy resins
- the plural types of epoxy resins are mixed in the same ratio as in the binder resin composition, and the mixture is measured.
- the Tg is preferably 30 to 80 ° C., more preferably 40 to 80 ° C.
- a bisphenol type epoxy resin is preferably used from the viewpoint of adhesiveness.
- Such bisphenol type epoxy resin is not particularly limited, but bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol Z type epoxy resin, and their Alkyl-substituted products, halogen-substituted products, hydrogenated products and the like can be used.
- the component [A] preferably contains a bisphenol type epoxy resin having an epoxy equivalent of 500 to 3500, and more preferably contains a bisphenol type epoxy resin having an epoxy equivalent of 500 to 2000.
- the epoxy equivalent is less than 500, it is necessary to add a large amount of thermoplastic resin in order to ensure storage stability, and the adhesiveness may be lowered during molding of the preform at a low temperature.
- the epoxy equivalent is larger than 3500, the binder resin composition does not melt when the preform is molded at a low temperature, and the adhesiveness may be lowered.
- the epoxy equivalent is a value obtained by dividing the mass (g) of the epoxy resin by the number of moles of all epoxy groups contained in the resin.
- the epoxy equivalent can be quantified by direct titration of the mixture of the epoxy resins according to JIS K7236 (2009).
- the epoxy equivalent of each epoxy resin component and its compounding quantity are known, it can also calculate by calculation.
- Component [A] is preferably contained in a proportion of 30 to 95% by mass, more preferably 50 to 95% by mass, in 100% by mass of the preform binder resin composition.
- the content of the component [A] in 100% by mass of the binder resin composition is less than 30% by mass, the adhesiveness with the reinforcing fiber substrate and the affinity with the matrix resin may be lowered.
- the content of component [B] in 100% by mass of the binder resin composition is more than 95% by mass, the adhesive strength between the preform layers may be lowered.
- Component [B] in the present invention thermoplastic resin soluble in component [A] provides stable adhesion between preform layers even when there is adhesiveness with reinforcing fibers or temperature unevenness during preform molding. It is suitably used for the purpose.
- the component [B] is soluble in the component [A] means that 90% by mass of the component [A] and 10% by mass of the component [B] thermoplastic resin are heated and stirred at 180 ° C. and uniformly mixed. This means that when the mixture is cooled to room temperature, phase separation is not observed when the mixture is observed with a 400 ⁇ optical microscope.
- Component [B] is not particularly limited, but polyamide, polycarbonate, polyacetal, polyphenylene oxide, polyphenylene sulfide, polyarylate, polyester, polyamideimide, polyimide, polyetherimide, polyimide having a phenyltrimethylindane structure , Polysulfone, Polyethersulfone, Polyetherketone, Polyetheretherketone, Polyaramid, Polyethernitrile, Polybenzimidazole, Polyurethane, Urea resin, Polyvinylpyrrolidone, Polyvinyl acetal, Polyvinyl formal, Polyvinyl alcohol and Phenoxy resin [A] is soluble.
- the component [B] is preferably a phenoxy resin.
- a phenoxy resin is used for component [B]
- the phenoxy resin preferably has a weight average molecular weight in the range of 10,000 to 2,000,000.
- the weight average molecular weight is more preferably 45,000 or more, and further preferably 70,000 or more.
- the weight average molecular weight is more preferably 1,500,000 or less.
- the weight average molecular weight of the phenoxy resin is smaller than 10,000, the adhesion may be lowered.
- a binder resin composition becomes difficult to melt
- the component [B] is polyetherimide, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, polyvinylpyrrolidone, polyvinyl acetal, polyvinyl formal and It is preferable that it consists of 1 or more types of resin chosen from the group which consists of polyvinyl alcohol.
- These resins preferably have a weight average molecular weight in the range of 10,000 to 2,000,000.
- the weight average molecular weight is more preferably 45,000 or more.
- the weight average molecular weight is more preferably 1,500,000 or less.
- the weight average molecular weight of the component [B] affects the rate of change of G * with respect to the temperature of the preform binder resin composition.
- the weight average molecular weight of the component [B] is less than 10,000, the binder resin composition easily penetrates into the reinforcing fiber base when the preform molding temperature becomes high, and sufficient adhesive strength cannot be obtained. In some cases, unevenness occurs in the adhesiveness in the preform.
- the weight average molecular weight is larger than 2,000,000, the binder resin composition is difficult to melt, so that the adhesiveness to the reinforcing fiber substrate may be inferior.
- the compatibility between the binder resin composition and the matrix resin is appropriate. If the binder resin composition is easily compatible with the matrix resin, the viscosity of the matrix resin may increase at the time of injection, and impregnation may decrease. On the other hand, if the binder resin composition is too incompatible with the matrix resin, the binder resin composition remains as a foreign substance in the molded body, and the physical properties of the molded body may decrease.
