JP6823738B2 - Fiber reinforced molded product and its manufacturing method - Google Patents

Description

The present invention relates to a fiber-reinforced molded product composed of a core material and a fiber reinforcing material laminated on both sides of the core material, and a method for producing the same.

Conventionally, metal materials such as iron and aluminum are generally used as vehicle members for railway vehicles and the like. However, due to the demand for weight reduction, a fiber reinforced composite material (FRP) molded body using glass fiber, carbon fiber, or the like is partially adopted for the interior material of the vehicle.
Further, as the vehicle member, a material that is hard to burn is basically used, and a nonflammable material is required depending on the part used. Some nonflammable fiber composite materials are described in Patent Documents 1 and 2.
In addition, there is one described in Patent Document 3 as a fiber-reinforced molded product suitable for a housing of a portable device such as a notebook computer.

Patent Document 1 discloses a fiber-reinforced phenol resin molded product using a flame retardant consisting of 3 to 8 parts by weight of sodium metaborate with respect to 1 part by weight of boric acid as a flame retardant.
In Patent Document 2, a fiber-reinforced molding material formed by impregnating carbon fiber or metal fiber having a thermal conductivity of 100 W / m · K or more with a matrix resin is arranged on at least one surface, and the Ordinance No. 151 of the Ministry of Land, Infrastructure, Transport and Tourism Disclosed are vehicle components that have been prevented from igniting in tests compliant with.
Patent Document 3 discloses a fiber-reinforced molded product composed of a laminate of a core material and a fiber-reinforced reinforcing material that are cured in a compressed state by impregnating a thermosetting resin foam having open cells with a thermosetting resin. ing.

However, the fiber-reinforced phenolic resin molded product of Cited Document 1 uses sodium metaborate as a flame retardant, and there is a problem that the addition of the flame retardant is complicated and the product cost increases.
The vehicle member of Reference 2 uses carbon fibers or metal fibers having a high thermal conductivity of 100 W / m · K or more, and such carbon fibers having a high thermal conductivity are very expensive. On the other hand, when metal fibers are used, there is a problem that the product weight increases, which is not preferable for vehicle members.
The fiber-reinforced fiber molded product of Patent Document 3 is insufficient for vehicle members in terms of nonflammability and high rigidity.

Japanese Unexamined Patent Publication No. 10-237185 Japanese Unexamined Patent Publication No. 2005-14449 Japanese Unexamined Patent Publication No. 2011-93175

The present invention has been made in view of the above points, and is a fiber having nonflammability suitable for vehicle members, high rigidity, high strength, and lightweight without using a flame retardant that increases costs. The purpose is to provide a reinforced molded product.

The invention of claim 1 is a fiber reinforced molded body composed of a core material and a fiber reinforcing material laminated on both sides of the core material. The core material is a melamine resin foam having open cells impregnated with a phenol resin. The phenol resin is cured in the compressed state of the melamine resin foam, and the fiber reinforcing material is made of a carbon fiber woven fabric impregnated with the phenol resin and cured, and the core material and the fiber reinforcing material Is integrated by curing the phenol resin impregnated in the melamine resin foam of the core material and the phenol resin impregnated in the carbon fiber woven fabric of the fiber reinforcing material, and the fiber reinforced molded body is formed on both sides of the core material. Two or more layers of the carbon fiber woven fabric are laminated, the thickness of the fiber reinforced plastic body is 1.5 to 5 mm, and the phenol resin specified by the following formula (A1) in the fiber reinforced plastic body. The ratio is 40 to 70%, and the fiber reinforced plastic body has a bending elasticity (JIS K 7074-1988 A method) of 30 GPa or more and a specific gravity (JIS K7112 compliant) of 0.70 to 1.30. It is characterized by having nonflammability in a test in accordance with the Ministry of Transport Ordinance No. 151.

The invention of claim 2 is characterized in that, in claim 1, the ratio of the thickness of the entire fiber reinforcing material to the fiber reinforced molded product is 30 to 80%.

The invention of claim 3 is characterized in that, in claim 1 or 2, the thickness of the fiber-reinforced molded product is 2 to 5 mm.

The invention of claim 4 is characterized in that, in any one of claims 1 to 3, the specific gravity of the fiber-reinforced molded product (in accordance with JIS K7112) is 0.70 to 1.25.

The invention of claim 5 is characterized in that, in any one of claims 1 to 4, the fiber reinforced reinforcing material has the same number of laminated carbon fiber woven fabrics on both sides of the core material.

The invention of claim 6 is characterized in that, in any one of claims 1 to 5, the fiber-reinforced molded product does not contain a flame retardant.

