WO2021200453A1 - プリプレグおよび繊維強化複合材料 - Google Patents

プリプレグおよび繊維強化複合材料 Download PDF

Info

Publication number
WO2021200453A1
WO2021200453A1 PCT/JP2021/012198 JP2021012198W WO2021200453A1 WO 2021200453 A1 WO2021200453 A1 WO 2021200453A1 JP 2021012198 W JP2021012198 W JP 2021012198W WO 2021200453 A1 WO2021200453 A1 WO 2021200453A1
Authority
WO
WIPO (PCT)
Prior art keywords
prepreg
resin
fiber
resin composition
slit
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/012198
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
青木惇一
藤原隆行
河内真二
城戸大輔
武田直也
相澤凡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Industries Inc
Original Assignee
Toray Industries Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Priority to JP2021518010A priority Critical patent/JPWO2021200453A1/ja
Priority to EP21782093.5A priority patent/EP4129603A4/en
Priority to US17/909,821 priority patent/US20240199831A1/en
Publication of WO2021200453A1 publication Critical patent/WO2021200453A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • C08J2363/02—Polyglycidyl ethers of bis-phenols
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • 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
    • C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2481/06—Polysulfones; Polyethersulfones

Definitions

  • the present invention relates to a prepreg that provides a slit tape having excellent processability and quality, which is suitably used for producing a fiber-reinforced composite material using an automatic laminating device.
  • Fiber reinforced composite consisting of reinforcing fibers such as glass fiber, carbon fiber and aramid fiber and cured product of thermosetting resin such as unsaturated polyester resin, vinyl ester resin, epoxy resin, phenol resin, cyanate ester resin and bismaleimide resin.
  • thermosetting resin such as unsaturated polyester resin, vinyl ester resin, epoxy resin, phenol resin, cyanate ester resin and bismaleimide resin.
  • the material is lightweight, it has excellent mechanical properties such as strength and elasticity, heat resistance, and corrosion resistance, so it is used in many fields such as aircraft parts, spacecraft parts, automobile parts, ship parts, civil engineering and building materials, and sporting goods. It has been applied.
  • fiber-reinforced composite materials using continuous fibers as reinforcing fibers have been used.
  • Carbon fibers having excellent specific strength and specific elastic modulus are widely used as reinforcing fibers
  • epoxy resins having high mechanical properties, heat resistance and chemical resistance and excellent adhesion to carbon fibers are widely used as matrix resins. ing.
  • the application ratio of fiber reinforced composite materials to aircraft has increased significantly in order to reduce the weight of the aircraft and improve fuel efficiency.
  • the ATL (Automated Type Layup) method and the AFP (Automated Fiber Placement) method are used as a method for laminating prepregs using an automatic laminating device that is superior in productivity to hand layup. Etc. are used.
  • the AFP method is a method in which about ten to several tens of slit tapes are passed through a guide roll, focused on the machine head, and laminated on the base material using an automatic laminating device. Parts with relatively many curved surfaces such as aircraft fuselage are laminated. Suitable for manufacturing.
  • the AFP method has been widely used in recent years because of its high material yield.
  • the slit tape used in the AFP method is a tape-like tape obtained by slitting a wide prepreg in which reinforcing fibers are arranged in one direction to a width of several mm to several cm in parallel with the fiber direction.
  • a large amount of prepregs are often processed in parallel at the same time, and the prepregs used need to have good slit workability.
  • Poor slit workability means that the resin composition contained in the prepreg adheres to the slitter blade, and troubles such as the reinforcing fibers wrapping around the blade occur. In that case, there is a problem that the working time is greatly increased and the productivity is greatly lowered, such as disassembling and cleaning the device.
  • the resin or fiber at the end of the prepreg is taken by the blade, so that the width of the slit tape fluctuates greatly, and the target width accuracy of the slit tape cannot be obtained. The quality and quality deteriorate.
  • Patent Document 1 a unidirectional prepreg using a twistless reinforcing fiber bundle is cured until the resin reaction rate of the matrix resin composition reaches 20 to 70% to obtain a semi-cured prepreg, and then the fibers of the reinforcing fiber are obtained. Slit tapes obtained by cutting along the direction are described.
  • This prepreg has excellent straightness of the reinforcing fiber, is less likely to be twisted, has reduced tack on the tape surface, and is excellent in handleability.
  • Patent Document 2 describes a prepreg provided with a flexible polymer sheet on the surface of the prepreg, and can suppress resin adhesion to the blade.
  • An object of the present invention is a prepreg for producing a slit tape suitable for producing a fiber-reinforced composite material using an automatic laminating device by solving the above-mentioned problems, which is excellent in slit workability and has a slit processability. It is to provide a prepreg that provides a slit tape of excellent quality.
  • the prepreg of the present invention is a prepreg containing reinforcing fibers and a resin composition, and when the average thickness of the prepreg is D, the resin present at a portion where the depth from the surface of the prepreg is located at D / 10.
  • the composition when the viscoelasticity measurement was performed at a measurement frequency of 50 rad / s or more, the loss tangent tan ⁇ at the slit processing temperature was y, the reinforcing fiber longitudinal direction 100 mm ⁇ width 100 mm, and 5 mm of the tip of the reinforcing fiber longitudinal direction was placed in water.
  • the impregnation rate evaluated by the amount of water absorbed during immersion for 5 minutes is x, it is a prepreg having the relationship of the following formula 1.
  • a prepreg for manufacturing a slit tape preferably used for manufacturing a fiber-reinforced composite material using an automatic laminating device, and provides a slit tape having excellent slit workability and excellent quality.
  • a prepreg can be provided.
  • FIG. 1 shows a cross section of the prepreg of the present invention.