- the component [B] is preferably contained in a proportion of 5 to 50% by mass in 100% by mass of the preform binder resin composition, and may be contained in a proportion of 5 to 30% by mass. More preferred.
- the content of the component [B] in 100% by mass of the binder resin composition is less than 5% by mass, the flow optimization at the time of molding the preform is insufficient, and the adhesive strength is reduced due to uneven molding temperature of the preform. There may be a shortage.
- the content of the component [B] in 100% by mass of the binder resin composition is more than 50% by mass, the low-temperature fixability may be deteriorated.
- the weight average molecular weight in the present invention can be measured by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- the polymer to be measured is dissolved in tetrahydrofuran so that the concentration thereof is 0.1% by weight to obtain a sample solution.
- 0.3 ⁇ L of sample solution was injected into the column using two Shodex 80M (manufactured by Showa Denko) and one Shodex 802 (manufactured by Showa Denko), and the sample retention time measured at a flow rate of 1 mL / min.
- the weight average molecular weight can be calculated by converting the molecular weight to the molecular weight using the retention time of the polystyrene calibration sample.
- the Tg of component [B] is preferably 80 to 180 ° C., more preferably 80 to 150 ° C. so that the preform binder resin composition has the rheological properties described above.
- Tg of component [B] is lower than 80 ° C., the storage stability of the binder resin composition may be insufficient.
- Tg of component [B] exceeds 180 ° C., sufficient adhesiveness may not be obtained at low temperatures.
- the preform binder resin composition contains a curing catalyst, it has curing reactivity, and G * does not monotonously decrease as the temperature rises in the range of 0 to 200 ° C. In that case, the curing reaction of the binder resin composition proceeds during storage, and the binder particles do not melt at the preform molding temperature during molding. Therefore, it is preferable that the preform binder resin composition does not contain a curing catalyst.
- the form of the binder resin composition for preform of the present invention is not particularly limited, but forms such as films, tapes, long fibers, short fibers, spun yarns, woven fabrics, knits, non-woven fabrics, nets, particles, etc. Can be adopted. Among these, the particle form can be particularly preferably used.
- the binder resin composition in the form of particles is also referred to as binder particles.
- the average particle size is preferably 10 to 1000 ⁇ m.
- the average particle diameter refers to the volume average particle diameter.
- the adhesive strength and workability may be lowered.
- the average particle size is larger than 1000 ⁇ m, the reinforced fiber swells when it is formed into a preform and the mechanical properties of the fiber reinforced composite material are lowered, or it becomes difficult to dissolve the particles in the liquid thermosetting resin. In addition, problems such as a decrease in chemical resistance occur.
- the average particle size of the binder particles can be measured using, for example, a laser diffraction type particle size distribution meter.
- the binder resin composition for preform of the present invention is used by being attached to a reinforcing fiber substrate. That is, the reinforcing fiber substrate with a binder of the present invention has a preform binder resin composition on at least one surface of the reinforcing fiber substrate.
- carbon fiber As the reinforcing fiber used for the reinforcing fiber substrate, carbon fiber, glass fiber, aramid fiber, metal fiber, or a combination thereof can be used. Among these, carbon fibers can be suitably used because they are excellent in lightness and strength.
- the reinforcing fiber may be either a short fiber or a continuous fiber, and both may be used in combination. In order to obtain a high Vf fiber-reinforced composite material, continuous fibers are preferred.
- the form of the reinforcing fiber base a form such as a strand, a mat, a woven fabric, a knit, a braid, and a unidirectional sheet is preferably used.
- a woven fabric which is easy to obtain a high Vf fiber-reinforced composite material and excellent in handleability is preferably used.
- plain weaving, satin weaving, twill weaving, non-crimp cloth and the like can be selected as appropriate.
- plain weaving, satin weaving, twill weaving, non-crimp cloth and the like can be selected as appropriate.
- plain weave or twill weave increases the design.
- satin weave and twill weave are good for draping and are therefore preferably used when shaping a three-dimensional shape with a deep depth.
- the ratio of the net volume of the reinforcing fibers to the apparent volume of the fabric is defined as the fabric filling rate.
- the filling rate of the woven fabric is obtained from the weight per unit area W (unit: g / m 2 ), the thickness t (unit: mm), and the density ⁇ f (unit: g / cm 3 ) of the reinforcing fiber by the formula of W / (1000 t ⁇ ⁇ f). It is done.
- the fabric weight and thickness are determined in accordance with JIS R 7602 (1995). The higher the woven fabric filling rate, the easier it is to obtain a fiber reinforced composite material having a high Vf. Therefore, the woven fabric filling rate is preferably 0.10 to 0.85, more preferably 0.40 to 0.85, and even more preferably. It is in the range of 0.50 to 0.85.
- the fiber volume content Vf is preferably in the range of 40 to 85%, preferably 45 to 85%.
