JP2014104641A - Laminate substrate and fiber-reinforced composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate substrate as an intermediate substrate for a fiber-reinforced plastic and a method for manufacturing the same.SOLUTION: The problem-solving laminate substrate is a laminate substrate obtained by laminating and integrating multiple members of a prepreg including unidirectionally oriented reinforcing fibers and a thermoplastic resin so as to orient the reinforcing fibers along at least three directions wherein each prepreg possesses a linear incision forming, in terms of absolute value, an angle θ of at least 30° in relation to the reinforcing fibers, wherein lengths L of the reinforcing fibers fragmented by the incision are confined to a range of 2 mm or above and 100 mm or below, and wherein the distance Ls between the terminal point of the incision and the terminal point of another incision adjacent thereto along the fiber direction is confined to a range of L/4 or above and L/2 or below.

Description

  In the present invention, the molded part has excellent mechanical properties applicable to structural materials and low variation, is excellent in shaping into a complex shape during stamping molding, and can be molded in a short time. The present invention relates to an intermediate substrate and a molded body. More specifically, an intermediate base of fiber reinforced plastic that easily follows the molding of three-dimensional shapes such as ribs and bosses, maintains mechanical strength as a structural member, and is suitably used for, for example, aircraft members, automobile members, sports equipment, and the like. The present invention relates to a laminated base material that is a material, and a fiber-reinforced composite material obtained by shaping the laminated base material into a three-dimensional shape.

  As a method for molding fiber-reinforced thermoplastics, an intermediate base material impregnated with a thermoplastic resin is laminated on continuous reinforcing fibers called prepregs, and shaped into a desired shape by heating and pressing with a press or the like. Stamping is most commonly performed. The fiber reinforced plastic obtained in this way is a continuous fiber and therefore has excellent mechanical properties. In addition, since the continuous fibers are regularly arranged, it is possible to design the mechanical properties required by the arrangement of the base material, and the variation in the mechanical properties is small. However, since it is a continuous fiber, it is difficult to form a complicated shape such as a three-dimensional shape, and it is mainly limited to members close to a planar shape.

  In recent years, for the purpose of improving production efficiency, LFT-D molding has also been carried out, in which reinforcing fibers are fed directly into the screw section of the molding machine, the fibers are cut and dispersed simultaneously, and then injection molding and extrusion molding are performed continuously. ing. According to this method, since the reinforcing fiber is cut to an appropriate length, it can easily flow and can follow a complicated shape such as a three-dimensional shape. However, since LFT-D causes unevenness in fiber length and unevenness in fiber distribution in the cutting and dispersing process, there is a problem that mechanical properties are deteriorated or the variation in value is increased.

  In order to fill the drawbacks of the above-mentioned materials, it is possible to form in a short time by cutting into a prepreg composed of continuous fibers and thermoplastic resin, and it exhibits excellent formability at the time of molding, and is a fiber-reinforced composite material A base material that is said to exhibit excellent mechanical properties when disclosed in Japanese Patent Application Laid-Open Nos. 2000-26883 and 2000-2015 is disclosed. However, compared with LFT-D, the mechanical properties are high and the variation is small, but it cannot be said that the strength is sufficient for application as a structural material.

  In addition, a method for improving the above-described strength and its variation by optimizing the cutting shape is disclosed (for example, Documents 3, 4, and 5). However, according to this method, improvement in mechanical properties and dispersion properties can be seen, but uniform fluidity to complicated three-dimensional shapes such as thin ribs and bosses has been insufficient.

Japanese Unexamined Patent Publication No. 63-247010 JP-A 63-267523 JP 2008-207544 A JP 2008-207545 A JP 2009-286817 A

  The present invention is intended to solve the problems associated with the prior art as described above, and has excellent mechanical properties such as bending strength and tensile elastic modulus applicable to structural materials, and its low variation properties, and is complicated. It is an object of the present invention to provide an intermediate base material that is excellent in formability into a simple shape and can be molded in a short time, and a fiber-reinforced composite material shaped into a target shape by stamping molding or the like.

