JP4899692B2 - Reinforcing fiber fabric and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reinforcing woven fabric having excellent deformability, following to complicated shapes, and having excellent retention of the formed shapes; a preform produced by using the woven fabric; a molded fiber-reinforced resin article; and a method for producing these products. <P>SOLUTION: A resin material is adhered to at least one surface of a woven fabric base containing a plurality of reinforcing fiber bundles. Thereafter, the relative positions of the plural number of reinforcing fiber bundles constituting the woven fabric base are varied to separate the resin material bonded to two or more reinforcing fiber bundles from a part of the two or more reinforcing fiber bundles, and obtain a reinforcing woven fabric having a maximum load of 0.01-0.75 N measured during the period to increase the tensile strain to 1% by a tensile test in a non-fiber-axis direction. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention uses a reinforced fiber fabric that is excellent in deformability and easy to form into a three-dimensional shape, has excellent handling properties, and has excellent shape retention when formed into a three-dimensional shape, and the like. The present invention relates to a preform, a fiber-reinforced resin molded article, and a method for producing them.

  Fiber reinforced resin molded products made of cured products of continuous reinforcing fibers such as carbon fiber, glass fiber, aramid fiber and matrix resin such as epoxy resin, unsaturated polyester resin, vinyl ester resin, phenol resin, etc. It has excellent mechanical properties such as impact resistance and fatigue resistance, and is lightweight, so it is used in a wide range of applications such as aviation, space, sports, automobiles, ships, home appliances, and civil engineering. ing.

  In the production of a fiber reinforced resin molded article, a prepreg, which is a sheet-like intermediate base material in which a woven base material composed of continuous reinforcing fibers is impregnated with an uncured thermosetting resin, is laminated on a mold, and then placed in an autoclave In many cases, a method of pressing and heating is used. However, the uncured thermosetting resin impregnated in the prepreg usually has a high viscosity, and the reinforcing fiber bundle constituting the woven base material is restrained by the resin impregnated in the relative position. Therefore, the prepreg is strong and has low deformability, poor followability to the mold, and difficult to form into a three-dimensional shape. This is one of the factors that hinder productivity improvement.

  To solve the above problem, after placing a dry reinforcing fiber base that is not pre-impregnated with matrix resin inside the mold, the matrix resin is impregnated into the reinforcing fiber base by injecting a low-viscosity liquid matrix resin. Then, in recent years, an injection molding method typified by an RTM (Resin Transfer Molding) method for obtaining a fiber-reinforced resin molded product by curing has attracted attention as a method capable of improving productivity.

  In the resin injection molding method, a dry reinforcing fiber base not impregnated with resin is usually laminated on the mold according to the shape of the mold, and then covered with a bag film or a mold, and the resin is injected and cured. Procedure is taken. In this method, since a dry reinforcing fiber base material is used, the deformability is large and the followability to a three-dimensional shape is good. However, on the other hand, there is a problem that an expensive molding die is occupied for a long time because the shape retention is poor and it takes time for the laminating work.

  In order to further improve the productivity with respect to the above problem, a method in which the reinforcing fiber base material laminating step and the resin injection step are separated has also been proposed. That is, first, a so-called preform is formed in which a dry reinforcing fiber base is shaped into substantially the same shape (near net shape) as in the case of lamination on a mold, and the shape is maintained. Thereafter, the preform is placed on the mold, and the matrix resin is quickly injected without requiring lamination and shape imparting operations on the mold.

  Specifically, for example, in Patent Documents 1 and 2, a thermoplastic-like resin or a thermosetting resin is applied to the surface of the reinforcing fiber base material, and the resin is melted and reinforced after being laminated on a shaping mold having a predetermined shape. There has been proposed a technique for forming a preform held in a predetermined shape by fusing layers of a fiber base material and cooling and solidifying. According to these proposals, a preform excellent in shape retention can be obtained by deforming the reinforcing fiber substrate into a predetermined shape and bonding the layers.

  However, according to such a method, the resin component adheres to the surface of the reinforcing fiber base before being preformed, and the reinforcing fiber base becomes firmer, the deformability is lowered, and the shape following property to the mold Has the adverse effect of worsening. That is, when trying to deform into a three-dimensional shape, the reinforcing fiber base material cannot follow the shape and wrinkles are generated, and as a result, the surface of the molded product obtained by impregnating and curing the matrix resin The wrinkles of the reinforcing fiber base are visible, and the design as a product is inferior. Alternatively, when the matrix resin is injected, there is a problem that impregnation failure occurs due to the wrinkle portion generated in the reinforcing fiber base material, and further, the reinforcing fiber base material is bent at the wrinkle portion and the mechanical properties of the molded product deteriorate. is there. This phenomenon is particularly noticeable when a method is used in which a reinforcing fiber substrate is pressed against a shaping mold to form a three-dimensional solid shape with large irregularities.

For this reason, it is strongly possible to provide a reinforcing fiber substrate having excellent deformability that can follow a complicated shape without causing wrinkles at the time of shape formation, while being excellent in shape retention after shape formation. It was desired.
US Pat. No. 5,071,711 JP-A-4-261810

  An object of the present invention is to provide a reinforced fiber fabric that is excellent in deformability and can follow a complicated shape, and has excellent shape retention, a preform using the same, a fiber reinforced resin molded product, and production thereof. By providing a method, it is in improving the productivity of a fiber reinforced resin molded product.

In order to solve this problem, the present invention has the following configurations (1) to (7). That is,
(1) A reinforcing fiber woven fabric in which a resin material is fixed to at least one surface of a woven fabric substrate including a plurality of reinforcing fiber bundles, wherein the woven fabric substrate is a bi-directional woven fabric, and the woven fabric substrate By changing the relative positions of the plurality of reinforcing fiber bundles constituting the resin material, the resin material that is fixed across the two or more reinforcing fiber bundles is peeled off from a part of the two or more reinforcing fiber bundles, A reinforced fiber fabric in which the maximum value of the load until the tensile strain in the non-fiber axial direction tensile test reaches 1% is in the range of 0.01 to 0.75N.
(2) The reinforcing fiber woven fabric according to (1), wherein the maximum value of the load until the tensile strain in the non-fiber axial direction tensile test reaches 5% is in the range of 0.1 to 1.0 N.
(3) The reinforcing fiber woven fabric according to (1) or (2), wherein the fixed amount of the resin material is 1 to 50 g / m ² .
(4) The reinforcing fiber woven fabric according to any one of (1) to (3), wherein the resin material contains a thermoplastic resin as a main component.
(5) The reinforcing fiber fabric according to any one of (1) to (4), wherein the reinforcing fiber bundle is a carbon fiber bundle.
(6) After fixing the resin material to at least one surface of the fabric base material including the plurality of reinforcing fiber bundles, by changing the relative positions of the plurality of reinforcing fiber bundles constituting the fabric base material Until the tensile strain in the non-fiber axial tensile test reaches 1% by peeling off the resin material fixed across two or more reinforcing fiber bundles from a part of the two or more reinforcing fiber bundles The manufacturing method of the reinforced fiber fabric whose maximum value of the load is in the range of 0.01-0.75N .
(7) The reinforcing fiber according to (6), wherein a change is given to a relative position of a plurality of reinforcing fiber bundles constituting the woven fabric base by applying a shear deformation of 5 to 45 ° to the woven base. A method for producing a woven fabric.

  In the present invention, the resin material is firmly fixed means that the surface of the reinforcing fiber bundle constituting the woven fabric substrate is in contact with the resin material, and the resin material constitutes a plurality of reinforcing fiber bundles constituting the reinforcing fiber bundle. It refers to a state in which the reinforcing fiber fabric and the resin material are bonded to each other through the single yarn.

  Even if the reinforced fiber fabric of the present invention has a complicated shape which has been difficult in the past, it can be deformed with good productivity and held in shape. Therefore, it is possible to produce a fiber reinforced resin molded article excellent in design and mechanical properties with high productivity.

  Hereinafter, the present invention will be described in detail along with preferred embodiments.

  In the reinforcing fiber fabric of the present invention, a resin material is fixed to at least one surface of a fabric base material including a plurality of reinforcing fiber bundles, and the tensile strain by the non-fiber axial tensile test reaches 1%. The maximum value of the load is in the range of 0.01 to 0.75N.

By fixing the resin material to the woven fabric substrate, a preform having excellent shape retention can be obtained. In other words, when manufacturing preforms by laminating reinforcing fiber fabrics and giving them shapes, heat is applied to melt the resin material, and the molten resin material penetrates both of the opposing reinforcing fiber fabrics, and then solidifies by cooling. By doing so, the layers of the reinforcing fiber fabric can be bonded, and as a result, a preform having excellent shape retention can be obtained.
The resin material may be fixed to both surfaces of the reinforcing fiber fabric. However, when the layers of the reinforcing fiber fabrics are bonded, an interlayer bonding effect can be obtained if a resin material is present in at least one of the opposing reinforcing fiber fabrics. Therefore, by devising the stacking order, if the resin material is fixed to one surface of the reinforcing fiber fabric in contact with each layer, the shape retention effect by adhesion between the layers can be sufficiently obtained.

  Further, it is sufficient that the resin material is fixed to at least the surface of the reinforcing fiber woven fabric. However, the resin material is reinforced fiber woven fabric, for example, when the woven fabric is composed of reinforcing fiber bundles containing the resin material. It may exist not only on the surface but also inside.

