JP2018079630A - Carbon fiber composite decorative plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a carbon fiber composite decorative plate which is excellent in incombustibility, has good shaping of three-dimensional bending shape, and is lightweight.SOLUTION: There are provided carbon fiber composite decorative plates 10A and 10B in which a core material 11 where a melamine resin foam having open cells is impregnated with a phenol resin and the phenol resin is cured in a compressive state of the melamine resin foam, a fiber reinforcement material 21 where a carbon fiber fabric is impregnated with the phenol resin and the phenol resin is cured, and a face material 31 formed of a woven cloth formed of a heat-resistant log fiber yarn coated with a fluororesin are laminated and integrated, where a resin ratio specified by resin ratio={(weight of melamine resin foam+weight of phenol resin in carbon fiber composite decorative plate)÷(weight of carbon fiber composite decorative plate excluding weight of face material)}×100 is 40-70%.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a carbon fiber composite decorative board having a good three-dimensional bent shape.

  Conventionally, molded articles of fiber reinforced composite materials (FRP) using glass fibers, carbon fibers, etc. have been partially used for interior parts, etc., for vehicle members such as railway vehicles, because of the demand for weight reduction. . Furthermore, depending on the use part, the vehicle member may need to be shaped into a three-dimensional bent shape, in which case the appearance of the surface of the three-dimensional bent shape portion does not deteriorate. Is required. In addition, the vehicle member is also required to be nonflammable and lightweight.

  In Patent Document 1, a melamine resin metal decorative plate in which a melamine resin layer having a surface decorative layer and a core material layer, an adhesive layer, and a metal layer are laminated in this order is subjected to a bending formability test of JIS K 6902 (A Example of performing the method) is described.

  Patent Document 2 discloses a metal core double-sided cosmetic that is formed by superimposing a fiber base material impregnated with a thermosetting resin on both surfaces of a metal plate, and further superimposing a fiber base material impregnated with a melamine resin on each surface, followed by heat and pressure molding. The example which measured the bending resistance by JISK6902 about what used organic or inorganic fiber nonwoven fabrics, such as polyester fiber, for one or both of the melamine resin impregnation fiber base materials of both surfaces in a board is indicated. .

  However, in the bending formability test (Method A) of JIS K 6902 described in Patent Document 1 and Patent Document 2, a specimen placed on a jig in which a V-shaped groove is formed is viewed from above the groove. Since it was pushed and bent, the bending portion of the test specimen became one place, and it was only possible to determine two-dimensional bending, and it was not possible to determine the practically required three-dimensional bending.

JP 2014-208453 A Japanese Patent Application Laid-Open No. 07-266497

  This invention is made | formed in view of the said point, Comprising: It aims at provision of the carbon fiber composite decorative board which is excellent in nonflammability, is good in the shaping of a three-dimensional bending shape, and is lightweight.

  The invention of claim 1 is a carbon comprising a core material, a fiber reinforcing material laminated on both surfaces of the core material, and a face material laminated on the surface of at least one of the fiber reinforcing materials on both surfaces. In the fiber composite decorative board, the core material is obtained by impregnating a melamine resin foam having open cells with a phenol resin and curing the phenol resin in a compressed state of the melamine resin foam. The carbon fiber woven fabric is made by impregnating and curing a phenol resin, the face material is a woven fabric made of heat-resistant long fiber yarn coated with a fluororesin, and the core material forms a single layer. The core material, the fiber reinforcing material, and the face material are bonded by curing the phenol resin impregnated in the melamine resin foam of the core material and the phenol resin impregnated in the carbon fiber fabric of the fiber reinforcing material. , Resin ratio = {(weight of melamine resin foam + weight of phenolic resin in carbon fiber composite decorative board) / (weight of carbon fiber composite decorative board excluding weight of face material)} × 100 Is 40 to 70%. The invention according to claim 1 is a carbon fiber composite decorative board in which a laminated member is integrally shaped during compression molding using a phenol resin having a resin ratio represented by the above formula of 40 to 70% as an adhesive. . When the molding process is integrally performed, the core material made of the melamine resin foam is compressed, and the adhesive that is the phenol resin forms a bonding layer with the core material, and fluorine The face material, which is a woven fabric made of heat-resistant long fiber yarns coated with a resin, also includes a step in which the adhesive is laminated and cured to form an adhesive layer. That is, in the integrally molded product that has undergone the plurality of steps, the melamine resin foam becomes a compressed core material to form one layer. After the molding, the core material as the layer for supplying the adhesive made of the melamine resin foam impregnated with the phenol resin no longer performs the function, and the integrally molded product according to the invention of claim 1 is formed after the molding. Even if expressed in the structure of, such a function cannot be expressed. Therefore, the invention of claim 1 cannot be specified directly by its structure or characteristics, and can be specified for the first time by a process (production method) for obtaining a polymerized composition.