  • the prepreg of the present invention contains a reinforcing fiber and a resin composition.
  • the reinforcing fiber is not particularly limited, but for example, carbon fiber, glass fiber, aramid fiber, silicon carbide fiber, polyester fiber, ceramic fiber, alumina fiber, boron fiber, metal fiber, mineral fiber, rock fiber, slug fiber and the like may be used. Can be done.
  • carbon fibers, glass fibers, and aramid fibers are preferable, carbon fibers having good specific strength and specific elastic coefficient, and a lightweight and high-strength fiber-reinforced composite material can be obtained are more preferable, and poly having excellent tensile strength.
  • Acrylonitrile (PAN) -based carbon fibers are particularly preferred.
  • As the form of the carbon fiber twisted yarn, untwisted yarn, untwisted yarn and the like can be appropriately used.
  • the resin composition is not particularly limited, but a composition containing a thermoplastic resin or a thermosetting resin can be used. These resins may be used alone or in combination of two or more. It is preferable to use two or more kinds of resins in combination because it is easy to adjust the viscoelasticity of the resin composition.
  • thermoplastic resin used in the present invention is not particularly limited, and for example, polyethersulfone (PES), polyetherethersulfone (PEES), polyphenylsulfone, polysulfone, polyester, and polymerizable macrocyclic molecule (for example, cyclic molecule).
  • PES polyethersulfone
  • PEES polyetherethersulfone
  • PES polyphenylsulfone
  • polyester polymerizable macrocyclic molecule
  • macrocyclic molecule for example, cyclic molecule
  • Butylene terephthalate liquid crystal polymer
  • polyimide polyetherimide
  • aramid polyamide
  • polyester polyketone
  • PEEK polyetherketoneketone
  • PEEK polyetherketoneketone
  • polyurethane polyurea
  • polyarylether polyarylsulfide
  • Polycarbonate polyphenylene oxide (PPO), modified PPO and the like
  • PPO polyphenylene oxide
  • thermoplastic resins may be used alone or in combination of two or more.
  • PES polyethersulfone
  • PEEK polyetheretherketone
  • PES is used during heat curing. It is preferable from the viewpoint of uniform solubility.
  • thermosetting resin used in the present invention is not particularly limited, and is, for example, a phenol formaldehyde resin, a urea formaldehyde resin, a 1,3,5-triazine-2,4,6-triamine (melamine) resin, and a bismaleimide resin.
  • Epoxy resin, vinyl ester resin, benzoxazine resin, phenol resin, polyester, unsaturated polyester, cyanic acid ester resin and the like can be used.
  • thermosetting resins may be used alone or in combination of two or more.
  • bismaleimide resin, epoxy resin, vinyl ester resin, cyanate ester resin, benzoxazine resin, and phenol resin are preferable, and epoxy resin is particularly preferable.
  • the epoxy resin is not particularly limited, but an epoxy resin having two or more glycidyl groups in one molecule is preferable, and for example, a bisphenol type such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol S type epoxy resin.
  • a bisphenol type such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol S type epoxy resin.
  • Epoxy resin Brominated epoxy resin such as tetrabromobisphenol A diglycidyl ether; Epoxy resin having biphenyl skeleton; Epoxy resin having naphthalene skeleton; Epoxy resin having dicyclopentadiene skeleton; Phenol novolac type epoxy resin; Cresol novolac type epoxy Resin; N, N, O-triglycidyl-m-aminophenol, N, N, O-triglycidyl-p-aminophenol, N, N, O-triglycidyl-4-amino-3-methylphenol, N, N, N', N'-tetraglycidyl-4,4'-methylenedianiline, N, N, N', N'-tetraglycidyl-2,2'-diethyl-4,4'-methylenedianiline, N , N, N', N'-tetraglycidyl-m-xylylene diamine, N, N-diglycidylan
  • epoxy resins may be used alone or in combination of two or more. It is preferable to use two or more kinds of epoxy resins in combination because it is easy to adjust the viscoelasticity of the resin composition, the tackiness of the obtained prepreg is excellent, and the rigidity and toughness of the cured product can be balanced.
  • two or more types of epoxy resins are used in combination, using an epoxy resin having high fluidity at an arbitrary temperature and an epoxy resin having low fluidity in combination causes the flow of the resin composition when the obtained prepreg is thermoset. Effective for sexual control. For example, when only a highly fluid epoxy resin is used, if the fluidity shown before the matrix resin gels during thermosetting is high, the orientation of the reinforcing fibers may be disturbed or the matrix resin may be systematic.
  • the fiber volume content of the obtained fiber-reinforced composite material may deviate from a predetermined range, and as a result, the mechanical properties of the obtained fiber-reinforced composite material may deteriorate.
  • an epoxy resin having low fluidity in combination such deterioration of physical properties can be suppressed.
  • the resin composition may contain a curing agent.
  • the curing agent used is not particularly limited, and for example, cyanoguanidine, aromatic amine compound, aliphatic amine compound, acid anhydride, Lewis acid, substituted urea, imidazole, hydrazine and the like can be used.
  • aromatic amine compounds are preferable from the viewpoint of heat resistance and mechanical properties. Examples of the aromatic amine compound include 3,3'-diisopropyl-4,4'-diaminodiphenylmethane, 3,3'-di-t-butyl-4,4'-diaminodiphenylmethane, and 3,3'-diethyl-.
  • the curing agent when mixed with other components is not particularly limited, and may be in either powder or liquid form, and the powder and liquid may be mixed and used. From the viewpoint of improving the stability during storage, the curing agent is preferably a powder at 22 ° C.
  • the resin composition may contain a curing accelerator.
  • the curing accelerator is not particularly limited, and examples thereof include a tertiary amine, a Lewis acid complex, an onium salt, an imidazole compound, and a urea compound.
  • the resin composition may contain a filler.
  • the filler is not particularly limited, and for example, rubber particles, a coupling agent, a thermosetting resin particle, a thermoplastic resin particle, silica gel, carbon black, clay, carbon nanotube, carbon particle, metal powder, or the like can be used. can.
  • the resin composition existing at the portion where the depth from the surface of the prepreg is located at D / 10 is set to a measurement frequency of 50 rad / s or more by using an 8 mm plate.