  As a resin material, it can be fixed to the surface of a woven fabric substrate containing reinforcing fiber bundles, and the laminated reinforcing fiber fabric is pressed and heated to bond the layers to form a deformed reinforcing fiber fabric. If the effect to hold | maintain can be expressed, it will not specifically limit. It can be used by appropriately selecting from a thermoplastic resin, a thermosetting resin, or a mixture thereof. Such a resin material is in a crystalline state or a glass state at room temperature, but needs to have a property of melting or softening by heat.

  The resin material is, for example, a resin in the form of fibers, powders, etc., is dispersed on the surface of the textile substrate and then softened by heating to bond the single yarn constituting the reinforcing fiber bundle and the resin, and then solidify by cooling. Alternatively, it can be fixed to the surface of the textile substrate by a method of solidifying after spraying a liquid resin on the surface of the textile substrate. Of course, it may be fixed by other methods.

  When the reinforcing fiber fabric is deformed into a three-dimensional shape, the reinforcing fiber fabric is composed of a reinforcing fiber bundle having a low elongation, and therefore deformation due to the elongation of the reinforcing fiber bundle is extremely small. Therefore, it is necessary to change into a three-dimensional shape by changing the relative position between the reinforcing fiber bundles constituting the reinforcing fiber fabric, that is, by changing the woven angle of the fabric.

  Also, when the reinforcing fiber fabric is deformed into a three-dimensional shape, if each portion of the reinforcing fiber fabric can be flexibly deformed even with a small deformation load, the reinforcing fiber fabric can be obtained by integrating the minute deformations of each portion. The whole can be deformed smoothly and smoothly, and as a result, it can follow a complicated three-dimensional shape without wrinkles. In addition, when trying to deform a reinforcing fiber fabric having poor deformability under a small deformation load into a three-dimensional shape, each part cannot be deformed until the deformation load reaches a certain size, but the load is When the value exceeds a certain value, local deformation occurs in a portion having low resistance to deformation. Therefore, if it sees as a whole, it cannot follow a three-dimensional shape, will produce a big wrinkle, and will cause a problem in all of design nature, resin impregnation nature, and mechanical properties.

  Therefore, in order for the reinforcing fiber fabric to follow the three-dimensional shape without wrinkles, it is important that each portion of the reinforcing fiber fabric is smoothly deformed even under a small deformation load.

  In general, in a woven fabric base material to which a resin material is not fixed, the relative position between the reinforcing fiber bundles constituting the woven fabric is mainly constrained by the frictional force generated between the reinforcing fiber bundles. Can be changed relatively easily, and the deformability of the reinforcing fiber fabric is good.

  On the other hand, as shown in FIGS. 1 and 2, in the reinforced fiber fabric in which the resin material 13 is fixed to the surface, generally, the resin materials 11 and 12 fixed over the plurality of reinforcing fiber bundles 14 and 15. Since these resin materials bind the reinforcing fiber bundles, a strong restraining force is generated between the reinforcing fiber bundles, and the deformability of the reinforcing fiber fabric is deteriorated. As a result, the deformation required when the reinforcing fiber fabric follows the three-dimensional shape is less likely to occur, and problems such as wrinkles tend to occur during the deformation to the three-dimensional shape.

However, the reinforcing fiber fabric according to the present invention is a reinforcing fiber fabric in which a resin material is fixed to at least one surface of a fabric base material including a plurality of reinforcing fiber bundles. Since the maximum value of the load until it reaches 1% is in the range of 0.01 to 0.75N, the interlayer adhesion effect by the resin material is exhibited and the generation of wrinkles is prevented to follow the three-dimensional shape. You can also.
Here, the non-fiber axial direction tensile test is a measurement of displacement and load in the direction in which the deformation of the reinforcing fiber fabric becomes the largest when a tensile load is applied in the in-plane direction of the reinforcing fiber fabric. According to the following method.

  First, a rectangular test piece (measurement part dimensions: length 150 mm × width 45 mm) is prepared so that the direction in which the reinforcing fiber fabric is most easily deformed is the long axis direction. The test piece is pulled in the major axis direction, and the amount of deformation (the amount of change in the length of the measuring section) and the tensile load at that time are measured.

For example, in the case of a bi-directional reinforcing fiber fabric having fiber axes of reinforcing fiber bundles in two directions of 0 ° and 90 °, directions that are most easily deformed when a tensile load is applied are + 45 ° and −45 °. Since it is in any direction, a test piece whose major axis is in any direction is cut out (see FIG. 3).
When a non-fiber axial direction tensile test is performed on the test piece, a tensile load is applied in a direction different from the fiber axis direction of the reinforcing fiber bundle, and accordingly, the relative position between the reinforcing fiber bundles constituting the reinforcing fiber fabric is determined. It shifts and the weaving angle changes. As a result, the test piece is deformed so as to increase the distance of the measurement section length (see FIG. 4). In other words, the deformation caused by the change in the weave angle in the non-fiber axial tensile test is due to the same mechanism as that required when the reinforcing fiber fabric follows the three-dimensional shape. By measuring the relationship of the deformation amount, it is possible to know the ease of deformation of the reinforcing fiber fabric. For example, it can be said that a reinforcing fiber woven fabric having a small load necessary for giving a certain amount of deformation is a reinforcing fiber woven fabric having excellent deformability and easily following a three-dimensional shape.

  In the non-fiber axial tensile test, it is necessary to pay attention to the fact that the measurement results differ when the test piece dimensions change because the test piece exhibits non-uniform deformation as shown in FIG. Therefore, in this invention, it shall test with the test piece of the said dimension.

  In addition, when a tensile load is applied, the measurement result is similarly different when the test piece is deformed in the width direction in the test piece mounting portion 41 shown in FIG. It is important to use a mounting jig having a structure in which a tightening pressure is applied uniformly over the entire tightening portion so that the test piece does not deform in the width direction.

The tensile strain of 1% in such a non-fiber axial direction tensile test means that when the test piece is pulled and deformed in the major axis direction, the measurement part length becomes 1.5 mm larger from the initial length, 151. This is the state of 5 mm.
If the maximum value of the load until the tensile strain in the non-fiber axial direction tensile test reaches 1% is within a range of 0.01 to 0.75 N, the reinforced fiber fabric is in a small deformation region at the initial stage of deformation. Since each part can be smoothly deformed with a small deformation load, it can smoothly follow a three-dimensional shape and is less likely to cause defects such as wrinkles. The upper limit of the maximum value of the load is preferably 0.6N, more preferably 0.45N. On the other hand, the lower limit of the maximum value of the load is preferably 0.05, and more preferably 0.1. If the maximum value of the load required until the tensile strain reaches 1% is in the range of 0.05 to 0.6N, the deformability is further excellent, and it should be in the range of 0.1 to 0.45N. Therefore, it is very easy to deform into a three-dimensional shape without wrinkles.

  Furthermore, in the present invention, the reinforced fiber fabric preferably has a maximum load within a range of 0.1 to 1.0 N until the tensile strain in the non-fiber axial tensile test reaches 5%. The tensile strain of 5% in the non-fiber axial direction tensile test is that when the test piece is pulled and deformed in the long axis direction, the measured length is 7.5 mm larger than the initial length and 157.5 mm. That is.

When the reinforcing fiber fabric is deformed into a three-dimensional shape, the reinforcing fiber fabric is accompanied by a minute deformation over almost the entire portion that is deformed into the three-dimensional shape and needs to be further deformed at a portion where the shape changes greatly.
If the maximum value of the load until the tensile strain in the non-fiber axial direction tensile test reaches 5% is in the range of 0.1 to 1.0 N, the reinforced fiber fabric is minutely deformed under a small deformation load. In addition, even when a large deformation is required, the relative position between the reinforcing fiber bundles is likely to change, and the possibility of causing defects such as wrinkles is low. The upper limit of the maximum value of the load is preferably 0.85N, more preferably 0.7N. On the other hand, the lower limit of the maximum value of the load is preferably 0.15, and more preferably 0.2. If the maximum value of the load until the tensile strain reaches 5% is 0.15 to 0.85N, the deformability is further excellent, and if it is 0.20 to 0.70N, the deformability is extremely excellent. Even when large deformation is required, it becomes easier to deform into a three-dimensional shape without wrinkles.

In the reinforced fiber fabric of the present invention, a resin material is fixed to at least one surface. When there are a lot of resin materials adhering to the surface, when a plurality of reinforcing fiber fabrics with resin materials are laminated, it is possible to obtain a strong action of adhering the layers, and excellent retention of the shaped shape A preform can be obtained. However, if the amount of the resin material is excessively large, the resin material strongly bonds the reinforcing fiber bundles constituting the reinforcing fiber fabric, and the deformability is remarkably deteriorated. Furthermore, as shown in FIG. 5, the surface of the reinforced fiber fabric is widely covered with the resin material 51, and the matrix resin is reinforced when a liquid matrix resin is injected into the reinforced fiber fabric to obtain a fiber reinforced resin molded product. Inflow into the fiber woven fabric is hindered, and it takes a long time to uniformly impregnate the matrix resin throughout, or a portion not impregnated with the matrix resin may be formed. From this viewpoint, it is preferable that the amount of the resin material fixed is 50 g / m ² or less. More preferably, it is 25 g / m < ² > or less, More preferably, it is 10 g / m < ² > or less. On the other hand, when the amount of the resin material adhering to the surface of the reinforcing fiber fabric is too small, a sufficient adhesive force cannot be obtained when the layers of the reinforcing fiber fabric are bonded, and the three-dimensional shape cannot be maintained. From this viewpoint, it is preferable that the amount of the resin material fixed is 1 g / m ² or more. More preferably, it is 1.5 g / m ² or more, and further preferably 2 g / m ² or more.

