WO2018150978A1 - Resin-attached reinforced fiber woven fabric, and method for producing fiber-reinforced resin molded article - Google Patents

Abstract

In a resin-attached reinforced woven fabric, a thermoplastic resin is attached onto at least one surface of a reinforced fiber woven fabric. The mass W of the reinforced fiber woven fabric per unit area is 25 to 400 g/m² inclusive. The ventilation degree P of the reinforced fiber woven fabric is 0.1 to 300 cm³/cm²/s inclusive. The melting point of the thermoplastic resin is 70 to 300ºC inclusive. The ratio of the mass of the reinforced fiber woven fabric to the whole mass of the resin-attached reinforced fiber woven fabric is 20 to 90% by mass inclusive. The coverage C of the surface of the reinforced fiber woven fabric with the thermoplastic resin is 30% or more and less than 100%. The resin attachment coefficient A represented by formula (1) is 35 to 135 inclusive. (1) A = W×(C/100)²/P^0.05

Description

Resin adhesion reinforced fiber fabric and method for producing fiber reinforced resin molded product

One aspect of the present invention relates to a resin-adhesive reinforced fiber fabric and a method for producing a fiber-reinforced resin molded product.

In recent years, in various fields such as automobiles and airplanes, for the purpose of improving fuel consumption, it has been studied to reduce the weight of the aircraft by replacing metal materials with resin materials. In particular, fiber reinforced resin materials containing reinforcing fibers such as glass fibers and carbon fibers have attracted attention as metal substitute materials for ensuring sufficient strength.

Examples of the material to which the fiber reinforced resin material can be applied include a material having a complicated shape such as an oil pan attached to the internal combustion engine. For example, in the oil pan described in Patent Document 1, a glass fiber reinforcing material is disposed in a flange portion and resin is injected.

JP-A-7-27289

However, in the prior art described in Patent Document 1 described above, the reinforcing fiber material is partially used, but the strength as a product is insufficient. In addition, the step of injecting the resin takes time as compared with the press molding step usually used for a metal material, and there is a possibility that the production efficiency is lowered. For example, in order to improve the production efficiency, it is considered that a solution can be achieved by processing a resin sheet containing a reinforcing fiber reinforcing material into a desired shape and processing by press molding. A resin sheet containing a reinforcing material is hard, has insufficient formability and is difficult to process into a complicated shape, and it is difficult to improve manufacturing efficiency.

One aspect of the present invention is made to solve such a problem, and has a formability and a shapeability that can be applied to press molding, and improves the handleability to manufacture a molded product. It aims at providing the resin adhesion reinforcement | strengthening textile fabric which can aim at the improvement of the production efficiency at the time of doing. An object of one aspect of the present invention is to provide a method for producing a fiber-reinforced resin molded article using such a resin-adhesion-reinforced fiber fabric.

One aspect of the present invention is a resin-attached reinforcing fiber fabric in which a thermoplastic resin is attached to at least one surface of a reinforcing fiber fabric, and the mass W per unit area of the reinforcing fiber fabric is 25 g / m ² or more and 400 g / m ^2. m ² or less, the air permeability P of the reinforcing fiber fabric is in the range of 0.1 cm ³ / cm ² / s to 300 cm ³ / cm ² / s, and the melting point of the thermoplastic resin is 70 ° C. or more. The proportion of the mass of the reinforcing fiber fabric is in the range of 20% by mass to 90% by mass with respect to the total mass of the resin-attached reinforcing fiber fabric in the range of 300 ° C. or less, and the reinforcing fiber fabric by the thermoplastic resin. The surface coverage C is in the range of 30% to less than 100%, and the resin adhesion coefficient A represented by the following formula (1) is in the range of 35 to 135.
A = W × (C / 100) ² / P ^0.05 (1)

In the resin-adhesion reinforced fiber fabric, the resin adhesion coefficient A according to the above formula (1) is in the range of 35 or more and 135 or less. It is possible to improve the manufacturing efficiency when manufacturing the molded product. In the resin-adhesion reinforced fiber fabric, tackiness is reduced, so that handling properties can be improved. The tackiness is a property indicating the ease of peeling from the resin-attached reinforcing fiber fabric in an overlapping state. For example, if the tackiness is low, the resin-attached reinforcing fiber fabric can be easily pulled out from the roll-like resin-attached reinforcing fiber fabric, so that it is easy to handle and the production efficiency when manufacturing a molded product can be improved. In addition, when manufacturing a molded product, it is not necessary to inject a resin as before, and a molded product can be obtained by press molding by heating and pressurization. Can be improved.