  The invention according to claim 2 is characterized in that, in claim 1, the total number of the fiber reinforcing members laminated on both surfaces of the core material is 2 to 10.

  The invention of claim 3 is the invention according to claim 1 or 2, wherein the carbon fiber composite decorative board has a breaking load (in accordance with JIS K7074) of 100 N or more and 850 N or less, and a specific gravity (in accordance with JIS K7112) of 0.50 to 1.10. It is characterized by being.

  Invention of Claim 4 has the shaping part shape | molded three-dimensionally in the said carbon fiber composite decorative board in any one of Claim 1 to 3, The convex part of the said shaping part, or The curvature radius at the top of the recess is 3 mm or more.

  The invention of claim 5 is characterized in that in any one of claims 1 to 4, the material combustibility test for railway vehicles (a test based on Ordinance No. 151 of the Ministry of Land, Infrastructure, Transport and Tourism) passes nonflammability.

  According to the sixth aspect of the present invention, a phenol resin is impregnated with a melamine resin foam having open cells and the phenol resin is cured in a state in which the melamine resin foam is compressed, and the carbon fiber fabric has a phenol resin. It consists of an impregnated and hardened fiber reinforcing material and a face material composed of a woven fabric made of heat-resistant long fiber yarns coated with a fluororesin, and one or more of the fiber reinforcing materials are laminated on both sides of the core material. A carbon fiber composite decorative board in which the face material is laminated on a surface of at least one of the fiber reinforcement materials on both sides, and the core material, the fiber reinforcement material, and the face material are laminated and integrated. In the production method, a phenol resin is added to one or both of a melamine resin foam having an open cell and a carbon fiber fabric, and a resin ratio = {(weight of melamine resin foam + feature in a carbon fiber composite decorative board. Impregnation step of impregnating so that the resin ratio specified by the weight of the carbon resin) ÷ (weight of the carbon fiber composite decorative board excluding the weight of the face material)} × 100 is in the range of 40 to 70%; After the step, a plurality of the carbon fiber fabrics are stacked on both sides of the melamine resin foam, and a face material is stacked on at least one of the carbon fiber fabrics stacked on both sides of the melamine resin foam. A lamination process, and the laminate obtained in the lamination process is deep-drawn with a mold and shaped three-dimensionally, the laminate is heated in a compressed state to cure the phenol resin, and the phenol A deep drawing forming step of integrating the melamine resin foam, the carbon fiber fabric, and the face material by curing the resin is performed.

  The present invention relating to a carbon fiber composite decorative board, the core material comprises a core material in which a phenol resin is impregnated with a melamine resin foam having open cells and the phenol resin is cured in a compressed state of the melamine resin foam, A woven fabric composed of heat-resistant long fiber yarns, which are composed of carbon fiber fabrics impregnated and hardened with a phenolic resin, and the face material laminated on the fiber reinforcement material is covered with fluororesin. The resin ratio is 40 to 70%, so that it can pass the nonflammability of the rail vehicle material flammability test, and the three-dimensional bending shape is good and lightweight. Therefore, the flame retardant is passed without using a means such as adding a flame retardant or using a metal member.

  The present invention relating to a method for producing a carbon fiber composite decorative board is to produce a lightweight carbon fiber composite decorative board that can pass the non-combustibility of the material flammability test for railway vehicles and has good three-dimensional bending shape shaping. Can do.

It is a fragmentary perspective view of 1st Embodiment of the carbon fiber composite decorative board in this invention. It is a fragmentary perspective view of 2nd Embodiment of the carbon fiber composite decorative board in this invention. It is partial sectional drawing of 1st Embodiment and 2nd Embodiment in this invention. It is a figure which shows the process of one Embodiment of the manufacturing method in this invention. It is a table | surface which shows the result of the structure and external appearance of an Example and a comparative example, an elasticity modulus, a fracture load, a flammability test, and specific gravity.

Hereinafter, the carbon fiber composite decorative board and the manufacturing method thereof of the present invention will be described with reference to the drawings.
A carbon fiber composite decorative board 10A according to the first embodiment of the present invention shown in FIG. 1 includes a core material 11 and two layers of fiber reinforcement laminated and integrated on both surfaces of the core material 11 as shown in FIG. 21 and 21 and a face material 31 laminated and integrated on the surface of the outermost fiber reinforcing material 21, and has a shaped portion 11A shaped three-dimensionally. In the shaping portion 11A, the convex shape side is the design surface side (see FIG. 1), and the opposite concave shape side is the back surface side.

  A carbon fiber composite decorative board 10B according to the second embodiment of the present invention shown in FIG. 2 includes a core material 11 and two layers of fiber reinforcement laminated and integrated on both surfaces of the core material 11 as shown in FIG. 21 and 21 and a face material 31 laminated and integrated on the surface of the outermost fiber reinforcing material 21, and has a shaped part 11B shaped three-dimensionally. In the shaping portion 11B, the concave shape side is a design surface (see FIG. 2), and the opposite convex shape side is a back surface.