In the invention of claim 7, a melamine resin foam having open cells is impregnated with a phenol resin, and the phenol resin is cured in a state where the melamine resin foam is compressed, and the carbon fiber woven fabric is covered with the phenol resin. A method for producing a fiber-reinforced molded body in which the fiber reinforcing material is laminated and integrated on both sides of the core material, which is composed of an impregnated and cured fiber reinforcing material, and is a melamine resin foam having open cells and a thickness of 3 to 50 mm. The carbon fiber woven fabric has two or more layers on both sides of the melamine resin foam after the impregnation step of impregnating either one or both of the body and the carbon fiber woven fabric with the phenol resin and the impregnation step. It is composed of a laminating step of obtaining a laminated body by arranging a plurality of laminated bodies as described above and a compression heating step of compressing and heating the laminated body, and the impregnation in the impregnation step has a resin ratio defined by the following formula (A1). The compression is performed so as to be in the range of 40 to 70%, and the compression in the compression heating step is performed by compressing so that the compression ratio defined by the following formula (B1) is 200 to 1500%. The phenol resin is cured to form the core material and the fiber reinforcing material in a state where the melamine resin foam of the laminated body is compressed, and the core material and the fiber reinforcing material are integrated to strengthen the fiber. The thickness of the molded body is 1.5 to 5 mm, the bending elastic coefficient (JIS K 7074-1988 A method) of the fiber-reinforced molded body is 30 GPa or more, and the specific gravity (JIS K7112 compliant) is 0.70 to 1.30. It is characterized by producing a nonflammable fiber-reinforced molded product in a test in accordance with Ordinance No. 151 of the Ministry of Land, Infrastructure, Transport and Tourism.

The invention of claim 8 is characterized in that, in claim 7, the ratio of the thickness of the entire fiber reinforcing material to the fiber reinforced molded product is 30 to 80%.

The invention of claim 9 is characterized in that, in claim 7 or 8, the thickness of the fiber-reinforced molded product is 2 to 5 mm.

The invention according to claim 10 is characterized in that, in any one of claims 7 to 9, the specific gravity of the fiber-reinforced molded product (in accordance with JIS K7112) is 0.70 to 1.25.

The invention of claim 11 is characterized in that, in the laminating step according to any one of claims 7 to 10, the number of laminated carbon fiber woven fabrics is made equal on both sides of the melamine resin foam. The fiber-reinforced molded product according to any one of 10.

The invention of claim 12 is characterized in that the compression ratio is 300 to 1000% in the compression heating step according to any one of claims 7 to 11.

The present invention relating to a fiber-reinforced molded product has a flexural modulus (JIS K 7074-1988 A method) of 30 GPa or more and a specific gravity (JIS K7112 compliant) of 0.70 to 1.30, which is an Ordinance of the Ministry of Land, Infrastructure, Transport and Tourism. Since it has nonflammability in a test conforming to No. 151, a fiber reinforced molded product having high rigidity, high strength, and light weight, which has nonflammability suitable for vehicle members, can be obtained. Furthermore, since no flame retardant is required, cost reduction can be realized.

The present invention relating to a method for producing a fiber-reinforced molded product has a flexural modulus (JIS K 7074-1988 A method) of 30 GPa or more and a specific gravity (JIS K7112 compliant) of 0.70 to 1.30. It is possible to manufacture nonflammable fiber-reinforced molded products in tests in accordance with the Ordinance No. 151 of the Ministry of Land, Infrastructure, Transport and Tourism, and it has nonflammable properties suitable for vehicle members, and is highly rigid, strong, and lightweight fiber reinforced. The molded product can be manufactured at low cost without using a flame retardant.

It is sectional drawing of one Embodiment of the fiber-reinforced molded article in this invention. It is a figure which shows the process of one Embodiment of the manufacturing method in this invention.

Hereinafter, the fiber-reinforced molded product of the present invention and a method for producing the same will be described with reference to the drawings.
The fiber-reinforced molded body 10 according to the embodiment of the present invention shown in FIG. 1 is composed of a core material 11 and a fiber reinforcing material 21 laminated and integrated on both sides of the core material 11 for vehicles such as railroad vehicles. It is suitable for members. Examples of vehicle members include ceiling materials, lining materials (wall materials, etc.), window frame materials, and the like. The fiber-reinforced molded product 10 does not contain a flame retardant.

