WO2016043156A1 - 切込プリプレグおよび切込プリプレグシート - Google Patents
切込プリプレグおよび切込プリプレグシート Download PDFInfo
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- WO2016043156A1 WO2016043156A1 PCT/JP2015/076001 JP2015076001W WO2016043156A1 WO 2016043156 A1 WO2016043156 A1 WO 2016043156A1 JP 2015076001 W JP2015076001 W JP 2015076001W WO 2016043156 A1 WO2016043156 A1 WO 2016043156A1
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Images
Classifications
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- B29C70/205—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in a single direction, e.g. roofing or other parallel fibres the structure being shaped to form a three-dimensional configuration
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/106—Carbon fibres, e.g. graphite fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/07—Parts immersed or impregnated in a matrix
- B32B2305/076—Prepregs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/08—Cars
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/18—Aircraft
-
- 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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic 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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/24—Thermosetting 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
Definitions
- the present invention relates to a prepreg having a layer containing reinforcing fibers impregnated with a resin composition and having a plurality of cuts. More specifically, the present invention relates to the cut prepreg preferably used as an intermediate base material of fiber reinforced plastic suitably used for aircraft members, automobile members, sports equipment and the like.
- Fiber reinforced plastic consisting of reinforced fiber and matrix resin is attracting attention in industrial applications because it has high specific properties, high specific modulus, excellent mechanical properties, weather resistance, chemical resistance, etc. Deployed in structural applications such as aircraft, spacecraft, automobiles, railways, ships, electrical appliances, sports, etc., the demand is increasing year by year. It is known that high-quality fiber-reinforced plastics can be obtained by laminating prepregs, which are intermediate base materials impregnated with thermosetting resins or thermoplastic resins, into continuous reinforcing fibers and then performing pressure molding with an autoclave or the like. ing.
- the object of the present invention is excellent not only in hot forming but also in shape and shape following a complicated shape in shaping and forming a two-dimensional sheet-like intermediate substrate into a three-dimensional shape.
- fiber-reinforced plastics are less likely to cause molding defects such as wrinkles and voids, resulting in good yields and excellent mechanics.
- An object of the present invention is to provide an intermediate substrate that exhibits characteristics and surface quality, and a method for producing fiber-reinforced plastic using the intermediate substrate.
- the present invention employs the following means in order to solve such problems. That is, a prepreg having a layer containing reinforcing fibers impregnated with a resin composition, wherein at least a part is constituted by reinforcing fibers having a fiber length (L) of 10 to 300 mm by a plurality of cuts, and A cut prepreg having a volume content Vf of reinforcing fibers in the range of 45 to 65%.
- an intermediate substrate of fiber reinforced plastic that is excellent in shaping into a three-dimensional shape and excellent in molding robustness that suppresses molding defects that cause a reduction in member strength.
- the present inventors have excellent shapeability to a three-dimensional shape, and voids hardly remain even in low-pressure molding, and the obtained molded product (fiber reinforced plastic) has excellent mechanical characteristics, low variation, and high
- three-dimensionality is studied by inserting a plurality of cuts to form a degassing path in the out-of-plane direction and making the reinforcing fiber discontinuous. It has been clarified that wrinkles and voids are suppressed by improving the conformability to the shape and preventing bridging to solve such problems.
- the thickness of the fiber-reinforced plastic after molding is smaller than the thickness of the prepreg laminate, so the prepreg has a curved surface such as a corner R section.
- a circumferential length difference occurs between the upper and lower surfaces of the laminate. In order to eliminate the difference in circumference, if the reinforcing fiber in the prepreg is composed only of continuous fibers, the prepreg cannot stretch in the direction of the reinforcing fiber.
- a plurality of cuts ensure a gas flow path in the out-of-plane direction during molding, and the reinforced fiber becomes discontinuous, so that the prepreg can extend in the fiber direction, and the prepreg lamination Bridging does not occur when the body is curved, and generation of wrinkles and voids can be suppressed.
- it can evaluate by the expansion
- the fiber length L of the reinforcing fiber divided by cutting is 300 mm or less, it is possible to effectively secure the number of gas degassing paths in the out-of-plane direction during molding and to suppress bridging. be able to.
- L is 10 mm or more, the distance between the cuts increases, so that when a load is applied to a fiber reinforced plastic molded using such a cut prepreg, the cracks are difficult to connect and have high strength. It becomes.
- the more preferable range of the fiber length L of the reinforcing fibers cut by the cut is 20 to 300 mm.
- the fiber length L is the length of the reinforcing fiber divided by an arbitrary cut and a cut closest to the reinforcing fiber direction (a pair of cuts). pointing. Since the escape of the reinforcing fiber occurs at the time of cutting insertion, sometimes a longer cutting is intentionally inserted, and there are reinforcing fibers that have a fiber length shorter than the fiber length L of the majority of reinforcing fibers, The proportion should be less than 5%.
- the plurality of cuts correspond to a portion where the shape change of the prepreg laminate formed into a three-dimensional shape is large.
- Vf volume content of the reinforcing fiber
- Vf is more preferably 60% or less.
- bridging can be suppressed as Vf is lower.
- Vf is smaller than 45%, it is difficult to obtain high mechanical properties necessary for the structural material. From this viewpoint, it is more preferable that Vf is 55% or more.
- the volume-containing chamber Vf of the reinforcing fiber can be measured by processing an image with an optical microscope after curing the prepreg by the method described in Example 1.
- a cut prepreg in which the reinforcing fiber is partially impregnated with the resin composition (that is, partly unimpregnated).
- the resin composition that is, partly unimpregnated.
- FIG. 1 it is a prepreg composed of a first layer made of reinforcing fibers and a second layer containing reinforcing fibers impregnated with the resin composition.
- gas such as volatile components from the cut prepreg is easily discharged out of the cut prepreg (such a gas flow path is called a degassing path).
- a degassing path such a gas flow path is called a degassing path.
- the impregnation rate is preferably 10 to 90% because there are cases where voids may remain unless the impregnation time during molding is long.
- the more preferable upper limit of the impregnation rate range is 70%, the more preferable upper limit is 50%, and the more preferable lower limit of the impregnation rate range is 20%.
- the impregnation ratio of the first layer and the second layer and the resin composition in the cut prepreg is such that the cut prepreg is gradually cured at a low temperature at which resin flow does not occur in the case of a thermosetting resin.
- the later section can be confirmed by observing the section with a microscope at room temperature in the case of a thermoplastic resin.
- the second layer is a layer impregnated with the resin from the surface to the inside of the cut prepreg, and the first layer sandwiched between the second layers is a layer not impregnated with the resin.
- the impregnation rate of the resin composition is calculated by determining the ratio of the cross-sectional area of the reinforcing fiber impregnated with the thermosetting resin composition to the total cross-sectional area of all the reinforcing fibers.
- the larger the size of the molded product the more difficult it is to deaerate during molding.
- a cutting prepreg with a controlled impregnation rate an in-plane deaeration path and an out-of-plane direction by cutting It is preferable because the void ratio can be reduced more easily by combining with the degassing path.
- a second layer containing reinforcing fibers impregnated with a resin composition is preferably provided on both sides of the first layer made of reinforcing fibers. If the resin is present on both surfaces during lamination, the prepregs are easily fixed together.
- the second layer is composed of a layer A composed of reinforcing fibers impregnated with a thermosetting resin composition, and a layer B containing particles or fibers of thermoplastic resin. Should face the cut prepreg surface.
- the B layer does not necessarily need to contain the reinforced fiber. That is, the B layer includes a case where only the thermosetting resin composition and thermoplastic resin particles or fibers are used. Thermosetting resins have lower viscosities than thermoplastic resins, and can easily be impregnated into reinforcing fibers, and can be molded at low temperatures, thereby reducing the investment in molding equipment.
- the B layer forms an interlayer resin layer between the reinforcing fiber layers of each layer.