  As the resin material that is fixed to the surface, particularly if it can be fixed to the surface of the woven base material by the method described above and can obtain the action of bonding the layers of the woven base material. It is not limited. A thermosetting resin and / or a thermoplastic resin can be appropriately selected and used, and among them, a thermoplastic resin as the main component is preferable. Examples of the thermoplastic resin include polyamide, polysulfone, polyetherimide, polyphenylene ether, polyimide, polyamideimide, and the like, but are not particularly limited. When the resin material is composed mainly of a thermoplastic resin, it is applied to the surface of the reinforcing fiber fabric when it is sprayed and fixed, and further, the reinforcing fiber fabric is laminated and deformed into a three-dimensional shape, and then the layers are bonded. Improve productivity and productivity. In addition, a main component means the component with the largest ratio among the components which comprise a resin material.

In the reinforced fiber fabric of the present invention, it is preferable that the resin material is scattered and fixed on the surface of the fabric substrate. Scattering refers to a state of being dispersed over the entire surface of the textile substrate. By interspersing the resin material, even when the amount of the resin material is small, it is easy to obtain a uniform adhesive force over the entire surface during interlayer adhesion. In this case, 90% or more of the resin material scattered and fixed on the surface of the reinforcing fiber fabric has a projected area in a direction perpendicular to the surface of the reinforcing fiber fabric within the range of 0.002 to ¹ mm ^2. Preferably there is. More preferably, it is 0.002-0.2 mm < ² >, More preferably, it is 0.002-0.05 mm < ² >. If the projected area is smaller than 0.002 mm ² , the number of resin materials buried in the unevenness associated with the woven structure on the surface of the woven fabric base increases, the adhesion between the layers becomes weak, and as a result, the shaped shape can be maintained. It becomes difficult. On the contrary, if the projected area is larger than 1 mm ² , the dispersion state of the resin material is likely to vary, and it becomes difficult to obtain uniform adhesion when the layers are bonded. Furthermore, there may be a case where the above-described inconvenience at the time of matrix resin injection is likely to occur.
As a woven fabric base material constituting the reinforcing fiber fabric of the present invention, a fabric substrate composed of a plurality of reinforcing fiber bundles can be appropriately selected. For example, a plurality of reinforcing fiber bundles arranged in one direction so as to be parallel to each other and auxiliary fibers (single yarns or fiber bundles) perpendicular to them and having a small diameter cross each other to form a woven structure. A directional fabric, or a bidirectional fabric formed by weaving a plurality of reinforcing fiber bundles in two directions (for example, two directions orthogonal to each other), or a plurality of reinforcing fiber bundles arranged in parallel with each other, It is possible to use a multiaxial woven fabric in which the fiber directions are laminated in different stages and joined together by stitching or the like. Among these, a bi-directional woven fabric is preferable. Examples of the woven form of the bi-directional woven fabric include plain weave, twill weave, and satin weave. Bidirectional woven fabrics are easily deformed into a three-dimensional shape due to changes in the relative position between reinforcing fiber bundles, and are easy to obtain a laminated structure that is mechanically pseudo-isotropic with a small number of sheets. Etc. are preferable.
A carbon fiber bundle, a graphite fiber bundle, a glass fiber bundle, an aramid fiber bundle, or the like can be used as the reinforcing fiber bundle constituting the woven fabric substrate. Among these, a carbon fiber bundle is preferable. The carbon fibers constituting the carbon fiber bundle include polyacrylonitrile-based, rayon-based and pitch-based types, and polyacrylonitrile-based carbon fibers are preferably used from the balance of strength, elastic modulus and the like. By using the carbon fiber bundle, the mechanical properties of the fiber reinforced resin molded product as the final product can be improved. From this point of view, the tensile elastic modulus of the carbon fiber bundle used in the present invention is preferably 110 to 600 GPa, and more preferably 210 to 600 GPa, since further excellent mechanical properties can be expressed. Here, the tensile modulus refers to a value measured based on JIS R7601 (1986), and the unit is GPa.

  The reinforcing fiber woven fabric of the present invention as described above has a plurality of reinforcing members constituting the woven fabric base material after the resin material is applied and fixed to at least one surface of the woven fabric base material including a plurality of reinforcing fiber bundles. It can be manufactured by changing the relative position of the fiber bundle.

The resin material can be fixed to the surface of the woven fabric substrate by the method described above. As shown in FIGS. 6 and 7, even when there is a resin material that is fixed across a plurality of reinforcing fiber bundles, the force that restrains the positional variation between the reinforcing fiber bundles caused by the fixing of the resin material By applying a larger external force, the relative position between the reinforcing fiber bundles constituting the fabric base material is forcibly changed, and the resin material is fixed to only some of the reinforcing fiber bundles as shown in FIGS. It can be made into the state which is carrying out.
The resin material that is fixed across the two reinforcing fiber bundles is usually more strongly fixed to one of the reinforcing fiber bundles. Therefore, when the relative position between the two reinforcing fiber bundles to which the resin material is fixed fluctuates, the resin material moves together with the reinforcing fiber bundle to which the resin material is more strongly fixed, and as a result, the other reinforcing fiber It is peeled off from the bundle.
Thus, by forcibly changing the relative position between the reinforcing fiber bundles by an external force, the resin material fixed to the two or more reinforcing fiber bundles peels off from some of the reinforcing fiber bundles and becomes stronger. It will be in the state which adhered only to the reinforced fiber bundle which has adhered.
As a result, even if it is a reinforced fiber woven fabric with the resin material fixed on the surface, the resin material has no effect of restraining deformation, so the maximum load until the tensile strain in the non-fiber axial tensile test reaches 1% The value is in a range of 0.01 to 0.75 N, and excellent deformability equivalent to that of a woven fabric base material to which no resin material is fixed can be exhibited.
In addition, as the whole reinforced fiber fabric, the resin material that is partially fixed across a plurality of reinforced fiber bundles may remain as it is without being peeled off from the reinforced fiber bundle.
Further, in order to peel off the fixing of the resin material from the reinforcing fiber bundle by changing the relative position between the plurality of reinforcing fiber bundles constituting the fabric base material, the resin material is substantially in a solid state. There is a need. That is, when the resin material is fixed by thermal fusion, the resin material is sufficiently cooled, and when sprayed as a solution, the resin material is sufficiently dried, and then the relative position of the reinforcing fiber bundle is changed. By carrying out like this, the resin material adhering efficiently can be peeled off.

  Once the relative position between the reinforcing fiber bundles is changed, even if the positional relationship is restored, the peeled resin material will not be fixed again unless the resin material is softened by reheating or the like. If the fiber woven fabric is returned to its original shape, a reinforced fiber woven fabric that maintains the same woven form as before the change is imparted without any disturbance in the texture can be obtained.

  As for the method of imparting fluctuation to the relative position between the reinforcing fiber bundles, any method can be used as long as it can overcome the restraining force generated by the adhesion between the reinforcing fiber bundles by the resin material and give the effect of changing the relative position between the reinforcing fiber bundles. The method is fine. For example, the relative position between the reinforcing fiber bundles may be efficiently varied by applying shear deformation in the in-plane direction of the woven fabric base material on which the resin material is fixed to the surface.

In order to give shear deformation to the woven fabric base material, for example, the unfolding mechanism of the woven fabric base material to which the resin material is fixed and the deformation in the width direction by swinging in the width direction while gripping the woven base material. What is necessary is just to use the apparatus which has the rocking | fluctuation mechanism to give and the winding mechanism of a textile base material.
The unwinding mechanism includes a shaft on which a roll of the fabric base material to which the resin material is fixed and a mechanism for appropriately applying tension to the fabric base drawn from the roll. As the mechanism for applying tension, any mechanism can be used as long as it can apply tension to the fabric substrate to be conveyed. For example, a device that applies torque such as a powder brake to the shaft on which the roll is installed. A mechanism for connecting and applying tension, a mechanism for applying tension by niping a conveyed fabric base with a pair of rotation-controlled rolls, or a friction force between a roll and a fabric base that controls rotation A mechanism for applying tension can be used.

  As a mechanism for swinging the woven base material in the width direction, any structure may be used as long as the woven base material can be swung in the width direction. For example, as shown in FIG. 16, an end gripping swinging mechanism 161 that grips the width direction end of the fabric base material and applies a tensile force in the width direction, or the fabric base material shown in FIG. For example, a nip swing mechanism 171 that sandwiches and swings the jig in the width direction of the fabric base material can be exemplified. Further, as shown in FIG. 18, a mechanism for swinging the fabric substrate while gripping the fabric substrate with frictional force by swinging a swing roll 181 having the width direction of the fabric substrate as the rotation axis direction in the rotation axis direction. Are also preferably used.