The illustrated fiber-reinforced molded body 10 is formed of a plate having a predetermined plane size, has a thickness of 1.5 to 5 mm, and has a ratio of the total thickness of the fiber-reinforced material 21 to the fiber-reinforced molded body 10 of 30 to 80%. , The flexural modulus (JIS K 7074-1988 A method) is 30 GPa or more, the breaking load (JIS K7074 compliant) is 200 N or more, and the specific gravity (JIS K7112 compliant) is 0.70 to 1.30. It is nonflammable in the test according to No.

If the thickness of the fiber-reinforced molded product 10 is less than 1.5 mm, the strength is insufficient, while if it exceeds 5 mm, the lightness is insufficient. Further, if the ratio of the thickness of the entire fiber reinforcing material 21 to the fiber reinforced molded body 10 is less than 30%, the breaking load is reduced and the material is not suitable as a vehicle member. On the other hand, if the ratio of the thickness of the entire fiber reinforcing material 21 to the fiber reinforced molded body 10 exceeds 80%, the weight becomes lacking and it becomes a factor of cost increase.

The total thickness of the fiber reinforcing material 21 is the total thickness of the fiber reinforcing materials 21 laminated on both sides of the core material 11. The ratio Z (%) of the thickness of the entire fiber reinforcing material 21 to the fiber reinforced molded body 10 is calculated by the following formula.
Z (%) = total thickness of fiber reinforced plastic / thickness of fiber reinforced molded product x 100
The total thickness of the fiber-reinforced reinforcing material may be calculated by subtracting the thickness of the core material 11 from the thickness of the fiber-reinforced molded body 10. Further, since the total thickness of the fiber-reinforced reinforcing material is equal to the total thickness of the carbon fiber woven fabric used for the fiber-reinforced reinforcing material 21, as will be described later, the total thickness of the carbon fiber woven fabric used. The ratio Z (%) of the thickness of the entire fiber reinforcing material 21 to the fiber reinforced molded body 10 may be calculated using the value.

Since the fiber-reinforced molded product 10 has a flexural modulus of 30 GPa or more, it has a rigidity suitable for a vehicle member, and since a breaking load of 200 N or more, it has a strength suitable for a vehicle member.
Further, since the fiber-reinforced molded product 10 has a specific gravity of 0.70 to 1.30, it is excellent in light weight and is a suitable material as a member for a vehicle.
Further, the fiber-reinforced molded product 10 is a material suitable as a vehicle member because it has nonflammability in a test in accordance with Ordinance No. 151 of the Ministry of Land, Infrastructure, Transport and Tourism. As for the judgment of the test based on the Ordinance No. 151 of the Ministry of Land, Infrastructure, Transport and Tourism, the judgment of "nonflammable" has the highest flame retardancy. The fiber-reinforced molded product 10 of the present invention is judged to be "nonflammable" with the highest flame retardancy.

The core material 11 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 melamine resin foam is suitable as a constituent material of the core material 11 because the resin itself has good flame retardancy. The original thickness of the melamine resin foam before compression varies depending on the thickness of the fiber-reinforced molded product 10, and examples thereof include 3 to 50 mm. Further, the melamine resin foam preferably has a density of 5 to 15 kg / m ³ before compression from the viewpoint of ease of compression, impregnation property, 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. In particular, a woven fabric in which the fibers are not only in one direction is preferable. For example, plain weave, twill weave, satin weave, and which are composed of warp and weft threads. A triaxial weave composed of threads in three directions is suitable. Further, the carbon fiber woven fabric preferably has a fiber weight of 90 to 400 g / m ² from the viewpoint of impregnation with phenol resin, rigidity and strength. The carbon fiber woven fabric constituting the fiber reinforcing material 21 is laminated on both sides of the core material 11 in two or more layers, and the number of layers is the same on both sides of the core material 11. It is preferable in terms of rigidity, strength improvement, and flame retardancy of 10. The total thickness of the fiber-reinforced reinforcing material 21 in the fiber-reinforced molded product 10 is equal to the total thickness of the carbon fiber woven fabric used in the fiber-reinforced reinforcing material 21.

The phenol resin impregnated in the melamine resin foam and the carbon fiber woven fabric enhances the rigidity, strength, and flame retardancy of the fiber-reinforced molded product 10 by curing after impregnation.