- an out-of-plane impact load is applied, cracks are induced in the flexible interlayer resin layer, and due to the high toughness due to the presence of the thermoplastic resin, peeling is suppressed, so that the residual compressive strength after the out-of-plane impact is reduced.
- the cut may sever the reinforcing fiber, and may penetrate through the prepreg thickness direction, or may penetrate only the A layer of the first layer and the second layer.
- the incision prepreg of the present invention exudes water from the opposite surface within one minute when water is brought into contact with one surface of the incision prepreg at a pressure of 10 water columns or less at room temperature.
- a pressure of 10 water columns or less at room temperature Preferably there is.
- Whether the incision functions effectively as a degassing path can be confirmed by the seepage of a low-viscosity liquid such as water even with a slight pressure difference.
- a cup having a depth of 10 cm or less is filled with water, the cut prepreg is placed on top, and the cup is sealed, and the cup is turned over so that the prepreg is on the lower surface. If there is water bleed, it can be judged by pressing the prepreg surface of the cut prepreg with a color that changes color and checking the presence or absence of water bleed after 1 minute.
- room temperature refers to 25 ° C.
- the cut prepreg of the present invention is a fiber in which the thickness (A) of a cut prepreg laminate formed by laminating cut prepregs and formed by the following method is heated to solidify the cut prepreg laminate.
- a cut prepreg that is 5 to 50% thicker than the thickness (B) of the reinforced plastic is preferable (in this specification, the difference between the thickness (A) and the thickness (B) is the thickness (B ) (AB) / B ⁇ 100 is expressed as “thickness change”).
- the method of forming the cut prepreg laminate is to form a sealed space with a single-sided mold and a bag film, place the laminate with the cut prepreg laminated in the sealed space, and vacuum the sealed space at room temperature to atmospheric pressure.
- stacked the cutting prepreg with a pressure difference with these is pressurized.
- the difference between the thickness of the cut prepreg laminate and the thickness of the fiber reinforced plastic after solidification by heating is due to internal voids, and the internal voids remain inside the fiber reinforced plastic even after solidification by heating. If this is the case, the thickness change will be small, and if no internal voids remain, the thickness change will be large. Gases such as air and volatile components from the prepreg are degassed through the internal voids during molding, and the reinforcing fiber part is impregnated with resin, and the internal voids are crushed by pressurization, so the thickness change is degassed during molding. It becomes an index of ease.
- the gas may not be easily degassed during molding and may remain in the molded product as a void.
- the internal gap is too large in the cut prepreg laminate, a resin is formed during molding.
- the circumferential difference between the upper and lower surfaces becomes too large, causing wrinkles, voids, etc.
- the change is preferably 5 to 50%, more preferably 15 to 30%.
- the cut prepreg of the present invention is substantially free of voids in the curved portion of the fiber reinforced plastic obtained by laminating 16 to 32 layers of the cut prepreg and performing the following curved surface molding.
- curved surface molding A closed space is formed by a female mold having a curved surface with a radius of curvature of 10 mm and a bag film, and a laminated body in which 16 to 32 layers of cut prepregs are stacked is disposed in the closed space, and the closed space is evacuated to atmospheric pressure While pressing the cut prepreg laminate with a differential pressure, it is heated and solidified to obtain a fiber reinforced plastic.
- the pressure on the curved surface is especially low compared to the plane, and in addition, when molding with a differential pressure from the atmospheric pressure using a vacuum pump etc., the molding pressure is low in the first place.
- the surface of the unimpregnated part is used for cutting and degassing to eliminate the difference in circumferential length between the upper and lower surfaces of the cut prepreg laminate. If the inside deaeration path and the out-of-plane deaeration path by cutting are not aligned, the generation of voids may not be suppressed.
- the curved surface forming for this evaluation is preferably carried out by laminating 24 layers from the balance between evaluation accuracy and laminating workability.
- the void ratio was calculated by observing with a light microscope after polishing the cross section of the fiber reinforced plastic, and by the area ratio of the area of the fiber reinforced plastic to the void by binarization treatment.
- the phrase “substantially free of voids” means that the void ratio is 0.1% or less.
- the cut prepreg of the present invention is provided with a plurality of intermittent cuts in a direction crossing the reinforcing fiber at least partially, and the projection is projected in the vertical direction of the reinforcing fiber in the plane of the cut prepreg
- the length Ws is in the range of 30 ⁇ m to 1.5 mm, and substantially all of the reinforcing fibers are divided by the cuts in the region surrounded by the longitudinal direction of the reinforcing fibers by the intermittent cuts. From the viewpoint of formability, it is preferable.
- the fact that all of the reinforcing fibers are divided by cutting indicates that the reinforcing fibers that are not divided are 5% or less (the same applies hereinafter).
- the projected length Ws projected by the cut in the vertical direction of the reinforcing fiber means that the cut is reinforced in the plane of the cut prepreg as shown in FIGS.
- the vertical direction (fiber vertical direction 6) is the projection plane, and the length when projected perpendicularly to the projection plane from the cut (fiber orientation direction 5) is indicated.
- the absolute value of ⁇ is preferably in the range of 2 to 25 °, where ⁇ is the angle between the cut and the reinforcing fiber.
- the fiber length L in the case of continuous cutting, the fiber length L can be controlled to be constant, and variations in mechanical characteristics and three-dimensional shape followability can be reduced.
- the projection length Ws in the case of intermittent cutting, the projection length Ws can be made smaller than the cutting length Y because the cutting angle is oblique. Therefore, it is possible to stably provide an extremely small cut of 1.5 mm or less industrially, and it is difficult for the prepreg to be separated by continuous cutting at the time of lamination, and the handleability as a prepreg is excellent.
- the absolute value of ⁇ is 25 ° or less, the mechanical properties, particularly the tensile strength, are remarkably improved. From this viewpoint, the absolute value of ⁇ is more preferably 15 ° or less. On the other hand, if the absolute value of ⁇ is smaller than 2 °, it becomes difficult to make a stable cut. That is, when the cut is laid on the reinforcing fiber, the reinforcing fiber easily escapes from the blade when making the cut, and the shortest distance between the rows 11 of the cut becomes small in the example of FIG. It becomes difficult to insert while ensuring the positional accuracy of the cut. From this viewpoint, the absolute value of ⁇ is more preferably 5 ° or more.
- the cut prepreg of the present invention As a preferable cut pattern of the cut prepreg of the present invention, as shown in FIG. 4, at least a part of the cut prepreg is provided with a plurality of intermittent cuts in a direction crossing the reinforcing fiber. Are linearly and parallelly inserted to form the rows 11, and the distance X between the rows is in the range of 1 to 5 mm. When the fiber lengths L are the same, the shortest distance between the cuts can be maximized by making a straight cut in the same direction.
- the incision is inserted by rolling the perforated rotating round blade on a straight line, or by inserting a cut corresponding to the pulse period by scanning a laser pulse laser at a high speed on a straight line. It is possible to apply a high-incision insertion method.
- At least a part of the cut prepreg is provided with a plurality of intermittent cuts in a direction crossing the reinforcing fiber, and intermittently.
- the absolute values of ⁇ are substantially the same, and the cuts that form positive and negative angles are approximately half each.
- the absolute value of ⁇ is substantially equal means that the angle is within ⁇ 1 °, and approximately half is 45 to 55% when expressed as a percentage based on the number. (The same shall apply hereinafter).
- the sign of ⁇ is the most equal
- the thing with four or more incisions C from which the positive / negative of (theta) where the shortest distance with the incision A is closer than the near incision B differs is mentioned. Since the movement of the fiber end is determined by the relationship between the cutting angle and the fiber direction, the adjacent cuttings have the same shape, an angle in the opposite direction, because the prepreg cut insertion part at the time of three-dimensional shape tracking When viewed macroscopically, in-plane isotropy after molding is ensured.
- a plurality of intermittent cuts are provided in at least a part of the cut prepreg in the direction crossing the reinforcing fiber,
- the notches are inserted with straight and substantially the same length Y, and the shortest distance between adjacent notches is longer than the notch length Y.