  • the loss tangent tan ⁇ at the slit processing temperature when the viscoelasticity is evaluated is y and the impregnation rate measured by the water pickup method described later is x, the relationship of the following equation 1 must be obtained.
  • FIG. 1 shows a cross section of the prepreg of the present invention composed of the reinforcing fiber 1 and the resin composition 2.
  • a cross section of the prepreg is photographed with an epi-illumination type optical microscope at a magnification of 200 times or more, an arbitrary position in the fiber direction is selected, and five positions in the width direction at the same position, for example, shown in FIG.
  • the average thickness D of the prepreg can be obtained by measuring the distances between the two surfaces at the positions a, b, c, d and e and calculating the average value thereof.
  • the surface layer portion of the prepreg is peeled off with a tape, and the thickness is confirmed with an epi-illumination type optical microscope in the same manner as described above.
  • it can be obtained by exposing a portion having a depth of D / 10 from the surface of either one and collecting the resin composition of that portion using a spatula.
  • the loss tangent tan ⁇ of the resin composition at the site where the depth from both surfaces is D / 10 satisfies the present invention.
  • the loss tangent tan ⁇ at the slit processing temperature when measured at a measurement frequency of 50 rad / s or more using an 8 mm plate is a resin composition measured by the following method using a dynamic viscoelasticity measuring device. It is the value of the loss tangent tan ⁇ obtained when A parallel plate with a diameter of 8 mm was used as the upper and lower measuring jig of the dynamic viscoelasticity measuring device, and the resin composition to be measured was set between the upper and lower plates so that the distance between the plates was 0.5 mm.
  • tan ⁇ is measured under the conditions of a twist mode, a measurement frequency of 50 rad / s or more, a temperature in the range of 5 to 200 ° C., and a heating rate of 2 ° C./min. From the obtained curve of temperature-loss tangent tan ⁇ , the value of tan ⁇ at the slit processing temperature is read to be the loss tangent tan ⁇ at the slit processing temperature in the present invention.
  • the measurement frequency is less than 50 rad / s, the viscoelasticity of the resin in the slit processing cannot be measured correctly, so the measurement frequency needs to be 50 rad / s or more.
  • ARES-G2 manufactured by TA Instruments
  • the slit processing temperature in the prepreg of the present invention is preferably any temperature in the range of 0 to 40 ° C, more preferably any temperature in the range of 10 to 30 ° C, and further. Preferably, it is any temperature in the range of 15-25 ° C.
  • the prepreg of the present invention needs to satisfy the above formula 1 at any temperature within the above range.
  • the lower the tan ⁇ of the resin composition the lower the viscosity of the resin composition, so that the resin adhesion to the blade when slitting the prepreg can be suppressed.
  • the viscosity of the resin composition becomes low, it becomes difficult for the resin composition to impregnate the reinforcing fibers.
  • Equation 1 If Equation 1 is not satisfied, resin adheres to the blade, reinforcing fibers are wrapped around the blade, and reinforcing fibers are pulled out from the end of the prepreg when slitting the prepreg, so that the width accuracy is good. Since the slit tape cannot be obtained, it becomes difficult to perform slit processing for a long time.
  • the impregnation rate x by the water pickup method (WPU method) of the prepreg in the present invention is an index indicating the degree of resin impregnation in the prepreg.
  • the impregnation rate x by the WPU method can be measured by the following method.
  • a test piece having a size of 100 mm ⁇ 100 mm in length in the fiber longitudinal direction ⁇ width direction (direction orthogonal to the fiber direction) is cut from the prepreg.
  • the width of the prepreg is less than 100 mm, the length of the test piece in the width direction may be 100 mm or less, but the length in the fiber direction is 100 mm.
  • the impregnation rate x is a value expressed as a percentage by dividing the mass (W2-W1) of water absorbed by the test piece by W1.
  • the impregnation rate x is 2.0% or less, the wrapping of the reinforcing fibers around the blade is reduced when the prepreg is slitted, and the workability is improved, which is preferable. It is more preferably 1.5% or less, still more preferably 0.1 to 1.5%.
  • the impregnation rate x by the WPU method By setting the impregnation rate x by the WPU method to 0.1% or more, it is easy to obtain a prepreg having good drapeability. In order to reduce the impregnation rate x by the WPU method, for example, it is effective to use the multi-stage impregnation hot melt method described later in the production of the prepreg.
  • the cut distance (hereinafter referred to as the cut distance) until the reinforcing fibers wind around the blade is preferably 10 m or more. If the cutting distance is 10 m or more, the frequency of unsustainable troubles that require cleaning by disassembling the device such as resin adhesion and fluff wrapping inside the device when slitting a large amount of prepreg is low, and mass production workability is possible. Tends to be excellent.
  • the cutting distance in the present invention is that when a 28 mm round blade is set in an automatic cutting machine and the prepreg is slit at a speed of 18 m / min along the fiber direction, the reinforcing fiber starts to wind around the round blade from the slit processing.
  • the processing distance of the prepreg up to.
  • the automatic cutting machine for example, GERBERcutter (R) DSC manufactured by Gerber Technology Co., Ltd. can be used.
  • As the 28 mm round blade a circular blade 28 mm (RB28) manufactured by OLFA can be used.
  • the prepreg of the present invention can be produced by various known methods.
  • the main resin composition is a thermoplastic resin
  • the prepreg can be produced by a melting method, a powder method, a resin film impregnation method, a mixed weaving method, or the like.
  • the melting method is a method in which a thermoplastic resin is melted by an extruder, continuous fibers are passed through a melting bath, and the resin is impregnated inside the fiber bundle.