  When the mechanism shown in FIG. 18 is used, when the oscillating roll 181 is installed so that the fabric base material passes through a large winding angle, a large frictional force can be obtained between the reinforcing fiber fabric and the fabric base material. Can be efficiently swung. Here, the winding angle is an angle at which the fabric base material is wound with respect to the circumference of the swing roll when the transport roll 182 passes through the swing roll 181 and moves to the next transport roll 182. Say that.

  In addition, by increasing the friction coefficient of the roll surface by, for example, using a rubber material for the roll surface, the fabric substrate can be prevented from slipping on the roll surface when the fabric substrate is swung in the width direction. . By doing so, the fabric base material can be more efficiently swung, and the surface of the fabric base material can be prevented from being scratched and damaged by sliding on the roll surface. Similarly, in order not to damage the textile base material, it is preferable that the swing roll is driven to rotate as the textile base material travels.

  When the fabric substrate is swung in the width direction, the length of the transport path changes. Therefore, as shown in FIG. 19, it is preferable that the swing roll 181 has a mechanism that can also move in a direction perpendicular to the rotation axis so as to absorb the change in path length when swinging in the axial direction.

  The winding mechanism may be configured to wind the woven base material around the roll by rotating the shaft on which the roll is installed. The winding may be a continuous operation at a constant speed, or an intermittent operation in which the winding and stopping are repeated, for example, stopping when the swing mechanism is activated and winding when the swing mechanism is stopped. May be.

  For example, when shear deformation is applied to the bidirectional fabric base material shown in FIG. 1 by the method described above, the fabric base material is deformed as shown in FIG. When shear deformation is applied, the rectangular portion having the vertex of the intersection of the reinforcing fiber bundles is deformed into a parallelogram while maintaining the length of each side. At this time, the woven angle between the reinforcing fiber bundles constituting the fabric is deformed, and the relative position between the reinforcing fiber bundles is changed. As a result, the resin material fixed across the plurality of reinforcing fiber bundles can be partially peeled from the reinforcing fiber bundle.

  The shear deformation angle θ shown in FIG. 10 (that is, the angle difference before and after the shear deformation of the reinforcing fiber bundle intersecting with a certain reinforcing fiber bundle as a reference) is preferably in the range of 5 to 45 °. When the shear deformation angle is less than 5 °, the relative position between the reinforcing fiber bundles is not sufficiently changed, so that it is not possible to sufficiently obtain the effect of peeling the resin material fixed across the plurality of reinforcing fiber bundles. On the other hand, when a shear deformation angle greater than 45 ° is given, even if the reinforcing fiber fabric is deformed and then returned to its original shape, the woven structure remains distorted or the reinforcing fiber bundle is damaged. It is not preferable because defects are likely to occur. In order to obtain the effect of peeling the resin material more efficiently, it is more preferably 10 ° or more, and further preferably 20 ° or more. On the other hand, in order to prevent damage to the reinforcing fiber fabric more reliably, it is more preferably 40 ° or less, and further preferably 30 ° or less.

  If the reinforcing fiber fabric of the present invention obtained as described above is used, a preform having no wrinkles can be obtained even if it is a three-dimensional shape.

  The preform is formed by laminating and integrating the reinforcing fiber woven fabric of the present invention together with a woven fabric base material to which a resin material is not fixed as required. The preform of the present invention includes a plurality of fabric base materials integrated with a resin material, and includes at least one layer of a reinforcing fiber fabric with the resin material.

  The preform maintains its three-dimensional shape by bonding a plurality of fabric base materials deformed into a three-dimensional shape to each other through a resin material between the layers. If the resin material is fixed to the surface of at least one of the woven fabric bases on the surface where the laminated woven fabric bases are in contact with each other, an adhesive action can be obtained between the layers. Therefore, in consideration of the form of the reinforcing fiber woven fabric of the present invention that is actually used, a part of the total number of necessary woven fabric bases constituting the preform may be replaced with the reinforcing fiber woven fabric of the present invention. That is, when the resin material adheres to both surfaces of the woven fabric base constituting the reinforcing fiber woven fabric, the reinforcing fiber woven fabric of the present invention and the other woven fabric base may be arranged alternately. Further, when a part of the woven fabric base constituting the preform has only to be fixed, the number of other woven base materials may be increased.

  However, if the adhesive action by the resin material can be obtained between all the layers, a preform having excellent handleability, efficient wrinkle-free and excellent shape stability can be obtained without peeling between the layers. Therefore, when an adhesive action is required between all layers, such as when the desired preform has a complicated shape, the reinforcing fiber fabric of the present invention in which the resin material is fixed on both sides of the fabric substrate, It is preferable to arrange the other woven fabric bases alternately, or to use the reinforced fiber woven fabric of the present invention except the total number or one of the necessary woven base materials constituting the preform. A preform that is not peeled off and has excellent handling properties can be obtained. Of course, the total number of necessary woven fabric bases constituting the preform may be the reinforcing fiber woven fabric of the present invention in which the resin material is fixed on both sides.

  A preform using the reinforcing fiber fabric of the present invention can be formed as follows.

First, the reinforcing fiber fabric of the present invention is laminated and arranged in a shaping mold together with other fabric substrates including reinforcing fiber bundles as necessary. Next, the laminate is pressurized and heated while being pressed along the shape of the shaping mold to soften the resin material fixed to the reinforced fiber fabric and adhere the layers of the laminate to maintain the shape. A preform is thus obtained.
As a method for pressurizing the laminate, for example, a pair of shaping molds that can be shaped in substantially the same shape as a desired fiber-reinforced resin molded product (that is, almost the same mold as a mold in which matrix resin is injected and cured) A mold having a shape), and after laminating the laminated body on one shaping mold, the other shaping mold is closed and tightened to pressurize the laminated body and deform the shape along the shaping mold. This can be illustrated (see FIG. 11). Also, using a single-sided shaping mold having the same mold shape as the molding die, the laminate is laminated on the shaping mold, and then the laminate is covered with a sheet from above to form the sheet and the shaping die. The interior of the space surrounded by and is evacuated or pressurized gas is introduced into the chamber box to pressurize the laminate through the sheet and press against the shaping mold to shape the shaping mold A method of deforming the film can be exemplified (see FIG. 12). Note that these methods are not limited. The pair of shaping molds may be such that one shaping mold constituting the pair is divided into a plurality of shaping molds.

  Examples of the method of heating the laminated body include a heated shaping mold and a method of heat conduction of the laminated body, a method of heating with an infrared heater or the like from the outside, or a method of spraying a heated gas or liquid. However, there is no particular limitation. The shaping mold can be heated by a method in which a pipe is provided inside and a heating medium is passed through the pipe, or a heater is provided inside.

  In order to produce a preform efficiently, a method in which the laminate is brought into close contact with a shaping mold heated to a temperature necessary for softening the resin material and heated by heat conduction is preferably used. In this case, if the resin material is softened before the laminate is deformed into a shape conforming to the shaping mold, the adhesiveness of the resin material is increased and the layers of the laminate are not easily displaced, and the three-dimensional shape is successfully deformed. Since there is a case where it does not go, it is preferable to pressurize and deform the resin material before heat is transmitted.

  The temperature at which the laminate is heated may be any temperature as long as the resin material is softened and can exert an effect of bonding the layers of the laminate. Reinforcing fibers constituting the reinforcing fiber woven fabric or the woven fabric base that the reinforced fiber woven fabric or the woven fabric base constituting the laminated body is strongly pressed against each other by being heated while the laminated body is pressurized. It penetrates between the single yarns of the bundle. Next, when the laminate is cooled, the resin material adheres to both the reinforcing fiber woven fabric and the woven fabric substrate facing each other, and exhibits an action of adhering the layers of the laminate. Examples of the method for cooling the laminated body include a method of cooling the shaping mold and cooling it by heat conduction between the shaping mold and the laminated body, or blowing cool air to the laminated body, but is not particularly limited.

  By deforming the laminated body into a three-dimensional shape and adhering the layers by such a method, it is possible to manufacture a preform that is deformed into a three-dimensional shape and has no wrinkles. In addition, since this preform is bonded between the layers of the laminate, it has high rigidity and excellent shape retention, and handling such as carrying the preform and placing it on a molding die for injecting matrix resin is possible. It also has the feature of being able to do it efficiently.

  In addition, the preform can be manufactured by disposing a laminate between at least two shaping molds facing each other, pressurizing a part of the laminate, and heating the remaining part while applying pressure. In this method, when a laminate is placed between the shaping molds and a part of the laminate is pressurized, the unpressurized portion of the laminate is not restrained and can move freely. Yes, the amount of laminate required for the part to be pressurized to conform to the shape of the shaping mold is drawn from the surroundings. Next, when the surrounding portion is pressed, the entire laminate is pressed and deformed along the shape of the shaping mold. The laminated body is heated in a state along the shape of the shaping mold, and the resin material is softened and becomes a preform in which the layers are bonded. By first pressurizing a part and then pressurizing the whole, the amount of laminate required to conform to the shape of the shaping mold will be supplied without delay, even in the vicinity of irregularities whose shape changes greatly. It is possible to efficiently produce a wrinkle-free preform without the need for manual assistance.

  The position of pressurization prior to pressurizing the entire laminate is not particularly limited. For example, when the laminate is deformed to a relatively smooth shape, the area around the center of the shape It is preferable because the laminated body can be easily pulled from. When the laminate is deformed into a shape having a step, it is preferably a stepped recess. By first pressurizing the concave portion, a necessary and sufficient amount of the laminated body is supplied to deform the laminated body into a shape along the concave portion, and can be shaped well. In addition, in the shape with multiple steps, if the pressure is applied in steps, such as sequentially pressing the adjacent concave portions and finally pressing the entire remaining, it is possible to effectively preform while preventing wrinkles. Can be manufactured.