In order to solve the above problems, the present invention uses the following means. That is, a laminated base material obtained by laminating a plurality of prepregs containing reinforcing fibers oriented in one direction and a thermoplastic resin so that the reinforcing fibers are oriented in at least three directions,
The prepreg has a linear incision with an absolute value of an angle θ of 30 ° or more with the reinforcing fiber, and the fiber length L of the reinforcing fiber divided by the incision is in the range of 2 mm to 100 mm. A laminated base material in which the distance Ls between the terminal point and the terminal point of another incision adjacent in the fiber direction is in a range of L / 4 or more and L / 2 or less.

  According to the present invention, it has excellent mechanical properties such as bending strength and tensile elastic modulus applicable to a structural material, and its low dispersion property, and is excellent in formability to complex shapes and can be molded in a short time. A fiber-reinforced composite material shaped into a target shape by stamping molding or the like can be obtained.

It is a figure which shows an example of the hat channel type rib metal mold | die used by the fluidity | liquidity evaluation used by this invention. The figure which shows the prepreg base material which made the notch used in Example 1 of this invention.

Hereinafter, the present invention will be described in detail.
(Laminated substrate)
A laminated base material obtained by laminating a plurality of prepregs including reinforced fibers oriented in one direction and a thermoplastic resin so that the reinforced fibers are oriented in at least three directions. The prepreg is made into a reinforced fiber. An absolute value of the angle θ has a linear incision of 30 ° or more, and the fiber length L of the reinforcing fiber divided by the incision is within a range of 2 mm or more and 100 mm or less and is adjacent to the end point of the incision in the fiber direction. It is necessary that the distance Ls to the other cutting end point is in the range of not less than L / 4 and not more than L / 2. When the reinforcing fibers are oriented in at least three directions in the laminated structure, good fluidity and mechanical properties can be obtained.

  The stacking structure consists of 4 layers of 0/45/90 / -45 repeated n times symmetrically ([0/45/90 / -45] ns) and 3 layers of 0/60 / -60 n times. It is preferable to be pseudo-isotropic expressed by symmetrically stacking repetitions ([0/60 / −60] ns) (n represents an integer of 1 or more). By using pseudo isotropic, warping of the laminated base material can be suppressed. Furthermore, for fluidity, the flow of the resin in the 90 ° direction of the reinforcing fiber is the driving force for moving the reinforcing fiber, so the fiber flow varies depending on the fiber orientation of the adjacent prepreg at the time of lamination, By doing so, the fluidity becomes isotropic, and it becomes an intermediate base material with less fluidity variation and excellent robustness. Moreover, when the laminated base material of the present invention is formed into a fiber-reinforced composite material that is molded and used as a structural material, it is necessary to withstand loads from multiple directions. Also from the viewpoint of fluidity and mechanical properties, the laminated base material of the present invention is preferably laminated in a pseudo isotropic manner to withstand general-purpose use.

  The fiber content Vf of the laminated base material is preferably 20 vol% or more and 40 vol% or less. Since the driving force of fluidity is resin flow, Vf is preferably as low as possible from the viewpoint of fluidity. By setting Vf to 40 vol% or less, good three-dimensional flow to the parts such as ribs and bosses during stamping molding Sex is obtained. If Vf is extremely low, mechanical properties required for the structural material cannot be obtained, but good mechanical properties can be obtained by setting Vf to 20 vol% or more. Moreover, it is more preferable to set Vf to 25 vol% or more, and the tensile elastic modulus required for the structural material can be obtained. In addition, the fiber content Vf concerning this invention can be measured based on JISK7075.

(Incision)
The prepreg used in the present invention has a linear incision in which the absolute value of the angle θ formed with the reinforcing fiber is 30 ° or more, and the fiber length L of the reinforcing fiber divided by the incision is in the range of 2 mm to 100 mm. Yes, the distance Ls between the end point of the cut and the other end point of the adjacent notch in the fiber direction needs to be in the range of L / 4 or more and L / 2 or less. By having a linear notch with an absolute value of the angle θ between the reinforcing fibers of 30 ° or more, a three-dimensional fluidity to the ribs and bosses during stamping molding and a fiber-reinforced composite material after stamping molding Excellent mechanical properties can be achieved at the same time. When the absolute value of the angle θ formed with the reinforcing fiber is 30 ° or more, in the fiber-reinforced composite material after stamping molding, it is possible to suppress a decrease in mechanical properties due to the bending of the fiber, and in particular, excellent tensile elasticity is exhibited. Further, the absolute value of the angle θ formed with the reinforcing fiber is more preferably 65 ° or less, and good three-dimensional fluidity to a portion such as a rib or boss at the time of stamping molding can be obtained, and the fiber reinforcement after stamping molding can be obtained. In the composite material, distribution spots and orientation spots of reinforcing fibers can be suppressed, and the mechanical properties are excellent in low variation.