  • the solvent method impregnates the inside of the fiber bundle with a solution in which a resin is dissolved in a solvent.
  • a thermoplastic resin powder is attached to a reinforcing fiber, and the powder is heated to melt and impregnate the fiber.
  • the prepreg can be produced by a known method such as a wet method, a hot melt method, extrusion, spraying, or printing.
  • a wet method the resin composition is dissolved in an organic solvent selected from acetone, methyl ethyl ketone, methanol, etc. to reduce the viscosity, impregnated in reinforcing fibers, pulled up, and the organic solvent is evaporated using an oven or the like to prepare a prepreg. Obtainable.
  • the hot melt method is a method of directly impregnating the reinforcing fibers with a matrix resin whose viscosity has been reduced by heating, or a release paper sheet with a resin film in which the matrix resin is once coated on a release paper or the like (hereinafter, "" (Sometimes referred to as “resin film”) is first produced, and then a resin film is layered on the reinforcing fiber side from both sides or one side of the reinforcing fiber, and the reinforcing fiber is impregnated with the matrix resin by heating and pressurizing. can.
  • Examples of the method for producing the prepreg of the present invention by the hot melt method include the following methods.
  • the first method is to impregnate the reinforcing fibers with the matrix resin in a single step by heating and pressurizing the resin film containing the resin composition which is the component of the present invention from both sides or one side of the reinforcing fibers, so-called one step. It is an impregnation hot melt method.
  • the second method is a multi-stage impregnation hot melt method in which the matrix resin is applied to the resin film in multiple stages and impregnated by heating and pressurizing them from both sides or one side of the reinforcing fibers.
  • a multi-stage impregnation hot melt method in which the reinforcing fibers are first impregnated with a low-viscosity resin composition and then further impregnated with a high-viscosity resin composition can obtain good slit processability. Easy and preferable.
  • the prepreg of the present invention can obtain a slit tape by slitting it to a predetermined width by a known method.
  • the slitting method of the prepreg is not particularly limited, and examples thereof include a commonly used cutter, a slitter equipped with a super hard blade cutter, an ultrasonic cutter, a round blade cutter, and the like.
  • the slit processing temperature at the time of processing the prepreg into the slit tape is preferably any temperature in the range of 0 to 40 ° C, more preferably any temperature in the range of 10 to 30 ° C. Yes, more preferably any temperature in the range of 15-25 ° C.
  • the slit processing temperature referred to here is the temperature of the prepreg when slitting the prepreg.
  • the processing temperature is set to 40 ° C. or lower, it is easy to suppress the deterioration of the resin composition with time and the tack of the prepreg, and it is easy to suppress the resin adhesion to the blade at the time of slitting, and it is easy to obtain good slit workability. ..
  • the temperature of the blade is preferably equal to or lower than the surface temperature of the prepreg to be slit, and it is also preferable to cool the blade, because resin adhesion to the blade can be suppressed.
  • the slit tape obtained by slitting the prepreg of the present invention is preferably used when producing a fiber-reinforced composite material using an automatic laminating device.
  • the slit tapes have an appropriate tack at room temperature. More specifically, when the tack at 22 ° C. is 0.21 kgf or more and 0.80 kgf, the stickability is good and it is easy to cope with repair at the time of stacking trouble, which is preferable.
  • the tack can be measured by measuring the prepreg using, for example, a tack tester (PICMA tack tester II: manufactured by Toyo Seiki Co., Ltd.).
  • a prepreg to be measured is installed on the tack tester, and a stainless plate (SUS304) with a glass plate of 18 mm x 18 mm is lowered from the top of the prepreg at a speed of 10 mm / min, and immediately after touching the prepreg, the speed reaches 10 mm / min.
  • the stainless steel plate is raised and the peeling load when peeling from the prepreg is measured and used as the tack value.
  • the resin composition existing at the portion where the depth from the surface of the prepreg is located at D / 10 is evaluated at 50 rad / s or more using an 8 mm plate.
  • tan ⁇ is preferably 1.7 or more and 3.0 or less.
  • the complex viscosity ⁇ * at 35 ° C. when the resin composition existing at the portion where the depth from the surface of the prepreg is located at D / 10 is evaluated at 50 rad / s or more using an 8 mm plate is 8 ⁇ 10 3. It is preferably Pa ⁇ s or more and 2 ⁇ 10 4 Pa ⁇ s or less.
  • the prepreg When slitting the prepreg, in order to lengthen the length of the obtained slit tape in the fiber direction, the prepreg may be lengthened by overlapping with other prepregs and pressure-bonding to form a splice portion.
  • the prepreg has sufficient adhesive strength so that the prepreg bonded by crimping at the splice portion does not come off when the splice portion comes into contact with the roll in the process and turns in a direction.
  • the prepreg In order to prevent the splice portion from peeling off during the process, it is preferable that the prepreg has a high shape-following property.
  • the prepreg Since the prepreg has high shape followability, when the prepreg changes the traveling direction along the guide roll of the automatic laminating device, the force of the peeling mode is less likely to be applied to the splice portion, and the splice portion is less likely to be peeled off. On the other hand, if the shape followability is too high, the slit tape tends to fold in the width direction when the prepreg changes direction so as to twist 90 degrees between the guide rolls. Therefore, it is preferable that the drape angle ⁇ (PP), which is an index of the shape followability of the prepreg, is 7 ° or more and 17 ° or less.
  • the drape angle ⁇ (PP) of the prepreg can be measured by the method shown below.
  • the prepared prepreg is cut into a length of 25 mm in the width direction and a length of 300 mm in the fiber direction.