  The carbon fiber composite decorative board 10A of the first embodiment and the carbon fiber composite decorative board 10B of the second embodiment are suitable as members for railway vehicles. As a member for rail vehicles, ceiling materials, lining materials (wall materials, etc.), window frame materials, and the like can be given.

The core material 11 is composed of a single layer, and is obtained by impregnating a melamine resin foam having open cells with a phenol resin and curing the phenol resin in a compressed state of the melamine resin foam. The core material 11 may be a single sheet or a single layer formed by laminating a plurality of melamine resin foams having open cells. The melamine resin foam is suitable as a constituent material of the core material 11 because the resin alone has good flame retardancy. Although the original thickness before compression of the said melamine resin foam changes with thickness of the said carbon fiber composite decorative board 10A, 10B, 3-50 mm is mentioned, for example. The melamine resin foam preferably has a density before compression of 5 to 15 kg / m ³ from the viewpoints of easy compression, impregnation, light weight, and rigidity.

The fiber reinforcing material 21 is made of a carbon fiber woven fabric impregnated with a phenol resin and cured.
The carbon fiber woven fabric is excellent in light weight, strength, and high rigidity, and in particular, a weaving method in which the fibers are not only in one direction is preferable, for example, a plain weave, a twill weave, a satin weave composed of warp and weft The above-described woven fabric obtained by weaving a triaxial weave composed of three-direction yarns and a spread yarn is preferable. The carbon fiber fabric preferably has a fiber weight of 90 to 400 g / m ² in view of impregnation with phenol resin, rigidity, and strength. The carbon fiber fabric constituting the fiber reinforcing material 21 may be laminated on one or more layers on both surfaces of the core material 11. If the number of laminated layers is increased too much, the carbon fiber composite decorative board becomes heavy and it is difficult to form a good three-dimensional shape. Therefore, the more preferable number of laminated layers is 2 to 10. Further, it is preferable that the number of laminated layers is equal on both surfaces of the core material 11 in terms of preventing rigidity and strength of the carbon fiber composite decorative board 10, improving flame retardancy, and deformation over time after molding.

  The phenol resin impregnated in the melamine resin foam and the carbon fiber fabric enhances the rigidity and strength of the carbon fiber composite decorative board 10 and flame retardancy by curing after impregnation.

The face material 31 is composed of a woven fabric made of heat-resistant long fiber yarns coated with a fluororesin.
The heat-resistant long fiber yarn is obtained by forming a heat-resistant long fiber into a yarn shape. Examples of the heat-resistant long fibers include polyimide fibers, aromatic polyamide fibers, carbon fibers, graphitized fibers, and flame-resistant fibers. The heat-resistant long fiber is not limited to one type, and a plurality of types may be combined.
Fluororesin is composed of polytetrafluoroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluorovinyl ether copolymer, polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoro. An ethylene copolymer etc. can be mentioned.

  As an example, an embodiment in which the face material 31 is provided on both sides of a carbon fiber composite decorative board is shown, but when used as an interior material of a housing or a vehicle, etc., only on one side of the carbon fiber composite decorative board. There are many embodiments (not shown) provided. Moreover, when the said face material 31 is provided only in the one side of a carbon fiber composite decorative board, it is provided in the design surface side.

  The core material 11, the fiber reinforcing material 21, and the face material 31 are formed by curing the phenol resin impregnated in the melamine resin foam of the core material 11 and the phenol resin impregnated in the carbon fiber fabric of the fiber reinforcing material 21. Glued.

The phenolic resin contained in the carbon fiber composite decorative boards 10A and 10B increases the rigidity of the carbon fiber composite decorative boards 10A and 10B, and the adhesive integration of the core material 11, the fiber reinforcing material 21, and the face material 31, and Has the effect of imparting incombustibility. If the amount of the phenolic resin is too small, the rigidity and adhesion integrity will decrease. On the other hand, if the amount is too large, the nonflammability test may not pass. It also oozes out and looks bad.
The amount of the phenol resin is preferably such that the resin ratio in the laminated portion including the core material 11 excluding the face material and the laminated fiber reinforcing material 21 is 40 to 70%.
This resin ratio is shown by the following formula. Resin ratio = {(weight of melamine resin foam + weight of phenol resin in carbon fiber composite decorative board) / (weight of carbon fiber composite decorative board excluding weight of face material)} × 100.

  The three-dimensionally shaped shaping portions 11A and 11B are three-dimensionally convex (in the case of the carbon fiber composite decorative board 10A) or concave shape (in the case of the carbon fiber composite decorative board 10B) by deep drawing. The curvature radius at the top 11Aa of the convex part or the top part 11Bb of the concave part is 3 mm or more. By setting the radius of curvature to 3 mm or more, it is possible to prevent a problem that impairs the appearance such as wrinkles and cracks in the shaped portions 11A and 11B of the face material 31.