- the fiber volume content Vf of a fiber reinforced composite material said here is a value defined and measured by the following based on ASTM D3171 (1999), and is liquid heat with respect to a reinforced fiber base material. The value in the state after injecting and hardening
- Fiber volume content Vf (%) (Af ⁇ N) / ( ⁇ f ⁇ h) / 10 (Formula 1) Af: reinforcing fiber substrate one ⁇ 1 m 2 per mass (g / m 2) N: Number of laminated reinforcing fiber substrates (sheets) ⁇ f: density of reinforcing fiber (g / cm 3 ) h: Thickness (mm) of the fiber reinforced composite material (test piece).
- the combustion method or nitric acid decomposition based on JIS K 7075 (1991) The fiber volume content of the fiber reinforced composite material is measured by either the method or the sulfuric acid decomposition method.
- the density of the reinforcing fiber used in this case a value measured based on JIS R 7603 (1999) is used.
- the preform binder resin composition of the present invention When adhered to at least one surface of the reinforcing fiber substrate, it adheres to at least one surface with a basis weight of 0.5 to 30 g / m 2 , preferably 1 to 10 g / m 2. It is preferable. If the basis weight is less than 0.5 g / m 2 , the effect of fixing the shape and increasing the toughness is small, and if it is more than 30 g / m 2 , the apparent volume of the reinforcing fiber strand or the reinforcing fiber base increases, so that the reinforcement There are disadvantages such as difficulty in producing a fiber-reinforced composite material having a high fiber volume content or poor impregnation of the thermosetting resin.
- the preform of the present invention is obtained by laminating the reinforcing fiber substrate with the binder of the present invention. More specifically, a reinforcing fiber base material having the binder resin composition described above on at least one surface is laminated and the form is fixed. Reinforcing fiber base material with binder has the binder resin composition for preform attached to at least one side of the reinforcing fiber base material, and usually the binder resin composition is cured and reinforced by laminating and heating. The form is fixed by fixing between fiber base materials.
- the preform can be produced by cutting out a sheet-like reinforcing fiber base to which the binder resin composition is adhered, into a predetermined shape, laminating on a mold, and applying appropriate heat and pressure.
- the pressurizing means may be a press, or a method of enclosing with a vacuum bag film and sucking the inside with a vacuum pump and pressurizing with atmospheric pressure.
- the fiber-reinforced composite material of the present invention comprises a cured product of the preform of the present invention and a thermosetting resin. That is, a fiber reinforced composite material can be produced by impregnating a preform containing the binder resin composition for a preform of the present invention with a liquid thermosetting resin and then curing the liquid thermosetting resin.
- the production method of the fiber reinforced composite material is not particularly limited, but a molding method using a two-component resin such as a hand layup method or an RTM method is preferably used.
- the RTM molding method is particularly preferably used from the viewpoints of productivity and the shape freedom of the molded body.
- a liquid thermosetting resin is injected into a reinforcing fiber base disposed in a mold and cured to obtain a reinforcing fiber composite material.
- the liquid thermosetting resin is composed of a liquid resin mainly composed of a monomer component and a curing agent or a curing catalyst for polymerizing the monomer component by three-dimensionally crosslinking the monomer component.
- the liquid resin is preferably an epoxy resin from the viewpoint of reactivity and compatibility with the preform binder resin composition of the present invention.
- the epoxy resin examples include an aromatic glycidyl ether obtained from a phenol having a plurality of hydroxyl groups, an aliphatic glycidyl ether obtained from an alcohol having a plurality of hydroxyl groups, a glycidyl amine obtained from an amine, and a carboxylic acid having a plurality of carboxyl groups. And an epoxy resin having an oxirane ring.
- aliphatic polyamines aromatic polyamines, acid anhydrides, imidazoles, Lewis acid complexes and the like are suitable, and they are appropriately selected and used depending on the intended use.
- the mold temperature during heat curing may be the same as the mold temperature during the injection of the liquid thermosetting resin, but in the case of curing at a low temperature, rigidity sufficient to prevent deformation of the fiber-reinforced composite material is obtained upon demolding. Since it may take time to advance the curing until it is completed, it is preferable to select a temperature higher than the mold temperature at the time of pouring, for example, a range of 60 to 180 ° C. is preferable.
- PKHH manufactured by InChem
- Curing catalyst “CUREZOL” registered trademark) 2E4MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.): 2-ethyl-4methylimidazole.
- ⁇ Preparation of binder resin composition An epoxy resin, a thermoplastic resin and a curing catalyst were mixed uniformly by heating and stirring at 180 ° C. for 1 hour in the mixing ratio of the raw materials described in Tables 1 to 3, thereby preparing a binder resin composition for preform.
- a curing catalyst was included, it was prepared under conditions where the curing reaction did not proceed substantially.
- Tg of Epoxy Resin, Tg of Resin Composition, Complex Elastic Modulus G * It determined by dynamic viscoelasticity measurement using an epoxy resin or a resin composition as a sample.
- ARES-G2 manufactured by TA Instruments
- a resin sample was set on an 8 mm parallel plate, a traction period of 0.5 Hz was added, and a complex elastic modulus G * was measured in a temperature range of 0 to 200 ° C. at a temperature rising rate of 5 ° C./min.