The mass W per unit area of the reinforcing fiber fabric may be in the range of 50 g / m ^{2 to} 250 g / m ² . Thereby, sufficient strength can be ensured and sufficient formability can be obtained.

The resin adhesion coefficient A may be 35 or more and 95 or less. According to such a resin-adhesion reinforced fiber fabric, sufficient formability can be obtained, a molded product having a more complicated shape can be produced by press molding, and the production efficiency when producing the molded product can be improved. Improvements can be made.

The reinforcing fiber fabric may be a glass fiber fabric. A silane coupling agent may adhere to the surface of the glass fiber fabric. The silane coupling agent may be epoxy silane. When the silane coupling agent adheres to the surface of the glass fiber fabric, the impregnation of the glass fiber fabric with the thermoplastic resin is improved, and the strength of the molded product of the resin-attached reinforcing fiber fabric can be improved.

The method for producing a fiber-reinforced resin molded product according to one aspect of the present invention includes a molding step of heating and pressing a single resin-adhesion-reinforced fiber fabric or a laminate in which a plurality of resin-adhesion-reinforced fiber fabrics are laminated.

In this method for producing a fiber reinforced resin molded product, the resin adhesion reinforced fiber fabric can be heated and pressed to obtain a molded product, and the production efficiency when producing the molded product can be improved. When manufacturing molded products, it is not necessary to inject resin as before, and by performing press molding with heat and pressure, molded products can be obtained, so manufacturing time is shortened and manufacturing efficiency is improved. Can be achieved.

In the molding process, a resin-attached reinforcing fiber fabric may be adopted as a metal substitute material, and the resin-attached reinforcing fiber fabric may be heated and pressed. In the molding process, a resin-attached reinforcing fiber fabric can be adopted as a metal substitute material for automobiles, and the resin-attached reinforcing fiber fabric can be heated and pressurized.

In the molding process, the resin-adhesive reinforcing fiber fabric can be heated and pressed to form a box shape. Furthermore, in the molding step, the resin-adhesion-reinforced fiber fabric can be heated and pressed to be molded into a box shape to produce an oil pan.

According to one aspect of the present invention, it has moldability that can be applied to press molding, can improve shaping and handling, and can improve manufacturing efficiency when manufacturing molded products. A method for producing a resin-adhesive reinforced fabric and a fiber-reinforced resin molded product can be provided.

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

The resin-attached reinforcing fiber fabric of this embodiment has a reinforcing fiber fabric. A thermoplastic resin is attached to at least one surface of the reinforcing fiber fabric. The woven structure of the reinforcing fiber fabric is not particularly limited. The woven structure of the reinforcing fiber fabric may be, for example, a plain woven structure, a twill woven structure, or a satin woven structure. The woven structure of the reinforcing fiber fabric may be a multi-woven structure such as a double woven structure and a triple woven structure. The woven structure of the reinforcing fiber woven fabric may be a changed structure such as an oblique woven structure and a woven structure. The woven structure of the reinforcing fiber woven fabric may be a special structure such as a patterned woven structure or a sand structure. The woven structure of the reinforcing fiber fabric may be another woven structure.

The reinforcing fiber fabric may be, for example, an inorganic reinforcing fiber fabric or an organic reinforcing fiber fabric. Examples of the inorganic reinforcing fiber fabric include glass fiber fabric, carbon fiber fabric, metal fiber fabric, and ceramic fiber fabric. Examples of the organic reinforcing fiber fabric include aramid fiber fabric, vinylon fiber fabric, high-strength polyethylene fiber fabric, and cellulose fiber fabric. When the reinforcing fiber fabric is a glass fiber fabric, the moldability is particularly excellent. A silane coupling agent may adhere to the surface of the glass fiber fabric. When the silane coupling agent adheres to the surface of the glass fiber fabric, the impregnation of the glass fiber fabric with the thermoplastic resin is improved, and the strength of the molded product of the resin-attached reinforcing fiber fabric can be improved.