- the substantially same length means that the difference is within ⁇ 5% (the same applies hereinafter).
- the fiber reinforced plastic breaks when the cuts that are discontinuities of the fibers are connected by cracks.
- the cut prepreg of the present invention at least a part of the cut prepreg is provided with a plurality of intermittent cuts in a direction crossing the reinforcing fiber, and the intermittent cuts are straight and substantially cut.
- the intermittent cuts are straight and substantially cut.
- the distance between adjacent cuts on the same straight line is larger than three times Y.
- the notches are easily recognized as an intermittent straight line pattern after molding, while the distance between the notches is increased. Therefore, it is not recognized as a pattern, and the surface quality is excellent.
- the presence of a cut on the same straight line means that the angle between the straight line extending the cut and the straight line connecting the closest points of the target cuts is within 2 °. Point to.
- the cut prepreg of the present invention is preferably in close contact with a tape-like support.
- the tape-like support that is in close contact with at least one surface of the cut prepreg is referred to as a cut prepreg sheet.
- a cut prepreg sheet is a cut prepreg sheet laminated so that the tape-like support A contacts one side of the cut prepreg, and is 5 to 75% from the surface of the tape-like support A that contacts the cut prepreg.
- It is a cut prepreg sheet which has a cut continuous with the cut of the cut prepreg in the range of.
- examples of the tape-shaped support include papers such as kraft paper, polymer films such as polyethylene and polypropylene, metal foils such as aluminum, etc.
- Silicone or “Teflon (registered trademark)” release agents, metal deposition, or the like may be applied to the surface.
- a so-called half cut is performed in which the cut is inserted in the prepreg without penetrating the cut in the thickness direction of the tape-shaped support A. Is good. Thereby, even if there is much amount of cutting, since the tape-shaped support body A suppresses a deformation
- the thickness is preferably 5 to 75%, more preferably 10 to 50% in the thickness direction of the tape-like support A.
- the cut prepreg sheet of the present invention is a cut prepreg sheet laminated so that the tape-shaped support B is in contact with the surface of the cut prepreg on the side not in contact with the tape-shaped support A.
- the tape-shaped support B includes a cut prepreg sheet in which a cut continuous with the cut of the cut prepreg penetrates in the thickness direction.
- the resin of the prepreg is a thermosetting resin and the tack is strong, it is possible to suppress the adhesion of the prepreg to the blade by providing the tape-like support B between the blade and the prepreg when inserting the cut. Prevents adhesion between prepreg sheets when winding the prepreg sheet.
- This form is a particularly preferable form of the cut prepreg sheet when the distance between the cuts is long.
- the tape-like support B is torn off and the cut prepreg is handled.
- the tape-like support B can be peeled off without being torn off when the distance between the cuts is large as in the cut pattern of FIG.
- the presence of different positive and negative cutting angles also has an effect of suppressing the connection of the tears since the tape-shaped support B is split in different directions.
- the tape-like support placed on the prepreg cut side during the insertion of the prepreg may be discarded once, and a new tape-like support may be reapplied to prevent adhesion between the prepreg sheets when winding the prepreg sheet. It is necessary to affix the tape-shaped support to the substrate, resulting in high cost.
- the reinforcing fiber used in the present invention may be glass fiber, Kevlar fiber, carbon fiber, graphite fiber or boron fiber.
- carbon fiber is preferable from the viewpoint of specific strength and specific modulus.
- the shape and orientation of the reinforcing fibers include long fibers arranged in one direction, bi-directional woven fabrics, multiaxial woven fabrics, nonwoven fabric materials, mats, knitted fabrics, braids, and the like. These can be freely selected according to the application and use area.
- fibers arranged in one direction are preferable because the fiber packing is good and Vf can be improved efficiently, and the mechanical properties can be expressed most highly.
- the resin composition impregnated in the second layer used in the present invention may be a thermoplastic resin or a thermosetting resin.
- the thermoplastic resin include polyamide (PA), polyacetal, polyacrylate, polysulfone, ABS, polyester, acrylic, polybutylene terephthalate (PBT), polycarbonate (PC), polyethylene terephthalate (PET), polyethylene, polypropylene, Examples thereof include polyphenylene sulfide (PPS), polyether ether ketone (PEEK), polyether imide (PEI), polyether ketone ketone (PEKK), liquid crystal polymer, vinyl chloride, fluorine resins such as polytetrafluoroethylene, and silicone.
- PA polyamide
- PBT polybutylene terephthalate
- PC polycarbonate
- PET polyethylene terephthalate
- PET polyethylene
- polypropylene examples thereof include polyphenylene sulfide (PPS), polyether ether ketone (PEEK), polyether imide (
- PA, PPS, PEEK, PEI, and PEKK are preferable in view of adhesiveness with reinforcing fibers and mechanical properties as a matrix resin. Further, PEEK and PEKK are preferable when particularly high mechanical properties are required for the fiber reinforced plastic, and PA and PPS are preferable when low cost is required.
- thermosetting resin is not particularly limited as long as the resin causes a crosslinking reaction by heat to form at least a partial three-dimensional crosslinked structure.
- thermosetting resins include unsaturated polyester resins, vinyl ester resins, epoxy resins, benzoxazine resins, phenol resins, urea resins, melamine resins, and polyimide resins. Deformation of these resins and resins of two or more blends can also be used. Further, these thermosetting resins may be resins that are self-cured by heat, or may include a curing agent, a curing accelerator, and the like.
- thermosetting resins an epoxy resin is preferably used because of its excellent balance of heat resistance, mechanical properties, and adhesion to carbon fibers.
- an epoxy resin having an amine, phenol and a compound having a carbon-carbon double bond as a precursor is preferably used.
- aminophenol type epoxy resins, glycidyl aniline type epoxy resins and tetraglycidyl amine type epoxy resins having amine as a precursor are preferably used.
- the glycidylamine type epoxy resin include modifications such as tetraglycidyldiaminodiphenyl, triglycidyl-p-aminophenol, and triglycidylaminocreosol.
- High-purity tetraglycidylamine-type epoxy resin average epoxide equivalent (EEW) in the range of 100-115
- tetraglycidylamine-type epoxy resin high-purity aminophenol-type epoxy resin, in the range of 90-104 amino
- a phenol type epoxy resin is preferably used for suppressing volatile components that may cause voids in the resulting fiber-reinforced composite material.
- Tetraglycidyldiaminodiphenylmethane is excellent in heat resistance and is preferably used as a resin for composite materials for aircraft structural members.
- a glycidyl ether type epoxy resin using phenol as a precursor is also preferably used as a thermosetting resin.
- these epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, creosole novolac type epoxy resins, and resorcinol type epoxy resins.
- Liquid bisphenol A type epoxy resin, bisphenol F type epoxy resin, and resorcinol type epoxy resin are preferably used in combination with other epoxy resins because of their low viscosity.
- a bisphenol A type epoxy resin that is solid at room temperature has a structure in which the crosslinking density in the cured resin is lower than that of a liquid bisphenol A type epoxy resin that is liquid at room temperature (about 25 ° C.).
- An epoxy resin having a naphthalene skeleton is a cured resin having low absorbency and high heat resistance.
- biphenyl type epoxy resins, dicyclopentadiene type epoxy resins, phenol aralkyl type epoxy resins, and phenyl fluorine type epoxy resins can be preferably used because they are cured resins having low absorbability.
- Urethane-modified epoxy resins and isocyanate-modified epoxy resins can be preferably used because they become cured resins having high fracture toughness and elongation.
- epoxy resins may be used alone or may be blended as appropriate. Addition of a bifunctional, trifunctional or higher epoxy resin to the resin is preferred because the system can provide both workability and processability as a prepreg and heat resistance under wet conditions as a fiber reinforced composite.
- the combination of glycidylamine type and glycidyl ether type epoxy can achieve processability, heat resistance and water resistance.