  The carbon fiber composite decorative boards 10A and 10B according to the embodiment have a box shape with one side opened, and the corner portions (corner portions) are formed by the three-dimensional shaped portions 11A and 11B. Yes. The three-dimensionally shaped shaping portions 11A and 11B are not limited to the shape of the corner portion, but are shaped according to the members formed of the carbon fiber composite decorative board. For example, a hemispherical convex portion or concave portion formed on a part of the plane may be used.

The carbon fiber composite decorative boards 10A and 10B pass the nonflammability of the railway vehicle material flammability test (non-metallic material for railway vehicles). The present invention relates to a ministerial ordinance Article 83, 2. Applicable to passenger cars and passenger linings, and can be used for passenger cars such as ordinary passenger cars, subways, Shinkansen passenger cars, and special railways.
Further, the carbon fiber composite decorative boards 10A and 10B have a modulus of elasticity (JIS K7074-1988 A method) of 10 GPa or more and a breaking load (JIS K7074 conformity) of 100 N or more and 850 N in order to maintain the strength as a railcar member. It is preferable that: In addition, the specific gravity (conforming to JIS K7112) is preferably about 0.50 to 1.10. That is, the specific strength which is the breaking load with respect to the specific gravity was calculated by [specific strength = breaking load / specific gravity]. The specific strength is preferably 100 to 1015.

The manufacturing method of the carbon fiber composite decorative board of the present invention will be described. The method for producing a carbon fiber composite decorative board includes an impregnation process, a lamination process, and a deep drawing process.
In the impregnation step, one or both of the melamine resin foam and carbon fiber fabric having open cells are impregnated with the phenol resin. In order to efficiently impregnate the entire core material and fiber reinforcing material with the phenol resin, it is preferable to impregnate both the melamine resin foam and the carbon fiber fabric with the phenol resin. In the following example, a case where both a melamine resin foam and a carbon fiber fabric are impregnated with a phenol resin is shown. Moreover, the melamine resin foam to be used has a thickness (thickness before compression) of 3 to 50 mm and a density (density before compression) of 5 to 15 kg / in terms of ease of compression, impregnation, lightness, and rigidity. Those of m ³ are preferred.

As shown in (4-1) shown in FIG. 4, the impregnation step includes two types of impregnation step A and impregnation step B.
In the impregnation step A, the melamine resin foam 110A having open cells is impregnated with the phenol resin 110B to obtain an impregnated melamine resin foam 110C.
On the other hand, in the impregnation step B, the carbon fiber fabric 210A is impregnated with the phenol resin 210B to form the impregnated carbon fiber fabric 210C.

The carbon fiber woven fabric 210A is impregnated with the phenol resin 210B on the number of carbon fiber woven fabrics corresponding to the number of carbon fiber woven fabrics laminated on both surfaces of the core material 110A. The phenol resins 110B and 210B at the time of impregnation are made of an uncured liquid. In order to facilitate impregnation, the phenol resins 110B and 210B are preferably dissolved in a solvent. After impregnation, the impregnated melamine resin foam 110C and the impregnated carbon fiber fabric 210C are subjected to a curing reaction of the phenol resin. By drying at a temperature that does not occur, the solvent is removed from the impregnated melamine resin foam 110C and the impregnated carbon fiber fabric 210C. The impregnation means is performed by an appropriate method such as a method of immersing the melamine resin foam or carbon fiber fabric in a tank containing a liquid phenolic resin, a method of spraying, or a method of using a roll coater. The amount of phenol resin impregnated is adjusted by passing it through two squeezing rollers with gaps appropriately adjusted. Excess phenolic resin can be squeezed by passing a melamine resin foam having open cells impregnated with phenolic resin and a carbon fiber fabric impregnated with phenolic resin through two squeezing rollers with appropriate adjustment of the gap, Furthermore, the phenol resin can be uniformly dispersed in the melamine resin foam having an open cell and the carbon fiber fabric.
In this embodiment, the solvent system is obtained by dissolving a phenol resin in a solvent, but it may be performed in a water system in which a phenol resin is dissolved in water.

  The impregnation of the melamine resin foam 110A with the phenol resin 110B and the impregnation of the carbon fiber fabric 210A with the phenol resin 210B are as follows: Resin ratio = {(Melamine resin foam weight + phenol resin in the carbon fiber composite decorative board ) (Weight of carbon fiber composite decorative board excluding weight of face material)} × 100, the resin ratio specified is 40 to 70%. Specifically, the weight of the melamine resin foam before impregnation, the weight of the entire carbon fiber fabric (total number of laminated layers) before impregnation, the weight of the melamine resin foam after impregnation (after drying), and after the impregnation (after drying) Measure the weight of the entire carbon fiber fabric (total number of layers) and the weight of the face material, calculate the resin ratio using the measured values, and adjust the resin ratio to be 40 to 70%. Manufacture of carbon fiber composite decorative board. In addition, the weight of the phenol resin in the carbon fiber composite decorative board in the formula of the resin ratio is [the entire carbon fiber fabric after impregnation (after drying) excluding the weight of the face material that can be converted from the basis weight of the face material (total lamination) Number) weight-weight of the entire carbon fiber fabric before impregnation (total number of laminated layers)], and the weight of the carbon fiber composite decorative board is measured after measuring the carbon fiber composite decorative board. It is the weight excluding the weight of the face material that can be converted from the amount.