The reinforcing fiber fabric is not limited to one composed of one kind of fiber. The reinforcing fiber fabric may be composed of, for example, different types of reinforcing fiber yarns of warp and weft. The reinforcing fiber fabric may include different types of reinforcing fiber yarns in a part of the warp or the weft. In the warp or weft constituting the reinforcing fiber fabric, the reinforcing fiber and the thermoplastic resin fiber made of a thermoplastic resin described later may be mixed, combined, or twisted. A thermoplastic resin fiber yarn may be included in a part of the warp or weft of the reinforcing fiber fabric.

Examples of the silane coupling agent include epoxy silane, amino silane, acrylic silane, methacryl silane, and cationic silane. The silane coupling agent is preferably epoxy silane. Examples of the epoxy silane include 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane. If the resin-adhesion-reinforced fiber fabric has a glass fiber fabric to which epoxy silane is adhered, the moldability becomes particularly excellent.

The thermoplastic resin may be attached to one surface of the reinforcing fiber fabric, and the thermoplastic resin may be attached to both surfaces of the reinforcing fiber fabric.

Examples of the thermoplastic resin include polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polyphenylene sulfide resin, polycarbonate resin, polypropylene resin, thermoplastic epoxy resin, polyethylene resin, polyvinyl chloride resin, polyphenylene ether resin, polyether ether. Examples thereof include ketone resins, polyaryl ether ketone resins, and liquid crystal polymers (LCP). The thermoplastic resin is preferably a polyamide resin.

The mass W per unit area of the reinforcing fiber fabric is in the range of 25 g / m ^{2 to} 400 g / m ² . This unit area is a unit area viewed from the thickness direction of the fabric. The mass W per unit area of the reinforcing fiber fabric is preferably 50 g / m ² or more and 250 g / m ² or less. Weight W per unit area of the reinforcing fiber fabric, more preferably more preferably 70 g / ^{m 2} or more 240 g / ^{m 2} or less, 90 g / ^{m 2} or more 230 g / ^{m 2} or less, 100 g / ^{m 2} It is particularly preferably 220 g / m ² or less, and most preferably 105 g / m ² or more and 215 g / m ² or less.

As a method of measuring the mass W per unit area of the reinforcing fiber fabric, when the reinforcing fiber fabric is an inorganic reinforcing fiber fabric, the resin adhering to the reinforcing fiber fabric is removed by heating, for example, at 625 ° C. for 1 hour. The mass of the subsequent reinforcing fiber fabric can be measured. When the reinforcing fiber fabric is an organic reinforcing fiber fabric, the organic reinforcing fiber is not dissolved, and the resin-adhering reinforcing fiber fabric is immersed in a solvent that dissolves the resin adhering to the reinforcing fiber fabric and adheres to the reinforcing fiber fabric. The mass of the reinforcing fiber fabric after removing the resin can be measured. In addition, for example, the mass W per unit area of the reinforcing fiber woven fabric (particularly glass fiber woven fabric) can be measured in accordance with JIS R3420.

When the mass W per unit area of the reinforcing fiber fabric is 25 g / m ² or more, insufficient strength can be avoided. When the mass W per unit area of the reinforcing fiber fabric is 400 g / m ² or less, sufficient shapeability can be obtained.

The air permeability P of the reinforcing fiber fabric is in the range of 0.1 cm ³ / cm ² / s to 300 cm ³ / cm ² / s. The air permeability P of the reinforced fiber fabric is preferably 1 cm ³ / cm ² / s or more and 250 cm ³ / cm ² / s or less. The air permeability P of the reinforcing fiber fabric is preferably 5 cm ³ / cm ² / s or more and 220 cm ³ / cm ² / s or less, and 7 cm ³ / cm ² / s or more and 80 cm ³ / cm ² / s or less. Is more preferable. The air permeability P of the reinforced fiber fabric is particularly preferably 10 cm ³ / cm ² / s or more and 40 cm ³ / cm ² / s or less, and is 12 cm ³ / cm ² / s or more and 30 cm ³ / cm ² / s or less. Is particularly preferably 13 cm ³ / cm ² / s or more and 25 cm ³ / cm ² / s or less, and most preferably 14 cm ³ / cm ² / s or more and 24 cm ³ / cm ² / s or less. preferable.

