WO2012165418A1 - 等方性を維持した成形体の製造方法 - Google Patents
等方性を維持した成形体の製造方法 Download PDFInfo
- Publication number
- WO2012165418A1 WO2012165418A1 PCT/JP2012/063731 JP2012063731W WO2012165418A1 WO 2012165418 A1 WO2012165418 A1 WO 2012165418A1 JP 2012063731 W JP2012063731 W JP 2012063731W WO 2012165418 A1 WO2012165418 A1 WO 2012165418A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- prepreg
- molded body
- fibers
- thermoplastic resin
- fiber
- Prior art date
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Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24628—Nonplanar uniform thickness material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
Definitions
- the present invention relates to a method for producing a molded body made of a fiber-reinforced composite material starting from a random mat containing reinforcing fibers and a thermoplastic resin. More specifically, even when the mold is closed and press-molded in a state where the charge rate of the prepreg to the mold is 100% or less, it is possible to obtain a molded body in which the isotropy of the fiber is maintained up to the end.
- the present invention relates to a method for producing a molded body.
- Fiber reinforced composite materials using carbon fibers, aramid fibers, glass fibers, etc. as reinforcing fibers make use of their high specific strength and specific elastic modulus to make structural materials such as aircraft and automobiles, tennis rackets, golf shafts, fishing rods. It has been widely used in general industries such as sports and sports applications.
- a preform is produced by laminating a base material containing discontinuous reinforcing fibers and a resin, and the preform is formed in a wider range than the total area of the mold cavity. It has been proposed to arrange and press-mold (see Patent Document 1).
- a composition containing a reinforcing fiber and a resin is molded by injection molding to obtain a molded body made of a fiber-reinforced composite (see Patent Document 2).
- this method uses so-called long fiber composite pellets, and the average length of the reinforcing fibers is about 5 to 15 mm, and the length of the reinforcing fibers is greatly reduced in the molded article after injection molding.
- JP 2010-253938 A Japanese Patent Laid-Open No. 04-193504
- An object of the present invention is a method for producing a molded body from a random mat containing reinforcing fibers and a thermoplastic resin, and even when the prepreg is charged with a low charge rate to the mold, An object of the present invention is to provide a production method capable of obtaining a molded product in which the isotropy of the fiber is maintained.
- the present inventors have found that the above-mentioned problems can be solved by using a prepreg obtained by impregnating a thermoplastic resin into a specific random mat-like reinforcing fiber, and molding the prepreg under specific conditions, thereby completing the present invention. It came to.
- the present invention is a method for producing a molded body comprising a fiber-reinforced composite material, 1) A random mat containing reinforcing fibers having an average fiber length of 5 to 100 mm and a thermoplastic resin, up to a temperature not lower than the melting point when the thermoplastic resin is crystalline and lower than the thermal decomposition temperature, and a glass transition temperature when amorphous.
- a prepreg production step for obtaining a prepreg by impregnating a thermoplastic resin by heating to a temperature lower than the thermal decomposition temperature 2)
- the thermoplastic resin is crystalline
- the prepreg is set to a temperature not lower than the melting point and lower than the thermal decomposition temperature, and in the case of amorphous, the prepreg is set to a temperature not lower than the glass transition temperature and lower than the thermal decomposition temperature.
- a prepreg placement step 3) Molding that presses the prepreg in the mold and completes the molding at a temperature lower than the melting point when the thermoplastic resin is crystalline, or less than the glass transition temperature when the thermoplastic resin is amorphous to obtain a molded body.
- the reinforcing fibers are substantially two-dimensionally oriented with a basis weight of 25 to 10,000 g / m 2 .
- the reinforcing fiber bundle (A) composed of the number of critical single yarns or more defined by the formula (1) is included in an amount of 20 Vol% or more and less than 99 Vol% with respect to the total amount of fibers in the random mat, And the average number of fibers (N) in the said reinforced fiber bundle (A) satisfy
- the manufacturing method of the molded object which consists of a fiber reinforced composite material characterized by the above-mentioned.
- Critical number of single yarns 600 / D (1) 0.7 ⁇ 104 / D2 ⁇ N ⁇ 1 ⁇ 105 / D2 (2)
- D is the average fiber diameter ( ⁇ m) of the reinforcing fibers
- Charge rate (%) 100 ⁇ [base material area (mm 2 ) / mold cavity projected area (mm 2 )] (3)
- the base material area is the projected area in the extraction direction of all the arranged prepregs, and the mold cavity projected area is the projected area in the extraction direction)
- a molded body can be formed using a minimum amount of material, and even when the prepreg charge rate with respect to the mold is 100% or less, It is possible to obtain a molded body in which the isotropy of the fiber is maintained up to the end. Therefore, according to the present invention, the trimming step can be omitted, and the waste material can be significantly reduced and the costs associated therewith can be reduced.
- a molded product having a thin wall, light weight, high rigidity and excellent design can be obtained, and the occupation time in the mold can be reduced by cold pressing, so that the molded product can be produced with high productivity. It can be manufactured.
- a molded body can be obtained with good shape followability even when a complicated three-dimensional mold is used, and the molded body can be manufactured in a short time, and trimming to a product shape is possible. It becomes possible to obtain a molded body that does not require.
- FIG. 3 is a schematic view of substrate arrangement on a mold in Examples 1 and 3. 6 is a schematic diagram of a three-dimensional mold used in Example 2.
- FIG. It is a schematic diagram (perspective view) of the molded product obtained in Examples 1 and 3. 6 is a schematic diagram of substrate arrangement on a mold in Example 2.
- FIG. 6 is a schematic diagram (perspective view) of a molded product obtained in Example 2.
- FIG. 6 is a schematic diagram of substrate arrangement on a mold in Example 4.
- FIG. 6 is a schematic diagram (perspective view) of a molded product obtained in Example 4. It is explanatory drawing of the edge part structure of a metal mold
- FIG. 10 is a schematic diagram of substrate arrangement on a mold in Example 11.
- the present invention is a method for producing a molded body comprising a fiber-reinforced composite material, 1) A random mat containing reinforcing fibers having an average fiber length of 5 to 100 mm and a thermoplastic resin, up to a temperature not lower than the melting point when the thermoplastic resin is crystalline and lower than the thermal decomposition temperature, and a glass transition temperature when amorphous.
- a prepreg production step for obtaining a prepreg by impregnating a thermoplastic resin by heating to a temperature lower than the thermal decomposition temperature 2) When the thermoplastic resin is crystalline, when the thermoplastic resin is crystalline, the prepreg is set to a temperature not lower than the melting point and lower than the thermal decomposition temperature, and in the case of amorphous, the prepreg having a temperature not lower than the glass transition temperature and lower than the thermal decomposition temperature. Is placed in a mold whose temperature is adjusted to be lower than the melting point temperature or, in the case of amorphous, lower than the glass transition temperature, so that the charge rate represented by the following formula (3) is 50% or more and 100% or less.
- a prepreg placement step 3) Molding that presses the prepreg in the mold and completes the molding at a temperature lower than the melting point when the thermoplastic resin is crystalline, or less than the glass transition temperature when the thermoplastic resin is amorphous to obtain a molded body.
- Charge rate (%) 100 ⁇ [base material area (mm 2 ) / mold cavity projected area (mm 2 )] (3) (In formula (3), the base material area is the projected area in the extraction direction of all the arranged prepregs, and the mold cavity projected area is the projected area in the extraction direction)
- the molded product obtained by the production method of the present invention is a molded product made of a fiber-reinforced composite material containing reinforcing fibers and a thermoplastic resin.
- the molded product obtained by the present invention has a layer that is two-dimensionally randomly oriented in the plane, and is substantially isotropic.
- substantially isotropic means that after molding a composite material, a tensile test based on an arbitrary direction of the molded plate and a direction orthogonal thereto is performed. It is defined that the ratio (E ⁇ ) obtained by dividing the value of the measured tensile elastic modulus by the smaller one (E ⁇ ) is 1.3 or less.
- the molded body obtained by the production method of the present invention is a molded body having a smooth surface and a uniform thickness.
- the variation in the thickness of the molded body is preferably within ⁇ 10% from the average value.
- “the surface is smooth” means that when the surface of the molded body is visually observed, a rough shape, wrinkles, unevenness and the like are not confirmed, and the surface is flat and smooth.
- the molded product obtained in the present invention is obtained through a prepreg form using a random mat containing reinforcing fibers and a thermoplastic resin as a starting material. Also in the molded body finally obtained, the average fiber length of the reinforcing fibers used, and the ratio of the reinforcing fiber bundle to the single yarn are kept in the random mat as the starting material.
- the reinforcing fiber used in the present invention is preferably at least one selected from the group consisting of carbon fiber, aramid fiber, and glass fiber. These can be used in combination, and it is preferable to use carbon fiber in that it can provide a composite material that is lightweight but excellent in strength.
- the reinforcing fibers used in the present invention are preferably those having a sizing agent attached thereto, and the amount of the sizing agent attached is preferably 0 to 10 parts by mass with respect to 100 parts by mass of the reinforcing fibers.
- the reinforcing fibers used in the present invention are discontinuous and have an average fiber length of 5 to 100 mm.
- the production method of the present invention is characterized in that a molded product capable of exhibiting a reinforcing function can be obtained even when long reinforcing fibers are contained.
- the average fiber length of the reinforcing fibers is preferably 10 to 100 mm, more preferably.
- the thickness is 10 to 50 mm, more preferably 10 to 30 mm.
- the length of the reinforcing fiber which comprises a random mat can be made into fixed length by employ
- the average fiber diameter is preferably 3 to 12 ⁇ m, more preferably 5 to 7 ⁇ m.
- Basis weight of the reinforcing fibers in the random mat is 25 ⁇ 10000g / m 2, preferably 25 ⁇ 6000g / m 2, more preferably 25 ⁇ 3000g / m 2.
- the basis weight is less than 25 g / m 2 , the distribution of the reinforcing fibers is likely to be non-uniform in the random mat and there is a possibility that a sufficient reinforcing effect is not exhibited.
- it exceeds 10,000 g / m 2 since there are too many reinforcing fibers, it is difficult to impregnate the resin during prepreg production, and voids that become defects in the molded body tend to occur.
- the reinforcing fiber has a higher specific gravity than the thermoplastic resin, the molded body becomes heavy.
- the content of reinforcing fibers in the random mat used in the present invention and the molded article obtained is preferably such that the reinforcing fiber volume content (Vf) defined by the following formula (5) is in the range of 5 to 80 Vol%. .
- Reinforcing fiber volume content (Vf) 100 ⁇ [volume of reinforcing fiber / (volume of reinforcing fiber + volume of thermoplastic resin)] (5)
- the reinforcing fiber volume content (Vf) indicates the composition of the reinforcing fiber and the thermoplastic resin contained in the fiber reinforced composite material (random mat) and the molded body obtained from the composite material (random mat).
- the reinforcing fiber volume content is lower than 5% Vol, the reinforcing effect may not be sufficiently exhibited.
- the content rate exceeds 80 Vol%, voids are likely to be generated during the preparation of the prepreg, and the physical properties of the obtained molded article may be lowered.
- the reinforcing fiber volume content is more preferably in the range of 20 to 60 Vol%.
- thermoplastic resin is removed from a sample such as a molded body, and the masses of the remaining reinforcing fiber and the thermoplastic resin are respectively determined.
- a method of obtaining these mass values by converting them into volumes using the density of each component and applying the obtained volume values to the above formula (5) can be mentioned.