- the prepared binder resin composition for preforms was freeze-pulverized using liquid nitrogen using a hammer mill (PULVERIZER, manufactured by Hosokawa Micron Corporation) with a screen having a pore size of 1 mm to obtain particles. By passing the obtained particles through a sieve having an opening size of 212 ⁇ m, coarse particles were eliminated to obtain preform binder particles.
- Preform production> The binder particles produced as described above were applied to one side of a carbon fiber woven fabric ("Treka (registered trademark)" cloth CO6343, carbon fiber: T300-3K, organization: plain weave, basis weight: 198 g / m 2 , manufactured by Toray Industries, Inc.) After spraying at a spraying amount of 6 g / m 2 , the surface was heated using a far-red heater to obtain a reinforcing fiber substrate with a binder. Two preformed reinforcing fiber bases were stacked and heated for 30 seconds at a molding temperature of Tg + 30 ° C. of the binder particles used while applying a pressure of 50 kPa to prepare a preform.
- the ratio of the adhesive strength of the preform produced at the molding temperature of Tg + 30 ° C. of the binder particles used to the adhesive strength of the preform produced at the molding temperature of Tg + 80 ° C. of the binder particles used is 0.8 or more.
- the ratio is 1.2 or less, good, and when the ratio of the adhesive strength values is 0.5 or more and less than 0.8 or more than 1.2 and 1.5 or less, the value is fair.
- Example 2 binder particles composed of 50% by mass of a bisphenol A type epoxy resin having a Tg of 35 ° C. and 50% by mass of a phenoxy resin having a weight average molecular weight of 70,000 were used.
- the produced binder particles were excellent in storage stability, sufficient adhesive strength was obtained at the time of preform molding at a temperature of Tg + 30 ° C., and the influence of unevenness in preform molding temperature was acceptable.
- the produced binder particles were excellent in storage stability, had excellent adhesive strength at the time of preform molding at a temperature of Tg + 30 ° C., and the influence of preform molding temperature unevenness was small.
- Example 4 binder particles composed of 72% by mass of a bisphenol A type epoxy resin having a Tg of 57 ° C. and 28% by mass of a phenoxy resin having a weight average molecular weight of 70,000 were used.
- the produced binder particles were excellent in storage stability, had excellent adhesive strength at the time of preform molding at a temperature of Tg + 30 ° C., and the influence of preform molding temperature unevenness was small.
- Example 5 binder particles composed of 40% by mass of a liquid bisphenol A type epoxy resin, 50% by mass of a bisphenol A type epoxy resin having a Tg of 82 ° C., and 10% by mass of a phenoxy resin having a weight average molecular weight of 70,000 were used.
- the produced binder particles were excellent in storage stability, had excellent adhesive strength at the time of preform molding at a temperature of Tg + 30 ° C., and the influence of preform molding temperature unevenness was small.
- the produced binder particles were excellent in storage stability, had excellent adhesive strength at the time of preform molding at a temperature of Tg + 30 ° C., and the influence of preform molding temperature unevenness was small.
- the produced binder particles were excellent in storage stability, had excellent adhesive strength at the time of preform molding at a temperature of Tg + 30 ° C., and the influence of preform molding temperature unevenness was small.
- the produced binder particles were excellent in storage stability, had excellent adhesive strength at the time of preform molding at a temperature of Tg + 30 ° C., and the influence of preform molding temperature unevenness was small.
- the produced binder particles were excellent in storage stability, had excellent adhesive strength at the time of preform molding at a temperature of Tg + 30 ° C., and the influence of preform molding temperature unevenness was small.
- the produced binder particles were excellent in storage stability, had excellent adhesive strength at the time of preform molding at a temperature of Tg + 30 ° C., and the influence of preform molding temperature unevenness was small.
- Example 11 binder particles composed of 75% by mass of a cresol novolac type epoxy resin having a Tg of 58 ° C. and 25% by mass of a polyvinyl pyrrolidone resin having a weight average molecular weight of 10,500 were used.
- the produced binder particles were excellent in storage stability, sufficient adhesive strength was obtained at the time of preform molding at a temperature of Tg + 30 ° C., and the influence of unevenness in preform molding temperature was acceptable.
- Example 12 binder particles composed of 85% by mass of a bisphenol A type epoxy resin having a Tg of 57 ° C. and 15% by mass of a polyvinyl pyrrolidone resin having a weight average molecular weight of 10,500 were used.
- the produced binder particles were excellent in storage stability, sufficient adhesive strength was obtained at the time of preform molding at a temperature of Tg + 30 ° C., and the influence of unevenness in preform molding temperature was acceptable.
- the produced binder particles were excellent in storage stability, and sufficient adhesive strength was obtained during preform molding at a temperature of Tg + 30 ° C., and the influence of preform molding temperature unevenness was small.