The ratio of the phenol resin in the fiber-reinforced molded product 10 (that is, the resin ratio of the fiber-reinforced molded product) is preferably 40 to 70%. By setting the phenol resin in the resin ratio range of the fiber-reinforced molded product, the lightness, rigidity, strength and flame retardancy of the fiber-reinforced molded product 10 can be further improved. The resin ratio (%) of the fiber-reinforced molded product is calculated by the formula (weight of fiber-reinforced molded product-weight of fiber-reinforced material in fiber-reinforced molded product) / weight of fiber-reinforced molded product x 100. To. The resin ratio (%) of the fiber-reinforced molded product and the resin ratio calculated by the formula (A1) when manufacturing the fiber-reinforced molded product 10 are the same values. "(Weight of fiber-reinforced molded article-Weight of fiber reinforcing material in fiber-reinforced molded article)" in the formula for calculating the resin ratio (%) of the fiber-reinforced molded article is "Melamine resin foam and melamine resin foam. The value matches the "total weight of the impregnated phenol resin and the phenol resin impregnated in the carbon fiber woven fabric".

The integration of the core material 11 and the fiber reinforcing material 21 is performed by curing the phenol resin in a state where the laminate of the melamine resin foam impregnated with the phenol resin and the carbon fiber woven fabric is compressed.

Next, a method for producing the fiber-reinforced molded product of the present invention will be described. The method for producing a fiber-reinforced molded product includes an impregnation step, a laminating step, and a compression heating step.
In the impregnation step, one or both of the melamine resin foam having open cells and the carbon fiber woven fabric are impregnated with the phenol resin. In order to efficiently impregnate the entire fiber-reinforced molded body with the phenol resin, it is preferable to impregnate both the melamine resin foam and the carbon fiber woven fabric with the phenol resin. In the following example, the case where both the melamine resin foam and the carbon fiber woven fabric are impregnated with the phenol resin is shown. The melamine resin foam used has a thickness (thickness before compression) of 3 to 50 mm and a density (density before compression) of 5 to 15 kg / from the viewpoint of ease of compression, impregnation property, light weight, and rigidity. those of m ³ is preferable.

As shown in FIG. 2 (2-1), the impregnation step comprises two types, an impregnation step A and an impregnation step B.
In the impregnation step A, the phenol resin 11B is impregnated with the melamine resin foam 11A having open cells to obtain the impregnated melamine resin foam 11C.
On the other hand, in the impregnation step B, the carbon fiber woven fabric 21A is impregnated with the phenol resin 21B to form the impregnated carbon fiber woven fabric 21C.

The work of impregnating the carbon fiber woven fabric 21A with the phenol resin 21B is performed on a number of carbon fiber woven fabrics corresponding to the number of carbon fiber woven fabrics laminated on both sides of the core material 11. The phenolic resins 11B and 21B at the time of impregnation are uncured liquids. Further, in order to facilitate impregnation, the phenol resins 11B and 21B are preferably dissolved in a solvent, and after impregnation, the impregnated melamine resin foam 11C and the impregnated carbon fiber woven fabric 21C are subjected to a curing reaction of the phenol resin. The solvent is removed from the impregnated melamine resin foam 11C and the impregnated carbon fiber woven fabric 21C by drying at a temperature at which it does not occur. The impregnation means is carried out by an appropriate method such as a method of immersing the melamine fat foam or the carbon fiber woven fabric in a tank containing a liquid phenol resin, a method of spraying, a method of using a roll coater, or the like. Further, the impregnation amount of the phenol resin is adjusted by passing it through two drawing rollers whose gaps are appropriately adjusted. As the impregnation amount of the phenol resin increases, the flame retardancy deteriorates. Therefore, it is desirable that the impregnation amount of the phenol resin is small. Excess phenol resin can be squeezed out by passing a melamine resin foam having open cells impregnated with phenol resin and a carbon fiber woven fabric impregnated with phenol resin through two drawing rollers whose gaps are appropriately adjusted. Further, the phenol resin can be uniformly dispersed in the melamine resin foam having open cells and the carbon fiber woven fabric.
In this example, the method was carried out in a solvent system in which the phenol resin was dissolved in a solvent, but it may be carried out in a water-soluble system in which the phenol resin was dissolved in water.

The impregnation of the melamine resin foam 11A with the phenol resin 11B and the impregnation of the carbon fiber woven fabric 21A with the phenol resin 21B are such that the resin ratio defined by the formula (A1) is 40 to 70%. Will be done. By setting the resin ratio, the lightness, rigidity, strength and flame retardancy of the fiber-reinforced molded product 10 can be further improved.

In the laminating step of (2-2) shown in FIG. 2, a plurality of the impregnated carbon fiber woven fabrics 21C are laminated and arranged on both sides of the impregnated melamine resin foam 11C to form a laminated body 10C. The number of laminated carbon fiber woven fabrics 21C is equalized on both sides of the impregnated melamine resin foam 11C. In the laminating work, a plurality of the impregnated carbon fiber woven fabric 21C and the impregnated melamine resin foam 11C are placed on the upper surface of the press molding lower mold 31 used in the next compression heating step (2-3). And a plurality of the impregnated carbon fiber woven fabric 21C may be stacked in this order. Further, the impregnated melamine resin foam 11C and the impregnated carbon fiber woven fabric 21C are preferably those having the same plane size, but if they are different, they are finally trimmed after the compression heating step described later. Just do it.