- thermoplastic resin (type)
- thermoplastic resin used in the present invention examples include vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, polyvinyl alcohol resin, polystyrene resin, acrylonitrile-styrene resin (AS resin), acrylonitrile-butadiene-styrene resin ( ABS resin), acrylic resin, methacrylic resin, polyethylene resin, polypropylene resin, polyamide 6 resin, polyamide 11 resin, polyamide 12 resin, polyamide 46 resin, polyamide 66 resin, polyamide 610 resin, polyacetal resin, polycarbonate resin, polyethylene terephthalate resin, Polyethylene naphthalate resin, boribylene terephthalate resin, polyarylate resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone Fat, polyether sulfone resins, polyether ether ketone resins, such as polylactic acid resins.
- 2 or more types of thermoplastic resin 2 or more types of
- thermoplastic resin shape of the thermoplastic resin is not particularly limited.
- the thermoplastic resin can be supplied as a fiber, a particle, a molten state, or a mixture thereof.
- thermoplastic resin When the thermoplastic resin is fibrous, its fineness is preferably 100 to 5000 dtex, more preferably 1000 to 2000 dtex.
- the average fiber length is preferably 0.5 to 50 mm, more preferably 1 to 10 mm.
- the thermoplastic resin is in the form of particles, it is preferably spherical, strip-like, or cylindrical like a pellet.
- a spherical shape a perfect circular or elliptical rotating body or an egg-like shape is preferable.
- the average particle diameter in the case of a sphere is preferably 0.01 to 1000 ⁇ m. More preferably, it is 0.1 to 900 ⁇ m, and further preferably 1 to 800 ⁇ m.
- the particle size distribution is not particularly limited, but a sharp distribution is preferable for the purpose of obtaining a thinner molded body. In addition, it can also use as desired particle size distribution by operation, such as classification.
- thermoplastic resin When the thermoplastic resin is in the form of strips, it is preferably in the form of a cylinder such as a pellet, a prism, or a flake. In this case, it may have a certain aspect ratio, but the preferred length is about the same as that of the above fibrous form.
- the content of thermoplastic resin is preferably 50 to 1000 parts by mass, more preferably 50 to 500 parts by mass with respect to 100 parts by mass of the reinforcing fibers.
- the content is less than 50 parts by mass, since there is little thermoplastic resin, voids are likely to occur during the preparation of the prepreg, and the physical properties of the resulting molded article may be reduced.
- the amount exceeds 1000 parts by mass, the proportion of reinforcing fibers is relatively low, and thus there is a possibility that the physical properties expected of a molded body using a fiber-reinforced composite material may not be reached.
- the random mat used in the production method of the present invention only needs to contain at least the above-described reinforcing fibers and thermoplastic resin, but may contain other third components as long as the purpose is not impaired.
- Examples of other components include various fibrous or non-fibrous fillers other than the above-described reinforcing fibers, flame retardants, UV-resistant agents, pigments, mold release agents, softeners, plasticizers, surfactants, and the like. it can. Particularly in electronic / electric equipment applications and automobile applications, high flame retardancy may be required, and therefore it is preferable to include a flame retardant in the thermoplastic resin.
- a flame retardant a well-known thing can be used and will not be specifically limited if it can provide a flame retardance. Specific examples include phosphorus flame retardants, nitrogen flame retardants, silicone compounds, organic alkali metal salts, organic alkaline earth metal salts, bromine flame retardants, etc. These flame retardants can be used alone.
- the content of the flame retardant is preferably 1 to 40 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin, from the balance of physical properties, moldability, and flame retardancy. .
- the random mat used in the present invention is one in which the above-described reinforcing fibers are substantially two-dimensionally oriented.
- two-dimensional random means that the reinforcing fibers are not oriented in a specific direction and are distributed in a random direction within the plane.
- the reinforcing fiber bundle (A) composed of the number of critical single yarns defined by the formula (1) is 20 Vol% or more and less than 99 Vol% with respect to the total amount of fibers in the random mat.
- Critical number of single yarns 600 / D (1)
- D is the average fiber diameter ( ⁇ m) of the reinforcing fibers)
- the reinforcing fibers in the mat exist in a single yarn state or a fiber bundle state composed of less than the critical single yarn number, in addition to the reinforcing fiber bundle (A). Therefore, the random mat used in the present invention controls the degree of opening of the reinforcing fibers and includes the reinforcing fiber bundle (A) composed of reinforcing fibers of a specific number or more and other reinforcing fibers at a specific ratio. It is characterized by that.
- the ratio of the reinforcing fiber bundle (A) to the total amount of the fibers is less than 20 Vol%, it becomes difficult to flow the fibers in the mold when the random mat is formed. For this reason, the fibers can be filled to the end of the mold cavity. Therefore, it becomes difficult to obtain a molded body as designed.
- the ratio of the reinforcing fiber bundle (A) is 99 Vol% or more, the entangled portion of the fibers is locally thick, and a thin-walled product cannot be obtained.
- the ratio of the reinforcing fiber bundle (A) to the total amount of fibers is preferably 30 Vol% or more and less than 90 Vol%, more preferably 30 Vol% or more and less than 80 Vol%.
- the ratio of a reinforced fiber bundle (A) can be controlled by combining conditions, such as a widening process, a slit process, a cutting process, and a fiber opening process, in the manufacturing method mentioned later, for example.
- the critical single yarn number is 86 to 120
- the average fiber diameter of the carbon fiber is 5 ⁇ m
- the reinforcing fiber The average number of fibers (N) in the bundle (A) is in the range of 280 to 4000.
- the average number of fibers (N) in the reinforcing fiber bundle (A) is 280.
- the number is preferably ⁇ 2000, and more preferably 600 to 1,600.
- the average number of fibers (N) in the reinforcing fiber bundle (A) is in the range of 142 to 2040, but when the average fiber diameter of the carbon fibers is 7 ⁇ m. Is preferably 142 to 1020, and more preferably 300 to 800.
- the random mat used in the present invention can have various thicknesses, but using this as a prepreg, a thin molded product having a thickness of about 0.2 to 1 mm can be suitably obtained. That is, a thin molded product such as a skin of a sandwich material can be obtained by preparing a random mat that matches the thickness of the target molded product.
- the average number of fibers (N) in the reinforcing fiber bundle (A) can be controlled by combining conditions such as a widening process, a slit process, a cutting process, and a fiber opening process in a manufacturing method described later.
- the method for producing the random mat is not particularly limited.
- the random mat may be produced so that a fibrous and / or particulate thermoplastic resin is mixed with the reinforcing fiber and includes a matrix resin component. It may be produced by supplying a molten thermoplastic resin to a random mat that is not present.
- the method for producing the random mat preferably includes a method of performing the following steps (I), (III), (IV), (V) or (V ′), and more preferably (I) And a method of performing the step (II) between the steps (III) and (III).
- each reinforcing fiber is drawn out from a plurality of reinforcing fiber wound bodies arranged in the creel portion, and consists of a single yarn or a single yarn. Supplied as reinforcing fiber strands that are drawn together.
- the strand width is preferably 10 to 50 mm (particularly 20 to 30 mm).
- the strand may be widened to a predetermined width in this strand supply step and supplied as a thin wide strand as necessary. This widening operation can be performed, for example, by bringing the strand into contact with a widening roller or bar.
- the supplied reinforcing fiber strand is preferably slit continuously in parallel with the longitudinal direction of the strand (that is, along the fiber axis direction), and the strand width is 0.05 to 5 mm.
- a plurality of narrow strands are used.
- the wide strand continuously transferred from the previous step is continuously cut in the longitudinal direction using a slitting device (slitter) having a blade parallel to the fiber axis direction, or the wide strand
- a slitting device having a blade parallel to the fiber axis direction
- One or a plurality of division guides are provided on the travel path, and the strands are divided into a plurality of pieces, for example.
- a widening guide or bar may be installed on the line, and a slit may be added while widening the reinforcing fiber.
- the strand not subjected to slit treatment or the narrow reinforcing fiber strand slit as described above is cut (cut) into an average fiber length of 5 to 100 mm.
- the “average fiber length” can be obtained by a method of measuring the fiber length of 100 fibers randomly extracted up to 1 mm using a caliper or the like and obtaining the average. Normally, the average fiber length matches the interval between strands cut by the cutter.
- a rotary cutter is preferable as an apparatus used when cutting reinforcing fibers into an average fiber length of 5 to 100 mm. Further, among rotary cutters, those equipped with a spiral knife having a specific angle are preferable.
- ⁇ is an angle formed by the circumferential direction and the arrangement direction of the knife.
- the fiber bundle can be slit in the longitudinal direction and simultaneously cut to a specific fiber length. If it does so, strand slit process (II) and reinforcement fiber cut (III) can be implemented simultaneously.
- (IV) Reinforcing Fiber Opening Step gas is blown onto a strand of reinforcing fibers cut to a predetermined fiber length (hereinafter sometimes referred to as “strand piece”), and the strand piece is formed in a desired shape.
- the fiber is opened so as to be divided into fiber bundles of size (number of bundles).
- the strand pieces are introduced into the path, and a gas such as air is blown onto the strand pieces that pass through the path, so that the strand pieces have a desired converging size. Separate and disperse in gas.
- the degree of opening can be appropriately controlled by the pressure of the gas to be blown.
- an air blowing nozzle is provided in the middle of the path or at the tip, and air with a wind speed of 5 to 500 m / sec is blown directly onto the strand piece from the compressed air blowing hole to appropriately open the reinforcing fiber.
- the method of making it fiber is mentioned. Specifically, several holes with a diameter of about 1 mm are formed in the path through which the reinforcing fiber pieces pass, and compressed air is blown directly from the holes to the strand pieces by applying a pressure of about 0.2 to 0.8 MPa from the outside. The method of using the gas spray nozzle which was made is mentioned.
- the degree of opening is such that the ratio of the reinforcing fiber bundle (A) consisting of the number of critical single yarns or more defined by the above formula (1) and the average number of fibers (N) in the reinforcing fiber bundle (A) are satisfied. It is necessary to.
- (V) Random mat forming step In the random mat forming step, the cut and opened reinforcing fibers are diffused in the air, and at the same time, a granular or short fiber thermoplastic resin (hereinafter referred to as "heat"). And the reinforcing fibers are dispersed on a breathable support provided below the opening device together with the thermoplastic resin particles, and the reinforcing fibers and the thermoplastic resin are dispersed on the support. A state in which particles and the like are mixed is formed, and a random mat is formed by depositing and fixing to a predetermined thickness.
- a granular or short fiber thermoplastic resin hereinafter referred to as "heat”
- the reinforcing fibers are dispersed on a breathable support provided below the opening device together with the thermoplastic resin particles, and the reinforcing fibers and the thermoplastic resin are dispersed on the support.
- a state in which particles and the like are mixed is formed, and a random mat is formed by depositing and fixing to a
- thermoplastic resin particles and the like are supplied from a different path from the reinforcing fibers opened with gas, and these are simultaneously sprayed on the breathable support so that they are mixed almost uniformly. In the combined state, it is deposited in a mat shape on a breathable support and fixed in that state.
- the air-permeable support is constituted by a conveyor made of a net and is deposited on the belt while continuously moving in one direction, a random mat can be formed continuously.
- uniform deposition can be realized by moving the support in the front-rear and left-right directions.
- the reinforcing fibers and the thermoplastic resin particles are preferably dispersed so as to be two-dimensional randomly oriented.
- a tapered tube having a conical shape or the like that is expanded downstream.
- the gas blown to the reinforcing fiber diffuses and the flow velocity in the pipe is reduced, so that a rotational force is applied to the reinforcing fiber.