- the produced binder particles were excellent in storage stability, and sufficient adhesive strength was obtained during preform molding at a temperature of Tg + 30 ° C., and the influence of preform molding temperature unevenness was small.
- binder particles composed of 40% by mass of a bisphenol A type epoxy resin having a Tg of 35 ° C. and 60% by mass of a phenoxy resin having a weight average molecular weight of 70,000 were used.
- the produced binder particles were excellent in storage stability, but sufficient adhesive strength was not obtained during preform molding at a temperature of Tg + 30 ° C.
- the produced binder particles were fused with each other during storage, and storage stability was insufficient.
- Comparative Example 3 binder particles composed of 40% by mass of a liquid bisphenol A type epoxy resin and 60% by mass of a phenoxy resin having a weight average molecular weight of 70,000 were used.
- the produced binder particles were fused with each other during storage, and storage stability was insufficient. Adhesive strength at the time of preform molding at a temperature of Tg + 30 ° C. was also insufficient.
- Comparative example 4 In Comparative Example 4, binder particles composed of 70% by mass of a bisphenol A type epoxy resin having a Tg of 35 ° C., 29% by mass of a phenoxy resin having a weight average molecular weight of 70,000, and 1% by mass of 2-ethyl-4-methylimidazole were used. .
- the produced binder particles undergo a resin curing reaction during storage, and the binder particles do not melt at a preform molding temperature of Tg + 30 ° C.
- the produced binder particles have a low adhesive strength, and the G * is remarkably lowered when heated at a high temperature.
- the polyamide resin does not dissolve in the epoxy resin, and the G * is remarkably lowered when heated to a high temperature.
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Abstract
Description
成分[B]:成分[A]に可溶な熱可塑性樹脂
成分[A]はTgが30~80℃のエポキシ樹脂であることが好ましい。成分[A]エポキシ樹脂は、強化繊維基材との接着性および繊維強化複合材料とする時のマトリックス樹脂との親和性の観点に加え、プリフォーム用バインダー樹脂組成物のTgを調整する、つまりプリフォーム用バインダー樹脂組成物のTgを50~100℃に制御するために好ましく用いられる。
本発明における成分[B](成分[A]に可溶な熱可塑性樹脂)は、強化繊維との接着性やプリフォーム成形時の温度ムラがあっても安定したプリフォーム層間の接着性を出す目的で好適に用いられる。
繊維体積含有率Vf(%)=(Af×N)/(ρf×h)/10 ・・・(式1)
Af:強化繊維基材1枚・1m2当たりの質量(g/m2)
N:強化繊維基材の積層枚数(枚)
ρf:強化繊維の密度(g/cm3)
h:繊維強化複合材料(試験片)の厚み(mm)。
各実施例の樹脂組成物を得るために、以下の樹脂原料を用いた。なお、表における樹脂組成物の含有割合の単位は、特に断らない限り「質量%」を意味する。