  In the laminating step (4-2) shown in FIG. 4, a plurality of impregnated carbon fiber fabrics 210C are laminated on both surfaces of the impregnated melamine resin foam 110C, and the impregnated carbon fiber fabric of the outermost layer is further disposed. A face material 310C is laminated on the surface of 210C to form a laminate 100C. The number of layers of the impregnated carbon fiber fabric 210C is equalized on both surfaces of the impregnated melamine resin foam 110C. The face material 310C is made of a woven fabric made of heat-resistant long fiber yarns coated with a fluororesin. When the face material 310C is provided only on one side, the face material 310C is laminated only on the surface of the outermost layer of the impregnated carbon fiber fabric 210C on one side of the impregnated melamine resin foam 110C. The impregnated melamine resin foam 110C, the impregnated carbon fiber woven fabric 210C and the face material 310C preferably have the same plane size, but if they are different, after the deep drawing process described later, Final trimming.

  In the deep drawing step (4-3) shown in FIG. 4, the laminate 100C is three-dimensionally shaped by deep drawing with a lower die 41 and an upper die 43 of a press molding die, Compress and heat. The lower die 41 is formed with a deep drawing recess 42. Further, the upper die 43 is formed with a deep drawing convex portion 44 that faces the deep drawing concave portion 42 of the lower die 41. In addition, when the surface shaped by the mold surface of the lower mold 41 is a design surface (in the case of the carbon fiber composite decorative board 10A of the first embodiment), the deep drawing concave portion 42 of the lower mold 41 is used. The curvature radius of the top is set to 3 mm or more. On the other hand, when the surface formed by the mold surface of the upper mold 43 is a design surface (in the case of the carbon fiber composite decorative board 10B of the second embodiment), the deep-drawing convex portion of the upper mold 43 No. 44 is set such that the radius of curvature of the top is 3 mm or more.

The compression ratio in the deep drawing step is 200 to 1500%, particularly preferably 300 to 1000%. The compression rate is defined as {(thickness of melamine resin foam before compression−thickness of core material) ÷ thickness of core material} × 100. The thickness of the core material is the thickness of the core material in the produced carbon fiber composite decorative board.
In addition, the carbon fiber composite decorative board is actually manufactured by changing the interval between the lower mold 41 and the upper mold 43, and the compression ratio is calculated from the obtained carbon fiber composite decorative board to obtain the target compression ratio. Find the space between the lower mold 41 and the upper mold 43. During the deep drawing process, a spacer is installed at an appropriate position between the lower die 41 and the upper die 43, and a predetermined interval (predetermined compression thickness of the laminate) is provided between the lower die 41 and the upper die 43. Like that.
The heating method is not particularly limited, but it is easy to perform heating through the lower mold 41 and the upper mold 43 by providing heating means such as a heater in the lower mold 41 and the upper mold 43. The heating temperature is set to be equal to or higher than the curing reaction temperature of the impregnated phenol resin.

  By the compression in the deep drawing process, the phenol resin of the impregnated carbon fiber fabric 210C and the phenol resin of the impregnated melamine resin foam 110C are reliably in contact. And by the heating in the deep drawing process, the phenol resin of the impregnated melamine resin foam 110C and the phenol resin of the impregnated carbon fiber fabric 210C start a curing reaction, respectively, the compressed state of the laminate 100C, that is, the The impregnated melamine resin foam 110C is cured in a compressed state. Thereby, the core material 110 is formed from the impregnated melamine resin foam 110C, and the fiber reinforcing material 210 is formed from the impregnated carbon fiber fabric 210C. The core material 11 and the fiber reinforcing material 21 The face material 31 is integrated by curing the phenol resin. Thereafter, the heat compression is released to obtain the carbon fiber composite decorative board 10.

Furthermore, the present invention is expressed as follows when providing the carbon fiber composite decorative board having a good three-dimensional bending shape with a woven cloth as a face material and a lightweight carbon fiber composite decorative board. The That is, according to another aspect of the present invention, there is provided a fiber reinforced molded body in which a surface material that can be decorated is laminated on at least one surface, a surface material of a woven fabric made of a heat-resistant long fiber yarn coated with a fluororesin, and The first fiber reinforcing material made of carbon fiber woven fabric laminated on one side of the face material and the foam laminated on the surface of the fiber reinforcing material on which the face material is not laminated are compression-shaped and free of bubbles. A core material composed of a melamine resin layer, and a second fiber reinforcement material composed of a carbon fiber woven fabric, laminated on a surface of the core material on which the fiber reinforcement material is not laminated,
The face material, the first fiber reinforcing material, the core material, and the second fiber reinforcing material are carbon fiber composite decorative boards that are impregnated and cured with a phenol resin adhesive.
Furthermore, the said phenol resin adhesive is the said carbon fiber composite decorative board which forms an adhesive layer between said 1st fiber reinforcement material and the said face material, without oozing out into the said face material. The carbon fiber composite decorative board is a carbon fiber composite decorative board provided with at least one top portion or concave portion formed of at least three planes and covered with a face material.