- the opened reinforcing fibers can be evenly sprayed together with the thermoplastic resin particles and the like.
- a movable ventilation support such as a net conveyor
- a suction mechanism below
- the amount of the thermoplastic resin supplied is preferably 50 to 1000 parts by mass with respect to 100 parts by mass of the reinforcing fiber. More preferably, it is 50 to 500 parts by mass, and still more preferably 60 to 300 parts by mass with respect to 100 parts by mass of the reinforcing fiber.
- the random mat forming step includes a step of fixing the reinforcing fiber and the thermoplastic resin.
- the step of fixing is a step of fixing the accumulated reinforcing fibers, thermoplastic resin particles, and the like.
- a method of fixing the reinforcing fibers by sucking air from the lower part of the breathable support can be mentioned.
- the thermoplastic resin sprayed at the same time as the reinforcing fiber can be fixed along with the reinforcing fiber even if it is in a particulate form by air suction if it is fibrous.
- thermoplastic resin particles and the like are uniformly present in the gaps and the vicinity of the reinforcing fibers constituting the random mat, so that the moving distance of the resin is short and relatively short in the heating and impregnation step described later.
- the resin can be impregnated with time.
- the openings of the sheet or net constituting the air-permeable support are large and some of the thermoplastic resin particles do not pass through the support and are not deposited, set a nonwoven fabric or the like on the surface of the support. Further, it is possible to fix the nonwoven fabric by spraying reinforcing fibers and thermoplastic resin particles.
- the strand piece and the reinforcing fiber separated into a single yarn state at the time of cutting are supplied to a transport path for sucking and transporting, and a gas blower installed in the middle or at the end of the transport path. Gas is blown to the reinforcing fibers from the attaching nozzle, and the cut strand pieces are separated and opened into the desired size (thickness) reinforcing fiber bundles, and at the same time, the reinforcing fibers together with the thermoplastic resin particles, etc. are continued in a certain direction. It is also possible to form a random mat by spraying toward the surface of a breathable support (hereinafter also referred to as “fixing net”) that moves periodically or intermittently, and depositing and fixing.
- fixing net a breathable support
- the random mat contains the reinforcing fiber and the granular and / or fibrous thermoplastic resin without any unevenness, so there is no need to greatly flow the fiber and resin in the mold.
- a plastic resin can be easily impregnated. As a result, it is possible to maintain the isotropy of the reinforcing fibers in the random mat also in the obtained molded body.
- a random mat composed of reinforcing fibers is obtained in the same manner as the random mat forming step (V) except that the matrix resin is not included, and a thermoplastic resin in a molten state is obtained. And a random mat containing a reinforcing fiber and a thermoplastic resin is obtained.
- the opened reinforcing fiber strands obtained in the reinforcing fiber opening step (VI) are deposited in a mat shape, and a molten thermoplastic resin is formed into a film from a die provided above.
- the thermoplastic resin can be supplied onto the mat that has been discharged and deposited as a melt and impregnated on almost the entire surface of the mat.
- thermoplastic resin supplied is the same as (V) above, but the amount of molten thermoplastic resin extruded from the die, specifically the thickness of the film when supplied in the form of a film from the die, and extrusion It is desirable to adjust the speed and the like.
- the random mat is heated to a temperature not lower than the melting point and lower than the thermal decomposition temperature when the thermoplastic resin contained in the random mat is crystalline, and heated to a glass transition temperature or higher when amorphous.
- a prepreg is obtained by heating to a temperature below the decomposition temperature and impregnating with a thermoplastic resin.
- the thermoplastic resin may be partially melted and welded.
- Prepreg Form of reinforcing fiber in prepreg
- the form of the reinforcing fiber in the prepreg maintains the state in the random mat. That is, the reinforcing fibers in the prepreg maintain the average fiber length, isotropy, and degree of opening in the random mat, and are the same as those described in the random mat.
- the thickness of the prepreg is preferably 1 to 10 times, preferably 1 to 5 times the thickness of the molded product to be obtained. Although there is no limitation on the thickness, it is preferably 0.1 mm or more, and the upper limit is a range that can be placed in a mold and molded, and is substantially about 30 mm.
- the void ratio of the prepreg is preferably 0 to 30%.
- the void ratio of the prepreg can be calculated by observing the cross section of the prepreg with an optical microscope and dividing the existing area of the void by the cross sectional area of the observation substrate.
- n 5 observations per prepreg, and the average value is defined as the void ratio.
- the obtained prepreg is kept at a temperature not lower than the melting point and lower than the thermal decomposition temperature when the thermoplastic resin is crystalline, or is maintained at a temperature not lower than the glass transition temperature and lower than the thermal decomposition temperature in the case of amorphous.
- the prepreg heated to the said temperature is arrange
- the temperature of the prepreg can be measured by, for example, a measuring instrument installed outside the heating furnace with a K-type thermocouple attached to the prepreg surface.
- the prepreg disposed in the mold may be used as it is without being cooled after being impregnated with the thermoplastic resin in the prepreg making process, or it is solidified after being impregnated with the thermoplastic resin and then reheated. You may pass through the process of.
- a prepreg obtained by superimposing one sheet or two to ten sheets is placed in a mold cavity.
- a part or the whole of the prepreg can be superposed depending on the molded product to be obtained.
- the prepreg end When placing, it is desirable that all surfaces of the prepreg end do not contact the mold end. Further, when a plurality of prepregs are arranged, the prepregs do not have to have the same shape as long as some or all of the prepregs are overlapped. For example, the end portions may be overlapped and placed in the mold. In the case of molding a large and complex shaped body, the overlapping arrangement is an effective means. In addition, the end material can be effectively used by overlapping.
- the size of the base material (prepreg) to be overlapped is not particularly limited, and a necessary size may be appropriately used according to the shape and size of the target molded body, but a size of 1 to 30000 cm 2 is preferably used. There is no restriction
- the overlap allowance for overlapping the base materials is preferably 1 to 100 mm, and more preferably 5 to 50 mm.
- the arrangement in which the end portions of the base material (prepreg) are overlapped with each other, and the arrangement in which the end portions of the other base material (prepreg) are overlapped may be repeated one or more times.
- the number of layers is preferably 2 to 100 layers.
- FIG. 9 the example in the case of arrange
- the mold used in the manufacturing method of the present invention is preferably capable of being sealed, and specifically, a mold having a very small clearance in a state where the core side and cavity side molds are closed. It is preferable to do.
- the present invention is a method for obtaining a molded body by press molding while flowing a prepreg (base material) in a closed mold, and according to the present invention, the isotropic property of the fiber is obtained up to the end of the molded body to be obtained. Can be obtained.
- the end clearance is 0.01 to 0.1 mm. More preferably, it is 0.03 to 0.05 mm.
- FIG. 8 is an explanatory diagram of the end structure of the mold used in the present invention.
- the angle at which the end is drawn is preferably 0 to 10 degrees, and more preferably 1 to 5 degrees.
- the angle at the end is preferably 0 to 10 degrees, and more preferably 1 to 5 degrees.
- it is easy to release the molded body after molding.
- it can seal suitably and can be press-molded because the extraction angle of an edge part shall be 5 degrees or less.
- setting the draft angle to 5 degrees or less is also effective in preventing the size of the molded body from being unnecessarily increased.
- the ends of the core side and the cavity side have a sharp structure and can be trimmed simultaneously with molding. In such a case, trimming can be performed at the same time as the molding even when the end material is generated.
- the surface of the mold may be polished according to the design required for the molded product to be obtained.
- the molded body is required to have a smooth surface property, it is preferably polished with # 400 or more.
- the mold temperature is from melting point ⁇ 200 ° C. to melting point ⁇ 10 ° C. or lower when the thermoplastic resin is crystalline, and when amorphous, it is glass transition temperature ⁇ 200 ° C. or higher and glass transition temperature ⁇ 10 ° C. or lower. It is preferable to be in the range.
- Charge rate (%) 100 ⁇ [base material area (mm 2 ) / mold cavity projected area (mm 2 )] (3) (In formula (3), the base material area is the projected area in the extraction direction of all the arranged prepregs, and the mold cavity projected area is the projected area in the extraction direction)
- the thickness of the prepreg can be appropriately selected according to the thickness of the molded product to be obtained.
- the charge rate of the base material (prepreg) to the mold is 50% or more and 80% or less, the flow is reduced.
- the thickness of the prepreg or the total thickness of the laminated prepregs is 1.0 mm or more.
- Total area charge rate 100 ⁇ [substrate total area (mm 2) / mold cavity total area (mm 2)] (4) (In the formula (4), the total base material area is an area obtained by subtracting the area of the lamination and the overlap portion from the projected area of all the prepregs horizontally developed, and the total mold cavity area is the mold cavity. This is the total area of the surface)
- FIG. 1 A top view and a side view of a specific example of a three-dimensional mold are shown in FIG.
- the total area of the surfaces of the mold cavities indicated by the hatched portion (4) in the figure is the total mold cavity area.
- the total area charge rate is the same value as the “charge rate” when the compact is a flat surface such as a flat plate.
- the placed prepreg is pressurized in the mold, and the molding is completed by molding at a temperature below the melting point if the thermoplastic resin is crystalline, or below the glass transition temperature if the thermoplastic resin is amorphous. Get the body. That is, a so-called cold press is performed to produce a molded body.
- the mold is clamped and the prepreg is cooled in the mold while being pressurized to the target pressure, and press molding is performed to complete the shaping. That is, heat is exchanged with the mold while being pressurized and shaped, and after cooling the prepreg to below the melting point when the thermoplastic resin is crystalline, and below the glass transition temperature when amorphous, the mold is removed. Open to obtain a molded body.
- the method for cooling the mold is not particularly limited, and the mold can be appropriately cooled by a method of flowing a cooling medium through the mold internal temperature control circuit.
- the time required to reach the target pressure in the molding process is preferably 1 to 10 seconds.
- the target pressure is preferably 3 MPa to 100 MPa, more preferably 5 MPa to 40 MPa.
- the method for obtaining the ratio of reinforcing fiber bundle (A) to the total amount of fibers in the mat is as follows.
- the random mat was cut into 100 mm ⁇ 100 mm, and the thickness (Ta) and weight (Wa) were measured. From the cut out mat, all fiber bundles were taken out with tweezers, and the fiber bundles were classified by thickness. In this example, the classification was performed in units of about 0.2 mm in thickness. For each classification, the length (Li) and weight (Wi) of all fiber bundles and the number of fiber bundles (I) were measured and recorded.
- the weight was collectively measured last (Wk).
- Wk weight of the fiber bundle
- a balance capable of measuring up to 1/1000 g was used.
- the reinforcing fiber is a carbon fiber or when the average fiber length is short, the weight of the fiber bundle is small, and measurement becomes difficult. In such a case, a plurality of classified fiber bundles were collectively measured for weight. After the measurement, the following calculation was performed. From the fineness (F) of the reinforcing fiber used, the number of fibers (Ni) of each fiber bundle was obtained by the following equation.
- N ⁇ Ni / I
- Va is the volume of the cut out mat
- Va 100 ⁇ 100 ⁇ Ta
- Average fiber length (La) of reinforcing fibers contained in the molded body and random mat The average fiber length (La) of the reinforcing fibers contained in the random mat was recorded by measuring the length of 100 randomly extracted reinforcing fibers up to 1 mm using a loupe. From the lengths (Li) of all the reinforcing fibers obtained, the average fiber length (La) was determined by the following formula.