- blending at least one epoxy resin that is liquid at room temperature and at least one epoxy resin that is solid at room temperature is effective in providing both tackiness and draping properties suitable for the prepreg.
- the phenol novolac type epoxy resin and the creosole novolac type epoxy resin have high heat resistance and low absorbability, and thus become a cured resin having high heat resistance and water resistance.
- the tackiness and draping properties of the prepreg can be adjusted while improving the heat and water resistance.
- the curing agent for the epoxy resin may be any compound having an active group capable of reacting with an epoxy group.
- a compound having an amino group, an acid anhydride group or an azide group is suitable as the curing agent. More specific examples of the curing agent include dicyandiamide, diaminodiphenylmethane, various isomers of diaminodiphenylsulfone, aminobenzoic acid esters, various acid anhydrides, phenol novolac resin, cresol novolac resin, polyphenol compound, imidazole derivative, fat Group amine, tetramethylguanidine, thiourea addition amine, methylhexahydrophthalic anhydride, other carboxylic anhydride, carboxylic hydrazide, carboxylic amide, polymercaptan, boron trifluoride ethylamine complex and other Lewis acid complexes Etc.
- These curing agents can be used alone or in combination.
- an aromatic diamine as a curing agent, a cured resin having good heat resistance can be obtained.
- various isomers of diaminodiphenylsulfone are most preferable because a cured resin having good heat resistance can be obtained.
- the addition amount of the aromatic diamine curing agent is preferably stoichiometrically equivalent, but in some cases, by using an equivalent ratio of about 0.7 to 0.9, a high elastic modulus cured resin can be obtained. Obtainable.
- imidazole or dicyandiamide and a urea compound for example, 3-phenol-1,1-dimethylurea, 3- (3-chlorophenyl) -1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1, 1-dimethylurea, 2,4-toluenebisdimethylurea, and 2,6-toluenebisdimethylurea
- a cured resin having a relatively low absorptivity compared to amine compound curing can be obtained.
- the storage stability of the prepreg can be increased by using a material having the possibility of forming one of these curing agents, for example, a microencapsulated material. It becomes difficult to change even if left unattended.
- these epoxy resins and curing agents, or products obtained by partially pre-reacting them can be added to the composition. In some cases, this method is effective for viscosity adjustment and storage stability improvement.
- the resin composition impregnated in the second layer may be blended by dispersing the thermoplastic resin as particles or fibers in the thermosetting resin, or dissolving the thermoplastic resin in the thermosetting resin.
- thermoplastic resins are usually thermoplastic having a bond selected from carbon-carbon bond, amide bond, imide bond, ester bond, ether bond, carbonate bond, urethane bond, thioether bond, sulfone bond and carbonyl bond. Although it is preferably a resin, it may have a partially crosslinked structure.
- thermoplastic resin may or may not have crystallinity.
- thermoplastic resins may be commercially available polymers or so-called oligomers having a molecular weight lower than that of commercially available polymers.
- oligomer an oligomer having a functional group capable of reacting with a thermosetting resin at a terminal or in a molecular chain is preferable.
- thermosetting resin When a blend of a thermosetting resin and a thermoplastic resin is used, when only one of these is used, the brittleness of the thermosetting resin can be covered with the toughness of the thermoplastic resin. Since the difficulty of molding can be covered with a thermosetting resin, a balanced main agent can be obtained.
- the ratio (parts by mass) of the thermosetting resin to the thermoplastic resin is preferably in the range of 100: 2 to 100: 50, more preferably in the range of 100: 5 to 100: 35, in terms of balance.
- the B layer of the second layer can realize excellent impact resistance because the particles or fibers of the thermoplastic resin are essential components.
- the thermoplastic resin particles or fiber material used in the present invention may be the same as the various thermoplastic resins exemplified above as the thermoplastic resin blended with the thermosetting resin.
- polyamide is most preferred because it greatly improves impact resistance due to excellent toughness.
- semi-IPN polymer interpenetrating network structure
- nylon 12, nylon 6, nylon 11, nylon 6/12 copolymer or an epoxy compound described in Example 1 of JP-A-01-104624 is formed with nylon 12, nylon 6, nylon 11, nylon 6/12 copolymer or an epoxy compound described in Example 1 of JP-A-01-104624.
- Nylon polymer interpenetrating network structure
- the shape of the thermoplastic resin particles may be spherical, non-spherical, porous, needle-like, whisker-like, or flake-like, but fibers exhibiting high impact resistance for the following reasons.
- a spherical shape is preferred because a reinforced composite material is obtained. Since the flow flow characteristics of the thermosetting resin do not deteriorate, the impregnation property to the reinforcing fiber should be excellent. Since the delamination caused by the local impact (or local impact) at the time of falling weight impact (or local impact) on the fiber reinforced composite material is further reduced, the stress is applied to the fiber reinforced composite material after impact. In such a case, the weakened area where delamination occurs due to local impact that becomes the starting point of fracture due to stress concentration becomes smaller.
- the shape of the thermoplastic resin fiber may be a short fiber or a long fiber.
- short fibers a method of using fibers in the same manner as particles as described in JP-A No. 02-69566, or a method of processing into a mat is possible.
- long fibers a method of arranging long fibers in parallel with the surface of the prepreg as shown in JP-A No. 04-292634 or a method of randomly arranging fibers as shown in International Publication No. 94/016003. Can be used.
- the fiber can be processed and used as a sheet-type substrate such as a woven fabric as disclosed in JP-A No.
- a plurality of prepregs including the cut prepreg may be laminated to form a prepreg laminate, and press-molded by a press. Further, the prepreg laminate is arranged between the single-sided mold and the bag film to form a sealed space, and the sealed space is evacuated and heated while pressing the prepreg laminate with a pressure difference from the atmospheric pressure, and further by an autoclave. You may shape
- the cut prepreg of the present invention is characterized by void suppression, and can produce high-quality fiber-reinforced plastic with good yield even in low-pressure molding, so there are few restrictions on the size of the molded product and little initial investment. Therefore, it is preferable to use a vacuum pump to form by differential pressure from atmospheric pressure.
- the cut prepreg is laminated on a part of the bag film side from the thickness center of the prepreg laminate disposed between the single-sided mold having a curved surface and the bag film.
- the thickness of the prepreg laminate decreases due to pressurization and degassing of the internal gas, the circumferential length difference changes at the site corresponding to the curved surface, so the fiber bridging that prevents the circumferential length difference from being eliminated by cutting
- the friction coefficient between the mold and the prepreg is high and difficult to shift during molding, but the bag film side can move relatively freely, so that the fiber bridging is caused by the notch on the bag film side from the thickness neutral axis. When released, wrinkles and voids can be effectively suppressed.
- the handleability of the cut prepreg sheet, the elongation ratio at the time of molding of the cut prepreg, the surface quality, and the mechanical properties were measured by the following methods.
- the polyethylene film may tear along the cut, It was necessary to re-apply a 10 mm x 10 mm cellophane tape 1 to 3 times to remove the polyethylene film.
- the polyethylene film may be frequently torn along the notches, It was necessary to re-apply a 10 mm x 10 mm cellophane tape at least 4 times and peel off the polyethylene film.
- ⁇ Elongation ratio when forming cut prepreg> A laminated body of cut prepreg having a size of 100 mm ⁇ 100 mm and a laminated structure of [45/0 / ⁇ 45 / 90] 2 s is sandwiched between metal plates previously heated to 130 ° inside the press machine, and a surface pressure of 3 MPa. And press-molded. The molding time was 90 minutes so that the cut prepreg was sufficiently cured, and the molding time was taken out 90 minutes after the start of pressurization. The area of the molded product stretched by press molding was divided by the area of the laminate of the cut prepreg before press molding to calculate the stretch rate.
- a test piece of 25 mm ⁇ 250 mm was cut out so that the 0-degree direction of the reinforcing fiber was the longitudinal direction, and a tensile test was performed by a method defined in ASTM D3039 (2008).