In the compression / heating step (2-3) shown in FIG. 2, the laminate 10C is compressed and heated by the lower die 31 and the upper die 33 for press molding. The compression is such that the compression ratio obtained by the above formula (B1) is 200 to 1500%, particularly preferably 300 to 1000%. The fiber-reinforced molded product is actually manufactured by changing the distance between the press-molded lower mold 31 and the upper mold 33, and the compression ratio is calculated from the obtained fiber-reinforced molded product to obtain the target compression ratio. Find the distance between the lower mold 31 for press molding and the upper mold 33. During the compression heating step, spacers are installed at appropriate positions between the press molding lower mold 31 and the upper mold 33, and the press molding lower mold 31 and the upper mold 33 are spaced apart from each other (predetermined stacking body). Compressed thickness). Further, the heating method is not particularly limited, but it is easy to provide a heating means such as a heater on the press molding lower mold 31 and the upper mold 33 and perform the pressing via the press molding lower mold 31 and the upper mold 33. is there. 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 compression heating step, the phenol resin of the impregnated carbon fiber woven fabric 21C and the phenol resin of the impregnated melamine resin foam 11C are surely brought into contact with each other. Then, by heating in the compression heating step, the phenol resin of the impregnated melamine resin foam 11C and the phenol resin of the impregnated carbon fiber woven fabric 21C each start a curing reaction, and the compressed state of the laminate 10C, that is, the impregnation. The finished melamine resin foam 11C is cured in a compressed state. As a result, the core material 11 is formed from the impregnated melamine resin foam 11C, the fiber reinforcing material 21 is formed from the impregnated carbon fiber woven fabric 21C, and the core material 11 and the fiber reinforcing material 21 are formed. The fiber-reinforced molded body 10 is integrally formed. After that, the heat compression is released to obtain the fiber-reinforced molded product 10.

As the phenol resin, a product name; PR-55791B manufactured by Sumitomo Bakelite Co., Ltd. and a resin concentration of 60 wt% ethanol solution was used. A plain weave carbon fiber woven fabric (manufactured by Toho Tex Co., Ltd., product name; W-3101, fiber weight 200 g / m ² ) is dipped in this phenol resin, taken out, and naturally dried at room temperature at 25 ° C. for 2 hours, and further 60 The impregnated carbon fiber woven fabric was formed by drying in an atmosphere of ° C. for 1 hour according to the required number of each Example and each Comparative Example in Table 1. As the carbon fiber woven fabric, one cut into a flat size of 200 × 300 mm (weight 12 g / sheet, thickness 0.23 mm) was used. The amount of the impregnated carbon fiber woven fabric after drying was 22 g per sheet. The impregnation amount was adjusted by passing the carbon fiber woven fabric taken out from the phenol resin through two drawing rollers having adjusted gaps.

Further, a melamine resin foam (manufactured by BASF, product name: Basotect G, density 9 kg / m ³ ) having open cells having the thickness of each Example and Comparative Example in Table 1 was cut out to a plane size of 200 × 300 mm. Immersed in a phenol resin solution in the same manner as the carbon fiber woven fabric, taken out, air-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. did. Weight of melamine resin foam before impregnation, weight of the entire carbon fiber woven fabric before impregnation (total number of layers), total weight of melamine resin foam and carbon fiber woven fabric after impregnation (after drying), resin ratio (the resin ratio) (Value calculated by the formula (A1)) is shown in Table 1.

Next, a plurality of impregnated carbon fiber woven fabrics, an impregnated melamine resin foam, and an impregnated carbon fiber woven fabric are placed on a SUS press-molding lower mold (flat plate) to which a mold release agent is previously applied to the surface. By arranging the plurality of sheets in this order, a laminate in which a plurality of impregnated carbon fiber woven fabrics were arranged on both sides of the impregnated melamine resin foam was set on the lower mold for press molding. In that state, the laminate on the lower mold for press molding is pressed by the upper mold for press molding (flat plate shape) by applying a surface pressure of 10 MPa at 150 ° C. for 10 minutes to compress and heat the compacted state. The phenol resin was reactively cured in. At that time, the molded product was heated by the cast heaters attached to the upper and lower press molds. Further, a SUS spacer having a thickness equal to the plate thickness in Table 2 was interposed between the lower mold for press molding and the upper mold to adjust the distance between the lower mold and the upper mold, that is, the compression thickness of the laminate. Then, after cooling the lower mold and the upper mold for press molding at room temperature, the lower mold and the upper mold were opened to obtain a fiber-reinforced molded product in which fiber reinforcing materials were laminated and integrated on both sides of the core material. This fiber-reinforced molded product was trimmed to 182 × 257 mm to obtain a fiber-reinforced molded product of each Example and each Comparative Example.