- Formability Formability was evaluated according to the following evaluation criteria by observing the shape of the molded body. ⁇ (Good): Filled with fiber reinforced composite material to the end and no defects are observed. ⁇ (Bad): Some chips and defects are found. ⁇ (Major defects): Many chips and defects.
- Carbon fiber “Tenax” (registered trademark) STS40-24KS (average fiber diameter 7 ⁇ m, fiber width 10 mm, tensile strength 4000 MPa) manufactured by Toho Tenax Co., Ltd. was used as the reinforcing fiber. Cut the carbon fiber into 20 mm length while opening the carbon fiber, introduce the carbon fiber into the taper tube at a supply rate of 300 g / min, and blow the air on the carbon fiber at a wind speed of 450 m / sec in the taper tube to partially separate the fiber bundle. The fiber was spread on a table movable in the X and Y directions installed at the lower part of the taper tube outlet while the fiber was being opened.
- polyamide 6 resin (A1030, manufactured by Unitika) as a matrix resin is supplied into the tapered tube at 360 g / min and dispersed simultaneously with the carbon fiber, so that a carbon fiber having an average fiber length of 20 mm and PA6 are mixed with a thickness of 7.5 mm. A random mat was obtained.
- the basis weight of the reinforcing fibers of the obtained random mat was 370 g / m 2 . Further, when the ratio of the reinforcing fiber bundle (A) and the average number of fibers (N) were examined for the obtained random mat, the critical single yarn number defined by the formula (1) was 86, and the reinforcing fiber bundle ( The ratio of A) to the total amount of fibers in the random mat was 35 vol%, and the average number of fibers (N) in the reinforcing fiber bundle (A) was 240. Table 1 shows the production conditions and measurement / evaluation results of the random mat.
- Prepreg production process The obtained random mat was heated to reach 250 ° C. and then pressurized at 3 MPa for 7 minutes, and then cooled to 80 ° C. to obtain a plate-like prepreg having a thickness of 1.5 mm.
- the void ratio of the prepreg was 0.09%.
- Table 2 shows the prepreg production conditions and the measurement / evaluation results.
- Prepreg placement process Two prepregs cut to 80% of the projected area of the mold cavity are placed in an infrared oven, heated to 255 ° C, stacked, and the end clearance adjusted to 130 ° C is 0 ° C. It was placed in a flat mold having a thickness of 0.02 mm (FIG. 1).
- the portion indicated by 5 is a charged portion of the base material (prepreg) into the mold, and the portion indicated by 6 outside thereof is a portion where the base material (prepreg) flows to the edge of the mold cavity.
- the fiber content (Vf) was examined for each of the places indicated by 7 in the figure, the average of the fluid part was 35.2%, the base (prepreg) charge part was 35.0%, and the fluid part was also the base.
- the (prepreg) charge part also showed an equivalent value.
- the ratio (E ⁇ ) obtained by dividing the larger one of the tensile modulus in two directions perpendicular to each other by the smaller one was 1.03.
- Table 3 shows the evaluation results of the thickness variation.
- Table 2 shows the manufacturing conditions of the molded body and the measurement / evaluation results.
- Example 2 [Production of random mat] Random with a thickness of 4.0 mm under the same conditions as in Example 1 except that the carbon fiber supply rate was 150 g / min, the polyamide 6 resin supply rate was 180 g / min, and the wind speed in the tapered tube was changed to 200 m / sec. A mat was obtained.
- the basis weight of the reinforcing fibers of the obtained random mat was 185 g / m 2 . Further, when the ratio of the reinforcing fiber bundle (A) and the average number of fibers (N) were examined for the obtained random mat, the critical single yarn number defined by the formula (1) was 86, and the reinforcing fiber bundle ( The ratio of A) to the total amount of fibers in the random mat was 35 vol%, and the average number of fibers (N) in the reinforcing fiber bundle (A) was 240. Table 1 shows the production conditions and measurement / evaluation results of the random mat.
- Prepreg placement process After stacking four prepregs cut to 80% of the projected area of the mold cavity, placing them in an infrared oven and heating to 255 ° C, the clearance at the end adjusted to a mold temperature of 130 ° C is 0. It was placed in a solid mold shown in FIG. 2 having a thickness of 0.05 mm (FIG. 4).
- the portion indicated by 5 is a charged portion of the base material (prepreg) into the mold, and the portion indicated by 6 outside thereof is a portion where the base material (prepreg) flows to the edge of the mold cavity.
- the fiber content (Vf) was examined for each of the parts indicated by 7 in the figure, the average of the fluidized part was 35.3%, the base (prepreg) charge part was 35.0%, and the fluidized part was also the base ( The prepreg) charge part also showed an equivalent value.
- the tensile modulus of elasticity at the location indicated by 8 in the figure for the fluidized portion was measured, and the ratio (E ⁇ ) obtained by dividing the tensile modulus of elasticity in two directions orthogonal to each other by the smaller one was 1.08, etc. It was confirmed that the orientation was maintained.
- Table 2 shows the production conditions and the measurement / evaluation results of the molded body.
- Carbon fiber manufactured by Toho Tenax Co., Ltd .: Tenax IMS 60-12K (average fiber diameter 5 ⁇ m, fiber width 6 mm) was used as the reinforcing fiber. Cut the carbon fiber into 20 mm length while opening the carbon fiber, introduce the carbon fiber into the taper tube at a feed rate of 100 g / min, and blow the air inside the taper tube at a wind speed of 250 m / sec. The fiber was spread on a table movable in the X and Y directions installed at the lower part of the taper tube outlet while the fiber was being opened.
- polycarbonate resin Panlite (registered trademark) L-1225L, manufactured by Teijin Chemicals Ltd.
- a matrix resin is supplied into the tapered tube at 300 g / min and sprayed simultaneously with the carbon fiber, so that carbon fiber and polycarbonate having an average fiber length of 20 mm are obtained.
- a random mat having a thickness of about 5.0 mm was obtained.
- the basis weight of the reinforcing fibers of the obtained random mat was 125 g / m 2 . Further, when the ratio of the reinforcing fiber bundle (A) and the average number of fibers (N) were examined for the obtained random mat, the critical single yarn number defined by the formula (1) was 120, and the reinforcing fiber bundle ( The ratio of A) to the total amount of fibers in the random mat was 80%, and the average number of fibers (N) in the reinforcing fiber bundle (A) was 1000. Table 1 shows the production conditions and measurement / evaluation results of the random mat.
- Prepreg production process The obtained random mat was heated to reach 260 ° C. and then pressurized at 5 MPa for 7 minutes and then cooled to 50 ° C. to obtain a prepreg having a thickness of 1.0 mm.
- the void ratio of the prepreg was 0.2%.
- Table 2 shows the prepreg production conditions and the measurement / evaluation results.
- Prepreg placement process Two base sheets (prepregs) cut to 50% of the projected area of the mold cavity are placed in an infrared oven and heated to 260 ° C., then stacked, and the temperature is adjusted to a mold temperature of 60 ° C. It was placed in a flat mold having a clearance of 0.02 mm (FIG. 1).
- the portion indicated by 5 is a charged portion of the base material (prepreg) into the mold, and the portion indicated by 6 outside thereof is a portion where the base material (prepreg) flows to the edge of the mold cavity.
- the fiber content (Vf) was examined for each of the locations indicated by 7 in the figure, the average value was 19.9% in the fluidized portion and 20.1% in the base material (prepreg) charged portion, indicating the same numerical values.
- the ratio (E ⁇ ) obtained by dividing the tensile modulus of elasticity in two directions orthogonal to each other by the smaller one was 1.21, and it was confirmed that the isotropic property was maintained.
- Table 2 shows the production conditions and the measurement / evaluation results of the molded body.
- Example 4 [Production of random mat] Random with a thickness of 15.0 mm under the same conditions as in Example 1 except that the supply amount of carbon fiber was 600 g / min, the supply amount of polyamide 6 resin was 720 g / min, and the wind speed in the tapered tube was changed to 1000 m / sec. A mat was obtained.
- the basis weight of the reinforcing fibers of the obtained random mat was 740 g / m 2 . Further, when the ratio of the reinforcing fiber bundle (A) and the average number of fibers (N) were examined for the obtained random mat, the critical single yarn number defined by the formula (1) was 86, and the reinforcing fiber bundle ( The ratio of A) to the total amount of fibers in the random mat was 35 vol%, and the average number of fibers (N) in the reinforcing fiber bundle (A) was 240. Table 1 shows the production conditions and measurement / evaluation results of the random mat.
- Prepreg placement process Two prepregs cut to 80% of the projected area of the mold cavity are placed in an infrared oven, heated to 255 ° C, stacked, and the end clearance adjusted to 130 ° C is 0 ° C. It was placed in a mold having a rib boss shape of 0.08 mm (FIG. 6).
- FIG. 7 shows a schematic diagram of the obtained molded body.
- the portion indicated by 5 is a charged portion of the base material (prepreg) into the mold, and the portion indicated by 6 outside thereof is a portion where the base material (prepreg) flows to the edge of the mold cavity.
- the fiber content (Vf) was examined for each part indicated by 7 in the figure, the average of the fluidized part was 34.6%, and the base material (prepreg) charged part was 34.8%, indicating an equivalent value.
- the ratio (E ⁇ ) obtained by dividing the larger one of the tensile elastic modulus in two directions perpendicular to each other by the smaller one (E ⁇ ) was 1.09, indicating that the isotropic property was maintained. confirmed.
- Table 2 shows the production conditions and the measurement / evaluation results of the molded body.
- Example 5 [Production of random mat] Random with a thickness of 7.0 mm under the same conditions as in Example 1 except that the supply amount of carbon fiber was 300 g / min, the supply amount of polyamide 6 resin was 360 g / min, and the wind speed in the tapered tube was changed to 400 m / sec. A mat was obtained.
- the basis weight of the reinforcing fibers of the obtained random mat was 370 g / m 2 . Further, when the ratio of the reinforcing fiber bundle (A) and the average number of fibers (N) were examined for the obtained random mat, the critical single yarn number defined by the formula (1) was 86, and the reinforcing fiber bundle ( The ratio of A) to the total amount of fibers in the random mat was 50 vol%, and the average number of fibers (N) in the reinforcing fiber bundle (A) was 500. Table 1 shows the production conditions and measurement / evaluation results of the random mat.
- Example 6 [Production of random mat] Random with a thickness of 4.0 mm under the same conditions as in Example 1 except that the carbon fiber supply rate was 100 g / min, the polyamide 6 resin supply rate was 300 g / min, and the wind speed in the tapered tube was changed to 250 m / sec. A mat was obtained.
- the basis weight of the reinforcing fibers of the obtained random mat was 125 g / m 2 . Further, when the ratio of the reinforcing fiber bundle (A) and the average number of fibers (N) were examined for the obtained random mat, the critical single yarn number defined by the formula (1) was 86, and the reinforcing fiber bundle ( The ratio of A) to the total amount of fibers in the random mat was 80 vol%, and the average number of fibers (N) in the reinforcing fiber bundle (A) was 1000. Table 1 shows the production conditions and measurement / evaluation results of the random mat.
- Prepreg placement process Two prepregs cut to 50% of the projected area of the mold cavity are placed in an infrared oven and heated to 255 ° C and then stacked, and the clearance at the end adjusted to a mold temperature of 130 ° C is 0. It was placed in a flat mold having a thickness of 0.02 mm (FIG. 1).