- the number of test specimens measured is 5 for each level, and the average value of tensile modulus and tensile strength is calculated as a representative value.
- Example 1 13 parts by mass of PES5003P was added to 60 parts by mass of “Araldite (registered trademark)” Y9655 and 40 parts by mass of “Epon (registered trademark)” 825 in a kneader, and dissolved to obtain fine particles which are thermoplastic resin particles. 20 parts by mass was kneaded, and then 45 parts by mass of “Aradour (registered trademark)” 9664-1 as a curing agent was kneaded to prepare a thermosetting resin composition.
- the fine particles are prepared by the following method. 90 parts by mass of transparent polyamide (product name: “Grillamide (registered trademark)”-TR55, EMSER Weke), 7.5 parts by mass of epoxy resin (product name: “Epicoat (registered trademark)” 828, manufactured by Shell Petrochemical Co., Ltd.) And 2.5 parts by mass of a curing agent (product name: “Tomide (registered trademark)” # 296, manufactured by Fuji Kasei Kogyo Co., Ltd.) is added uniformly to a solvent mixture containing 300 parts by mass of chloroform and 100 parts by mass of methanol. It was set as the solution.
- transparent polyamide product name: “Grillamide (registered trademark)”-TR55, EMSER Weke
- epoxy resin product name: “Epicoat (registered trademark)” 828, manufactured by Shell Petrochemical Co., Ltd.
- a curing agent product name: “Tomide (registered trademark)” # 296, manufactured by Fuji Kasei Kog
- the obtained uniform solution was atomized with a spray gun for coating, mixed well, and sprayed toward a liquid surface of 3000 parts by mass of n-hexane to precipitate the solution.
- the precipitated solid was separated by filtration, washed thoroughly with n-hexane, and then vacuum-dried at 100 ° C. for 24 hours to obtain spherical epoxy-modified nylon particles.
- Epoxy-modified nylon particles were classified using a CCE classifier manufactured by CCE Technologies. The fine particles obtained had a 90% particle size of 28 ⁇ m and a CV value of 60%.
- thermosetting resin composition was applied to release paper with a knife coater to prepare two 52 g / m 2 resin films.
- the produced two resin films are laminated on both sides of a sheet-like carbon fiber (T800S-12K-10E) arranged in one direction, and the resin is applied at a roller temperature of 100 ° C. and a roller pressure of 0.07 MPa.
- one release paper is peeled off, and the tape-like support A having a unit area mass of carbon fibers of 190 g / m 2 and a mass fraction of the matrix resin of 35.4% is a release paper.
- a prepreg sheet was prepared.
- the term “unidirectional prepreg” refers to the release paper released from the unidirectional prepreg sheet.
- the measurement of the impregnation rate of the thermosetting resin composition of the obtained unidirectional prepreg was performed by the following method.
- the prepreg was sandwiched between the surfaces of two smooth polytetrafluoroethylene resin plates and gradually cured at 40 ° C. for 10 days to produce a plate-like cured prepreg.
- the film was cut in a direction perpendicular to the adhesive surface, magnified 50 times or more so that the upper and lower surfaces of the prepreg were within the field of view, and a cross-sectional photograph was taken with an optical microscope.
- the area ratio of the resin-impregnated portion relative to the cross-sectional area of the cured prepreg was calculated and used as the impregnation rate of the thermosetting resin composition in the prepreg. As a result, the impregnation rate was 30%.
- the unidirectional prepreg sheet obtained by a roller cutter having a blade disposed on a cylinder was inserted in the fiber direction, and intermittent linear cuts were inserted with the cut pattern of FIG.
- the fiber length L is 24 mm
- ⁇ is ⁇ 14 °
- Ws is 0.25 mm.
- the same number of + 14 ° cuts and ⁇ 14 ° cuts were inserted into the prepreg of the unidirectional prepreg sheet. All the incisions were closest to the incision with the opposite inversion angle, and there were incisions with the opposite in positive and negative of the four incision angles closer to the incision with the same sign. . Moreover, there was no adjacent cut within the radius of the cut length Y from every point of the cut.
- the incision row 11 has incisions having a incision length of Y1 mm arranged at a pitch of 1 mm.
- the fibers are divided by incisions corresponding to every other incision row to produce incision prepreg sheets. .
- the distance between adjacent cuts on the same straight line is about 10 times Y.
- the obtained cut prepreg was cut into a 25 cm square size in the 0 ° direction, 8 layers were laminated with the fiber direction aligned, covered with a bag film, and deaerated at 25 ° C. and a vacuum degree of 3 kPa using a vacuum pump. . Then, the temperature was raised to 120 ° C. at a rate of 1.5 ° C./min, held for 180 minutes while maintaining the degree of vacuum at 3 kPa, and then raised to a temperature of 180 ° C. at a rate of 1.5 ° C./min. And held for 120 minutes to cure the prepreg to produce a flat plate of fiber reinforced plastic.
- a small piece of 10 mm ⁇ 10 mm was cut out from approximately the center of the formed flat plate so as to include a cross section in a direction perpendicular to the fiber, embedded in an epoxy resin, and polished in a cross section in the direction perpendicular to the fiber.
- the polished cross section was magnified 200 times or more with an optical microscope, and an area of 300 ⁇ m ⁇ 300 ⁇ m was obtained as a digital image of 900 pixels ⁇ 900 pixels.
- the pixel corresponding to the fiber portion is binarized so that the pixel corresponding to the fiber portion is 1 and the pixel corresponding to the resin is 0.
- the direction perpendicular to the fiber The area ratio of the carbon fiber in the cross section was acquired. Since the carbon fibers are arranged in one direction in the longitudinal direction, the area ratio is regarded as the volume content Vf of the carbon fibers. A total of 10 digital images were randomly obtained from the two pieces so that the regions did not overlap, and the average value of the volume content Vf of the carbon fiber was calculated to be 56%.
- the obtained cut prepreg was cut into a size of 30 cm square in the 0 ° and 45 ° directions.
- the layers are laminated while forming into a quasi-isotropic lamination [45/0 / -45 / 90] 3S layer by layer.
- the laminated body 12 of 24ply cutting prepreg was set. Since the same number of cuts with different positive and negative cut angles were included, it was possible to laminate in the same manner as a normal continuous fiber prepreg without worrying about the relationship between the cut angle and the fiber direction.
- the thickness of the cut prepreg laminate formed by covering with a bag film and degassing using a vacuum pump at 25 ° C. and a degree of vacuum of 3 kPa was measured with a micrometer (5.5 mm). Thereafter, the temperature is raised to a temperature of 120 ° C. at a rate of 1.5 ° C./min, held for 180 minutes while maintaining the degree of vacuum at 3 kPa, and then raised to a temperature of 180 ° C. at a rate of 1.5 ° C./min. For 120 minutes, the prepreg was cured to produce a fiber reinforced plastic L-shaped member. When the thickness of the flat part was measured, it was 4.5 mm, and it was found that the thickness of the cut prepreg laminate before molding was 22% thicker than the obtained fiber-reinforced plastic.
- the R part entering between 10 mm in length and 10 mm in width is observed with an optical microscope, and the area of the void in the fiber-reinforced plastic is compared with the binarization process. The ratio was calculated. As a result, it was confirmed that the void ratio was 0.0%. Moreover, generation
- Example 1 An L-shaped member was formed in the same manner as in Example 1 except that the unidirectional prepreg sheet of Example 1 was used and no cut was inserted, and the void ratio of the R portion was measured. Small voids were scattered in the layer, and the void ratio was 1.5%. In addition, wrinkles were generated on the single-sided mold side from the thickness center of the prepreg laminate.