  Since the fiber length L of the reinforcing fiber divided by the cutting is in the range of 2 mm to 100 mm, the three-dimensional fluidity to the parts such as ribs and bosses during stamping molding and the fiber reinforced composite material after stamping molding are obtained. Excellent mechanical properties can be achieved at the same time. From the viewpoint of fluidity, the shorter the fiber length L is, the better. However, by setting the fiber length L to 100 mm or less, good three-dimensional fluidity to parts such as ribs and bosses can be obtained during stamping molding. The fiber length L is preferably longer from the viewpoint of mechanical properties. However, by setting the length to 2 mm or more, the fiber-reinforced composite material after stamping can obtain bending strength applicable to the structural member. Considering the relationship between fluidity and mechanical properties, the fiber length L is more preferably 15 mm or greater and 55 mm or less.

  In the incision of the present invention, it is necessary that the distance Ls between the end point of the incision and the end point of another adjacent notch in the fiber direction is in the range of L / 4 or more and L / 2 or less. By setting Ls to L / 4 or more, in the fiber-reinforced composite material after stamping molding, it is possible to suppress the fracture starting from the cut portion, and it is excellent in the expression of bending strength and also in the low variation property. . On the other hand, when the length of Ls is extremely long, tearing or cracking occurs between the cuts of the prepreg, making it difficult to handle lamination and the like, so Ls needs to be L / 2 or less.

  Moreover, it is preferable that the length l of the notch | incision of this invention exists in the range of 4 mm or more and 300 mm or less. By making the cut length l to 300 mm or less, in the fiber reinforced composite material after stamping molding, it is possible to suppress the break starting from the cut portion, and it has excellent bending strength and low variation. Excellent. On the other hand, when the cut length l is extremely short, it is difficult to substantially insert the cut into the prepreg.

  Note that the reinforcing fiber of the prepreg has substantially all of the fibers cut, and the area where the continuous fibers that are not divided by the incision of the present invention are oriented is more than 5% of the proportion of the area of the prepreg layer. Mean small.

(Prepreg)
The thickness of the prepreg used in the present invention is preferably 50 μm or more and 200 μm or less. The present invention does not depend on the thickness of the prepreg, and good fluidity can be obtained. However, since the prepreg according to the present invention has a cut, the larger the layer thickness is, the lower the mechanical properties tend to be. The thickness of the prepreg is preferably 200 μm or less. On the other hand, even if the thickness of the prepreg is 50 μm, the fluidity and mechanical properties are good, but it is difficult to stably produce an extremely thin prepreg, so the thickness of the prepreg is preferably 50 μm or more. .

  The reinforcing fiber of the prepreg used in the present invention is not particularly limited, and examples thereof include inorganic fibers, organic fibers, metal fibers, or fibers having a hybrid configuration in which these are combined. Examples of the inorganic fiber include carbon fiber, graphite fiber, silicon carbide fiber, alumina fiber, tungsten carbide fiber, boron fiber, and glass fiber. Examples of organic fibers include aramid fibers, high density polyethylene fibers, other general nylon fibers, and polyesters. Examples of the metal fibers include fibers such as stainless steel and iron, and may be carbon fibers coated with metal. Among these, in consideration of mechanical properties such as strength of the final molded product, carbon fibers are preferable, and PAN-based carbon fibers are more preferable.

  The matrix resin of the prepreg used in the present invention needs to use a thermoplastic resin. That is, in the case of a fiber reinforced plastic using discontinuous reinforcing fibers, a thermoplastic resin generally having a higher toughness value than a thermosetting resin is used as a matrix resin in order to break the fiber ends so as to connect each other. As a result, strength, particularly impact resistance is improved. Furthermore, since the thermoplastic resin is cooled and solidified without a chemical reaction to determine the shape, it can be molded in a short time and has excellent productivity.