- Example 7 [Production of random mat] Carbon fiber “Tenax” (registered trademark) STS40-24KS (average fiber diameter: 7 ⁇ m, fiber width: 10 mm) manufactured by Toho Tenax Co., Ltd. was used as the reinforcing fiber. After slitting to a width of 2 mm or less using a vertical slitting device, it was cut to a fiber length of 20 mm. As the cutting device, a rotary cutter capable of continuously cutting reinforcing fibers was used. The strand that passed through the rotary cutter was introduced into a taper tube and treated at a wind speed of 250 m / sec to partially open the fiber bundle. Then, it spread
- a molten matrix resin was supplied onto the obtained mat.
- the matrix resin polyamide 6 resin (A1030) manufactured by Unitika Co., Ltd. was used, and this was melted by an extruder and supplied from the T-die to the entire surface of the mat. At this time, the place where the resin on the mat surface is supplied is heated by an infrared heater to prevent the resin from being cooled and solidified.
- the apparatus was operated with a polyamide 6 resin supply rate of 300 g / min with respect to a reinforcement fiber supply rate of 100 g / min, and a random mat made of reinforcement fibers and a thermoplastic resin was formed.
- the basis weight of the reinforcing fibers of the obtained random mat was 125 g / m 2 . Further, when the ratio of the reinforcing fiber bundle (A) and the average number of fibers (N) were examined for the obtained random mat, the critical single yarn number defined by the formula (1) was 86, and the reinforcing fiber bundle ( The ratio of A) to the total amount of fibers in the random mat was 80%, and the average number of fibers (N) in the reinforcing fiber bundle (A) was 1000. Table 1 shows the production conditions and measurement / evaluation results of the random mat.
- Prepreg production process The obtained random mat was heated and pressurized with a pair of heating rollers set at 280 ° C. to prepare a prepreg impregnated with resin.
- the thickness of the prepreg after cooling was 1.0 mm, and the void ratio was 0.6%.
- Table 2 shows the prepreg production conditions and the measurement / evaluation results.
- Prepreg placement process Two base sheets cut to 50% of the projected area of the mold cavity are placed in an infrared oven, heated to 255 ° C, stacked, and the end clearance adjusted to a mold temperature of 130 ° C. Was placed in a flat mold having a thickness of 0.02 mm (FIG. 1).
- Example 8 [Production of random mat] A random mat with a thickness of 7.0 mm was obtained under the same conditions as in Example 1 except that the average fiber length of the reinforcing fibers was 10 mm and the wind speed in the tapered tube was changed to 50 m / sec.
- the basis weight of the reinforcing fibers of the obtained random mat was 370 g / m 2 . Further, when the ratio of the reinforcing fiber bundle (A) and the average number of fibers (N) were examined for the obtained random mat, the critical single yarn number defined by the formula (1) was 86, and the reinforcing fiber bundle ( The ratio of A) to the total amount of fibers in the random mat was 95 vol%, and the average number of fibers (N) in the reinforcing fiber bundle (A) was 1200. Table 1 shows the production conditions and measurement / evaluation results of the random mat.
- Example 9 [Production of random mat] A random mat having a thickness of 7.0 mm was obtained under the same conditions as in Example 1 except that the average fiber length of the reinforcing fibers was 40 mm and the wind speed in the tapered tube was changed to 250 m / sec.
- the basis weight of the reinforcing fibers of the obtained random mat was 370 g / m 2 . Further, when the ratio of the reinforcing fiber bundle (A) and the average number of fibers (N) were examined for the obtained random mat, the critical single yarn number defined by the formula (1) was 86, and the reinforcing fiber bundle ( The ratio of A) to the total amount of fibers in the random mat was 80 vol%, and the average number of fibers (N) in the reinforcing fiber bundle (A) was 1000. Table 1 shows the production conditions and measurement / evaluation results of the random mat.
- glass fiber EX-2500 (average fiber diameter 15 ⁇ m, fiber width 9 mm) manufactured by Nippon Electric Glass Co., Ltd. was used. Cut the glass fiber into 50 mm length while opening the glass fiber, introduce the glass fiber supply rate into the taper tube at 300 g / min, and blow the air inside the taper tube at a wind speed of 300 m / sec to partially break the fiber bundle The fiber was spread on a table movable in the X and Y directions installed at the lower part of the taper tube outlet while the fiber was being opened.
- a polyamide 6 resin (A1030 manufactured by Unitika) as a matrix resin is supplied into the tapered tube at 360 g / min and dispersed simultaneously with the glass fiber, so that a glass fiber having an average fiber length of 50 mm and PA6 are mixed with a thickness of 6.5 mm. A random mat of a degree was obtained.
- the basis weight of the reinforcing fibers of the obtained random mat was 370 g / m 2 . Further, when the ratio of the reinforcing fiber bundle (A) and the average number of fibers (N) were examined for the obtained random mat, the critical single yarn number defined by the formula (1) was 40, and the reinforcing fiber bundle ( The ratio of A) to the total amount of fibers in the random mat was 80%, and the average number of fibers (N) in the reinforcing fiber bundle (A) was 150. Table 1 shows the production conditions and measurement / evaluation results of the random mat.
- Prepreg production process The obtained random mat was heated and, after reaching 250 ° C., was pressurized with a pressure of 3 MPa for 5 minutes and then cooled to 80 ° C. to obtain a plate-like prepreg having a thickness of 1.5 mm.
- the void ratio of the prepreg was 0.1%.
- Table 2 shows the prepreg production conditions and the measurement / evaluation results.
- Example 11 [Prepreg placement process] Using the prepreg obtained in Example 1, two pieces cut out to 50% of the projected area of the mold cavity were placed in an infrared oven and heated to 255 ° C, and then heated to a mold temperature of 130 ° C. As shown in FIG. 9, one side end portion was overlapped by about 30 mm as shown in FIG. 9 in a flat mold having a prepared end clearance of 0.02 mm. The charge rate of the base material (prepreg) after the overlapping arrangement was 95% with respect to the mold cavity projected area.
- the fiber content (Vf) was equivalent to 34.5% for the fluidized part and 35.1% for the base (prepreg) charged part.
- the ratio (E ⁇ ) of the tensile elastic modulus in two directions perpendicular to each other was 1.10, confirming that the isotropic property was maintained.
- the tensile strength of the overlap part was not significantly different from other parts.
- Table 2 shows the production conditions and the measurement / evaluation results of the molded body.
- Basis weight of the reinforcing fibers of the resulting random mat was 370 g / m 2. Further, when the ratio of the reinforcing fiber bundle (A) and the average number of fibers (N) were examined for the obtained random mat, the critical single yarn number defined by the formula (1) was 86, and the reinforcing fiber bundle ( The ratio of A) to the total amount of fibers in the random mat was 10 vol%, and the average number of fibers (N) in the reinforcing fiber bundle (A) was 100. Table 1 shows the production conditions and measurement / evaluation results of the random mat.
- Prepreg production process A plate-shaped prepreg having a thickness of 1.7 mm was obtained in the same manner as in Example 1 using the obtained random mat.
- the void ratio of the prepreg was 10.5%.
- Table 2 shows the prepreg production conditions and the measurement / evaluation results.
- Example 2 A random mat with a thickness of 6.5 mm was produced under the same conditions as in Example 1 except that the wind speed in the tapered tube was set to 10 m / sec.
- the basis weight of the reinforcing fibers of the obtained random mat was 370 g / m 2 . Further, when the ratio of the reinforcing fiber bundle (A) and the average number of fibers (N) were examined for the obtained random mat, the critical single yarn number defined by the formula (1) was 86, and the reinforcing fiber bundle ( The ratio of A) to the total amount of fibers in the random mat was 100 vol%, and the average number of fibers (N) in the reinforcing fiber bundle (A) was 3000. Table 1 shows the production conditions and measurement / evaluation results of the random mat.
- the fiber content (Vf) is 33.7% in the average of the fluidized part and 35.5% in the base (prepreg) charged part.
- the tensile modulus ratio (E ⁇ ) in the direction was 1.38, and anisotropy was observed.
- Table 2 shows the production conditions and the measurement / evaluation results of the molded body.
- the molded body containing the reinforcing fiber and the thermoplastic resin obtained by the production method of the present invention is lightweight and has a degree of freedom in shape, and even when press-molded in a state where the charge rate of the prepreg with respect to the mold is low, the end of the fiber The molded body is maintained isotropic.
- it because it is excellent in moldability, thin wall, specific rigidity, productivity, and economy, it can be used for electrical / electronic equipment parts, automotive parts, personal computers, OA equipment, AV equipment, mobile phones, telephones, facsimiles, home appliances, toy supplies. It can be effectively used for electrical and electronic parts and casings. In particular, it can be preferably used for automobile parts mounted on environment-friendly vehicles.