As the phenol resin, Sumitomo Bakelite Co., Ltd., product name: PR-55791B, resin concentration 60 wt% ethanol solution was used. A plain-woven carbon fiber fabric (manufactured by Toho Tex Co., Ltd., product name; W-3101, fiber weight 200 g / m ² ) is soaked in this phenolic resin, taken out, air-dried at room temperature of 25 ° C. for 2 hours, and further 60 The carbon fiber woven fabric impregnated by drying for 1 hour in an atmosphere at 0 ° C. was formed in accordance with the number of laminated fiber reinforcing materials in the examples and comparative examples shown in the table of FIG. In addition, [the number of laminated fiber reinforcing materials] in the table of FIG. 5 is the total number of laminated laminates of the molded bodies arranged evenly on the front and back sides. The carbon fiber woven fabric was cut into a plane size of 200 × 300 mm (weight 12 g / sheet, thickness 0.23 mm). The impregnated carbon fiber fabric after drying was 22 g per sheet. The amount of impregnation was adjusted by passing the carbon fiber woven fabric taken out from the phenol resin through two squeezing rollers with adjusted gaps.

Further, a melamine resin foam having an open cell thickness of 5 mm (manufactured by BASF, product name: Bathotect G, density 9 kg / m ³ ) was cut into a plane size of 200 × 300 mm, and phenol was obtained in the same manner as the carbon fiber fabric. After being immersed in the resin solution and taken out, it was naturally dried at room temperature of 25 ° C. for 2 hours and further dried in an atmosphere of 60 ° C. for 1 hour to form an impregnated melamine resin foam.
As a face material made of a woven fabric made of heat-resistant long fiber yarn coated with a fluororesin, I.K. S. T-made, Istoflon non-combustible cloth was used.
Weight of melamine resin foam before impregnation, weight of entire carbon fiber fabric before impregnation (total number of laminated layers), weight of melamine resin foam after impregnation (after drying), whole carbon fiber fabric after impregnation (after drying) The weight of (total number of layers) and the weight of the face material are measured, and the resin ratio calculated using the measured values is shown in the table of FIG.

  Next, as a die for iron press molding in which a mold release agent is previously applied to the surface, a three-dimensional deep drawing concave portion having a top radius of curvature of 3 mm (in the comparative example 4, a radius of curvature of 1.5 mm). A lower mold having concave mold surfaces at four corners, an upper mold corresponding to the lower mold, a melamine resin foam after impregnation (after drying), a carbon fiber fabric after impregnation (after drying), The face material was deep-drawn with a lower mold and an upper mold in a state of being laminated as shown in (4-3) of FIG. Deep drawing is performed by pressing the laminated body with a lower mold and an upper mold at a surface pressure of 10 MPa at 150 ° C. for 10 minutes, compressing to form three-dimensionally and heating, The phenolic resin was reacted and cured. The heating at that time was performed by a cast heater attached to the lower mold and the upper mold. Further, an iron spacer having a thickness equal to the [product plate thickness] shown in the table of FIG. 5 is interposed between the lower mold and the upper mold to adjust the interval between the lower mold and the upper mold, that is, the compression thickness of the laminate. . Thereafter, the lower mold and the upper mold were opened, and carbon fiber composite decorative boards of Examples and Comparative Examples in which the fiber reinforcing material and the face material were laminated and integrated on both surfaces of the core material were obtained. The obtained carbon fiber composite decorative board has a box shape (depth 10 mm × length 150 × width 250 mm) with one side opened, and three-dimensionally shaped portions (deep-drawn molded portions) are formed at the four corners. Have.

For each example and each comparative example, the fiber reinforcement ratio (%) and the compression ratio (%) were calculated. The reinforcing material ratio (%) is the ratio (%) of the thickness of the entire fiber reinforcing material to the carbon fiber composite decorative board.
About the carbon fiber composite decorative board of each example and each comparative example, visual observation of the appearance of the shaped part (deep drawing molded part) shaped with a curvature radius of the mold of 3.0 mm, thickness (product thickness), Specific gravity (JIS K7112 compliant), flexural modulus (JIS K7074-1988 A method), fracture load (JIS K7074 compliant) were measured, and railcar material flammability tests were performed. The measurement results are shown in the table of FIG.