エポキシ樹脂
・YD-128(新日鉄住金化学(株)製):2官能ビスフェノールA型エポキシ樹脂、液状、エポキシ当量=189
・“jER” (登録商標)834(三菱化学(株)製):2官能ビスフェノールA型エポキシ樹脂、半固形、エポキシ当量=250
・“jER” (登録商標)1001(三菱化学(株)製):2官能ビスフェノールA型エポキシ樹脂、Tg=35℃、エポキシ当量=475
・“jER” (登録商標)1004(三菱化学(株)製):2官能ビスフェノールA型エポキシ樹脂、Tg=57℃、エポキシ当量=975
・“jER” (登録商標)1007(三菱化学(株)製):2官能ビスフェノールA型エポキシ樹脂、Tg=76℃、エポキシ当量=1925
・“jER” (登録商標)1010(三菱化学(株)製):2官能ビスフェノールA型エポキシ樹脂、Tg=82℃、エポキシ当量=4000
・“EPICLON” (登録商標)N-695(DIC(株)製):クレゾールノボラック型エポキシ樹脂、Tg=58℃
熱可塑性樹脂
・YP-50(新日鉄住金化学(株)製):フェノキシ樹脂、重量平均分子量70,000、Tg=88℃
・YP-55(新日鉄住金化学(株)製):フェノキシ樹脂、重量平均分子量47,500、Tg=86℃
・PKHH(InChem社製):フェノキシ樹脂、重量平均分子量42,600、Tg=88℃
・“ビニレック” (商標登録)K(チッソ(株)製):ポリビニルホルマール、重量平均分子量47300、Tg=90
・“スミカエクセル” (商標登録)PES5003P(住友化学(株)製):ポリエーテルスルホン、重量平均分子量47000、Tg=225℃
・“ウルテム” (商標登録)1010(Sabic社製):ポリエーテルイミド、重量平均分子量41000、Tg=217℃
・ポリビニルピロリドン K15(東京化成(株)製):ポリビニルピロリドン樹脂、重量平均分子量10,500、Tg=130℃
・ポリビニルピロリドン K30(東京化成(株)製):ポリビニルピロリドン樹脂、重量平均分子量60,0000、Tg=170℃
・ポリビニルピロリドン K90(東京化成(株)製):ポリビニルピロリドン樹脂、重量平均分子量1,350,000、Tg=174℃
・“グリルアミド” (商標登録)TR-55(エムザベルケ(株)製):ポリアミド樹脂、重量平均分子量18,000、Tg=160℃
硬化触媒
・“キュアゾール” (登録商標)2E4MZ(四国化成工業(株)製)):2-エチル-4メチルイミダゾール。
表1~3に記載した原料と配合比でエポキシ樹脂、熱可塑性樹脂および硬化触媒を180℃、1時間加熱攪拌することにより均一に混合し、プリフォーム用バインダー樹脂組成物を調製した。硬化触媒を含む場合、硬化反応が実質的に進まない条件で調製した。
エポキシ樹脂または樹脂組成物を試料として、動的粘弾性測定により求めた。測定装置にはARES-G2(TA Instruments社製)を使用した。樹脂サンプルを8mmのパラレルプレートにセットし、0.5Hzの牽引周期を加え、昇温速度5℃/分で、0~200℃の温度範囲で複素弾性率G*測定した。得られたG*の対数を縦軸に、温度を横軸にとったグラフにおいて、ガラス領域の接線と、ガラス転移領域の変曲点における接線の交点の温度をTgとして求めた。
調製したプリフォーム用バインダー樹脂組成物をハンマーミル(PULVERIZER、ホソカワミクロン(株)製)を用いて、孔サイズ1mmのスクリーンを使用し、液体窒素を用いて凍結粉砕して粒子を得た。得られた粒子を目開きサイズ212μmの篩いに通すことで粗大な粒子を排除し、プリフォーム用バインダー粒子を得た。
作製したプリフォーム用バインダー粒子を40℃環境で1ヶ月間静置した時に、バインダー粒子同士の凝集・融着がない、および前記手法(つまり、〈エポキシ樹脂のTg、樹脂組成物のTg、複素弾性率G*の測定〉の項に記載した方法)で測定したG*の値が、0~200℃の範囲で昇温するにつれて単調に減少する場合をgood、バインダー粒子同士の凝集・融着がある、または前記手法で昇温測定したG*の値が単調に減少しない場合をbadとした。
前述のように作製したバインダー粒子を炭素繊維織物(”トレカ(登録商標)”クロスCO6343、炭素繊維:T300-3K、組織:平織、目付:198g/m2、東レ(株)製)の片面に6g/m2の散布量で散布した後、表面を遠赤ヒーターを用いて加熱することによりバインダー付強化繊維基材を得た。バインダー付強化繊維基材を2枚重ね、50kPaの圧力を加えながら使用したバインダー粒子のTg+30℃の成形温度で30秒間加熱することによりプリフォームを作製した。
上記のようにして作製したプリフォームについて、強化繊維基材間の引き剥がし試験を行った。試験はJIS K6854(1977)に従い、インストロン万能試験機(インストロン社製)を用いて実施した。試験片は作製したプリフォームを長さ150mm(接着部分は100mm)、幅25mmにカットして仕上げた。同一試験に用いる試験片の数は5個とし、試験結果にはその平均値を使用した。引っ張り速さは50mm/分とした。
使用したバインダー粒子のTg+80℃の成形温度で作製したプリフォームの接着強度に対して、使用したバインダー粒子のTg+30℃の成形温度で作製したプリフォームの接着強度の値の比が、0.8以上1.2以下となる場合good、接着強度の値の比が、0.5以上0.8未満または1.2を超え1.5以下となる場合fair、それ以外となる場合badとした。