  The thermoplastic resin used in the present invention is not particularly limited. For example, polycarbonate resin, polyester resin, polyamide resin, liquid crystal polymer resin, polyether sulfone resin, polyether ether ketone resin, polyarylate resin, polyphenylene ether resin, polyphenylene Sulfide resin, polyacetal resin, polysulfone resin, polyimide resin, polyolefin resin, polystyrene resin, modified polystyrene resin, ABS resin, modified ABS resin, MBS resin, polymethyl methacrylate resin, and modified resins thereof, and polymer alloy resins thereof Is mentioned. Any one of these may be used alone, or two or more may be used in combination, but a polypropylene resin and / or polyamide resin, or a modified resin of polypropylene resin and / or polyamide resin is preferable. More preferably, it is an acid-modified polypropylene resin from the viewpoint of adhesiveness with reinforcing fibers.

(Manufacturing method of prepreg)
A prepreg made by impregnating a reinforced fiber oriented in one direction with a thermoplastic resin is a method of impregnating a molten resin with an extruder, a method of dispersing and melting a powder resin in a fiber layer, and forming a resin film. Laminating, dissolving the resin in a solvent and impregnating it in the form of a solution, then volatilizing the solvent, making the resin into a mixed yarn, impregnating it in the state of a thermoplastic resin monomer, and then polymerizing it. There is a method of making it into a polymer. The method of impregnating the molten resin with an extruder has the advantage that the resin does not need to be processed, but it is difficult to produce a stable prepreg. The method of dispersing the powder resin in the fiber layer has an advantage that it is easily impregnated, but it is difficult to uniformly disperse the powder in the fiber layer. The method of laminating the resin into a film requires film processing, but tends to produce a relatively good quality. The step of impregnating the thermoplastic resin by the melting method is not only the extruder, but also a method of solidifying the prepreg after melt impregnation by a combination of a heating press and a cooling press, and a heating zone and a cooling zone are provided using a double belt press. There is a way. The method using a double belt press is excellent in productivity because it can be produced continuously.

(Insertion method of cutting)
The prepreg obtained by the prepreg manufacturing method can be cut using, for example, a laser marker, a cutting plotter, a cutting die, or the like to obtain the cut prepreg according to the present invention.

(Lamination substrate manufacturing method)
The cut prepreg obtained by the above insertion method is laminated so that the reinforcing fibers are oriented in at least three directions to obtain a laminate. This laminated body is spot welded with an ultrasonic welder (for example, product name: 2000LPt, manufactured by Nippon Emerson Co., Ltd.) and integrated into a flat laminated base material.

  It is also possible to obtain a laminated substrate in which the laminate is integrated by heating and pressing (hot stamping). This step can be performed using a normal apparatus, for example, a hot press machine, and a mold having a desired shape can be used as the mold used at that time. As for the material of the mold, those usually used in hot stamping molding of a fiber reinforced thermoplastic resin sheet can be adopted, and a so-called metal mold can be used. Specifically, this step can be performed, for example, by placing the laminate in a mold and heating and pressing. In the heating, although it depends on the kind of the thermoplastic resin, the heating is usually performed at 100 to 400 ° C, preferably 150 to 350 ° C. Regarding heating, preliminary heating may be performed. About preheating, although it is based also on the kind of thermoplastic resin used for the said prepreg, it heats at 150-400 degreeC normally, Preferably it is 200-380 degreeC.

  The pressure applied to the laminate in the pressurization is preferably 0.1 to 10.0 MPa, more preferably 0.2 to 2.0 MPa. The pressure is a value obtained by dividing the pressing force by the initial area of the laminated base material. The heating and pressurizing time is usually 0.1 to 30 minutes, preferably 0.5 to 10 minutes. Moreover, the cooling time provided after a heating and pressurization is 0.5 to 30 minutes normally. The thickness of the integrated laminated base material according to the present invention that has undergone the hot stamping molding is usually 0.5 to 10 mm.

Moreover, the laminated base material of this invention is excellent in fracture strength (bending strength). Such bending strength can be measured based on JIS K7074. The bending strength of the laminated base material of the present invention is usually preferably 200 MPa or more, more preferably 300 MPa or more.
Furthermore, the laminated base material of the present invention has a small variation in bending strength, that is, isotropic. Here, the CV value is an index (coefficient of variation) representing relative dispersion, and the smaller this value, the smaller the variation in physical properties between measurement points, that is, the isotropic property. Such a CV value can be calculated, for example, by measuring the bending strength at five points for a sample and CV value (%) = (standard deviation / average value of measured values) × 100. The CV value of the fiber-reinforced thermoplastic resin random sheet of the present invention is usually preferably less than 15%, more preferably less than 8%.