In the visual observation of the appearance, the presence or absence of wrinkles, cracks, or phenol resin exudation was determined with respect to the appearance of the outer surface and the inner surface including the shaped portion (deep drawing portion) of the carbon fiber composite decorative board.
As for the thickness of the carbon fiber composite decorative board (product board thickness), the thickness of the flat portion was measured with a digital micrometer. The thickness of the carbon fiber composite decorative board (product board thickness) was equal to the distance between the lower mold for press molding and the upper mold.
The rail vehicle material flammability test was conducted according to the 2016 new method.

  In Example 1, the thickness of the carbon fiber composite decorative board is 2 mm, the number of laminated fiber reinforcements on each side of the core material is 2, the total number of front and back is 4, the fiber reinforcement ratio is 46.0%, and the compression ratio is 363%. , Resin ratio 60.0%, mold radius of curvature is 3.0mm, no appearance problem of shaped part (deep drawing part), elastic modulus 20GPa, breaking load 210N, flammability test passed nonflammable, specific gravity Was 0.81.

  Example 2 is the same production conditions as in Example 1 except that the resin ratio is 68.0%, and the measurement results show no appearance problem of the shaped part (deep-drawn part), elastic modulus 24 GPa, breaking load 230 N, flammability test passed nonflammability, specific gravity was 1.08.

  Example 3 is the same production conditions as in Example 1 except that the resin ratio is 42.9%, and the measurement result is no appearance problem of the shaped part (drawing part deep drawing part), The elastic modulus was 15 GPa, the breaking load was 170 N, the flammability test was non-combustible, and the specific gravity was 0.60.

  In Example 4, the thickness of the carbon fiber composite decorative board is 3 mm, the number of laminated fiber reinforcements on each side of the core material is 2, the total number of front and back is 4, the fiber reinforcement ratio is 30.7%, the compression ratio is 381%, The resin ratio is 66.7%, the radius of curvature of the mold is 3.0 mm, the measurement result is no appearance problem of the shaped part (deep drawing part), the elastic modulus is 17 GPa, the breaking load is 180 N, and the flammability test is nonflammable. The specific gravity was 0.65.

  In Example 5, the thickness of the carbon fiber composite decorative board is 3 mm, the number of laminated fiber reinforcements on each side of the core material is 5, the total number of front and back 10 sheets, fiber reinforcement ratio 76.7%, compression ratio 614%, The resin ratio is 44.4%, the radius of curvature of the mold is 3.0 mm, the measurement results are no appearance problems of the shaped part (deep drawing part), the elastic modulus is 25 GPa, the breaking load is 520 N, and the flammability test is nonflammable. The specific gravity was 0.98.

  In Example 6, the thickness of the carbon fiber composite decorative board is 3 mm, the number of laminated fiber reinforcements on each side of the core material is 3, the total number of front and back is 6, fiber reinforcement ratio is 46.0%, compression rate is 209%, The resin ratio is 60.0%, the radius of curvature of the mold is 3.0 mm, the measurement results are no appearance problems of the shaped part (deep drawing part), the elastic modulus is 18 GPa, the breaking load is 300 N, and the flammability test is nonflammable. The specific gravity was 0.81.

  In Example 7, the thickness of the carbon fiber composite decorative board is 5 mm, the number of laminated fiber reinforcements on each side of the core material is 5, the total number of front and back 10 sheets, the fiber reinforcement ratio 46.0%, the compression ratio 270%, The resin ratio is 60.0%, the radius of curvature of the mold is 3.0 mm, the measurement results are no appearance problems of the shaped part (deep drawing part), the elastic modulus is 20 GPa, the breaking load is 840 N, and the flammability test is nonflammable The specific gravity was 0.83.

  In Example 8, the thickness of the carbon fiber composite decorative board is 1 mm, the number of laminated fiber reinforcements on each side of the core material is 1, the total number of front and back is 2, the fiber reinforcement ratio is 46.0%, the compression ratio is 826%, The resin ratio is 66.7%, the radius of curvature of the mold is 3.0 mm, the measurement results are no appearance problems of the shaped part (deep drawing part), the elastic modulus is 20 GPa, the breaking load is 110 N, and the flammability test is nonflammable. The specific gravity was 1.06.

  Thus, each of the carbon fiber composite decorative boards of Examples 1 to 8 passed the non-flammability test, had a good appearance at the shaped part (deep drawing part), and had a specific gravity of 0.60 to 1. .08 and light weight. Although an example where the radius of curvature of the mold is larger than 3 mm is not shown, it is well known that if the radius of curvature of the mold is increased, wrinkles and tears are less likely to occur. -8, the carbon fiber composite decorative board obtained even if the radius of curvature of the mold is 3 mm or more has a good appearance in the shaped part (deep drawing part).

  Comparative Example 1 was manufactured under the same conditions as in Example 1 except that the resin ratio was 71.4%, and the measurement result was a molded part (deep drawing part) and the resin was applied to the face material. It exuded and had a poor appearance. Since the appearance was poor, other tests were not tested.