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Abstract
Description
1)平均繊維長5~100mmの強化繊維と熱可塑性樹脂とを含むランダムマットを、熱可塑性樹脂が結晶性の場合は融点以上熱分解温度未満の温度まで、非晶性の場合はガラス転移温度以上熱分解温度未満の温度まで加熱することにより熱可塑性樹脂を含浸させプリプレグを得るプリプレグ作製工程と、
2)熱可塑性樹脂が結晶性の場合は融点以上熱分解温度未満の温度、非晶性の場合はガラス転移温度以上熱分解温度未満の温度とした前記プリプレグを、熱可塑性樹脂が結晶性の場合には融点温度未満、非晶性の場合にはガラス転移温度未満となるよう温度調節された金型に、下記式(3)で表されるチャージ率が50%以上100%以下となるよう配置するプリプレグ配置工程と、
3)前記金型内で、前記プリプレグを加圧するとともに、熱可塑性樹脂が結晶性の場合は融点未満、非晶性の場合はガラス転移温度未満の温度で成形を完結させて成形体を得る成形工程とを含み、
前記ランダムマットは、25~10000g/m2の目付けにて前記強化繊維が実質的に2次元ランダムに配向しており、
式(1)で定義される臨界単糸数以上で構成される強化繊維束(A)が、前記ランダムマットにおける繊維全量に対して20Vol%以上99Vol%未満含まれており、
かつ前記強化繊維束(A)における平均繊維数(N)が、下記式(2)を満たすことを特徴とする、繊維強化複合材料からなる成形体の製造方法。
臨界単糸数=600/D (1)
0.7×104/D2<N<1×105/D2 (2)
(式(1)および式(2)中、Dは強化繊維の平均繊維径(μm)である)
チャージ率(%)=100×[基材面積(mm2)/金型キャビティ投影面積(mm2)] (3)
(式(3)中、基材面積とは配置した全てのプリプレグの抜き方向への投影面積であり、金型キャビティ投影面積とは抜き方向への投影面積である)
1)平均繊維長5~100mmの強化繊維と熱可塑性樹脂とを含むランダムマットを、熱可塑性樹脂が結晶性の場合は融点以上熱分解温度未満の温度まで、非晶性の場合はガラス転移温度以上熱分解温度未満の温度まで加熱することにより熱可塑性樹脂を含浸させプリプレグを得るプリプレグ作製工程と、
2)熱可塑性樹脂が結晶性の場合は融点以上熱分解温度未満の温度、非晶性の場合はガラス転移温度以上熱分解温度未満の温度とした前記プリプレグを、熱可塑性樹脂が結晶性の場合には融点温度未満、非晶性の場合にはガラス転移温度未満となるよう温度調節された金型に、下記式(3)で表されるチャージ率が50%以上100%以下となるよう配置するプリプレグ配置工程と、
3)前記金型内で、前記プリプレグを加圧するとともに、熱可塑性樹脂が結晶性の場合は融点未満、非晶性の場合はガラス転移温度未満の温度で成形を完結させて成形体を得る成形工程とを含むものである。
チャージ率(%)=100×[基材面積(mm2)/金型キャビティ投影面積(mm2)] (3)
(式(3)中、基材面積とは配置した全てのプリプレグの抜き方向への投影面積であり、金型キャビティ投影面積とは抜き方向への投影面積である)
本発明の製造方法で得られる成形体は、強化繊維と熱可塑性樹脂とを含む繊維強化複合材料からなる成形体である。本発明で得られる成形体は、面内2次元ランダム配向する層を有し、実質的に等方性を示す。
(種類)
本発明に用いられる強化繊維としては、炭素繊維、アラミド繊維、およびガラス繊維からなる群から選ばれる少なくとも一種であることが好ましい。これらは併用することもでき、軽量でありながら強度に優れた複合材料が提供できる点で、炭素繊維を用いることが好ましい。
また、本発明に用いられる強化繊維は、不連続であり、平均繊維長が5~100mm以下である。本発明の製造方法は、長い強化繊維を含んでいても強化機能が発現できる成形体が得られることを特長とし、強化繊維の平均繊維長としては、好ましくは10~100mmであり、より好ましくは10~50mmであり、さらに好ましくは10~30mmである。なお、後述する好ましい強化繊維のカット方法を採用することで、ランダムマットを構成する強化繊維の長さを固定長とすることができる。
ランダムマットにおける強化繊維の目付量は、25~10000g/m2であり、好ましくは25~6000g/m2、より好ましくは25~3000g/m2である。目付量が25g/m2未満の場合には、ランダムマット中で強化繊維の分布が不均一になりやすく、十分な補強効果が発現しないおそれがある。一方で、10000g/m2を超える場合には、強化繊維が多すぎるためにプリプレグ作製時に樹脂が含浸しにくく、成形体中で欠点となるボイドが発生しやすい傾向となる。また、熱可塑性樹脂と比べて強化繊維は比重が大きいため、成形体が重くなる。
本発明に用いられるランダムマットおよび得られる成形品における強化繊維の含有率としては、下記式(5)で定義される強化繊維体積含有率(Vf)が5~80Vol%の範囲であることが好ましい。
強化繊維体積含有率(Vf)=100×[強化繊維の体積/(強化繊維の体積+熱可塑性樹脂の体積)] (5)
(種類)
本発明に用いられる熱可塑性樹脂の種類としては、例えば、塩化ビニル樹脂、塩化ビニリデン樹脂、酢酸ビニル樹脂、ポリビニルアルコール樹脂、ポリスチレン樹脂、アクリロニトリル-スチレン樹脂(AS樹脂)、アクリロニトリル-ブタジエン-スチレン樹脂(ABS樹脂)、アクリル樹脂、メタクリル樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、ポリアミド6樹脂、ポリアミド11樹脂、ポリアミド12樹脂、ポリアミド46樹脂、ポリアミド66樹脂、ポリアミド610樹脂、ポリアセタール樹脂、ポリカーボネート樹脂、ポリエチレンテレフタレート樹脂、ポリエチレンナフタレート樹脂、ボリブチレンテレフタレート樹脂、ポリアリレート樹脂、ポリフェニレンエーテル樹脂、ポリフェニレンスルフィド樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリエーテルエーテルケトン樹脂、ポリ乳酸樹脂などが挙げられる。なお、熱可塑性樹脂は、2種以上を併用することもできる。
熱可塑性樹脂の形状としては、特に限定されるものではなく、例えば、繊維状、粒子状、溶融状態、さらにはこれらのミクスチャーとして供給することができる。
出発材料となるランダムマットおよび得られる成形品における熱可塑性樹脂の含有量は、強化繊維100質量部に対し、好ましくは50~1000質量部、より好ましくは50~500質量部である。含有量が50質量部未満の場合には、熱可塑性樹脂が少ないためにプリプレグ作製時にボイドが発生しやすく、得られる成形体の物性が低下するおそれがある。一方で、1000質量部を超える場合には、強化繊維の割合が相対的に低くなることから、繊維強化複合材料による成形体に期待する物性までに到達しない可能性がある。
本発明の製造方法に用いられるランダムマットは、少なくとも上記した強化繊維と熱可塑性樹脂とを含むものであればよいが、目的を損なわない範囲で、その他の第3成分を含んでいてもよい。
本発明で用いるランダムマットは、上記した強化繊維が実質的に2次元ランダムに配向したものである。ここで「2次元ランダム」とは、面内において、強化繊維が特定の方向には配向しておらず、無作為な方向に分散して配置されていることを意味する。
本発明に用いられるランダムマットは、式(1)で定義する臨界単糸数以上で構成される強化繊維束(A)が、ランダムマットにおける繊維全量に対して20Vol%以上99Vol%未満であることを特徴とする。
臨界単糸数=600/D (1)
(式(1)中、Dは強化繊維の平均繊維径(μm)である)
さらに強化繊維束(A)における平均繊維数(N)が、下記式(2)を満たすことを特徴とする。
0.7×104/D2<N<1×105/D2 (2)
(式(2)中、Dは強化繊維の平均繊維径(μm)である)
ランダムマットの製造方法は、特に限定されるものではなく、例えば、繊維状および/または粒子状の熱可塑性樹脂を強化繊維と混合して存在させるように製造してもよく、マトリクス樹脂成分を含まないランダムマットに溶融状態の熱可塑性樹脂を供給して製造してもよい。
強化繊維ストランド供給工程では、クリール部に配置された複数の強化繊維巻糸体から、強化繊維それぞれの糸条を引出し、単独の糸条からなるかまたは単糸を複数本引き揃えてなる強化繊維ストランドとして供給する。このとき、ストランド幅は10~50mm(特に20~30mm)とすることが好ましい。供給される強化繊維のストランド幅が小さい場合には、必要に応じて、当ストランド供給工程にて所定幅まで拡幅して、薄い広幅のストランドとして供給してもよい。この拡幅操作は、例えば、ストランドを拡幅用のローラーやバー等と接触させることにより行うことができる。
ストランドスリット工程では、供給された強化繊維ストランドを、好ましくはストランド長手方向と平行に(すなわち繊維軸方向に沿って)連続的にスリットし、ストランド幅が0.05~5mm、好ましくは0.1~1.0mmの複数本の細幅ストランドとする。具体的には、前工程から連続的に移送されてくる広幅のストランドを、繊維軸方向と平行な刃を有する縦スリット装置(スリッター)を用いて縦方向に連続的にカットするか、広幅ストランドの走行路に1個または複数個の分割ガイドを設け、それによりストランドを複数本に分割すること等により実施することができる。この工程においては、ライン上に拡幅用のガイドやバーなどを設置して、強化繊維を拡幅処理しながらスリットを加えてもよい。
次に、強化繊維カット工程にて、スリット処理を行っていないストランド、または上記のごとくスリットした細幅の強化繊維ストランドを、平均繊維長5~100mmにカット(切断)する。なお、ここでいう「平均繊維長」とは、無作為に抽出した100本の繊維の繊維長をノギス等を用いて1mm単位まで測定し、その平均を求める方法により求めることができる。通常であれば、平均繊維長はカッターによるストランドの切断間隔と一致する。
例えば、繊維方向に交叉するナイフと繊維軸方向と平行なナイフとを有するカッターを用いれば、繊維束を縦方向にスリットすると同時に特定の繊維長にカットすることができ、このようなカッターを使用すれば、ストランドスリット工程(II)と強化繊維カット(III)とを同時に実施することができる。
強化繊維開繊工程では、所定の繊維長にカットされた強化繊維のストランド(以下「ストランド片」ということがある)に気体を吹付け、該ストランド片を所望のサイズ(集束本数)の繊維束に分割するように開繊する。
ランダムマット形成工程においては、カットし開繊させた強化繊維を空気中に拡散させると同時に、粉粒体状または短繊維状の熱可塑性樹脂(以下、これらを「熱可塑性樹脂粒子等」と総称する)を供給し、強化繊維を熱可塑性樹脂粒子等とともに開繊装置下方に設けた通気性支持体上に散布して、該支持体上で強化繊維と熱可塑性樹脂粒子等が混在する状態を形成し、所定の厚さとなるよう堆積・定着させてランダムマットを形成させる。
また別のランダムマット形成工程としては、マトリクス樹脂を含まない以外は上記(V)ののランダムマット形成工程と同様に強化繊維から構成されるランダムマットを得て、これに溶融状態の熱可塑性樹脂を供給し、強化繊維と熱可塑性樹脂とを含むランダムマットを得る方法が挙げられる。このような方法としては、例えば、強化繊維開繊工程(VI)で得られる開繊された強化繊維ストランドをマット状に堆積させるとともに、上方に設けたダイから溶融状態の熱可塑性樹脂を膜状溶融体として吐出し、堆積したマット上に該熱可塑性樹脂を供給して、マットのほぼ全面に含浸させることができる。
本発明のプリプレグ作成工程においては、上記のランダムマットを、ランダムマットに含まれる熱可塑性樹脂が結晶性の場合は融点以上熱分解温度未満の温度まで、非晶性の場合はガラス転移温度以上熱分解温度未満の温度まで加熱して、熱可塑性樹脂を含浸させてプリプレグを得る。なお、熱可塑性樹脂は部分的に溶けて溶着されていてもよい。
(プリプレグ中の強化繊維の形態)
プリプレグにおける強化繊維の形態は、ランダムマット中における状態を保っている。すなわち、プリプレグ中の強化繊維はランダムマットにおける平均繊維長や等方性、開繊程度を維持しており、上記のランダムマットに記載したものと同様となっている。