  • the length of the cut prepreg The part having a width direction of 25 mm and the fiber direction length of 100 mm is fixed in close contact with the gantry, and the remaining part of the prepreg, that is, the part having a width direction of 25 mm and a fiber direction length of 200 mm. Is in the state of a cantilever protruding from the side of the gantry.
  • the distance A from the side surface of the pedestal to the end of the prepreg and the height B from the surface of the prepreg fixed to the gantry to the unfixed end of the prepreg are set.
  • the drape value C of the reinforcing fiber bundle is 3 cm or more and 22 cm or less. By setting the drape value C in this range, it is easy to obtain a prepreg having a preferable drape angle ⁇ .
  • the drape value C of the reinforcing fiber bundle can be measured by, for example, the following method. Cut the reinforcing fiber bundle to a length of 1 m, fix the upper tip of the reinforcing fiber bundle, attach a weight of 30 g to the lower tip, and leave it for 30 minutes. Then, the weight is removed from the reinforcing fiber bundle and cut into a length of 30 cm. 5 cm of one end of the cut reinforcing fiber bundle is fixed to the measuring table, and the length of the reinforcing fiber bundle is 25 cm, which is a cantilever protruding from the table. Let the horizontal distance (cm) of be the drape value.
  • the carbon fiber reinforced composite material of the present invention can be obtained by laminating the prepreg or slit tape of the present invention and then heating to cure the resin when a thermosetting resin is contained. It is preferable to pressurize during molding from the viewpoint of suppressing voids and obtaining a uniform cured product.
  • a method for applying heat and pressure known methods such as an autoclave molding method, a press molding method, a bagging molding method, a lapping tape method, and an internal pressure molding method can be used.
  • the present invention will be described in detail by way of examples.
  • the present invention is not limited to the following examples.
  • the materials used in this example and the comparative example, and various measurement methods are as follows.
  • the unit of the blending amount of the resin composition in Tables 1 to 8 is parts by mass, and the measurement of various characteristics (physical properties) was carried out in an environment of a temperature of 22 ° C. and a relative humidity of 50% unless otherwise specified. ..
  • Reinforcing fiber Carbon fiber, "Treca (registered trademark)" T800S-24K-10E (24,000 fibers, fineness: 1.033tex, tensile elastic modulus: 294 GPa, density 1.8 g / cm 3 , Toray Industries, Inc. ) Made).
  • thermosetting resin composition Epoxy resins and thermoplastic resins having the compositions and ratios shown in Tables 1 to 8 are added to the kneader, and the temperature is raised to 160 ° C. while kneading for 1 hour. By stirring, the thermoplastic resin was dissolved to obtain a transparent viscous liquid. The temperature of this liquid was lowered to 70 ° C. while kneading, and then the curing agents shown in Tables 1 to 8 were added and further kneaded to obtain a thermosetting resin composition.
  • thermosetting resin composition prepared as described above was applied onto a paper pattern using a coater to prepare a resin sheet having a resin basis weight of 31 g / m 2.
  • 72 "Trading Cards (registered trademarks)" T800S-24K-10E were aligned in parallel to form a sheet so that the basis weight of the carbon fibers was 270 g / m 2.
  • the resin sheet is laminated from both sides of the carbon fiber to impregnate the carbon fiber with the thermosetting resin composition, and then the resin sheet is further laminated from both sides again to impregnate the thermosetting resin composition in one direction.
  • a prepreg was prepared. If necessary, the heating and pressurizing was performed a plurality of times and the heating and pressurizing time was extended so that the impregnation rate x shown in Tables 1 to 8 was obtained.
  • the viscoelasticity of the resin composition thus collected was measured using a viscoelasticity measuring device (ARES-G2 (manufactured by TA Instruments)). Using a flat plate parallel plate with a diameter of 8 mm as the upper and lower measuring jig of the measuring device, set the resin composition between the upper and lower plates so that the distance between the plates is 0.5 mm, and then twist mode (measurement). The measurement was performed at a frequency of 77.25 rad / s) in a measurement temperature range of 5 to 200 ° C. and a heating rate of 2 ° C./min. In the obtained temperature-loss tangent tan ⁇ curve, tan ⁇ at the slit processing temperature and in the temperature-complex viscosity curve, the complex viscosity ⁇ * at 35 ° C. were read.
  • impregnation rate x Measurement method of impregnation rate (hereinafter, impregnation rate x) by WPU method
  • Five test pieces were cut from a wide prepreg into a size of 100 mm ⁇ 100 mm in width direction ⁇ fiber direction.
  • one side of the test piece was arranged so that the fiber direction of the test piece was perpendicular to the water surface, and a range of 5 mm from the end of the prepreg (that is, 100 mm ⁇ ). 5 mm) was immersed in water for 5 minutes.
  • the immersed test piece was taken out from water, and the water adhering to the surface of the test piece was wiped off with a waste cloth or the like, and then the mass W2 of the test piece was measured.
  • the impregnation rate x was an average value expressed as a percentage by dividing the mass of water (W2-W1) absorbed by the test piece by W1.
  • the prepreg is set at a speed of 18 m / min along the fiber direction.
  • the processing distance of the prepreg from the start of the slit processing to the start of the reinforcing fiber winding around the round blade was measured.
  • Those with a processing distance of 10 m or more were excellent in slit processability and were evaluated as "good” in terms of cutability. If the processing distance is less than 10 m, the slit workability is insufficient and the cutability is judged as "poor".
  • Prepreg tack measurement method The prepreg tack is a tack tester (PICMA tack tester II: manufactured by Toyo Seiki Co., Ltd.). ) was used for measurement. A prepreg to be measured is installed on the tack tester, and a stainless plate (SUS304) with a glass plate of 18 mm x 18 mm is lowered from the top of the prepreg at a speed of 10 mm / min, and immediately after touching the prepreg, the speed reaches 10 mm / min. The stainless steel plate was raised and the peeling load at the time of peeling from the prepreg was measured and used as the tack value of the prepreg. Those with a prepreg tack value of 0.21 kgf or more and 0.80 kgf or less were rated as "excellent" in stickiness and repairability at the start of AFP, and those other than that were rated as "possible”.