As a method for measuring the permeability P of the reinforcing fiber fabric, when the reinforcing fiber fabric is an inorganic reinforcing fiber fabric, the resin adhering to the reinforcing fiber fabric is removed by heating, for example, at 625 ° C. for 1 hour. The air permeability P of the fiber fabric can be measured. When the reinforcing fiber fabric is an organic reinforcing fiber fabric, the organic reinforcing fiber is not dissolved, and the resin-adhering reinforcing fiber fabric is immersed in a solvent that dissolves the resin adhering to the reinforcing fiber fabric and adheres to the reinforcing fiber fabric. The air permeability P of the reinforcing fiber fabric after removing the resin can be measured. In addition, the air permeability P of a reinforced fiber fabric (especially a glass fiber fabric) can be measured based on JIS R3420.

When the air permeability P of the reinforcing fiber fabric is 0.1 cm ³ / cm ² / s or more, it is possible to prevent the resin-attached reinforcing fiber fabric from becoming too hard. Further, when the air permeability P of the reinforcing fiber fabric is 300 cm ³ / cm ² / s or less, it is possible to prevent insufficient strength as the resin-adhesion reinforcing fiber fabric.

The melting point of the thermoplastic resin is in the range of 70 ° C to 300 ° C. The melting point of the thermoplastic resin is preferably 100 ° C. or higher and 270 ° C. or lower. The melting point of the thermoplastic resin is preferably 150 ° C. or higher and 250 ° C. or lower, and more preferably 180 ° C. or higher and 230 ° C. or lower. The melting point of the thermoplastic resin can be measured according to JIS K7121.

When the melting point of the thermoplastic resin is 70 ° C. or higher, tackiness in the resin-adhesive reinforcing fiber fabric can be reduced. When the melting point of the thermoplastic resin is 300 ° C. or lower, it is possible to suppress a decrease in production efficiency when producing a fiber-reinforced resin molded product.

The ratio R of the mass of the reinforcing fiber fabric to the total mass of the resin-attached reinforcing fiber fabric is in the range of 20% by mass to 90% by mass. The ratio R is preferably 30% by mass or more and 85% by mass or less. The ratio R is preferably 50% by mass or more and 80% by mass or less, and more preferably 60% by mass or more and 75% by mass or less.

When the ratio R of the mass of the reinforcing fiber fabric to the total mass of the resin-adhering reinforcing fiber fabric is 20% by mass or more, insufficient strength of the resin-adhering reinforcing fiber fabric can be avoided. When the ratio R is 90% by mass or less, insufficient penetration of the thermoplastic resin into the reinforcing fiber fabric can be avoided. The total mass T of the resin-attached reinforcing fiber fabric is, for example, the sum of the mass W per unit area of the reinforcing fiber fabric and the mass B per unit area of the thermoplastic resin attached to at least one surface of the reinforcing fiber fabric. (T = W + B). The ratio R (reinforcing fiber content) is a ratio of the mass B of the reinforcing fiber fabric to the total mass T of the resin-attached reinforcing fiber fabric (R = B / T).

The coverage C of the surface of the reinforcing fiber fabric with the thermoplastic resin is in the range of 30% or more and less than 100%. The coverage C is a ratio of the area covered with the thermoplastic resin on the surface of the reinforcing fiber fabric. The coverage C is preferably 40% or more and 95%. The coverage C is more preferably 45% or more and 90% or less, further preferably 48% or more and 85% or less, particularly preferably 51% or more and 80% or less, and 53% or more and 75% or less. Is particularly preferably 55% or more and 70% or less, and most preferably 57% or more and 65% or less.

When the covering ratio C is less than 30%, the resin-adhesive reinforcing fiber fabric does not have sufficient moldability. On the other hand, when the coverage C is 100%, the resin-adhesive reinforcing fiber fabric is hardly deformed and does not have sufficient shapeability.