プリプレグの厚みは、得ようとする成形体の厚みの1~10倍、好ましくは1~5倍とすることが好ましい。厚みの限定はないが、好ましくは0.1mm以上であり、上限は金型に配置して成形可能な範囲までであり、実質的には30mm程度である。
プリプレグ成形時の樹脂の含浸不良を極力抑えるために、プリプレグのボイド率は0~30%とすることが好ましい。プリプレグのボイド率は、プリプレグの断面を光学顕微鏡で観察し、ボイドの存在面積を観察基材の断面積で除して算出することができる。本発明においては、1つのプリプレグあたりn=5の観察とし、その平均値をボイド率とする。
プリプレグ配置工程においては、得られたプリプレグを、熱可塑性樹脂が結晶性の場合は融点以上熱分解温度未満の温度、非晶性の場合はガラス転移温度以上熱分解温度未満の温度に保つか再加熱し、当該温度としたプリプレグを、熱可塑性樹脂が結晶性の場合は融点未満、非晶性の場合はガラス転移温度未満に温度調節された金型内に配置する。
プリプレグ配置工程においては、例えば図1に示す通り、1枚または2~10枚を重ね合わせたプリプレグを金型キャビティへ配置する。重ね合わせる場合には、得ようとする成形体に応じて、プリプレグの一部、または全体を重ね合わせることができる。
本発明の製造方法に用いる金型は、密閉することが可能なものとすることが好ましく、具体的には、コア側とキャビティ側の金型を閉じた状態でのクリアランスが極めて小さい金型とすることが好ましい。本発明は、密閉された型内でプリプレグ(基材)を流動させつつプレス成形して成形体を得る方法であり、本発明によれば、得られる成形体の端部まで繊維の等方性が維持された成形体を得ることができる。
また、金型の温度としては、熱可塑性樹脂が結晶性の場合は融点-200℃以上融点-10℃以下、非晶性の場合はガラス転移温度-200℃以上ガラス転移温度-10℃以下の範囲とすることが好ましい。
リプレグ配置工程においては、ランダムマットを、下記式(3)で表されるチャージ率が50%以上100%以下となるように金型に配置する必要がある。本発明においては、チャージ率を50%以上100%以下とすることにより、強化繊維が実質的に面内2次元配向する層を確保しつつ、材料ロスやトリミングの手間を発生させることなく、軽量な成形体を高い生産性で製造することが可能となる。
チャージ率(%)=100×[基材面積(mm2)/金型キャビティ投影面積(mm2)] (3)
(式(3)中、基材面積とは配置した全てのプリプレグの抜き方向への投影面積であり、金型キャビティ投影面積とは抜き方向への投影面積である)
さらに、得ようとする成形体が立体形状の場合には、ランダムマットを、下記式(4)で表される総面積チャージ率が30%~100%となるよう金型に配することが好ましい。
総面積チャージ率(%)=100×[基材総面積(mm2)/金型キャビティ総面積(mm2)] (4)
(式(4)中、基材総面積とは、水平展開した全てのプリプレグの投影面積から、積層およびオーバーラップ部の面積を差し引いた面積であり、金型キャビティ総面積とは、金型キャビティ表面の面積の総和である)
成形工程においては、金型内で、配置されたプリプレグを加圧するとともに、熱可塑性樹脂が結晶性の場合は融点未満、非晶性の場合はガラス転移温度未満の温度で成形を完結させて成形体を得る。すなわち、いわゆるコールドプレスを実施して成形体を作製する。
成形工程における目標圧力に達するまでの時間は、1~10秒であることが望ましい。また、目標圧力は、好ましくは3MPa~100MPa、さらに好ましくは5MPa~40MPaである。
強化繊維束(A)のマットの繊維全量に対する割合の求め方は、以下の通りである。
ランダムマットを100mm×100mmに切り出し、厚み(Ta)と重量(Wa)を測定した。
切り出したマットより、繊維束をピンセットで全て取り出し、繊維束を太さ毎に分類した。なお、本実施例においては、太さ0.2mm程度単位で分類を実施した。
分類毎に、全ての繊維束の長さ(Li)と重量(Wi)、繊維束数(I)を測定し、記録した。ピンセットにて取り出すことができない程度に繊維束が小さいものについては、まとめて最後に重量を測定した(Wk)。重量の測定にあたっては、1/1000gまで測定可能な天秤を用いた。なお、特に強化繊維を炭素繊維とした場合や、平均繊維長が短い場合には、繊維束の重量が小さく、測定が困難になる。こういった場合には、分類した繊維束を複数本まとめて重量を測定した。
測定後、以下の計算を行った。使用している強化繊維の繊度(F)より、個々の繊維束の繊維本数(Ni)は、次式により求めた。
繊維本数(Ni)=Wi/(Li×F)
強化繊維束(A)中の平均繊維数(N)は、以下の式により求めた。
N=ΣNi/I
また、個々の繊維束の体積(Vi)、および、強化繊維束(A)の繊維全体に対する割合(VR)は、使用した強化繊維の繊維比重(ρ)を用いて次式により求めた。
Vi=Wi/ρ
VR=ΣVi/Va×100
ここで、Vaは切り出したマットの体積であり、Va=100×100×Ta
成形体における強化繊維束(A)の含有量については、500℃×1時間程度、炉内にて樹脂を除去した後、上記のランダムマットにおける方法と同様にして測定した。
成形体を成形した後、成形体の任意の方向、およびこれと直交する方向について引張試験を行って引張弾性率を測定した。得られた引張弾性率の値のうち大きいものを小さいもので割った比(Eδ)を求めることで繊維の配向の度合いを確認した。弾性率の比が1に近いほど、等方性に優れた材料である。
ランダムマットに含まれる強化繊維の平均繊維長(La)は、無作為に抽出した強化繊維100本の長さを、ルーペを用いて1mm単位まで測定して記録した。得られた全ての強化繊維の長さ(Li)から、次式により平均繊維長(La)を求めた。
成形体に含まれる強化繊維の平均繊維長(La)は、500℃×1時間程度、炉内にて樹脂を除去した後、無作為に抽出した強化繊維100本の長さを、ルーペを用いて1mm単位まで測定して記録した。得られた全ての強化繊維の長さ(Li)から、次式により平均繊維長(La)を求めた。
平均繊維長(La)=ΣLi/100
成形体の外観は、目視、光学顕微鏡、および手で触れて評価し、強化繊維への樹脂の含浸が不十分な(ドライな)部位、シワ、割れなどについて、以下の評価基準で評価した。
○(良好) :外観に特に異常が見られない
△(不良) :わずかにドライな部位やシワが見られる
×(重大不良):ドライな部位やシワが多く見られたり、割れが確認される
成形体の反りについては、目視および手で触れて、以下の評価基準で評価した。
○(良好) :反りが見られない
△(不良) :わずかに反りが認められる
×(重大不良):大きく反っている
成形性の評価は、成形体の形状観察により以下の評価基準で評価した。
○(良好) :端部まで繊維強化複合材料が充填され、欠陥が見られない
△(不良) :一部に欠けや不良が見られる
×(重大不良):欠けや不良が多い
マイクロメーターを用いて、得られた成形体全体から10ヶ所の厚みを測定し、厚みの(算術)平均値および標準偏差を求めた。さらに、10ヶ所の厚みの測定値のうち、その最小値および最大値と、上記の厚みの平均値を用いて、それぞれ下記式(6)および(7)で定義される「厚みの最小値のバラつき」と「厚みの最大値のバラつき」を算出し、成形体の厚みのバラつきが平均値から±10%以内を満たしているかを確認した。
厚みの最小値のバラつき(%)=100×[(厚みの最小値-厚みの平均値)/厚みの平均値] (6)
厚みの最大値のバラつき(%)=100×[(厚みの最大値-厚みの平均値)/厚みの平均値] (7)
プリプレグのボイド率は、試験片の断面を光学顕微鏡で観察し、ボイドの存在面積を観察に用いた試験片の断面積で除して算出した。観察は1つの試料あたりn=5とし、その平均値をその試料のボイド率とした。
[ランダムマットの作製]
強化繊維として、東邦テナックス社製の炭素繊維“テナックス”(登録商標)STS40-24KS(平均繊維径7μm、繊維幅10mm、引張強度4000MPa)を使用した。炭素繊維を開繊させながら20mmの長さにカットし、炭素繊維の供給量を300g/minでテーパー管内に導入し、テーパー管内で空気を風速450m/secで炭素繊維に吹き付けて繊維束を部分的に開繊しつつ、テーパー管出口の下部に設置したXY方向に移動可能なテーブル上に、テーブル下部よりブロワにて吸引を行いながら散布した。
得られたランダムマットを加熱して250℃に達した後に、3MPaの圧力で7分間加圧した後、80℃まで冷却し、厚み1.5mmの板状のプリプレグを得た。プリプレグのボイド率は0.09%であった。プリプレグの製造条件および測定・評価結果を表2に示す。
金型キャビティ投影面積に対して80%に切り出したプリプレグを2枚、赤外線オーブンの中に入れて255℃に加熱した後に積層し、金型温度130℃に温調された端部のクリアランスが0.02mmである平板状の金型内に配置した(図1)。
10MPaの圧力で30秒間のプレス成形を実施し、厚み2.4mmの成形体を得た。得られた成形体は、材料の割れやシワの発生が無く、表面外観は良好で、製品反りの見られないものであり、金型末端まで樹脂と繊維が充填されていることを確認した。得られた成形体の模式図を図3に示す。
[ランダムマットの作製]
炭素繊維の供給量を150g/min、ポリアミド6樹脂の供給量を180g/minとし、テーパー管内の風速を200m/secに変更した以外は実施例1と同様の条件で、厚み4.0mmのランダムマットを得た。
得られたランダムマットを用いて、実施例1と同様の方法で、厚みが0.8mmの板状のプリプレグを得た。プリプレグのボイド率は0.3%であった。プリプレグの製造条件および測定・評価結果を表2に示す。
金型キャビティ投影面積に対して80%に切り出したプリプレグを4枚積層し、赤外線オーブンの中に入れて255℃に加熱した後に、金型温度130℃に温調された端部のクリアランスが0.05mmである図2に示す立体形状の金型内に配置した(図4)。
10MPaの圧力で30秒間のプレス成形を実施し、厚み2.4mmの成形体を得た。得られた成形体は、材料の割れやシワの発生が無く、表面外観は良好で、製品反りの見られないものであり、金型末端まで樹脂と繊維が充填されていることを確認した。得られた成形体の模式図を図5に示す。
[ランダムマットの作製]
強化繊維として、炭素繊維(東邦テナックス社製:テナックスIMS60-12K(平均繊維径5μm、繊維幅6mm))を使用した。炭素繊維を開繊させながら20mmの長さにカットし、炭素繊維の供給量を100g/minでテーパー管内に導入し、テーパー管内で空気を風速250m/secで炭素繊維に吹き付けて繊維束を部分的に開繊しつつ、テーパー管出口の下部に設置したXY方向に移動可能なテーブル上に、テーブル下部よりブロワにて吸引を行いながら散布した。
得られたランダムマットを加熱し260℃に達した後に、5MPaの圧力で7分加圧した後、50℃まで冷却し、厚み1.0mmのプリプレグを得た。プリプレグのボイド率は0.2%であった。プリプレグの製造条件および測定・評価結果を表2に示す。
金型キャビティ投影面積に対して50%に切り出した基材シート(プリプレグ)を2枚、赤外線オーブンの中に入れて260℃に加熱した後に積層し、金型温度60℃に温調された端部のクリアランスが0.02mmである平板状の金型内に配置した(図1)。
10MPaの圧力で30秒間のプレス成形を実施し、厚み1.0mmの成形体を得た。得られた成形体は、材料の割れやシワの発生が無く、表面外観は良好で、製品反りの見られないものであり、金型末端まで樹脂と繊維が充填されていることを確認した。得られた成形体の模式図を図3に示す。
[ランダムマットの作製]
炭素繊維の供給量を600g/min、ポリアミド6樹脂の供給量を720g/minとし、テーパー管内の風速を1000m/secに変更した以外は実施例1と同様の条件で、厚み15.0mmのランダムマットを得た。
得られたランダムマットを用いて、実施例1と同様の方法で、厚みが3.0mmの板状のプリプレグを得た。プリプレグのボイド率は0.5%であった。プリプレグの製造条件および測定・評価結果を表2に示す。
金型キャビティ投影面積に対して80%に切り出したプリプレグを2枚、赤外線オーブンの中に入れて255℃に加熱した後に積層し、金型温度130℃に温調された端部のクリアランスが0.08mmであるリブ・ボス形状を有する金型内に配置した(図6)。