  As a method of pressurizing and heating the remaining part after pressurizing a part of the laminated body, as shown in FIG. 13, as shown in FIG. An example is a method in which a pressurizing action is applied by 134 and then the whole is sandwiched and pressed by an opposing shaping mold 132. Here, the partial mold means a member for deforming a part of the laminated body into a shape along the shaping mold. By pressing the laminated body using the partial mold, the laminated body is sandwiched between the shaping mold and the partial mold and deformed into a shape along the shaping mold.

  The partial mold needs to have a shape that conforms to the shaping mold corresponding to that part in the part where the laminate is pressed, and the shaping mold or sheet is laminated even in the part that is not in contact with the laminate. It must have a shape that does not interfere with the action of sandwiching and pressing the body. As the partial mold, a material obtained by cutting or molding a metal, resin, rubber or the like into a desired shape can be used. In order to heat the laminate efficiently, the partial mold may be heated, but the laminate is not essential because it is also heated from the shaping mold.

  As shown in FIG. 14, the partial mold may be constituted by a movable part 144 that can be protruded and provided in at least one of the facing shaping molds 141 and 142. In the case of this aspect, first, the shaping molds are brought close to each other with the movable part 144 projecting, and a part of the laminate 143 is pressurized with the other shaping mold 141 and the projecting movable part. Next, the shaping molds are brought closer to each other, and the projecting movable part 144 is drawn in the interior direction of the shaping mold, and the entire laminated body is pressurized and heated by the entire shaping molds 141 and 142 facing each other.

  Furthermore, after the preform is pressed against the shaping mold after a part of the laminated structure laminated on the shaping mold is covered with a sheet, the laminate is pressurized and heated with gas or liquid. Can also be manufactured. In this method, for example, as shown in FIG. 15, a part of the laminated body 152 laminated on the shaping mold 151 is pressed against the shaping mold by the partial mold 155, and a part of the laminated body is aligned with the shaping mold. Transform into shape. The shape of the partial mold is set along the corresponding shaped mold portion. At this time, the non-pressed portion of the laminated body is not restrained and can move freely, and an amount of the laminated body necessary to follow the shaping mold is drawn from the surroundings. Next, the sheet 153 is covered from above the laminated body, and the space between the peripheral portion and the shaping mold is sealed with the sealing material 154, and the inside of the space surrounded by the shaping mold and the sheet 153 is vacuumed using the vacuum pump 157. The laminate can be pressurized by pressing the gas or liquid inside the space surrounded by the sheet 153 and the chamber box 159 using the pressurizing device 158. Moreover, a laminated body can be heated by heating a shaping type | mold with the heater 156, or heating gas and a liquid. By carrying out like this, preform can be manufactured because the whole laminated body deform | transforms into the shape along the shaping type | mold, and also the resin material inside a laminated body softens, and an interlayer adhesion effect | action expresses. .

  Examples of the material for the sheet include, but are not limited to, silicone rubber, natural rubber, nylon resin, polyethylene resin, and polypropylene resin.

  If the sheet has a property of extending, it is preferable that the shape is easily conformed even if the desired preform shape is complicated. Therefore, the elongation of the sheet is preferably 5% or more. In addition, although there is no problem even if the elongation of the film is large, it is preferable that the upper limit of the elongation of the film that can withstand practical use is 400% in view of repeated use and heating.

  In addition, it is also effective to efficiently deform the laminate in advance by shaping the sheet into a shape substantially the same as the shape of the laminate.

  The fiber-reinforced resin molded article of the present invention is produced by injecting and impregnating a liquid matrix resin into the preform produced by the above method and then curing or solidifying the preform.

  The above-mentioned preform having excellent shape retention while being deformed without wrinkles into a three-dimensional shape is not easily deformed even when carried and is easy to handle, so it can be easily placed in a mold. Moreover, since the shape retainability is excellent, the outer shape is clear, and the positioning when mounting on the mold is easy.

As a method of impregnating the resin, the preform is placed on a single-sided mold, covered with a film, the inside of the space surrounded by the film and the mold is evacuated, and then the liquid resin is preformed with vacuum pressure Preferably, a method of impregnating the preform or a method in which the preform is sandwiched between opposing molds and a matrix resin is injected into the mold under pressure to impregnate the preform can be preferably used. Next, after the resin is cured or solidified at a temperature and time suitable for the resin, it is demolded to produce a fiber-reinforced resin molded product.
Although it does not specifically limit as matrix resin, For example, thermosetting resins, such as an epoxy resin, a phenol resin, a vinyl ester resin, an unsaturated polyester resin, are used preferably. Of these, epoxy resins are particularly preferred because they are excellent in handleability and mechanical properties.

  Since the fiber reinforced resin molded product of the present invention uses a reinforced fiber fabric excellent in deformability to a curved shape or a three-dimensional shape, it can be manufactured with high productivity even in a complicated three-dimensional shape. Since continuous reinforcing fibers are used, excellent mechanical properties can be exhibited while being lightweight. Here, the three-dimensional shape refers to a shape (including a shape having a branched cross section) including a plane or a curved surface.

  In addition, the reinforced fiber fabric used in the fiber reinforced resin molded product of the present invention has a feature that even when it is deformed, the texture and the wrinkle are not easily generated. It has the characteristics that the texture pattern is less disturbed and the design is excellent, and further, the orientation property of the reinforcing fiber bundle is less disturbed and the mechanical properties are excellent. Due to these features, the fiber reinforced resin molded product of the present invention is required to have a complicated shape, design, and high mechanical properties such as exterior members and structural members in applications such as automobiles, aircraft, ships, home appliances, and architecture. It can use suitably for the use which is.

  Hereinafter, the present invention will be described based on examples and comparative examples.

Example 1:
Using a embossing roll and a doctor blade, an embossing roll and a doctor blade are used to make the mass per unit area 5 g / m ^{2 on} one surface of the bi-directional textile base material. The sample was dropped while being weighed and dispersed uniformly. Subsequently, the resin material is fixed on the fabric substrate by passing under a far-infrared heater set so that the surface temperature of the fabric substrate becomes 185 ° C. at a rate of 0.3 m / min. The fixed reinforcing fiber fabric was wound on a roll.

For bi-directional woven fabric base material, CO6343B manufactured by Toray Industries, Inc. (woven structure: plain weave, woven fabric weight: 198 g / m ² , thickness: 0.25 mm, warp weave density: 12.5 / 25 mm, weft weave Density: 12.5 fibers / 25 mm), and the reinforcing fiber bundle used for this bidirectional fabric base material is carbon fiber T300-3K (number of filaments: 3,000, tensile elastic modulus) manufactured by Toray Industries, Inc. : 230 GPa, tensile strength: 3.5 GPa, fineness: 198 tex, elongation at break: 1.5%).

  Subsequently, the reinforcing fiber fabric was unwound from the roll, passed through an oscillating roll capable of oscillating in the axial direction so that the winding angle was 180 °, and then wound around another roll. The reinforcing fiber fabric moves intermittently from the unwinding side to the winding side, and the rocking roll is swung while the intermittent operation is stopped, and the shear deformation angle in the in-plane direction with respect to the reinforcing fiber fabric is maximum. A deformation history of 30 ° was given. Then, the reinforcing fiber fabric was wound around a roll in a state where the shear deformation angle returned to the state of substantially 0 °. When the surface of the reinforced fiber fabric was observed, the resin material was scattered and fixed on the surface of the fabric substrate. Further, the resin material did not fall off from the fabric base material due to the shear deformation.

Then, from the wound reinforcing fiber woven fabric, a test piece having a size of 250 mm × 45 mm is used so that the direction of 45 ° becomes the major axis direction when the directions of warp and weft are 0 ° and 90 °, respectively. Cut out. Next, 50 mm each of both ends in the major axis direction of the test piece was fixed with a jig, and attached to the measuring apparatus via the jigs at both ends. The reinforcing fiber fabric was fixed so that the portion fixed by the jig was not deformed in the width direction, and the exposed portion between the jigs at both ends was set to 150 mm in the major axis direction and 45 mm in the width direction. . In addition, Shimadzu Corporation autograph AGS-100 was used for the measuring apparatus.
Thereafter, a non-fiber axial tensile test is performed by pulling the test piece in the major axis direction through a jig, and the tensile strain (corresponding to the displacement of the tensile test apparatus) of the test piece is 5% (tensile test apparatus displacement 7.5 mm). The load was continuously measured until reaching) to obtain the relationship between the strain of the test piece and the load. In addition, since it is thought that there is variation in the measured value, three test pieces are prepared, and each test piece has a strain of 1% (tensile test apparatus displacement 1.5 mm) and 5% (tensile test apparatus displacement 7. The maximum load until reaching 5 mm) was read, and the average of the three test pieces was taken as the maximum value of the load at each tensile strain.

  As a result of measurement according to this procedure, the maximum value (average value of three sheets) applied until the tensile strain reaches 1% is 0.24 N, and the tensile strain is applied until the tensile strain reaches 5%. The maximum load (average value of 3 sheets) is 0.5. N.