  Comparative Example 2 was manufactured under the same conditions as in Example 1 except that the resin ratio was 38.4%, and the measurement result was that the resin was applied to the face material at the shaped part (deep drawing part). It exuded and had a poor appearance. Since the appearance was poor, other tests were not tested.

  In Comparative Example 3, the thickness of the carbon fiber composite decorative board is 2 mm, the number of laminated fiber reinforcements on each side of the core material is 1, the total number of front and back is 2, the fiber reinforcement ratio is 23.0%, and the compression ratio is 225% The resin ratio was 71.4%, the radius of curvature of the mold was 3.0 mm, and the resin exuded into the face material at the shaped part (deep drawing part), resulting in poor appearance. Since the appearance was poor, other tests were not tested.

  In Comparative Examples 1 to 3, since the resin ratio is out of the range of the present invention, the resin exudes to the face material at the shaping part (deep drawing part). It is not suitable for members that require aesthetics.

  As described above, the carbon fiber composite decorative board of the present invention can pass the noncombustibility of the material flammability test for railway vehicles, has a good three-dimensional bent shape, and is lightweight.

10A, 10B Carbon fiber composite decorative plate 11A, 11B Three-dimensionally shaped shaped part 11 Core material 21 Fiber reinforcing material 31 Face material 41 Lower mold 43 Upper mold 100C Laminate 110A Melamine resin foam 110B Phenolic resin 110C Impregnated melamine resin foam 210A Carbon fiber fabric 210B Phenolic resin 210C Impregnated carbon fiber fabric

Claims (6)

In a carbon fiber composite decorative board comprising a core, a fiber reinforcement laminated on both sides of the core, and a face laminated on the surface of at least one of the fiber reinforcements on both sides,
The core material is obtained by impregnating a melamine resin foam having open cells with a phenol resin and curing the phenol resin in a compressed state of the melamine resin foam,
The fiber reinforcing material consists of a carbon fiber fabric impregnated and cured with a phenol resin,
The face material is a woven fabric made of heat-resistant long fiber yarns coated with a fluorine resin,
The core material forms one layer,
The core material, the fiber reinforcing material, and the face material are bonded by curing the phenol resin impregnated in the melamine resin foam of the core material and the phenol resin impregnated in the carbon fiber fabric of the fiber reinforcing material,
Resin ratio = {(weight of melamine resin foam + weight of phenol resin in carbon fiber composite decorative board) ÷ (weight of carbon fiber composite decorative board excluding weight of face material)} × 100 A carbon fiber composite decorative board characterized by being 40 to 70%.   2. The carbon fiber composite decorative board according to claim 1, wherein the number of all the fiber reinforcements laminated on both surfaces of the core material is 2 to 10 sheets.   The carbon fiber composite makeup according to claim 1 or 2, wherein the carbon fiber composite decorative board has a breaking load (conforming to JIS K7074) of 100N or more and 850N or less and a specific gravity (conforming to JIS K7112) of 0.50 to 1.10. Board   The carbon fiber composite decorative board has a three-dimensionally shaped shaping portion, and a curvature radius at a top of the convex portion or the concave portion of the shaping portion is 3 mm or more. To 5. The carbon fiber composite decorative board according to any one of 3 to 4.   The carbon fiber composite decorative board according to any one of claims 1 to 4, wherein the carbon fiber composite decorative board passes the nonflammability test of the material flammability test for railway vehicles. A core material in which a phenol resin is impregnated in a melamine resin foam having open cells, and the phenol resin is cured in a state in which the melamine resin foam is compressed, and a fiber reinforcing material in which a carbon fiber fabric is impregnated and cured with a phenol resin; And a face material composed of a woven fabric made of heat-resistant long fiber yarns coated with a fluororesin, and at least one fiber reinforcing material is laminated on both sides of the core material, A method for producing a carbon fiber composite decorative board in which the face material is laminated on the surface of at least one fiber reinforcing material of the material, and the core material, the fiber reinforcing material, and the face material are laminated and integrated,
Either one or both of the melamine resin foam and carbon fiber woven fabric having open cells, the resin ratio = {(weight of melamine resin foam + weight of phenol resin in the carbon fiber composite decorative board) / (surface The weight of the carbon fiber composite decorative board excluding the weight of the material)} impregnation step for impregnation so that the resin ratio defined by × 100 is in the range of 40 to 70%;
After the impregnation step, a plurality of the carbon fiber fabrics are laminated on both sides of the melamine resin foam, and a face material is applied to at least one of the carbon fiber fabrics arranged on both sides of the melamine resin foam. A laminating process for laminating;
The laminate obtained in the laminating step is deep-drawn with a mold and shaped three-dimensionally, and the laminate is heated in a compressed state to cure the phenol resin, and by curing the phenol resin A deep drawing process for integrating the melamine resin foam, the carbon fiber fabric and the face material;
A method for producing a carbon fiber composite decorative board, comprising:

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