10MPaの圧力で30秒間のプレス成形を実施し、厚み4.8mmの成形体を得た。得られた成形体は、材料の割れやシワの発生が無く、表面外観は良好で、製品反りの見られないものであり、金型末端まで樹脂と繊維が充填されていることを確認した。得られた成形体の模式図を図7に示す。
[ランダムマットの作製]
炭素繊維の供給量を300g/min、ポリアミド6樹脂の供給量を360g/minとし、テーパー管内の風速を400m/secに変更した以外は実施例1と同様の条件で、厚み7.0mmのランダムマットを得た。
得られたランダムマットを用いて、実施例1と同様の方法で、厚みが1.5mmの板状のプリプレグを得た。プリプレグのボイド率は0.3%であった。プリプレグの製造条件および測定・評価結果を表2に示す。
実施例1と同様に、プリプレグの配置および成形体の成形を実施し、厚み2.4mmの成形体を得た。得られた成形体は、材料の割れやシワの発生が無く、表面外観は良好で、製品反りの見られないものであり、金型末端まで樹脂と繊維が充填されていることを確認した。
[ランダムマットの作製]
炭素繊維の供給量を100g/min、ポリアミド6樹脂の供給量を300g/minとし、テーパー管内の風速を250m/secに変更した以外は実施例1と同様の条件で、厚み4.0mmのランダムマットを得た。
得られたランダムマットを用いて、実施例1と同様の方法で、厚みが1.0mmの板状のプリプレグを得た。プリプレグのボイド率は0.3%であった。プリプレグの製造条件および測定・評価結果を表2に示す。
金型キャビティ投影面積に対して50%に切り出したプリプレグを2枚、赤外線オーブンの中に入れて255℃に加熱した後に積層し、金型温度130℃に温調された端部のクリアランスが0.02mmである平板状の金型内に配置した(図1)。
10MPaの圧力で30秒間のプレス成形を実施し、厚み1.0mmの成形体を得た。得られた成形体は、材料の割れやシワの発生が無く、表面外観は良好で、製品反りの見られないものであり、金型末端まで樹脂と繊維が充填されていることを確認した。
[ランダムマットの作製]
強化繊維として、東邦テナックス社製の炭素繊維“テナックス”(登録商標)STS40-24KS(平均繊維径7μm、繊維幅10mm)を使用した。縦スリット装置を使用して幅2mm以下にスリットした後、繊維長20mmにカットした。カット装置は連続的に強化繊維をカットできるロータリーカッターを用いた。ロータリーカッターを通過したストランドをテーパー管に導入し、風速250m/secで処理して繊維束を部分的に開繊した。その後、テーパー管出口の下部に設置したXY方向に移動可能なテーブル上に、テーブル下部よりブロワにて吸引しながら散布して、厚み約4mmのマットを作製した。
得られたランダムマットを280℃に設定した1対の加熱ローラーで加熱加圧して、樹脂が含浸したプリプレグを作製した。冷却後のプリプレグの厚みは1.0mmで、ボイド率は0.6%であった。プリプレグの製造条件および測定・評価結果を表2に示す。
金型キャビティ投影面積に対して50%に切り出した基材シートを2枚、赤外線オーブンの中に入れて255℃に加熱した後に積層し、金型温度130℃に温調された端部のクリアランスが0.02mmである平板状の金型内に配置した(図1)。
10MPaの圧力で30秒間のプレス成形を実施し、厚み1.0mmの成形体を得た。得られた成形体は、材料の割れやシワの発生が無く、表面外観は良好で、製品反りの見られないものであり、金型末端まで樹脂と繊維が充填されていることを確認した。
[ランダムマットの作製]
強化繊維の平均繊維長を10mmとし、テーパー管内の風速を50m/secに変更した以外は実施例1と同様の条件で、厚み7.0mmのランダムマットを得た。
得られたランダムマットを用いて、実施例1と同様の方法で、厚みが1.5mmの板状のプリプレグを得た。プリプレグのボイド率は0.2%であった。プリプレグの製造条件および測定・評価結果を表2に示す。
実施例1と同様に、プリプレグの配置および成形体の成形を実施し、厚み2.4mmの成形体を得た。得られた成形体は、材料の割れやシワの発生が無く、表面外観は良好で、製品反りの見られないものであり、金型末端まで樹脂と繊維が充填されていることを確認した。
[ランダムマットの作製]
強化繊維の平均繊維長を40mmとし、テーパー管内の風速を250m/secに変更した以外は実施例1と同様の条件で、厚み7.0mmのランダムマットを得た。
得られたランダムマットを用いて、実施例1と同様の方法で、厚みが1.5mmの板状のプリプレグを得た。プリプレグのボイド率は0.4%であった。プリプレグの製造条件および測定・評価結果を表2に示す。
実施例1と同様に、プリプレグの配置および成形体の成形を実施し、厚み2.4mmの成形体を得た。得られた成形体は、材料の割れやシワの発生が無く、表面外観は良好で、製品反りの見られないものであり、金型末端まで樹脂と繊維が充填されていることを確認した。
[ランダムマットの作製]
強化繊維として、日本電気硝子社製のガラス繊維EX-2500(平均繊維径15μm、繊維幅9mm)を使用した。ガラス繊維を開繊させながら50mmの長さにカットし、ガラス繊維の供給量を300g/minでテーパー管内に導入し、テーパー管内で空気を風速300m/secでガラス繊維に吹き付けて繊維束を部分的に開繊しつつ、テーパー管出口の下部に設置したXY方向に移動可能なテーブル上に、テーブル下部よりブロワにて吸引を行いながら散布した。
得られたランダムマットを加熱し、250℃に達した後に3MPaの圧力で5分加圧した後、80℃まで冷却し、厚み1.5mmの板状のプリプレグを得た。プリプレグのボイド率は0.1%であった。プリプレグの製造条件および測定・評価結果を表2に示す。
実施例1と同様に、プリプレグの配置および成形体の成形を実施し、厚み2.4mmの成形体を得た。得られた成形体は、材料の割れやシワの発生が無く、表面外観は良好で、製品反りの見られないものであり、金型末端まで樹脂と繊維が充填されていることを確認した。
[プリプレグ配置工程]
実施例1で得られたプリプレグを用いて、金型キャビティ投影面積に対して50%に切り出した2枚を、赤外線オーブンの中に入れて255℃に加熱した後に、金型温度130℃に温調された端部のクリアランスが0.02mmである平板状の金型内に、図9に示すように片側の端部を約30mmオーバーラップさせて配置した。オーバーラップ配置後の基材(プリプレグ)のチャージ率は、金型キャビティ投影面積に対して95%であった。
10MPaの圧力で30秒間のプレス成形を実施し、厚み1.5mmの成形体を得た。得られた成形体は、材料の割れやシワの発生が無く、表面外観は良好で、製品反りの見られないものであり、金型末端まで樹脂と繊維が充填されていることを確認した。
[ランダムマットの作製]
テーパー管内の風速を700m/secとした以外は実施例1と同様の条件で、厚み8.0mmのランダムマットを作製した。
得られたランダムマットを用いて、実施例1と同様の方法で、厚みが1.7mmの板状のプリプレグを得た。プリプレグのボイド率は10.5%であった。プリプレグの製造条件および測定・評価結果を表2に示す。
実施例1と同様に、プリプレグの配置および成形体の成形を実施し、厚み3.0mmの成形体を得た。得られた成形体は、端部まで材料が行き渡らず、欠落部が認められた。成形体の製造条件および測定・評価結果を表2に示す。
テーパー管内の風速を10m/secとした以外は実施例1と同様の条件で、厚み6.5mmのランダムマットを作製した。
得られたランダムマットを用いて、実施例1と同様の方法で、厚みが1.5mmの板状のプリプレグを得た。プリプレグのボイド率は3.8%であった。プリプレグの製造条件および測定・評価結果を表2に示す。
実施例1と同様に、プリプレグの配置および成形体の成形を実施し、厚み2.4mmの成形体を得た。成形性、および得られた成形体の表面外観は良好で製品反りも見られなかった。
2 金型キャビティ
3 金型キャビティエッジ部
4 金型キャビティ総面積
5 基材(プリプレグ)チャージ部
6 流動部
7 Vfの計測点
8 引張弾性率計測点
9 ボス形状部
10 リブ形状部
11 金型の端部の抜き角
12 金型のクリアランス
13 プリプレグのオーバーラップ部
Claims (10)
- 繊維強化複合材料からなる成形体の製造方法であって、
1)平均繊維長5~100mmの強化繊維と熱可塑性樹脂とを含むランダムマットを、熱可塑性樹脂が結晶性の場合は融点以上熱分解温度未満の温度まで、非晶性の場合はガラス転移温度以上熱分解温度未満の温度まで加熱することにより熱可塑性樹脂を含浸させプリプレグを得るプリプレグ作製工程と、
2)熱可塑性樹脂が結晶性の場合は融点以上熱分解温度未満の温度、非晶性の場合はガラス転移温度以上熱分解温度未満の温度とした前記プリプレグを、熱可塑性樹脂が結晶性の場合には融点温度未満、非晶性の場合にはガラス転移温度未満となるよう温度調節された金型に、下記式(3)で表されるチャージ率が50%以上100%以下となるよう配置するプリプレグ配置工程と、
3)前記金型内で、前記プリプレグを加圧するとともに、熱可塑性樹脂が結晶性の場合は融点未満、非晶性の場合はガラス転移温度未満の温度で成形を完結させて成形体を得る成形工程とを含み、
前記ランダムマットは、25~10000g/m2の目付けにて前記強化繊維が実質的に2次元ランダムに配向しており、
式(1)で定義される臨界単糸数以上で構成される強化繊維束(A)が、前記ランダムマットにおける繊維全量に対して20Vol%以上99Vol%未満含まれており、
かつ前記強化繊維束(A)における平均繊維数(N)が、下記式(2)を満たすことを特徴とする、繊維強化複合材料からなる成形体の製造方法。
臨界単糸数=600/D (1)
0.7×104/D2<N<1×105/D2 (2)
(式(1)および式(2)中、Dは強化繊維の平均繊維径(μm)である)
チャージ率(%)=100×[基材面積(mm2)/金型キャビティ投影面積(mm2)] (3)
(式(3)中、基材面積とは配置した全てのプリプレグの抜き方向への投影面積であり、金型キャビティ投影面積とは抜き方向への投影面積である) - 前記ランダムマットにおける熱可塑性樹脂の含有量は、前記強化繊維100質量部に対して50~1000質量部である請求項1に記載の成形体の製造方法。
- 前記プリプレグ配置工程において、前記金型の温度を、熱可塑性樹脂が結晶性の場合は融点-200℃以上融点-10℃以下、非晶性の場合はガラス転移温度-200℃以上ガラス転移温度-10℃以下に温度調節する請求項1または2に記載の成形体の製造方法。
- 前記プリプレグ配置工程において、前記プリプレグを、下記式(4)で表される総面積チャージ率が30%以上100%以下となるよう配置する請求項1~3のいずれかに記載の成形体の製造方法。
総面積チャージ率(%)=100×[基材総面積(mm2)/金型キャビティ総面積(mm2)] (4)
(式(4)中、基材総面積とは、水平展開した全てのプリプレグの投影面積から、積層およびオーバーラップ部の面積を差し引いた面積であり、金型キャビティ総面積とは、金型キャビティ表面の面積の総和である) - 前記プリプレグ配置工程において、複数枚のプリプレグの端部をオーバーラップさせる請求項1~4のいずれかに記載の成形体の製造方法。
- 前記強化繊維の平均繊維長は、10~30mmである請求項1~5のいずれかに記載の成形体の製造方法。
- 前記金型は、端部のクリアランスが0.01~0.1mmであり、密閉することが可能なものである請求項1~6のいずれかに記載の成形体の製造方法。
- 前記プリプレグのボイド率が、0~30%である請求項1~7のいずれかに記載の成形体の製造方法。
- 前記成形工程において、プリプレグを加圧する圧力を3MPa~100MPaとする請求項1~8のいずれかに記載の成形体の製造方法。
- 請求項1~9のいずれかに記載の製造方法によって得られる成形体であって、
任意の方向についての引張弾性率、およびこれと直交する方向についての引張弾性率について、大きい方の値を小さい方の値で割った比(Eδ)が1.0から1.3である成形体。
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