表1の配合比に従って、前記したようにして調製したプリフォーム用バインダー樹脂組成物のTgおよび複素弾性率G*の測定を行った。また、そのプリフォーム用バインダー樹脂組成物を用いて作製したバインダー粒子を用い接着強度評価を行った
実施例1では、Tg=35℃のビスフェノールA型エポキシ樹脂68質量%、重量平均分子量70,000のフェノキシ樹脂32質量%からなるバインダー粒子を使用した。このプリフォーム用バインダー樹脂組成物は、Tg=53℃、Tg+30℃におけるG*=120、(Tg+30℃におけるG*/Tg+80℃におけるG*)=90であった。作製したバインダー粒子は保管安定性に問題がなく、Tg+30℃の温度におけるプリフォーム成形時に十分な接着強度が得られ、プリフォーム成形温度ムラの影響も小さかった。
実施例2では、Tg=35℃のビスフェノールA型エポキシ樹脂50質量%、重量平均分子量70,000のフェノキシ樹脂50質量%からなるバインダー粒子を使用した。このプリフォーム用バインダー樹脂組成物は、Tg=62℃、Tg+30℃におけるG*=400、(Tg+30℃におけるG*/Tg+80℃におけるG*)=20であった。作製したバインダー粒子は保管安定性に優れ、Tg+30℃の温度におけるプリフォーム成形時に十分な接着強度が得られ、プリフォーム成形温度ムラの影響も許容できるレベルであった。
実施例3では、Tg=76℃のビスフェノールA型エポキシ樹脂90質量%、重量平均分子量70,000のフェノキシ樹脂10質量%からなるバインダー粒子を使用した。このプリフォーム用バインダー樹脂組成物は、Tg=79℃、Tg+30℃におけるG*=180、(Tg+30℃におけるG*/Tg+80℃におけるG*)=150であった。作製したバインダー粒子は保管安定性に優れ、Tg+30℃の温度におけるプリフォーム成形時に優れた接着強度が得られ、プリフォーム成形温度ムラの影響も小さかった。
実施例4では、Tg=57℃のビスフェノールA型エポキシ樹脂72質量%、重量平均分子量70,000のフェノキシ樹脂28質量%からなるバインダー粒子を使用した。このプリフォーム用バインダー樹脂組成物は、Tg=75℃、Tg+30℃におけるG*=300、(Tg+30℃におけるG*/Tg+80℃におけるG*)=100であった。作製したバインダー粒子は保管安定性に優れ、Tg+30℃の温度におけるプリフォーム成形時に優れた接着強度が得られ、プリフォーム成形温度ムラの影響も小さかった。
実施例5では、液状のビスフェノールA型エポキシ樹脂40質量%、Tg=82℃のビスフェノールA型エポキシ樹脂50質量%、重量平均分子量70,000のフェノキシ樹脂10質量%からなるバインダー粒子を使用した。このプリフォーム用バインダー樹脂組成物は、Tg=51℃、Tg+30℃におけるG*=350、(Tg+30℃におけるG*/Tg+80℃におけるG*)=80であった。作製したバインダー粒子は保管安定性に優れ、Tg+30℃の温度におけるプリフォーム成形時に優れた接着強度が得られ、プリフォーム成形温度ムラの影響も小さかった。
実施例6では、Tg=57℃のビスフェノールA型エポキシ樹脂80質量%、重量平均分子量70,000のフェノキシ樹脂20質量%からなるバインダー粒子を使用した。このプリフォーム用バインダー樹脂組成物は、Tg=68℃、Tg+30℃におけるG*=80、(Tg+30℃におけるG*/Tg+80℃におけるG*)=160であった。作製したバインダー粒子は保管安定性に優れ、Tg+30℃の温度におけるプリフォーム成形時に優れた接着強度が得られ、プリフォーム成形温度ムラの影響も小さかった。
実施例11では、Tg=58℃のクレゾールノボラック型エポキシ樹脂75質量%、重量平均分子量10,500のポリビニルピロリドン樹脂25質量%からなるバインダー粒子を使用した。このプリフォーム用バインダー樹脂組成物は、Tg=88℃、Tg+30℃におけるG*=450、(Tg+30℃におけるG*/Tg+80℃におけるG*)=80であった。作製したバインダー粒子は保管安定性に優れ、Tg+30℃の温度におけるプリフォーム成形時に十分な接着強度が得られ、プリフォーム成形温度ムラの影響も許容できるレベルであった。
実施例12では、Tg=57℃のビスフェノールA型エポキシ樹脂85質量%、重量平均分子量10,500のポリビニルピロリドン樹脂15質量%からなるバインダー粒子を使用した。このプリフォーム用バインダー樹脂組成物は、Tg=79℃、Tg+30℃におけるG*=140、(Tg+30℃におけるG*/Tg+80℃におけるG*)=250であった。作製したバインダー粒子は保管安定性に優れ、Tg+30℃の温度におけるプリフォーム成形時に十分な接着強度が得られ、プリフォーム成形温度ムラの影響も許容できるレベルであった。
表3の配合比に従う以外は実施例1と同様にしてプリフォーム用バインダー樹脂組成物の調製および評価並びにプリフォームの作製および評価を行った。
比較例2では、液状のビスフェノールA型エポキシ樹脂25質量%、Tg=35℃のビスフェノールA型エポキシ樹脂25質量%、重量平均分子量70,000のフェノキシ樹脂50質量%からなるバインダー粒子を使用した。このプリフォーム用バインダー樹脂組成物は、Tg=45℃、Tg+30℃におけるG*=100、(Tg+30℃におけるG*/Tg+80℃におけるG*)=40であった。作製したバインダー粒子は保管時に粒子同士が融着しており、保管安定性が不足した。