- thermosetting resin composition In the unidirectional prepreg sheet manufacturing step of Example 1, impregnation with the thermosetting resin composition was performed at a roller temperature of 140 ° C. and a roller pressure of 0.14 MPa. When the impregnation rate was measured by the method of Example 1, it was 100%. Thereafter, incisions were inserted in the same manner as in Example 1, L-shaped members were molded, and the void ratio of the R portion was measured. Many voids remained between the layers, and the void ratio was 2.0%. Moreover, generation
- Comparative Example 3 A unidirectional prepreg with a 100% impregnation rate as in Comparative Example 2 was used, and an L-shaped member was molded in the same manner as in Example 1 without inserting a notch, and the void ratio in the R portion was measured. The bridging of the fibers was conspicuous, and a large void was formed immediately below, and the void ratio was 8.1%. In addition, wrinkles were generated on the single-sided mold side from the thickness center of the prepreg laminate.
- TORAYCA (registered trademark) prepreg sheet P3252S-15 (reinforced fiber: T700S, resin: 2592, volume content of reinforcing fiber: 56%, single-sided polyethylene film, laminated release paper on the other side), blade was placed on the cylinder A prepreg sheet was produced by inserting the roller cutter into the fiber direction, as shown in Fig. 2. Intermittent cuts were provided in the direction perpendicular to the reinforcing fibers, and the cuts were perpendicular to the reinforcing fibers.
- the projected length Ws projected in the direction is 1 mm equal to the cut length Y, and substantially all of the reinforcing fibers are in the fiber length in the region surrounded by the intermittent cuts in the longitudinal direction of the reinforcing fibers.
- the cut pattern was divided into reinforced fibers with a length of 24 mm L.
- a polyethylene film was in close contact with the surface of the prepreg sheet, and the prepreg sheet was prepreg. When inserting the blade in the fiber direction and making a cut, the polyethylene film was inserted through the prepreg so that the tip of the blade stayed inside the release paper. When it cut
- the handleability of the cut prepreg sheet was good, and the polyethylene film could be peeled off at once without being broken by the cut.
- the notch prepreg had an elongation ratio of 1.5, and the surface quality of the stretch molded product was conspicuous in the opening of the notch.
- the mechanical properties of the stretch molded product were a tensile elastic modulus of 46 GPa and a tensile strength of 670 MPa.
- Example 3 The cut pattern was cut in the same manner as in Example 2 except that the cut pattern was a continuous cut pattern with a fiber length L of 24 mm and an angle between the cut and the reinforcing fiber of 14 ° shown in FIG.
- a prepreg sheet was prepared and evaluated in the same manner.
- the handling property of the cut prepreg sheet is that the polyethylene film is cut into strips along the cut and only the polyethylene film piece to which the cellophane tape is bonded is peeled off. It took time and effort to remove it.
- the notched prepreg had an expansion ratio of 2.1, and the surface quality of the stretched molded product was not only the opening of the notch but also the flow of fibers and the undulation was visible.
- the mechanical properties of the stretch molded product were a tensile elastic modulus of 46 GPa and a tensile strength of 710 MPa.
- Example 4 The cut pattern shown in FIG. 4 is provided with intermittent cuts in the direction in which the cuts cross the reinforcing fibers, and the intermittent cuts are inserted linearly and in parallel to form rows. Cut prepreg in the same manner as in Example 2 except that the cut pattern was 2.9 mm, the fiber length L was 24 mm, Ws was 1 mm, and the angle ⁇ between the reinforcing fiber and the cut was 14 °. Sheets were prepared and evaluated in the same manner.
- the polyethylene film may tear along the cut, and it was necessary to re-apply the cellophane tape several times and peel off the polyethylene film.
- the notched prepreg had a molding elongation ratio of 1.7, and as the surface quality of the stretch molded product, almost no opening was found in the cut, but the notch was recognized as a linear pattern.
- the mechanical properties of the stretch molded product were a tensile strength of 48 GPa and a tensile modulus of 740 MPa.
- the cut pattern is provided with intermittent cuts in the direction in which the cuts cross the reinforcing fibers, and the intermittent cuts are inserted linearly, and the angle ⁇ formed between the reinforcing fibers and the cuts.
- the absolute values of are substantially the same, and there are approximately half of the cuts with positive and negative angles, and among the cuts close to any cut, the shortest is the cut with the same positive and negative ⁇
- An embedded prepreg sheet was produced and evaluated in the same manner.
- the polyethylene film may tear along the cut, and it was necessary to re-apply the cellophane tape several times and peel off the polyethylene film.
- the notch prepreg had an elongation ratio of 1.7, and the surface quality of the stretch-molded product showed almost no opening of the notch, but the presence of individual notches could be visually confirmed.
- the mechanical properties of the stretch-molded product were a tensile strength of 48 GPa and a tensile elastic modulus of 770 MPa.
- Example 6 A cut prepreg sheet was prepared in the same manner as in Example 2 except that the cut pattern was the same as that in Example 1 shown in FIG.
- the handling property of the cut prepreg was good because the polyethylene film was not torn along the cut and the entire polyethylene film could be peeled off at once.
- the notched prepreg had an elongation ratio of 1.7, and the surface quality of the stretched molded product was so good that there was no opening of the notch and the presence of the notch was almost invisible.
- the mechanical properties of the stretch molded product were a tensile strength of 48 GPa and a tensile modulus of 810 MPa.
- Example 7 Intermittent cuts are provided in the direction in which the cuts cross the reinforcing fibers, and intermittent notches are inserted linearly and in parallel to form rows, and the distance between the rows is 8.5 mm.
- a cut prepreg sheet was prepared in the same manner as in Example 2 except that the cut pattern with a cut angle of 45 °, a fiber length L of 24 mm, and Ws of 1.0 mm was prepared. Evaluation was performed.
- the notch prepreg had a molding elongation ratio of 1.8, and as a surface quality of the stretch molded product, a notch opening was observed.
- the mechanical properties of the stretch molded product were a tensile strength of 48 GPa and a tensile modulus of 610 MPa.
- Example 8 Intermittent cuts are provided in the direction in which the cuts cross the reinforcing fibers, and the intermittent cuts are inserted linearly and in parallel to form rows, and the distance between the rows is 12 mm.
- a cut prepreg sheet was produced and evaluated in the same manner as in Example 2 except that the cut angle pattern ⁇ was 90 °, the fiber length L was 24 mm, and Ws was 20 mm. .
- the opening of the polyethylene film was large at the cutting part and the resin oozed out, and the resin sometimes adhered to the hand during handling. It was necessary to reapply the tape and peel off the polyethylene film.
- the notched prepreg had an elongation ratio of 1.9 when molded, and the surface quality of the stretched molded product was found to have an opening in the notch and a fiber flow.
- the mechanical properties of the stretch-molded product were a tensile strength of 46 GPa and a tensile modulus of 450 MPa.
- Example 9 Intermittent cuts are provided in the direction in which the cuts cross the reinforcing fibers, intermittent cuts are provided, and intermittent cuts are inserted linearly and in parallel to form rows, Except for the cut pattern in which the distance between the rows was 8.5 mm, the angle ⁇ between the reinforcing fiber and the cut was 45 °, the fiber length L was 24 mm, and Ws was 17.0 mm, the same as in Example 2 A cut prepreg sheet was prepared and evaluated in the same manner.
- the polyethylene film was torn along the cut, and it was necessary to re-apply the cellophane tape several times and peel off the polyethylene film.
- the notched prepreg had an expansion ratio of 2.0, and the surface quality of the stretch-molded product was found to have an opening in the notch and fiber flow.
- the mechanical properties of the stretch molded product were a tensile strength of 45 GPa and a tensile elastic modulus of 380 MPa.
- Example 4 The prepreg sheet used in Example 1 was used without being inserted. As in Example 1, the elongation ratio during molding, the surface quality of the stretch molded product, and the mechanical properties were evaluated. The prepreg has an expansion ratio of 1.1, and an attempt was made to stretch, but it was not able to stretch to the size of the mold, and the resin oozed out and the surface resin was insufficient, resulting in poor quality. .
- the mechanical properties of the stretch molded product were a tensile elastic modulus of 48 GPa and a tensile strength of 920 MPa.