  Moreover, the laminated base material of this invention is excellent in rigidity (tensile elastic modulus). Such tensile elastic modulus can be measured based on JIS K7164. The tensile modulus of the laminated base material of the present invention is usually preferably 20 GPa or more, more preferably 25 GPa or more.

In addition, the laminated base material of the present invention has good fluidity at the time of molding, and can be molded into various complicated shapes. Such fluidity can be evaluated by, for example, filling the ribs.
Specifically, for example, four laminated base materials having a thickness of 2 mm cut out to 300 mm × 50 mm are held for 3 minutes in an infrared heater (product name: QU-95469V-S01) set at 280 ° C. Four laminated base materials are stacked and placed in a grid-shaped rib mold (FIG. 1) set at 130 ° C., and a 100 t press molding machine (manufactured by Press, manufactured by Yamamoto Iron Works, product name: PPM1-100) Was used for 3 minutes at 90 t. The filling of the ribs is preferably 85% or more, and more preferably 98% or more.

(Manufacturing method of fiber reinforced composite material)
A fiber-reinforced composite material is obtained by heating and then cooling the laminated substrate obtained by the method for producing a laminated substrate. The fiber-reinforced composite material in the present invention can be produced by a known method. As an example, it is obtained by stamping.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to the invention as described in an Example.
Example 1
Carbon fiber (Mitsubishi Rayon, product name: Pyrofil TR 50S) is aligned in one direction to form a fiber sheet with a basis weight of 72 g / m ^{2. From} both sides of the fiber sheet, acid-modified polypropylene resin (Mitsubishi Chemical) , Product name: Modic (registered trademark) P958) sandwiching a film with a basis weight of 27 g / m ² , impregnating the resin into the fiber sheet by heating and pressurizing the calender roll several times, and the fiber volume content Vf40 vol. %, And a prepreg having a thickness of 100 μm was produced.

  This prepreg is cut into a 295 mm square, and using a cutting plotter (product name: L-2500), the absolute value of the angle θ formed with the fiber is 45 °, the fiber length L of the reinforcing fiber is 25 mm, and the end of the cut Cuts were made so that the distance Ls between the end points of adjacent cuts in the fiber direction from the point was 12.5 mm, and the cut length l was 20 mm to obtain a cut prepreg.

This cut prepreg was laminated so that the laminated configuration was [0/45/90 / −45] 3s and the cut direction was [−45/0/45/90] 3s to obtain a laminate.
The laminate thus obtained was placed in a stamping die having a size of 300 mm square and a depth of 1.5 mm, heated to 200 ° C., and then subjected to a multistage press (compression molding machine manufactured by Shinto Metal Industry, product name: SFA-). 50HH0) at 220 ° C. at a pressure of 0.55 MPa for 7 minutes, and then cooled to room temperature at the same pressure to obtain a laminated substrate.

  The obtained laminated base material had no fiber undulation, the fibers were flowing evenly to the end, no warpage, and good appearance and smoothness were maintained.

  A bending strength test piece having a length of 100 mm and a width of 25 mm was cut out from the obtained laminated base material. According to the test method specified in JIS K-7074, the distance between the gauge points was 80 mm, and a three-point bending test was performed at a crosshead speed of 5.0 mm / min. As a testing machine, an Instron universal testing machine 4465 type was used. The number of the test pieces measured was n = 6, and the total average value was the bending strength. Further, the standard deviation was calculated from the measured value, and the standard deviation was divided by the average value, thereby calculating the coefficient of variation (CV value%) as an index of variation.

  The bending strength was evaluated in three stages (◯: 300 MPa or more, Δ: 200 MPa or more and less than 300 MPa, x: less than 200 MPa). Further, the CV value was evaluated in three stages (◯: less than 8%, Δ: 8% or more and less than 15%, x: 15% or more). The results are shown in Table 1.