  Subsequently, four rectangles having a size of 500 mm × 400 mm were cut out from the reinforcing fiber fabric. At this time, when the directions of the sides of the rectangle are 0 ° and 90 °, respectively, the fiber axis directions are approximately 0 and 90 °, and two are approximately ± 45 ° and the two are approximately ± 45 °. . The cut-out reinforcing fiber woven fabric was laminated with the upper surface of the reinforcing fiber woven fabric having the resin material adhered to the lower side and the other surface to which the resin material adhered was laminated. In addition, the upper and lower two sheets have a fiber axis direction of 0 ° / 90 ° direction, and the two inner layers have a fiber axis direction of ± 45 ° direction. The obtained laminated body was arrange | positioned on the shaping type | mold heated at 90 degreeC. In addition, as a shaping type | mold, the thing which has the groove | channel which draws a curve with a plane dimension of 450 mm x 350 mm, depth of 40 mm, and slope angle of 45 degrees was used.

  Next, the laminate was sandwiched between the shaping mold and the facing shaping mold heated to 90 ° C., and a pressure of 0.4 MPa was applied to the laminate for 5 minutes. In addition, it took about 10 seconds for the laminated body to be sandwiched between the two shaping molds after being arranged on the shaping mold.

  When the facing shaping mold was removed and the laminated body cooled by blowing cold air was taken out of the shaping mold, the laminated body was deformed into a shape along the shape of the shaping mold and the shape was fixed. In addition, wrinkles were not generated on the surface of the laminate provided with the shape. The layers of the laminate were not peeled off, the three-dimensionally deformed shape was stable, and even when the end portion was grabbed and lifted, it was not deformed. That is, the preform obtained by this method does not have wrinkles on the surface, develops a shape as it is shaped, and is excellent in that it does not deform from the shape. It was very preferable as a reform.

  This preform was placed on the lower mold of the RTM molding double-sided mold maintained at 100 ° C., the upper mold was closed, and the air in the mold was discharged with a vacuum pump. Next, a liquid epoxy resin was injected into the mold at an injection pressure of 0.5 MPa, impregnated into the preform, and left for 20 minutes. In this way, a fiber reinforced resin molded product was obtained. The resin is a liquid epoxy resin obtained by mixing a main agent: “Epicoat (registered trademark)” 828 (manufactured by Yuka Shell Epoxy Co., Ltd., epoxy resin) and a curing agent: blend TR-C35H (imidazole derivative) manufactured by Toray. Was used.

  In the obtained fiber reinforced resin molded product, the resin was sufficiently spread throughout and cured, and there was no portion where the reinforcing fiber bundle was exposed without being impregnated with the resin. Further, the texture of the reinforcing fiber woven fabric visible on the surface of the molded article has a smooth surface with no significant disturbance and no wrinkles, and was excellent as a fiber reinforced resin molded article.

Example 2:
The same reinforcing fiber fabric as in Example 1 was laminated in the same laminated configuration (size: 500 mm × 400 mm, number of laminated sheets: 4).

  This laminate was placed on a single-sided shaping mold having the same shape as in Example 1 and kept at room temperature, and then a 2 mm thick silicon rubber sheet was placed over the shaping mold and the laminate, and shaped. The mold and the sheet were brought into close contact with a sealant tape. As a result, the space surrounded by the shaping mold and the sheet became a sealed space in which the laminate was confined. Next, air in the sealed space was discharged using a vacuum pump, and the laminate was pressed against the shaping mold by atmospheric pressure through the sheet. In this state, hot water was allowed to flow through the piping provided in the shaping mold to raise the shaping mold to 90 ° C. and held for 5 minutes. When the sheet was removed from the shaping mold and the laminated body cooled by blowing cold air was removed from the shaping mold, the laminated body was deformed into a shape along the shape of the shaping mold and the shape was fixed. In addition, wrinkles were not generated on the surface of the laminate provided with the shape. The layers of the laminate were not peeled off, the three-dimensionally deformed shape was stable, and even when the end portion was grabbed and lifted, it was not deformed. That is, the preform obtained by this method does not have wrinkles on the surface, develops a shape as it is shaped, and is excellent in that it does not deform from the shape. It was very preferable as a reform.

  Next, the preform was impregnated and cured in the same manner as in Example 1 to obtain a fiber-reinforced resin molded product. In the obtained fiber reinforced resin molded product, the resin was sufficiently spread throughout and cured, and there was no portion where the reinforcing fiber bundle was exposed without being impregnated with the resin. Further, the texture of the reinforcing fiber woven fabric visible on the surface of the molded article has a smooth surface with no significant disturbance and no wrinkles, and was excellent as a fiber reinforced resin molded article.

Example 3:
A reinforced fiber fabric having resin particles fixed thereto was prepared in the same manner as in Example 1 except that the amount of the resin material fixed to the surface of the fabric substrate was 10 g / m ^2. Gave. When the surface of the obtained reinforcing fiber fabric was observed, the resin material was scattered and fixed on the surface of the fabric substrate. Further, the resin material did not fall off from the fabric base material due to the shear deformation.

This reinforcing fiber fabric was subjected to the same non-fiber axial tensile test as in Example 1. As a result, the maximum value of the load applied until the tensile strain reaches 1% (average value of three sheets) is 0.24 N, and the maximum value of the load applied until the tensile strain reaches 5% (3 The average value of the sheets was 0.55N.
This reinforcing fiber fabric was laminated by the same method as in Example 1, and the laminate was deformed by the same method using the same shaping mold as in Example 1. As a result, the laminated body was deformed into a shape along the shape of the shaping mold, and the shape was fixed. In addition, wrinkles were not generated on the surface of the laminate provided with the shape. The layers of the laminate were not peeled off, the three-dimensionally deformed shape was stable, and even when the end portion was grabbed and lifted, it was not deformed. That is, the preform obtained by this method does not have wrinkles on the surface, develops a shape as it is shaped, and is excellent in that it does not deform from the shape. It was very preferable as a reform.

  Next, the preform was impregnated and cured in the same manner as in Example 1 to obtain a fiber-reinforced resin molded product. In the obtained fiber reinforced resin molded product, the resin was sufficiently spread throughout and cured, and there was no portion where the reinforcing fiber bundle was exposed without being impregnated with the resin. Further, the texture of the reinforcing fiber woven fabric visible on the surface of the molded article has a smooth surface with no significant disturbance and no wrinkles, and was excellent as a fiber reinforced resin molded article.

Example 4:
BT70-20 manufactured by Toray Industries, Inc. (woven structure: plain weave, fabric weight: 213 g / m ² , warp weave density: 3.27 / 25 mm, weft weave density: 3.27 / 25 mm) A reinforced fiber fabric was prepared in the same manner as in Example 1 except that. In addition, the reinforcing fiber bundle used for this bidirectional fabric base material is Toray Industries, Inc. carbon fiber T700S-12K (number of filaments: 12,000, tensile modulus: 230 GPa, tensile strength: 4.9 GPa, Fineness: 800 tex, breaking elongation: 2.1%).

A deformation history similar to that of Example 1 was given to this reinforcing fiber fabric. When the surface of the obtained reinforcing fiber fabric was observed, the resin material was scattered and fixed on the surface of the fabric substrate. Further, the resin material did not fall off from the fabric base material due to the shear deformation.
This reinforcing fiber fabric was subjected to the same non-fiber axial tensile test as in Example 1. As a result, the maximum value of the load applied until the tensile strain reaches 1% (average value of three sheets) is 0.17 N, and the maximum value of the load applied until the tensile strain reaches 5% (3 The average value of the sheets was 0.4N.

  This reinforcing fiber fabric was laminated by the same method as in Example 1, and the laminate was deformed by the same method using the same shaping mold as in Example 1. As a result, the laminated body was deformed into a shape along the shape of the shaping mold, and the shape was fixed. In addition, wrinkles were not generated on the surface of the laminate provided with the shape. The layers of the laminate were not peeled off, the three-dimensionally deformed shape was stable, and even when the end portion was grabbed and lifted, it was not deformed. That is, the preform obtained by this method does not have wrinkles on the surface, develops a shape as it is shaped, and is excellent in that it does not deform from the shape. It was very preferable as a reform.

  Next, the preform was impregnated and cured in the same manner as in Example 1 to obtain a fiber-reinforced resin molded product. In the obtained fiber reinforced resin molded product, the resin was sufficiently spread throughout and cured, and there was no portion where the reinforcing fiber bundle was exposed without being impregnated with the resin. Further, the texture of the reinforcing fiber woven fabric visible on the surface of the molded article has a smooth surface with no significant disturbance and no wrinkles, and was excellent as a fiber reinforced resin molded article.

Example 5:
A preform was formed in the same manner as in Example 1 except that the reinforcing fiber fabric was laminated and the laminate was deformed as follows.