The thickness (plate thickness) and specific gravity (JIS K7112 compliant) of the fiber-reinforced molded product of each Example and each Comparative Example were measured. The thickness (plate thickness) of the fiber-reinforced molded product was measured with a digital micrometer. The thickness (plate thickness) of the fiber-reinforced molded product was equal to the distance between the lower mold and the upper mold for press molding. In addition, the ratio (%) of the total thickness of the fiber reinforced plastic to the fiber reinforced molded product and the compression ratio were calculated. As the thickness of the melamine resin foam before compression in the calculation formula (B1) of the compressibility, the thickness of the melamine resin foam shown in Table 1 was used.
The flexural modulus (JIS K7074-1988 A method) and fracture load (JIS K7074 compliant) were measured for the fiber-reinforced molded products of each example and each comparative example, and a combustion test was conducted in accordance with the Ordinance No. 151 of the Ministry of Land, Infrastructure, Transport and Tourism. went.
The results are shown in Table 2. The resin ratio in Table 2 is the resin ratio shown in Table 1.

In Examples 1 to 3, the plate thickness of the fiber reinforced molded product is 2 mm, the total number of laminated carbon fiber fabrics on both sides of the core material is 4, and the ratio of the total thickness of the fiber reinforced plastic to the fiber reinforced molded product is 46.0. %, The compression ratio is 362.96%, and the resin ratio is 42.9 to 68.0%. In addition, the specific gravity is as light as 0.70 to 1.25, the elastic modulus is 31 to 46 GPa, the rigidity is high, the breaking load is 200 to 270 N, the strength is high, the combustion test result is nonflammable, and the flame retardancy is high. Is expensive.

In Example 4, the plate thickness of the fiber reinforced molded product is 3 mm, the total number of laminated carbon fiber fabrics on both sides of the core material is 4, the ratio of the total thickness of the fiber reinforced plastic to the fiber reinforced molded product is 30.7%, and the compression ratio. Is 380.77%, and the resin ratio is 66.7%. Further, the specific gravity is as light as 0.80, the elastic modulus is 35 GPa and the rigidity is high, the breaking load is 210 N and the strength is high, the combustion test result is nonflammable, and the flame retardancy is high.

In Example 5, the plate thickness of the fiber reinforced molded product is 3 mm, the total number of laminated carbon fiber fabrics on both sides of the core material is 10, the ratio of the total thickness of the fiber reinforced plastic to the fiber reinforced molded product is 76.7%, and the compression ratio. Is 614.29%, and the resin ratio is 44.4%. Further, the specific gravity is as light as 1.20, the elastic modulus is 49 GPa and the rigidity is high, the breaking load is 620 N and the strength is high, the combustion test result is nonflammable, and the flame retardancy is high.

In Example 6, the plate thickness of the fiber reinforced molded product is 3 mm, the total number of laminated carbon fiber fabrics on both sides of the core material is 6, the ratio of the total thickness of the fiber reinforced plastic to the fiber reinforced molded product is 46.0%, and the compression ratio. Is 208.64%, and the resin ratio is 60.0%. Further, the specific gravity is as light as 1.00, the elastic modulus is 37 GPa and the rigidity is high, the breaking load is 350 N and the strength is high, the combustion test result is nonflammable, and the flame retardancy is high.

In Example 7, the plate thickness of the fiber reinforced molded product is 5 mm, the total number of laminated carbon fiber fabrics on both sides of the core material is 10, the ratio of the total thickness of the fiber reinforced plastic to the fiber reinforced molded product is 46.0%, and the compression ratio. Is 270.37%, and the resin ratio is 60.0%. Further, the specific gravity is as light as 1.00, the elastic modulus is 40 GPa, the rigidity is high, the breaking load is 1000 N, the strength is high, the combustion test result is nonflammable, and the flame retardancy is high.

In Example 8, the plate thickness of the fiber-reinforced molded product was 1.5 mm, the total number of laminated carbon fiber fabrics on both sides of the core material was 4, and the ratio of the total thickness of the fiber-reinforced material to the fiber-reinforced molded product was 61.3%. The compression ratio is 762.07% and the resin ratio is 46.7%. Further, the specific gravity is as light as 1.00, the elastic modulus is 43 GPa, the rigidity is high, the breaking load is 210 N, the strength is high, the combustion test result is nonflammable, and the flame retardancy is high.