In the resin-attached reinforcing fiber fabric, it is preferable that the resin is evenly attached to the reinforcing fiber fabric in order to improve the moldability and formability of the resin-attached reinforcing fiber fabric. For example, the ratio of the standard error (standard error / average value) to the average value when at least 20 1 cm × 1 cm square samples are taken out from the resin-attached reinforcing fiber fabric and the mass of the sample is measured is 15.0%. The following is preferable. The ratio of the standard error to the average value is more preferably 0.05% or more and 10.0% or less, and further preferably 0.1% or more and 7.5% or less. The ratio of the standard error to the average value is particularly preferably 0.15% or more and 5.0% or less, and most preferably 0.2% or more and 2.5% or less. It is preferable that the thermoplastic resin adhering to the reinforcing fiber fabric is, for example, in the form of a dot and is dispersed without being distributed.

The resin adhesion reinforcing fiber fabric has a resin adhesion coefficient A represented by the following formula (1) in the range of 35 to 135.
A = W × (C / 100) ² / P ^0.05 (1)
(W: mass per unit area of the reinforcing fiber fabric, P: air permeability of the reinforcing fiber fabric, C: coverage of the surface of the reinforcing fiber fabric with the thermoplastic resin)

The resin adhesion coefficient A is preferably 35 or more and 95 or less. The resin adhesion coefficient A is more preferably 45 or more and 85 or less, and further preferably 50 or more and 80 or less. The resin adhesion coefficient A is particularly preferably 55 or more and 75 or less, and most preferably 60 or more and 70 or less.

When the resin adhesion coefficient A is 35 or more, it is possible to suppress a decrease in moldability of the resin adhesion reinforcing fiber fabric. Moreover, the fall of a shaping property can be suppressed as the resin adhesion coefficient A is 135 or less.

Next, the fiber reinforced resin molded product will be described.

The fiber reinforced resin molded article includes a resin-adhesive reinforced fiber fabric and is obtained by molding the resin-adhesive reinforced fiber fabric. The fiber reinforced resin molded product is, for example, a product using a resin-adhesion reinforced fiber fabric as a metal substitute material. The metal substitute material is a metal substitute material for automobiles applied to parts for automobiles, for example. The fiber reinforced resin molded product includes, for example, a box-shaped structure. The fiber reinforced resin molded product may be entirely box-shaped or may partially include a box-shaped portion.

An example of a fiber reinforced resin molded product that is a part for an automobile and includes a box-shaped structure is an oil pan. The oil pan is, for example, a box-shaped container that is provided below a crankshaft of an internal combustion engine and stores lubricating oil. The oil pan has, for example, an inclined surface at the bottom so as to collect the stored lubricating oil at a predetermined location. The oil pan may include a complicated structure or a simple structure.

Next, a method for manufacturing a fiber reinforced resin molded product will be described.

First, prepare a resin-bonded reinforcing fiber fabric. A laminate obtained by laminating a plurality of resin-attached fiber fabrics of a predetermined size is molded by heating and pressing (molding step). At this time, the laminate is pressurized and molded using a mold for molding a fiber-reinforced resin molded product. In the heating and pressing step, the laminate is heated to a temperature equal to or higher than the melting point of the thermoplastic resin using, for example, a heater, and then pressed and molded. The fiber-reinforced resin molded product is not limited to a product formed by laminating a plurality of resin-attached fiber fabrics, and heat-pressing one resin-attached fiber fabric to form a fiber-reinforced resin product. Also good.

The fiber-reinforced resin molded product is not limited to one using only resin-adhesion-reinforced fiber fabric. For example, a fiber reinforced resin molded article may be formed by heating and pressing a laminate obtained by laminating another substrate on the resin adhesion surface of the resin adhesion reinforced fiber fabric. Here, as other base materials, metal foil (for example, aluminum foil), thermoplastic resin sheet (for example, vinyl chloride resin sheet), mineral wool sheet (for example, glass wool sheet), inorganic board (for example, gypsum board, Ceramic board), paper (non-combustible paper, honeycomb board) and the like can be used.