  As a shaping mold, it has a first recess that draws a curve with a plane dimension of 450 mm × 350 mm, a depth of 30 mm, and a slope angle of 45 °, and further has a depth of 30 mm and a slope angle from the bottom of the first recess. Using a shaping mold having a second recess of 45 °, the laminate was disposed thereon. At this time, the temperature of the shaping mold was 90 ° C. Next, the laminate was pressed against the second recess and pressed using a partial mold having the same shape as the second recess of the shaping mold and heated to 90 ° C. After that, an opposing shaping die having the same shape as the first concave portion similarly heated to 90 ° C. is installed, and a pressure of 0.4 MPa is applied to the entire laminate including the portion not pressurized by the partial die. Added for 5 minutes. The time required from placing the laminated body on the shaping mold to installing the opposing shaping mold and pressurizing the entire laminated body was about 15 seconds. After that, the opposing shaping mold and partial mold were removed, and the laminated body cooled by blowing cold air was taken out of the shaping mold, and the laminated body was shaped in accordance with the shape of the shaping mold having two recesses. It was deformed and its shape was fixed. In addition, wrinkles were not generated on the surface of the laminate provided with the shape. The layers of the laminate were not peeled off, the three-dimensionally deformed shape was stable, and even when the end portion was grabbed and lifted, it was not deformed. That is, the preform obtained by this method does not have wrinkles on the surface, develops a shape as it is shaped, and is excellent in that it does not deform from the shape. It was very preferable as a reform.

  Next, the resin was impregnated and cured in the same manner as in Example 1 except that the shape of the mold used for this preform was different, and a fiber-reinforced resin molded product was obtained. As the mold, a mold having a first concave portion and a second concave portion was used in the same manner as the preform. In the obtained fiber reinforced resin molded product, the resin was sufficiently spread throughout and cured, and there was no portion where the reinforcing fiber bundle was exposed without being impregnated with the resin. Further, the texture of the reinforcing fiber woven fabric visible on the surface of the molded article has a smooth surface with no significant disturbance and no wrinkles, and was excellent as a fiber reinforced resin molded article.

Example 6
A reinforced fiber fabric having resin particles fixed thereto was prepared in the same manner as in Example 1 except that the amount of the resin material fixed to the surface of the fabric substrate was 3 g / m ^2. Gave. When the surface of the obtained reinforcing fiber fabric was observed, the resin material was scattered and fixed on the surface of the fabric substrate. Further, the resin material did not fall off from the fabric base material due to the shear deformation.

This reinforcing fiber fabric was subjected to the same non-fiber axial tensile test as in Example 1. As a result, the maximum value of the load applied until the tensile strain reaches 1% (average value of three sheets) is 0.23 N, and the maximum value of the load applied until the tensile strain reaches 5% (3 The average value of the sheets was 0.5N.
This reinforcing fiber fabric was laminated by the same method as in Example 1, and the laminate was deformed by the same method using the same shaping mold as in Example 1. As a result, the laminated body was deformed into a shape along the shape of the shaping mold, and the shape was fixed. In addition, wrinkles were not generated on the surface of the laminate provided with the shape. The layers of the laminate were not peeled off, the three-dimensionally deformed shape was stable, and even when the end portion was grabbed and lifted, it was not deformed. That is, the preform obtained by this method does not have wrinkles on the surface, develops a shape as it is shaped, and is excellent in that it does not deform from the shape. It was very preferable as a reform.

  Next, the preform was impregnated and cured in the same manner as in Example 1 to obtain a fiber-reinforced resin molded product. In the obtained fiber reinforced resin molded product, the resin was sufficiently spread throughout and cured, and there was no portion where the reinforcing fiber bundle was exposed without being impregnated with the resin. Further, the texture of the reinforcing fiber woven fabric visible on the surface of the molded article has a smooth surface with no significant disturbance and no wrinkles, and was excellent as a fiber reinforced resin molded article.

Comparative Example 1:
A reinforced fiber fabric (resin material fixing amount: 5 g / m ² ) was produced in the same manner as in Example 1 except that no shear deformation in the in-plane direction was given.
This reinforcing fiber fabric was subjected to the same non-fiber axial tensile test as in Example 1. As a result, the maximum value of the load applied until the tensile strain reaches 1% (average value of three sheets) is 1.5 N, and the maximum value of the load applied until the tensile strain reaches 5% (3 The average value of the sheets was 2.2N.
This reinforcing fiber fabric was laminated by the same method as in Example 1, and the laminate was deformed by the same method using the same shaping mold as in Example 1. As a result, the texture of the reinforced fiber fabric is often disturbed on the surface of the deformed laminate, and a large number of wrinkles are generated particularly in the portion where the three-dimensional deformation becomes large, and the shape is as expected. It was not deformed. On the other hand, the layers of the laminate were not peeled off, and were not deformed even when they were grabbed and lifted. That is, the preform obtained by this method is excellent in that the shape does not deform, but a large number of wrinkles are generated on the surface, and the shape along the shaping mold is not expressed. It was not resistant to use as a preform for resin molded products.

  Next, the preform was impregnated and cured in the same manner as in Example 1 to obtain a fiber-reinforced resin molded product. In the obtained fiber reinforced resin molded product, the resin was spread over almost the whole, but the resin was not sufficiently impregnated in the portion where the laminate was thick due to wrinkles, and a reinforced fiber bundle was exposed. In addition, the resin layer was partially thickened at the periphery, and the surface was not smooth accordingly. Furthermore, there was a great disturbance in the texture of the reinforcing fiber fabric visible on the surface. That is, the obtained fiber reinforced resin molded article was not durable.

Comparative Example 2:
The same reinforcing fiber fabric as in Comparative Example 1 (resin material fixing amount: 5 g / m ² ) was laminated in the same laminated configuration.

  This laminate was deformed by the same method using the same shaping mold as in Example 2. As a result, the texture of the reinforced fiber fabric is often disturbed on the surface of the deformed laminate, and a large number of wrinkles are generated particularly in the portion where the three-dimensional deformation becomes large, and the shape is as expected. It was not deformed. On the other hand, the layers of the laminate were not peeled off, and were not deformed even when the end was grabbed and lifted. That is, the preform obtained by this method is excellent in that the shape does not deform, but a lot of wrinkles are generated on the surface, and the shape along the shaping mold is not expressed, so that the fiber reinforcement It was not resistant to use as a preform for resin molded products.

  Next, the preform was impregnated and cured in the same manner as in Example 1 to obtain a fiber-reinforced resin molded product. In the obtained fiber reinforced resin molded product, the resin was spread over almost the whole, but the resin was not sufficiently impregnated in the portion where the laminate was thick due to wrinkles, and a reinforced fiber bundle was exposed. In addition, the resin layer was partially thickened at the periphery, and the surface was not smooth accordingly. Furthermore, there was a great disturbance in the texture of the reinforcing fiber fabric visible on the surface. That is, the obtained fiber reinforced resin molded article was not durable.

Comparative Example 3:
A reinforced fiber fabric (resin material fixing amount: 10 g / m ² ) was produced in the same manner as in Example 3 except that no shear deformation was applied in the in-plane direction.

   This reinforcing fiber fabric was subjected to the same non-fiber axial tensile test as in Example 1. As a result, the maximum value of the load applied until the tensile strain reaches 1% (average value of three sheets) is 2.6 N, and the maximum value of the load applied until the tensile strain reaches 5% (3 The average value of the sheets was 3.5N.

  This reinforcing fiber fabric was laminated by the same method as in Example 1, and the laminate was deformed by the same method using the same shaping mold as in Example 1. As a result, the texture of the reinforced fiber fabric is often disturbed on the surface of the deformed laminate, and a large number of wrinkles are generated particularly in the portion where the three-dimensional deformation becomes large, and the shape is as expected. It was not deformed. On the other hand, the layers of the laminate were not peeled off, and were not deformed even when they were grabbed and lifted. That is, the preform obtained by this method is excellent in that the shape does not deform, but a large number of wrinkles are generated on the surface, and the shape along the shaping mold is not expressed. It was not resistant to use as a preform for resin molded products.

  Next, the preform was impregnated and cured in the same manner as in Example 1 to obtain a fiber-reinforced resin molded product. In the obtained fiber reinforced resin molded product, the resin was spread over almost the whole, but the resin was not sufficiently impregnated in the portion where the laminate was thick due to wrinkles, and a reinforced fiber bundle was exposed. In addition, the resin layer was partially thickened at the periphery, and the surface was not smooth accordingly. Furthermore, there was a great disturbance in the texture of the reinforcing fiber fabric visible on the surface. That is, the obtained fiber reinforced resin molded article was not durable.

Comparative Example 4:
A reinforced fiber fabric (resin material fixing amount: 5 g / m ² ) was produced in the same manner as in Example 4 except that no shear deformation in the in-plane direction was given.

  As a result of conducting a non-fiber axial tensile test similar to Example 1 on this reinforced fiber fabric, the maximum load (average value of three sheets) applied until the tensile strain reached 1% was 0.90 N. The maximum value of the load applied until the tensile strain reached 5% (average value of 3 sheets) was 1.2N.

  This reinforcing fiber fabric was laminated by the same method as in Example 1, and the laminate was deformed by the same method using the same shaping mold as in Example 1. As a result, the texture of the reinforced fiber fabric is often disturbed on the surface of the deformed laminate, and a large number of wrinkles are generated particularly in the portion where the three-dimensional deformation becomes large, and the shape is as expected. It was not deformed. On the other hand, the layers of the laminate were not peeled off, and were not deformed even when they were grabbed and lifted. That is, the preform obtained by this method is excellent in that the shape does not deform, but a large number of wrinkles are generated on the surface, and the shape along the shaping mold is not expressed. It was not resistant to use as a preform for resin molded products.