  • Example 1 With the composition described in Example 1 of Table 1, the resin composition was prepared by the method described in the above (1) Method for preparing a thermosetting resin composition. Next, using this resin composition and the carbon fiber, a prepreg was prepared by the method described in (2) Method for producing a prepreg.
  • the tan ⁇ (y) of the resin composition present at the site located at the depth D / 10 of the obtained prepreg (hereinafter referred to as the D / 10 site) at 31 ° C. is 1.45
  • the impregnation rate (x) is 0. It was .50 and satisfied Equation 1. Further, the cutting distance when slitting was performed at 31 ° C. was 21 m, and the cutability was judged to be "good".
  • Examples 2 to 10 A prepreg was prepared in the same manner as in Example 1 except that the resin compositions shown in Tables 1 and 2 were used. The evaluation results are shown in Tables 1 and 2.
  • Example 11 With the composition shown in Table 2, polyetheretherketone resin ("Vestakeep” 2000G (polyetheretherketone, manufactured by Dycel Evonic) powder) is dispersed in ethanol to prepare a suspension with a concentration of 5.5% by mass in a suspension bathtub. The 36 carbon fibers were arranged in parallel to form a sheet so that the grain size of the carbon fibers was 125 g / m 2.
  • the two sheets were introduced into the suspension, immersed for 15 seconds, and then the two sheets were stacked and taken out from the suspension bathtub as one laminated sheet.
  • the obtained laminated sheet was dried at 150 ° C. for 5 minutes. Subsequently, the laminated sheet was passed through a roller having a surface temperature of 400 ° C. to melt and impregnate the resin to obtain a prepreg having a basis weight of 374 g / m 2.
  • the tan ⁇ (y) of the resin composition present at the D / 10 site of the obtained prepreg at 19 ° C. was 0.03, and the impregnation rate (x) evaluated by the water pickup method was 0.05. Was satisfied. Further, when the slit was processed at 19 ° C., the cutting distance until it was wound around the round blade was 35 m, and the cutability was judged to be "excellent".
  • Example 12 to 18> A prepreg was prepared in the same manner as in Example 1 except that the resin compositions shown in Table 3 were used. The evaluation results are shown in Table 3.
  • Examples 17, 19, 20, 21, 22> A prepreg was prepared in the same manner as in Example 1 except that the resin compositions shown in Table 4 were used. The evaluation results are shown in Table 4.
  • the loss coefficient tan ⁇ at 22 ° C. of the resin composition present at the D / 10 site of Examples 17, 20, and 21 was 1.7, 2.4, and 3.0, respectively, and the tack of the prepreg was 0.21 kgf. At 0.60 kgf and 0.80 kgf, the sticking property and repair property at the time of AFP lamination were "excellent".
  • the loss coefficient tan ⁇ of the resin composition present at the D / 10 site of Example 19 at 22 ° C. is 1.4, the tack of the prepreg is 0.10 kgf, and the stickability and repairability at the time of AFP lamination are “possible”. Met.
  • the loss coefficient tan ⁇ of the resin composition present at the D / 10 site of Example 22 at 22 ° C. is 3.4, the tack of the prepreg is 1.00 kgf, and the stickability and repairability at the time of AFP lamination are “possible”. Met.
  • Examples 17, 19, 21, 22, 23> A prepreg was prepared in the same manner as in Example 1 except that the resin compositions shown in Table 5 were used. The evaluation results are shown in Table 5.
  • the complex viscosity ⁇ * of the resin composition present at the D / 10 site at 35 ° C. was 6 ⁇ 10 3 Pa ⁇ s, 8 ⁇ 10 3 Pa ⁇ s, in the order of Examples 22, 21, 23, 17, and 19. It is 1 ⁇ 10 4 Pa ⁇ s, 2 ⁇ 10 4 Pa ⁇ s, 3 ⁇ 10 4 Pa ⁇ s, and the stickiness / repairability at the time of AFP lamination is “excellent” in Examples 17, 21 and 23.
  • Examples 19 and 22 were "OK".
  • Example 17 ⁇ Examples 17, 24, 25, 26> Examples except that the resin compositions shown in Table 6 were used, and a drape value C of 12 cm was used in Examples 17 and 26, a reinforcing fiber bundle of 24 cm was used in Example 24, and a reinforcing fiber bundle of 4 cm was used in Example 25, respectively.
  • a prepreg was prepared in the same manner as in 1. The evaluation results are shown in Table 6.
  • the drape angle ⁇ (PP) of the prepreg is 13 ° in Example 17, 5 ° in Example 24, and 18 ° in Example 25, in Example 17 being “excellent” in AFP processability, and in Examples 24 and 25 being AFP.
  • the processability was "OK".
  • Example 26 is a prepreg having the same resin composition as that of Example 17 and a drape value C of the same reinforcing fiber bundle, the impregnation rate is 0.05%, and the drape angle ⁇ (PP) of the prepreg is 6 °. AFP processability was "OK".
  • the fiber-reinforced composite material obtained from the prepreg of the present invention includes primary structural members such as aircraft fuselage, main wings, tail wings and floor beams, secondary structural members such as flaps, ellons, cowls, fairings and interior materials, and rocket motor cases.
  • primary structural members such as aircraft fuselage, main wings, tail wings and floor beams
  • secondary structural members such as flaps, ellons, cowls, fairings and interior materials
  • rocket motor cases included in the fiber-reinforced composite material obtained from the prepreg of the present invention.
  • Wide range of applications such as aviation / space applications such as artificial satellite structural materials, structural materials for moving objects such as automobiles, ships and railroad vehicles, building materials, blades of windmills, and computer applications such as IC trays and laptop housings. It can be suitably used for various purposes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Reinforced Plastic Materials (AREA)
PCT/JP2021/012198 2020-03-31 2021-03-24 プリプレグおよび繊維強化複合材料 Ceased WO2021200453A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2021518010A JPWO2021200453A1 (https=) 2020-03-31 2021-03-24
EP21782093.5A EP4129603A4 (en) 2020-03-31 2021-03-24 PRE-PREG AND FIBER REINFORCED COMPOSITE MATERIAL
US17/909,821 US20240199831A1 (en) 2020-03-31 2021-03-24 Prepreg and fiber-reinforced composite material