In addition, according to the test method defined in JIS K-7074, from the obtained laminated base material, emery abrasive paper # 400 manufactured by Koyo Co., Ltd. was used as the tab material, and Aron Alpha GEL-10 manufactured by Toa Gosei Co., Ltd. was used as the adhesive. Tensile test pieces are prepared, a tensile test is performed at a distance between the gauge points of 50 mm and a crosshead speed of 1.0 mm / min, and a tensile elastic modulus is obtained in a stress-strain curve in a range of 0.0005 to 0.0025. Calculated. As a testing machine, an Instron universal testing machine 5882 type was used. The number of test pieces measured was n = 6, and the total average value was taken as the tensile modulus.
The tensile modulus was evaluated in three stages (◯: 30 GPa or more, Δ: 20 GPa or more and less than 30 GPa, x: less than 20 GPa). The results are shown in Table 1.

  Four 300 mm × 50 mm plate-like objects were cut out from the obtained laminated base material. It was heated for 3 minutes at 280 ° C. using an infrared heater (manufactured by NGK, product name: QU-95469-S01) and placed in a pigeon channel rib mold (FIG. 1) set at 130 ° C. Then, using a 100 t press (manufactured by Yamamoto Iron Works, press molding machine PPM1-100), pressing was performed at 90 t for 3 minutes to obtain a fiber-reinforced composite material. The filling state into the ribs was visually evaluated in two stages (◯: 98% or more, Δ: 85% or more and less than 98%, ×: less than 85%). The results are shown in Table 1.

(Examples 2, 3, and 4)
The same operation as in Example 1 was performed except that the cutting angle θ was changed as shown in Table 1. The results are shown in Table 1.

(Comparative Example 1)
This was performed in the same manner as in Example 1 except that the distance Ls between the cut end points and the adjacent cut end points in the fiber direction was changed to 5 mm. The results are shown in Table 1.

(Example 5)
The same operation as in Example 1 was performed except that the cutting length l was changed to 5 mm. The results are shown in Table 1.

(Example 6)
The same procedure as in Example 1 was performed except that the fiber sheet basis weight was 72 g / m ² , the resin film basis weight was 35 g / m ^2, and the prepreg had a fiber volume content Vf 30 vol% and a thickness 110 μmm. The results are shown in Table 1.

(Comparative Example 2)
The same operation as in Example 6 was performed except that the cutting angle θ was changed to 15 °. The results are shown in Table 1.

(Example 7 and Comparative Example 3)
The same procedure as in Example 6 was performed except that the fiber length L of the reinforcing fiber and the distance Ls between the end points of the adjacent cuts in the fiber direction from the end points of the cut were changed as shown in Table 1. The results are shown in Table 1.

(Example 8)
The same operation as in Example 6 was performed except that the distance Ls between the cut end point and the adjacent cut end point in the fiber direction was changed to 8.3 mm and the cut length l was changed to 28.3 mm. The results are shown in Table 1.

Example 9
The same procedure as in Example 1 was performed except that the fiber sheet weight was 45 g / m ² , the resin film weight was 40 g / m ^2, and the prepreg had a fiber volume content Vf 22 vol% and a thickness 112 μmm. The results are shown in Table 1.

DESCRIPTION OF SYMBOLS 1 ... Rib part 2 ... Hat part 3 ... Prepreg 4 ... Cutting 5 ... Reinforcing fiber 6 ... End point of cutting

Claims (7)

A laminated base material obtained by laminating a plurality of prepregs containing reinforcing fibers oriented in one direction and a thermoplastic resin so that the reinforcing fibers are oriented in at least three directions,
The prepreg has a linear incision with an absolute value of an angle θ of 30 ° or more with the reinforcing fiber, and the fiber length L of the reinforcing fiber divided by the incision is in the range of 2 mm to 100 mm. A laminated base material in which the distance Ls between the terminal point and the terminal point of another incision adjacent in the fiber direction is in a range of L / 4 or more and L / 2 or less.   The laminated base material according to claim 1, wherein the absolute value of the angle θ is in the range of 30 ° to 65 °.   The laminated substrate according to claim 1 or 2, wherein the length l of the cut is within a range of 4 mm to 300 mm.   The thickness of the said prepreg is 50 micrometers or more and 200 micrometers or less, The laminated base material of Claims 1-3.   The laminated base material according to claim 1, wherein the laminated structure of the laminated base material is pseudo-isotropic.   The laminated substrate according to any one of claims 1 to 5, wherein a fiber content Vf of the laminated substrate is 20 vol% or more and 40 vol% or less.   The fiber reinforced composite material which shape | molded the laminated base material in any one of Claims 1-6 in the three-dimensional shape.