比較例3では、液状のビスフェノールA型エポキシ樹脂40質量%、重量平均分子量70,000のフェノキシ樹脂60質量%からなるバインダー粒子を使用した。このプリフォーム用バインダー樹脂組成物は、Tg=40℃、Tg+30℃におけるG*=1200、(Tg+30℃におけるG*/Tg+80℃におけるG*)=30であった。作製したバインダー粒子は保管時に粒子同士が融着し、保管安定性が不足した。Tg+30℃の温度におけるプリフォーム成形時の接着強度も不十分であった。
比較例4では、Tg=35℃のビスフェノールA型エポキシ樹脂70質量%、重量平均分子量70,000のフェノキシ樹脂29質量%、2-エチル-4-メチルイミダゾール1質量%からなるバインダー粒子を使用した。このプリフォーム用バインダー樹脂組成物は、Tg=50℃、Tg+30℃におけるG*=80、(Tg+30℃におけるG*/Tg+80℃におけるG*)=1.6×10-3であった。作製したバインダー粒子は保管時に樹脂の硬化反応が進行し、Tg+30℃のプリフォーム成形温度ではバインダー粒子が溶融しなくなった。
比較例5では、半固形のビスフェノールA型エポキシ樹脂75質量%、Tg=88℃のフェノキシ樹脂25質量%からなるバインダー粒子を使用した。このプリフォーム用バインダー樹脂組成物は、Tg=36℃、Tg+30℃におけるG*=50、(Tg+30℃におけるG*/Tg+80℃におけるG*)=330であった。作製したバインダー粒子は接着強度が低く、高温加熱時に著しくG*が低下するため、プリフォーム成形温度ムラの影響が大きかった。
比較例6では、Tg=57℃のビスフェノールA型エポキシ樹脂50質量%、Tg=76℃のビスフェノールA型エポキシ樹脂50質量%からなるバインダー粒子を使用した。このプリフォーム用バインダー樹脂組成物は、Tg=70℃、Tg+30℃におけるG*=50、(Tg+30℃におけるG*/Tg+80℃におけるG*)=400であった。作製したバインダー粒子は高温に加熱時に著しくG*が低下するため、プリフォーム成形温度ムラの影響が大きかった。
比較例7では、Tg=57℃のビスフェノールA型エポキシ樹脂80質量%、ポリアミド樹脂20質量%からなるバインダー粒子を使用した。このプリフォーム用バインダー樹脂組成物は、Tg=62℃、Tg+30℃におけるG*=30、(Tg+30℃におけるG*/Tg+80℃)におけるG*=500であった。作製したバインダー粒子は、ポリアミド樹脂がエポキシ樹脂に溶解せず、高温に加熱時に著しくG*が低下するため、プリフォーム成形温度ムラの影響が大きかった。
Claims (11)
- Tgが50℃~100℃であり、動的粘弾性測定による複素弾性率G*がTg+30℃で10kPa~500kPaであり、(Tg+30℃におけるG*/Tg+80℃におけるG*)が10~300であり、0~200℃の範囲で昇温するにつれてG*が単調に減少するプリフォーム用バインダー樹脂組成物。
- 成分[A]および成分[B]を含むプリフォーム用バインダー樹脂組成物であって、成分[A]のTgが30~80℃である請求項1に記載のプリフォーム用バインダー樹脂組成物;
成分[A]:エポキシ樹脂;
成分[B]:成分[A]に可溶な熱可塑性樹脂。 - 成分[A]が、エポキシ当量500~3500であるビスフェノール型エポキシ樹脂を含む、請求項2に記載のプリフォーム用バインダー樹脂組成物。
- 成分[A]のTgが40~80℃である請求項2または3に記載のプリフォーム用バインダー樹脂組成物。
- 成分[B]が、フェノキシ樹脂である、請求項2~4のいずれかに記載のプリフォーム用バインダー樹脂組成物。
- 成分[B]が、ポリエーテルイミド、ポリスルホン、ポリエーテルスルホン、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリビニルピロリドン、ポリビニルアセタール、ポリビニルホルマールおよびポリビニルアルコールから選ばれた1種以上の樹脂からなる、請求項2~4のいずれかに記載のプリフォーム用バインダー樹脂組成物。
- バインダー樹脂組成物100質量%中に、成分[B]を5~50質量%の範囲で含む、請求項2~6のいずれかに記載のプリフォーム用バインダー樹脂組成物。
- 請求項1~7のいずれかに記載のプリフォーム用バインダー樹脂組成物からなるバインダー粒子。
- 請求項1~7のいずれかに記載のプリフォーム用バインダー樹脂組成物を、強化繊維基材の少なくとも一方の表面に有するバインダー付強化繊維基材。
- 請求項9に記載のバインダー付強化繊維基材が積層されたプリフォーム。
- 請求項10に記載のプリフォームと熱硬化性樹脂の硬化物からなる繊維強化複合材料。
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KR1020187012919A KR20180094851A (ko) | 2015-12-17 | 2016-12-02 | 프리폼용 바인더 수지 조성물, 바인더 입자, 강화 섬유 기재, 프리폼 및 섬유 강화 복합재료 |
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US15/778,055 US20180340047A1 (en) | 2015-12-17 | 2016-12-02 | Binder resin composition for preform, binder particles, reinforcing fiber base material, preform, and fiber reinforced composite material |
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