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020-063088 2020-03-31
JP2020063088 2020-03-31

Publications (1)

Publication Number Publication Date
WO2021200453A1 true WO2021200453A1 (ja) 2021-10-07

Family

ID=77928763

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/012198 Ceased WO2021200453A1 (ja) 2020-03-31 2021-03-24 プリプレグおよび繊維強化複合材料

Country Status (4)

Country Link
US (1) US20240199831A1 (https=)
EP (1) EP4129603A4 (https=)
JP (1) JPWO2021200453A1 (https=)
WO (1) WO2021200453A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023539692A (ja) * 2020-08-28 2023-09-15 トウレ アドバンスト コンポジッツ 改善された加工性を有するｕｄテープおよびその製造方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05208396A (ja) * 1992-01-30 1993-08-20 Toshiba Mach Co Ltd プリプレグの切断編集装置
WO2012147401A1 (ja) * 2011-04-27 2012-11-01 東レ株式会社 プリプレグ、繊維強化複合材料およびプリプレグの製造方法
JP2016155915A (ja) 2015-02-24 2016-09-01 三菱レイヨン株式会社 繊維強化プラスチック線材及びその製造方法、並びに繊維強化プラスチック線材の製造システム
JP6250393B2 (ja) 2010-08-12 2017-12-20 ヘクセル コンポジッツ、リミテッド 改善された複合材料
JP2019147876A (ja) * 2018-02-27 2019-09-05 三菱ケミカル株式会社 繊維強化熱可塑性樹脂プリプレグおよび成形体
WO2020040153A1 (ja) * 2018-08-22 2020-02-27 東レ株式会社 プリプレグの製造方法および製造装置