In Comparative Example 1, the thickness of the fiber-reinforced molded product is 1 mm, which is thinner than the range of the present invention, the total number of laminated carbon fiber fabrics on both sides of the core material is 2 (1 each on one side), and the entire fiber-reinforced material for the fiber-reinforced molded product. The thickness ratio is 46.0%, the compression ratio is 825.93%, and the resin ratio is 66.7%. Further, it has a light specific gravity of 1.20 and a high rigidity with an elastic modulus of 44 GPa. However, the breaking load was 130 N, which was lower than that of the examples. The combustion test results are non-combustible and highly flame-retardant.

In Comparative Example 2, the plate thickness of the fiber reinforced molded body is 2 mm, the total number of laminated carbon fiber woven fabrics on both sides of the core material is 2 (one for each side), and the ratio of the total thickness of the fiber reinforced material to the fiber reinforced molded body is the present. It is 23.0%, which is lower than the range of the present invention, the compression ratio is 224.68%, and the resin ratio is 71.4%, which exceeds the range of the present invention. The specific gravity was 0.70, which was light, but the elastic modulus was 29 GPa, and the rigidity was lower than that of the examples. Further, the breaking load was 140 N, and the strength was lower than that of the examples. In addition, the combustion test result shows that the flame retardancy is lower than that of the non-combustible example, and the flame retardancy is inferior to that of the example.

In Comparative Example 3, the plate thickness of the fiber-reinforced molded product is 2 mm, the total number of laminated carbon fiber fabrics on both sides of the core material is 4, the ratio of the total thickness of the fiber-reinforced plastic to the fiber-reinforced molded product is 46.0%, and the compression ratio. Is 362.96%, and the resin ratio is 71.4%, which exceeds the range of the present invention. Further, the specific gravity is 1.40, which exceeds the range of the present invention, and is inferior in lightness to the examples. The elastic modulus is 45 GPa and the rigidity is high, and the breaking load is 300 N and the strength is high. In addition, the combustion test result shows that the flame retardancy is lower than that of the non-combustible example, and the flame retardancy is inferior to that of the example.

In Comparative Example 4, the plate thickness of the fiber reinforced molded product is 2 mm, the total number of laminated carbon fiber fabrics on both sides of the core material is 4, the ratio of the total thickness of the fiber reinforced plastic to the fiber reinforced molded product is 46.0%, and the compression ratio. Is 362.96%, and the resin ratio is 38.5%, which is lower than the range of the present invention. The specific gravity was as light as 0.65, but the elastic modulus was 28 GPa, the rigidity was lower than that of the example, and the breaking load was 180 N, which was lower than that of the example. The combustion test results are non-combustible and highly flame-retardant.

In this embodiment, a flame retardant is not used, but a known flame retardant such as boric acid or sodium metaborate may be used as long as the nonflammability is not affected.

As described above, the example product of the present invention has nonflammability suitable for vehicle members, has high rigidity, high strength, and is lightweight. Further, since an expensive flame retardant is not required, cost reduction can be realized.

Further, the present invention is also expressed as follows when the subject is only to provide a fiber-reinforced molded product which is nonflammable. That is, another aspect of the present invention is a fiber reinforced molded body composed of a core material and a fiber reinforcing material laminated on both sides of the core material, wherein the core material is a melamine resin foam having open cells and phenol. The phenol resin is hardened in a compressed state of the melamine resin foam impregnated with the resin, and the fiber reinforcing material is made of a carbon fiber woven fabric impregnated with the phenol resin and hardened, and the core material is one piece. A plurality of the carbon fiber woven fabrics are laminated on both sides thereof, and the core material and the fiber reinforcing material are a phenol resin impregnated in a melamine resin foam of the core material and carbon fibers of the fiber reinforcing material. It is integrated by curing the phenol resin impregnated in the woven fabric, and is characterized by having nonflammability in a test in accordance with the Ministry of Land, Infrastructure, Transport and Tourism Ordinance No. 151, where the resin ratio specified by the formula (A1) is 40 to 70%. It is a fiber reinforced molded body.