  Next, the preform was impregnated and cured in the same manner as in Example 1 to obtain a fiber-reinforced resin molded product. In the obtained fiber reinforced resin molded product, the resin was spread over almost the whole, but the resin was not sufficiently impregnated in the portion where the laminate was thick due to wrinkles, and a reinforced fiber bundle was exposed. In addition, the resin layer was partially thickened at the periphery, and the surface was not smooth accordingly. Furthermore, there was a great disturbance in the texture of the reinforcing fiber fabric visible on the surface. That is, the obtained fiber reinforced resin molded article was not durable.

Comparative example: 5
A non-fiber axial tensile test was carried out in the same manner as in Example 1 without fixing the resin material to the same bi-directional textile substrate as in Example 1 and without giving shear deformation in the in-plane direction. went. As a result, the maximum value of the load applied until the tensile strain reaches 1% (average value of three sheets) is 0.22 N, and the maximum value of the load applied until the tensile strain reaches 5% (3 The average value of the sheets was 0.45N.

  This textile base material was laminated by the same method as in Example 1, and the laminate was deformed by the same method using the same shaping mold as in Example 1. In addition, since the resin material is not fixed to the woven fabric base material, the direction of the surface when laminating is not limited.

  When the facing shaping mold was removed, the laminate was deformed without wrinkles into a shape that conformed to the shape of the shaping mold. When the laminated body cooled by blowing cold air was taken out from the shaping mold, the layers of the laminated body were not adhered at all, the shape of the laminated body collapsed, and the shape along the shaping mold could not be maintained at all It was.

  In this method, even if the woven base material is deformed into a three-dimensional shape, the layers cannot be maintained because the layers do not adhere to each other, and the fabric substrate cannot be used as a preform for a fiber-reinforced resin molded product.

Comparative example: 6
A reinforced fiber fabric having resin particles fixed thereto was prepared in the same manner as in Example 1 except that the amount of the resin material fixed to the surface of the bidirectional fabric base was 60 g / m ² . A deformation history is given. When the surface of the obtained reinforcing fiber fabric was observed, there were many cases where adjacent point-shaped resin materials were bonded to each other, and the surface of the fabric base material was widely covered with the resin material. Further, the resin material did not fall off from the fabric base material due to the shear deformation.

  This reinforcing fiber fabric was subjected to the same non-fiber axial tensile test as in Example 1. As a result, the maximum value of the load applied until the tensile strain reaches 1% (average value of three sheets) is 1.3 N, and the maximum value of the load applied until the tensile strain reaches 5% (3 The average value of the sheets was 2.1N.

  This reinforcing fiber fabric was laminated by the same method as in Example 1, and the laminate was deformed by the same method using the same shaping mold as in Example 1. As a result, the texture of the reinforced fiber fabric is often disturbed on the surface of the deformed laminate, and a large number of wrinkles are generated particularly in the portion where the three-dimensional deformation becomes large, and the shape is as expected. It was not deformed. The interlayer of the laminate was not peeled off, and it did not deform even when it was grabbed and lifted. That is, the preform obtained by this method is excellent in that the shape does not deform, but a large number of wrinkles are generated on the surface, and the shape along the shaping mold is not expressed. It was not resistant to use as a preform for resin molded products.

  Next, the preform was impregnated and cured in the same manner as in Example 1 to obtain a fiber-reinforced resin molded product. The obtained fiber reinforced resin molded product is partially impregnated and cured with resin, but there are many portions where the fiber bundle is exposed without spreading the resin. As it did not endure use.

  By using the reinforced fiber fabric of the present invention, a member having a three-dimensional shape can be shaped efficiently and satisfactorily, and as a result, the productivity and quality of the fiber reinforced resin molded product can be improved. Therefore, the present invention can be widely applied in the fields of automobiles, aircraft, ships, home appliances, OA equipment, building materials, and the like. Of course, the application of the present invention is not limited to these.

It is a plane schematic diagram which shows the reinforced fiber fabric by which the resin material was fixed to the surface. It is a cross-sectional schematic diagram which shows the reinforced fiber fabric by which the resin material was fixed to the surface. It is a plane schematic diagram which shows the test piece shape of a non-fiber axial direction tensile test. It is a plane schematic diagram which shows the reinforced fiber fabric deform | transformed by the non-fiber axial direction tensile test. It is a plane schematic diagram which shows the reinforced fiber fabric by which the resin material adhered to the surface in large quantities. It is a plane schematic diagram which shows the reinforced fiber fabric by which the resin material was fixed to the surface. It is a cross-sectional schematic diagram which shows the reinforced fiber fabric by which the resin material was fixed to the surface. It is a schematic plan view showing a reinforcing fiber fabric in which a resin material is fixed only to a part of reinforcing fiber bundles. It is a cross-sectional schematic diagram which shows the reinforced fiber fabric in which the resin material adheres to only some of the reinforced fiber bundles. It is a plane schematic diagram which shows the reinforced fiber fabric provided with the shear deformation. It is a side surface schematic diagram which shows the one aspect | mode of the method which deform | transforms a laminated body into the shape along a shaping type | mold, and pressurizes and heats. It is a side surface schematic diagram which shows another aspect of the method of changing a laminated body into the shape along a shaping type | mold, and pressurizing and heating. It is a side surface schematic diagram which shows another aspect of the method of changing a laminated body into the shape along a shaping type | mold, and pressurizing and heating. It is a side surface schematic diagram which shows another aspect of the method of changing a laminated body into the shape along a shaping type | mold, and pressurizing and heating. It is a side surface schematic diagram which shows another aspect of the method of changing a laminated body into the shape along a shaping type | mold, and pressurizing and heating. It is a schematic perspective view which shows one aspect | mode of the mechanism which rocks a textile fabric base material in the width direction. It is a schematic perspective view which shows another aspect of the mechanism in which a textile fabric base material is rock | fluctuated in the width direction. It is a schematic perspective view which shows another aspect of the mechanism in which a textile fabric base material is rock | fluctuated in the width direction. It is a schematic front view which shows another aspect of the mechanism which rocks a textile fabric base material in the width direction.

Explanation of symbols

11 Resin Material Adhering Across Two Reinforcing Fiber Bundles of Fabric Base 12 Resin Material Adhering Across Three Reinforcing Fiber Bundles of Textile Base 13 Only One Reinforcing Fiber Bundle of Textile Base Fixed resin material 14 Reinforcing fiber bundle (warp yarn) that constitutes the fabric base material
15 Reinforcing fiber bundles (wefts) composing the fabric base material
31 Test piece 41 of fabric base material Test piece mounting part 42 Test piece 51 of fabric base material Resin material 81 fixed to the surface of the fabric base material Resin material 111 fixed only to a part of the reinforcing fiber bundles Lower mold)
112 Shaped mold (upper mold)
113 Laminated body 121 Molding mold 122 Laminated body 123 Sheet 124 Sealing material 125 Chamber box 126 Vacuum pump 127 Pressurizing device 131 Molding mold (lower mold)
132 Shaped mold (upper mold)
133 Laminated body 134 Partial mold 135 Heating means 141 Shaping mold (lower mold)
142 Shaped mold (upper mold)
143 Laminated body 144 Projectable movable part 145 Heating means 151 Shaped mold 152 Laminated body 153 Sheet 154 Sealing material 155 Partial mold 156 Heater 157 Vacuum pump 158 Pressure device 159 Chamber box 161 End gripping swing mechanism 162 Textile base material Unwinding mechanism 163 Woven fabric winding mechanism 164 Woven fabric substrate 171 Nip swing mechanism 181 Swing roll 182 Conveying roll θ Shear deformation angle

Claims (7)

A reinforced fiber fabric in which a resin material is fixed to at least one surface of a fabric base material including a plurality of reinforcing fiber bundles, wherein the fabric base material is a bidirectional fabric and constitutes the fabric base material By changing the relative position of the plurality of reinforcing fiber bundles, the resin material fixed across the two or more reinforcing fiber bundles is peeled off from a part of the two or more reinforcing fiber bundles, and the non-fiber axis A reinforcing fiber fabric in which the maximum value of the load until the tensile strain by the directional tensile test reaches 1% is in the range of 0.01 to 0.75N.   The reinforcing fiber fabric according to claim 1, wherein the maximum value of the load until the tensile strain by the non-fiber axial direction tensile test reaches 5% is in the range of 0.1 to 1.0N. Amount sticking of the resin material is 1 to 50 g / ^{m 2,} reinforcing fiber woven fabric according to claim 1 or 2.   The reinforcing fiber fabric according to any one of claims 1 to 3, wherein the resin material contains a thermoplastic resin as a main component.   The reinforcing fiber fabric according to any one of claims 1 to 4, wherein the reinforcing fiber bundle is a carbon fiber bundle. After fixing the resin material to at least one surface of the fabric base material including a plurality of reinforcing fiber bundles, the relative position of the plurality of reinforcing fiber bundles constituting the fabric base material is changed to provide two By removing the resin material fixed across the above-mentioned reinforcing fiber bundles from a part of the two or more reinforcing fiber bundles, the load until the tensile strain in the non-fiber axial tensile test reaches 1% The manufacturing method of the reinforced fiber fabric whose maximum value exists in the range of 0.01-0.75N .   The method for producing a reinforced fiber fabric according to claim 6, wherein the relative position of a plurality of reinforcing fiber bundles constituting the woven fabric base material is changed by applying a shear deformation of 5 to 45 ° to the woven fabric base material. .

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