- Pre-preg first layer 2 Pre-preg second layer 3: Incision 4: Incision prepreg 5: Fiber direction 6: Fiber orthogonal direction 7: Intermittent incision 8: Continuous incision 9: Intermittent Diagonal cut (positive angle with respect to fiber direction) 10: Intermittent diagonal cut (negative angle with respect to fiber direction) 11: Row of intermittent notches 12: L-shaped prepreg laminate 13: L-shaped single-sided type 14: Inner diameter of corner portion 15: Cut-out section of L-shaped member 16: Blade 17: Tape-shaped support A 18: Tape-shaped support B
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Abstract
Description
(曲面成形)
曲率半径10mmの曲面を有する雌型とバグフィルムにより密閉空間を形成し、当該密閉空間に切込プリプレグを16~32層積層した積層体を配置し、密閉空間を真空引きして大気圧との差圧で切込プリプレグ積層体を加圧しながら、加熱して固化させ繊維強化プラスチックを得る。
テープ状支持体Bとしてポリエチレンフィルムを貼り付けた切込プリプレグシートを100mm×100mmのサイズに切り取り、一つの角を含む10mm×10mmの領域にセロハンテープを貼り、セロハンテープ対角に向かってめくることでポリエチレンフィルムを剥がし、ポリエチレンフィルムの剥がしやすさを評価した。表1では、全てのポリエチレンフィルムを剥がすために要する手間を以下の3段階にわけた。
ポリエチレンフィルムを一度に剥がすことができたもの。
1~3回10mm×10mmのセロハンテープを貼りなおして
ポリエチレンフィルムを剥がす必要があったもの。
4回以上10mm×10mmのセロハンテープを貼りなおして
ポリエチレンフィルムを剥がす必要があったもの。
サイズが100mm×100mmで、積層構成が[45/0/-45/90]2sの切込プリプレグの積層体を予めプレス機の内部で130°に加熱された金属板に挟み、3MPaの面圧をかけてプレス成形した。成形時間は、切込プリプレグが十分硬化させるため90分とし、加圧開始から90分後に取り出した。プレス成形により伸張した成形品の面積をプレス成形前の切込プリプレグの積層体の面積で割り、伸張率を計算した。
切込プリプレグから300mm×300mm、積層構成が[+45/0/-45/90]2sの切込プリプレグの積層体を作製し、350mm×350mmの型を用いてプレス機により3MPaの面圧の下でプレス成形し、350mm×350mmの繊維強化プラスチックを成形した。プレス時の温度は130度、プレス後に90分保持してから脱型し、室温に放置して冷却した。成形された繊維強化プラスチックの表面品位を目視により確認した。表1では、切込の存在がほとんど認識できないものをA、切込の開口は少ないものの切込の存在が認識されるものをB、切込が開口し表面品位が損なわれている場合にCと評価した。
切込プリプレグから300mm×300mm、積層構成が[+45/0/-45/90]2sの切込プリプレグの積層体を作製し、350mm×350mmの型を用いてプレス機により3MPaの面圧の下でプレス成形し、350mm×350mmの繊維強化プラスチックを成形した。プレス時の温度は130度、プレス後に90分保持してから脱型し、室温に放置して冷却した。強化繊維の0度方向が長手方向となるように、25mm×250mmの試験片を切り出し、ASTM D3039(2008)に規定された方法で引張試験を行った。測定した試験片の数は各水準5本とし、引張弾性率および引張強度の平均値を代表値として算出する。
13質量部のPES5003Pを、混練機中の60質量部の“アラルダイト(登録商標)”Y9655および40質量部の“エポン(登録商標)”825に加えて溶解させ、熱可塑性樹脂粒子である微粒子を20質量部混練し、次いで硬化剤として“アラドゥール(登録商標)”9664-1を45質量部混練して熱硬化性樹脂組成物を作製した。
実施例1の一方向プリプレグシートを用い、切込を挿入しない以外は、実施例1と同様にL字部材を成形し、R部のボイド率を計測した。層内に小さなボイドが点在し、ボイド率は1.5%であった。また、プリプレグ積層体の厚み中心より片面型側にシワが発生した。
実施例1の一方向プリプレグシート作製工程において、熱硬化性樹脂組成物の含浸をローラー温度140℃、ローラー圧力0.14MPaで実施した。含浸率を実施例1の方法で計測したところ、100%であった。その後、実施例1と同様に切込を挿入し、L字部材を成形し、R部のボイド率を計測した。層間に残留するボイドが多数みられ、ボイド率は2.0%であった。また、シワの発生は見られなかった。
比較例2と同様の含浸率100%の一方向プリプレグを用い、切込を挿入することなく、実施例1と同様にL字部材を成形し、R部のボイド率を計測した。繊維のブリッジングが目立ち、その直下に大きなボイドが生成されており、ボイド率は8.1%であった。また、プリプレグ積層体の厚み中心より片面型側にシワが発生した。
トレカ”(登録商標)プリプレグシートP3252S-15(強化繊維:T700S、樹脂:2592、強化繊維の体積含有率:56%、片面ポリエチレンフィルム、もう片面離型紙を積層)を、シリンダーに刃を配置したローラーカッターに繊維方向に挿入し、切込プリプレグシートを作製した。図2に示すように、強化繊維を垂直に横切る方向へ断続的な切込が設けられており、切込を強化繊維の垂直方向に投影した投影長さWsは、切込の長さYと等しく1mmであり、強化繊維の長手方向に断続的な切込同士に囲まれる領域において実質的に強化繊維のすべてが繊維長さLが24mmの強化繊維に分断されているカットパターンとした。プリプレグシートの表面にはポリエチレンフィルムが密着しており、ローラーカッターにプリプレグを繊維方向に挿入し切込を入れる際に、ポリエチレンフィルムを貫通してプリプレグに切込を挿入し、刃の先端が離型紙の内部に留まるようにした。切込挿入後の離型紙を切込を横切るように裁断し、その断面を光学顕微鏡で観察したところ、離型紙の厚み方向に40%まで切込が侵入していた。
カットパターンを、図3に示す、繊維長さLが24mmで、切込と強化繊維とのなす角度が14°の連続的なカットパターンとした以外は、実施例2と同様にして、切込プリプレグシートを作製し、同様の評価を行った。切込プリプレグシートの取り扱い性はポリエチレンフィルムが切込に沿って短冊状に切断されており、セロハンテープが接着されたポリエチレンフィルム片のみが剥がれるため、切込プリプレグに密着した全てのポリエチレンフィルム片を剥がすのに手間を要した。切込プリプレグの成形時伸張率は2.1であり、伸張成形品の表面品位は切込の開口に加え、繊維が流動してうねりが見えていた。伸張成形品の力学特性は、引張弾性率46GPa、引張強度710MPaとなった。
カットパターンを、図4に示す、切込が強化繊維を横切る方向へ断続的な切込が設けられており、断続的な切込が直線状かつ平行に挿入されて列を形成し、列間の距離が2.9mm、繊維長さLは24mm、Wsは1mm、強化繊維と切込のなす角度θが14°であるカットパターンとした以外は、実施例2と同様にして、切込プリプレグシートを作製し、同様の評価を行った。
カットパターンを、図5に示す、切込が強化繊維を横切る方向へ断続的な切込が設けられており、断続的な切込が直線状に挿入され、強化繊維と切込のなす角度θの絶対値が実質的に同一であり、正と負の角度となる切込が略半数ずつあり、任意の切込と近接する切込のうち、θの正負が同一である切込よりも最短距離が近いθの正負が異なる切込が4つ存在するカットパターンであり、繊維長さLを24mm、θを±14°、Wsを1mmとした以外は、実施例2と同様にして、切込プリプレグシートを作製し、同様の評価を行った。