As described above, according to the resin-adhesion reinforcing fiber fabric of the present embodiment, the resin adhesion coefficient A according to the above formula (1) is in the range of 35 or more and 135 or less. It has shapeability, improves handling, and can improve manufacturing efficiency when manufacturing a molded product. When manufacturing molded products, it is not necessary to inject resin as before, and by performing press molding with heat and pressure, molded products can be obtained, so manufacturing time is shortened and manufacturing efficiency is improved. Can be achieved.

The present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the gist of the present invention. For example, the fiber reinforced resin molded product is not limited to an oil pan, and may have another box shape, a plate shape, or a molded product having another shape. Further, the fiber reinforced resin molded product is not limited to a part for an automobile, and may be a part for other transportation equipment, a machine, or a structure.

Next, resin-adhesive reinforcing fiber fabrics according to Examples 1 to 10 and Comparative Examples 1 to 5 will be described.

[Example 1]
In Example 1, first, 135 tex glass fiber yarns were used as warp yarns and weft yarns, and woven at a weaving density of 19 warps / 25 mm and 18 wefts / 25 mm to obtain a reinforced fiber fabric. Next, in Example 1, heat cleaning treatment and fiber opening treatment with a vibro washer were performed, and surface treatment was performed with 3-glycidoxypropyltrimethoxysilane (a kind of epoxy silane). Thereby, the mass W per unit area was 210 g / m < ² >, the air permeability P was 15 cm < ³ > / cm < ² > / s, and the reinforced fiber fabric which the epoxy silane adhered to the surface was obtained. The mass per unit area of the reinforcing fiber fabric and the air permeability P of the reinforcing fiber fabric were measured according to JIS R3420. In Tables 1 to 4 below, the glass fiber is described as “GF”.

Next, a polyamide resin (nylon 6, Amilan CM1017 manufactured by Toray Industries, Inc.), which is a thermoplastic resin having a melting point of 225 ° C., was adhered to the surface of the reinforcing fiber fabric. Specifically, using a screen provided with a dot-shaped opening, a polyamide resin is uniformly arranged in a shape of 30 dots per 0.67 mm in diameter and 2.54 cm (1 inch), and then heat-fixed to room temperature. By allowing to cool, 90 g / m ^{2 was} deposited. In Example 1, the mass per unit area of the polyamide resin by a 90 g / ^{m 2,} the total mass of the resin adhesion reinforcing fiber fabric (300g / ^{m 2)} Weight of reinforcing woven fabric for W (210g ^{/ m} 2) The ratio (reinforcing fiber content) R was 70% by mass (wt%). Thereby, in Example 1, the resin adhesion reinforcement | strengthening fiber fabric whose coverage C on the surface of a reinforcement fiber fabric is 60% was obtained. In Example 1, the resin adhesion coefficient A according to the above formula (1) was 66.

The coverage ratio C of the surface of the reinforcing fiber fabric is the area S1 (the area occupied by the reinforcing fiber yarn) of the entire surface of the reinforcing fiber fabric by observing the surface of the reinforcing fiber fabric using a microscope VHX-600 manufactured by Keyence Corporation. Yes, it does not include the area of the void portion existing between the reinforcing fiber yarns), and the area S2 of the portion where the resin in the surface of the reinforcing fiber fabric adheres was obtained by S2 / S1. The melting point of the thermoplastic resin can be measured according to JIS K7121.

Immediately after the thermoplastic resin is heated and fixed and allowed to cool to room temperature, immediately after the resin-adhesive reinforcing fiber fabric of Example 1 is obtained, the two resin-adhesive reinforcing fiber fabrics of Example 1 are stacked and pressed, and then peeled off. The tackiness of the resin-adhesive reinforcing fiber fabric was evaluated based on the degree of peeling at the time. Here, when the two resin-adhesive reinforcing fiber fabrics can be peeled without sticking, or when the sticking easily peels off and there is no resin transfer between the resin-adhesive reinforcing fiber fabrics, “1” (possible), easy The case where peeling was not possible was evaluated as “2” (impossible). The results are shown in Table 1 below.