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6045898A (en) * 1996-02-02 2000-04-04 Toray Industried, Inc. Resin compositions for fiber-reinforced composite materials and processes for producing the same, prepregs, fiber-reinforced composite materials, and honeycomb structures
CN104105589A (zh) * 2012-01-25 2014-10-15 赫克赛尔控股有限责任公司 层压件的改进或关于层压件的改进
GB2510835A (en) * 2013-02-13 2014-08-20 Hexcel Composites Ltd Fire retardant epoxy resin formulations and their use
JP6414315B2 (ja) * 2015-12-16 2018-10-31 三菱ケミカル株式会社 プリプレグテープ及びその利用
KR20210022664A (ko) * 2018-06-26 2021-03-03 도레이 카부시키가이샤 프리프레그 및 그 제조 방법, 슬릿 테이프 프리프레그, 탄소섬유강화 복합재료
JP7140131B2 (ja) * 2018-08-22 2022-09-21 東レ株式会社 離型シート付き多層構造プリプレグ、プリプレグロール、プリプレグテープおよび複合材料

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05208396A (ja) * 1992-01-30 1993-08-20 Toshiba Mach Co Ltd プリプレグの切断編集装置
JP6250393B2 (ja) 2010-08-12 2017-12-20 ヘクセル コンポジッツ、リミテッド 改善された複合材料
WO2012147401A1 (ja) * 2011-04-27 2012-11-01 東レ株式会社 プリプレグ、繊維強化複合材料およびプリプレグの製造方法
JP2016155915A (ja) 2015-02-24 2016-09-01 三菱レイヨン株式会社 繊維強化プラスチック線材及びその製造方法、並びに繊維強化プラスチック線材の製造システム
JP2019147876A (ja) * 2018-02-27 2019-09-05 三菱ケミカル株式会社 繊維強化熱可塑性樹脂プリプレグおよび成形体
WO2020040153A1 (ja) * 2018-08-22 2020-02-27 東レ株式会社 プリプレグの製造方法および製造装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4129603A4

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023539692A (ja) * 2020-08-28 2023-09-15 トウレ アドバンスト コンポジッツ 改善された加工性を有するｕｄテープおよびその製造方法
JP7644242B2 (ja) 2020-08-28 2025-03-11 トウレ アドバンスト コンポジッツ 改善された加工性を有するｕｄテープおよびその製造方法

Also Published As

Publication number Publication date
EP4129603A1 (en) 2023-02-08
US20240199831A1 (en) 2024-06-20
EP4129603A4 (en) 2024-04-24
JPWO2021200453A1 (https=) 2021-10-07

Similar Documents

Publication Publication Date Title
KR101096855B1 (ko) 섬유 강화 복합 재료용 에폭시 수지 조성물, 프리프레그 및 섬유 강화 복합 재료
US20110111663A1 (en) Epoxy resin composition and prepreg using the same
JP6812794B2 (ja) エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料
CA2813867C (en) Solvent resistant thermoplastic toughened epoxy
JP7183793B2 (ja) プリプレグおよび繊維強化複合材料
JP7200928B2 (ja) 熱硬化性樹脂組成物、プリプレグおよび繊維強化複合材料
JP6710972B2 (ja) エポキシ樹脂組成物、プリプレグ、樹脂硬化物および繊維強化複合材料
CN102099402A (zh) 具有改善的韧性的结构复合材料
WO2017130659A1 (ja) エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料
WO2022230800A1 (ja) プリプレグ
JP7803040B2 (ja) プリプレグ、積層体および一体化成形品
JP7014153B2 (ja) エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料
JP7180790B2 (ja) プリプレグ、繊維強化樹脂成形体および一体化成形品
WO2021200453A1 (ja) プリプレグおよび繊維強化複合材料
JP7088320B2 (ja) プリプレグ、積層体および一体化成形品
JP2017066218A (ja) エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料
JP2018012797A (ja) エポキシ樹脂組成物、プリプレグ、樹脂硬化物および繊維強化複合材料
JP5034176B2 (ja) プリフォーム用バインダー組成物、プリフォーム用強化繊維基材、プリフォームの製造方法および繊維強化複合材料の製造方法
JP2019059827A (ja) エポキシ樹脂組成物、プリプレグ、樹脂硬化物および繊維強化複合材料
JP2018012798A (ja) エポキシ樹脂組成物、プリプレグ、樹脂硬化物および繊維強化複合材料
JP2018012796A (ja) エポキシ樹脂組成物、プリプレグ、樹脂硬化物および繊維強化複合材料

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2021518010

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21782093

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 17909821

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2021782093

Country of ref document: EP

Effective date: 20221031