カットパターンを、図6に示す、実施例1と同じカットパターンとした以外は実施例2と同様にして、切込プリプレグシートを作製し、同様の評価を行った。
切込が強化繊維を横切る方向へ断続的な切込が設けられており、断続的な切込が直線状かつ平行に挿入されて列を形成し、列間の距離を8.5mm、強化繊維と切込のなす角度θを45°、繊維長さLを24mm、Wsを1.0mmとしたカットパターンとした以外は、実施例2と同様にして、切込プリプレグシートを作製し、同様の評価を行った。
切込が強化繊維を横切る方向へ断続的な切込が設けられており、断続的な切込が直線状かつ平行に挿入されて列を形成し、列間の距離を12mm、強化繊維と切込のなす角度θを90°、繊維長さLを24mm、Wsを20mmとしたカットパターンとした以外は、実施例2と同様にして、切込プリプレグシートを作製し、同様の評価を行った。
切込が強化繊維を横切る方向へ断続的な切込が設けられており、断続的な切込が設けられており、断続的な切込が直線状かつ平行に挿入されて列を形成し、列間の距離を8.5mm、強化繊維と切込のなす角度θを45°、繊維長さLを24mm、Wsを17.0mmとしたカットパターンとした以外は、実施例2と同様にして、切込プリプレグシートを作製し、同様の評価を行った。
実施例1で用いたプリプレグシートに切込を挿入せずに使用した。実施例1と同様、成形時伸張率、伸張成形品の表面品位、力学特性を評価した。プリプレグの成形時伸張率は1.1、伸張成形を試みたが金型の大きさまで伸張することができておらず、樹脂が周囲に染み出して表面の樹脂が不足して品位は低くなった。伸張成形品の力学特性は、引張弾性率48GPa、引張強度920MPaであった。
2:プリプレグ第2の層
3:切込
4:切込プリプレグ
5:繊維方向
6:繊維直交方向
7:断続的な切込
8:連続的な切込
9:断続的な斜め切込(繊維方向に対して正の角度)
10:断続的な斜め切込(繊維方向に対して負の角度)
11:断続的な切込の列
12:L字に賦形されたプリプレグ積層体
13:L字片面型
14:コーナー部内径
15:L字部材の切り出し断面
16:刃
17:テープ状支持体A
18:テープ状支持体B
Claims (15)
- 樹脂組成物が含浸した強化繊維を含む層を有するプリプレグであって、複数の切込によって少なくとも一部が繊維長さ(L)10~300mmの強化繊維で構成され、かつ、強化繊維の体積含有率Vfが45~65%の範囲内である、切込プリプレグ。
- 強化繊維からなる第1の層と、樹脂組成物が含浸した強化繊維を含む第2の層とからなるプリプレグであって、第1の層の両側に第2の層が設けられ、プリプレグ中における樹脂組成物の含浸率が10~90%である、請求項1に記載の切込プリプレグ。
- 第2の層が、熱硬化性樹脂組成物を含浸した強化繊維からなるA層と、熱可塑性樹脂の粒子または繊維を含むB層とからなり、B層は切込プリプレグ表面に面している、請求項2に記載の切込プリプレグ。
- 前記切込プリプレグが、室温にて切込プリプレグの一方の表面に10水柱cmの圧力で水を接触させた場合に、1分以内に反対の面から水が染み出すものである、請求項1~3のいずれかにに記載の切込プリプレグ。
- 切込プリプレグが、該切込プリプレグを積層し以下に示す方法にて形成した切込プリプレグ積層体の厚みが、当該切込プリプレグ積層体を加熱して固化させ、繊維強化プラスチックとした際の厚みに対して5~50%厚いものである、請求項1~4のいずれかに記載の切込プリプレグ。
(切込プリプレグ積層体の形成方法)片面型とバグフィルムにより密閉空間を形成し、当該密閉空間に切込プリプレグを積層した積層体を配置し、室温にて密閉空間を真空引きして大気圧との差圧で切込プリプレグを積層した積層体を加圧して切込プリプレグ積層体を形成する。 - 切込プリプレグが、該切込プリプレグを16~32層積層し以下に示す曲面成形を行って得られた繊維強化プラスチックの曲面の部分に実質的にボイドが含まれないものである、請求項1~5のいずれかに記載の切込プリプレグ。
(曲面成形)曲率半径10mmの曲面を有する雌型とバグフィルムにより密閉空間を形成し、当該密閉空間に切込プリプレグを16~32層積層した積層体を配置し、密閉空間を真空引きして大気圧との差圧で前記切込プリプレグを16~32層積層した積層体を加圧しながら、加熱して固化させ繊維強化プラスチックを得る。 - 切込プリプレグの少なくとも一部に強化繊維を横切る方向へ断続的な切込が複数設けられており、前記切込を切込プリプレグの面内における強化繊維の垂直方向に投影した投影長さWsが30μm~1.5mmであり、断続的な切込同士によって、強化繊維の長手方向に囲まれる領域において実質的に強化繊維のすべてが切込により分断されている、請求項1~6のいずれかに記載の切込プリプレグ。
- 切込と強化繊維とのなす角度をθとしたとき、θの絶対値が2~25°の範囲内である、請求項1~7のいずれかに記載の切込プリプレグ。
- 切込プリプレグの少なくとも一部に強化繊維を横切る方向へ断続的な切込が複数設けられており、断続的な切込が直線状かつ平行に挿入されて列を形成し、列間の距離Xが1~5mmの範囲内である、請求項1~8のいずれかに記載の切込プリプレグ。
- 切込プリプレグの少なくとも一部に強化繊維を横切る方向へ断続的な切込が複数設けられており、断続的な切込が直線状に挿入され、θの絶対値が実質的に同一であり、正と負の角度となる切込が略半数ずつである、請求項1~9のいずれかに記載の切込プリプレグ。
- 任意の1つの切込Aに着目したとき、該切込と近接する切込のうち、θの正負が同一である最も近い切込Bよりも切込Aとの最短距離が近いθの正負が異なる切込Cが4つ以上存在する、請求項10に記載の切込プリプレグ。
- 切込プリプレグの少なくとも一部に強化繊維を横切る方向へ断続的な切込が複数設けられており、断続的な切込が直線かつ実質的に同一の長さYで挿入され、近接する切込同士の最短距離が切込の長さYよりも長い、請求項1~11のいずれかに記載の切込プリプレグ。
- 切込プリプレグの少なくとも一部に強化繊維を横切る方向へ断続的な切込が複数設けられており、断続的な切込が直線かつ実質的に同一の長さYで挿入され、同一直線状の近接する切込間距離がYの3倍より大きい、請求項1~12のいずれかに記載の切込プリプレグ。
- 請求項1~13のいずれかに記載の切込プリプレグの片面にテープ状支持体Aが接触するように積層された切込プリプレグシートであって、テープ状支持体Aの厚み方向に、テープ状支持体Aの切込プリプレグと接触する面から5~75%の範囲で切込プリプレグの切込と連続した切込を有する、切込プリプレグシート。
- テープ状支持体Aとは接しない側の切込プリプレグの面に、テープ状支持体Bが接触するように積層された切込プリプレグシートであって、テープ状支持体Bは、切込プリプレグの切込と連続した切込が厚み方向に貫通して存在している、請求項14に記載の切込プリプレグシート。
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TWI677418B (zh) | 2019-11-21 |
JP6597309B2 (ja) | 2019-10-30 |
US10808091B2 (en) | 2020-10-20 |
EP3196238A1 (en) | 2017-07-26 |
PT3196238T (pt) | 2019-08-06 |
ES2738708T3 (es) | 2020-01-24 |
CN106715547B (zh) | 2020-01-17 |
KR102417660B1 (ko) | 2022-07-07 |
EP3196238A4 (en) | 2018-04-18 |
KR20170057316A (ko) | 2017-05-24 |
EP3196238B1 (en) | 2019-07-03 |
JPWO2016043156A1 (ja) | 2017-06-29 |
CN106715547A (zh) | 2017-05-24 |
TW201618918A (zh) | 2016-06-01 |
US20170283571A1 (en) | 2017-10-05 |
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