10 Fiber reinforced molded body 10C Laminated body 11 Core material 11A Melamine resin foam 11B Phenol resin 11C Impregnated melamine resin foam 21 Fiber reinforcing material 21A Carbon fiber woven fabric 21B Phenol resin 21C Impregnated carbon fiber woven fabric

Claims (12)

In a fiber reinforced molded body composed of a core material and a fiber reinforcing material laminated on both sides of the core material.
The core material is a melamine resin foam having open cells impregnated with a phenol resin, and the phenol resin is cured in a compressed state of the melamine resin foam.
The fiber reinforcing material is made of a carbon fiber woven fabric impregnated with a phenol resin and cured.
The core material and the fiber reinforcing material are integrated by curing the phenol resin impregnated in the melamine resin foam of the core material and the phenol resin impregnated in the carbon fiber woven fabric of the fiber reinforcing material.
In the fiber-reinforced molded product, two or more layers of the carbon fiber woven fabric are laminated on both sides of the core material.
The thickness of the fiber-reinforced molded product is 1.5 to 5 mm.
The phenol resin ratio specified by the following formula (A1) in the fiber-reinforced molded product is 40 to 70%.
The fiber-reinforced molded product has a flexural modulus (JIS K 7074-1988 A method) of 30 GPa or more and a specific gravity (JIS K7112 compliant) of 0.70 to 1.30, and is a test conforming to the Ordinance No. 151 of the Ministry of Land, Infrastructure, Transport and Tourism. A fiber-reinforced molded product characterized by being nonflammable.

The fiber-reinforced molded product according to claim 1, wherein the ratio of the total thickness of the fiber-reinforced material to the fiber-reinforced molded product is 30 to 80%. The fiber-reinforced molded product according to claim 1 or 2, wherein the fiber-reinforced molded product has a thickness of 2 to 5 mm. The fiber-reinforced molded product according to any one of claims 1 to 3, wherein the fiber-reinforced molded product has a specific gravity (JIS K7112 compliant) of 0.70 to 1.25. The fiber-reinforced molded product according to any one of claims 1 to 4, wherein the fiber-reinforced reinforcing material has the same number of laminated carbon fiber woven fabrics on both sides of the core material. The fiber-reinforced molded product according to any one of claims 1 to 5, wherein the fiber-reinforced molded product does not contain a flame retardant. A core material in which a melamine resin foam having open cells is impregnated with a phenol resin and the phenol resin is cured in a state where the melamine resin foam is compressed, and a fiber reinforcing material in which a carbon fiber woven fabric is impregnated with a phenol resin and cured. This is a method for manufacturing a fiber-reinforced molded body in which the fiber reinforcing material is laminated and integrated on both sides of the core material.
An impregnation step of impregnating one or both of a melamine resin foam having open cells and a thickness of 3 to 50 mm and a carbon fiber woven fabric with a phenol resin.
After the impregnation step, a laminating step of arranging a plurality of the carbon fiber woven fabrics on both sides of the melamine resin foam so that the carbon fiber woven fabrics have two or more layers to obtain a laminated body.
It consists of a compression heating step of compressing and heating the laminate.
The impregnation in the impregnation step is performed so that the resin ratio defined by the following formula (A1) is in the range of 40 to 70%.
The compression in the compression heating step is performed by compressing so that the compression ratio defined by the following formula (B1) is 200 to 1500%.
In the compression heating step, the phenol resin is cured to form the core material and the fiber reinforcing material in a state where the melamine resin foam of the laminated body is compressed, and the core material and the fiber reinforcing material are integrated. The thickness of the fiber-reinforced molded product is 1.5 to 5 mm, the flexural modulus of the fiber-reinforced molded product (JIS K 7074-1988 A method) is 30 GPa or more, and the specific gravity (JIS K7112 compliant) is 0.70 to 0. A method for producing a fiber-reinforced molded product, which is 1.30 and is characterized by producing a fiber-reinforced molded product having nonflammability in a test in accordance with Ordinance No. 151 of the Ministry of Land, Infrastructure, Transport and Tourism.

The method for producing a fiber-reinforced molded product according to claim 7, wherein the ratio of the total thickness of the fiber-reinforced material to the fiber-reinforced molded product is 30 to 80%. The method for producing a fiber-reinforced molded product according to claim 7 or 8, wherein the fiber-reinforced molded product has a thickness of 2 to 5 mm. The method for producing a fiber-reinforced molded product according to any one of claims 7 to 9, wherein the specific gravity of the fiber-reinforced molded product (in accordance with JIS K7112) is 0.70 to 1.25. The method for producing a fiber-reinforced molded product according to any one of claims 7 to 10, wherein in the laminating step, the number of laminated carbon fiber woven fabrics is made equal on both sides of the melamine resin foam. The method for producing a fiber-reinforced molded product according to any one of claims 7 to 11, wherein in the compression heating step, the compression ratio is 300 to 1000%.

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