Next, a test piece having a width of 25 mm and a length of 200 mm was cut out from the resin-attached reinforcing fiber fabric obtained in Example 1, and 50 mm in the length direction of the test piece was placed on a test bench, and 150 mm in the length direction was tested. By measuring the angle from the vertical surface (side wall surface of the test table) when it hangs out from the table, the formability of the resin-attached reinforcing fiber fabric was evaluated. Here, “1” (good) when the angle from the vertical plane is 0 ° or more and less than 45 ° (that is, when the test piece has a large degree of sag), and “2” (45 ° or more when less than 70 °). Yes), and the case where it is 70 ° or more and less than 90 ° (when the degree of sag of the test piece is small) was evaluated as “3” (impossible). The results are shown in Table 1 below.

Next, the resin-adhesion reinforced fiber fabric obtained in Example 1 was heated to a temperature 20 ° C. higher than the melting point of the thermoplastic resin, pressurized at 5 MPa, and press-molded to prepare a fiber reinforced resin flat plate. By observing the appearance of the obtained fiber-reinforced resin flat plate, the moldability of the resin-adhesion-reinforced fiber fabric was evaluated. Here, “1” (good) is a glass fiber that is impregnated with a thermoplastic resin and the glass fiber is transparent, but the glass fiber is not completely transparent, but the resin sink, blurring, misalignment, and misalignment The case where neither could be confirmed was evaluated as “2” (possible), and the case where resin sink marks, blurring, misalignment or misalignment could be confirmed was evaluated as “3” (impossible). The results are shown in Table 1 below.

In Example 1, as shown in Table 1, the evaluation of tackiness is “1” (possible), the evaluation of formability is “1” (good), and the evaluation of moldability is It was “1” (good). When the resin-attached reinforced fiber fabric of Example 1 was placed in a die of a square drawing press and heated under pressure at 260 ° C. and 5 MPa, a box-shaped fiber reinforced resin molded article having a good depth of 50 mm was obtained. I was able to.

[Example 2]
In Example 2, a resin-attached reinforcing fiber woven fabric was used under the same conditions as in Example 1 except that the surface treatment of the reinforcing fiber fabric was performed with 3-aminopropyltriethoxysilane (a kind of aminosilane) as a silane coupling agent. Got. In Example 2, the resin adhesion coefficient A according to the above formula (1) was 66.

Next, the tackiness, formability, and moldability of the resin-attached reinforcing fiber fabric obtained in Example 2 were evaluated under the same conditions as in Example 1. The results are shown in Table 1 below. In Example 2, the evaluation of tackiness is “1” (good), the evaluation of formability is “1” (good), and the evaluation of formability is “2” (good). It was. When the resin-attached reinforced fiber fabric of Example 2 was placed in a die of a square drawing press and heated under pressure at 260 ° C. and 5 MPa, a box-shaped fiber reinforced resin molded article having a good depth of 50 mm was obtained. I was able to.

[Example 3]
In Example 3, first, 67.5 tex glass fiber yarns were used as warps and wefts to weave them at a weave density of 57 warps / 25 mm and 53 wefts / 25 mm to obtain a reinforced fiber fabric. In Example 3, the reinforcing fiber fabric was surface-treated with 3-glycidoxypropyltrimethoxysilane (a kind of epoxy silane) which is a silane coupling agent. Thereby, the mass W per unit area was 300 g / m < ² >, the air permeability P was 25 cm < ³ > / cm < ² > / s, and the reinforced fiber fabric which the epoxy silane adhered to the surface was obtained.

Next, a polyamide resin was adhered to the surface of the reinforcing fiber fabric in the same manner as in Example 1. Specifically, the conditions were exactly the same as in Example 1 except that the diameter of the dot shape was 0.80 mm. In Example 3, 129 g / m ^{2 of} polyamide resin was adhered, and the reinforcing fiber content was 70% by mass. In Example 3, a resin-attached reinforced fiber fabric having a coverage C of 70% on the surface of the reinforced fiber fabric with a thermoplastic resin was obtained. In Example 3, the resin adhesion coefficient A according to the above formula (1) was 125.

Next, the tackiness, formability, and moldability of the resin-adhesion reinforced fiber fabric obtained in Example 3 were evaluated under the same conditions as in Example 1. The results are shown in Table 1 below. In Example 3, the evaluation of tackiness is “1” (possible), the evaluation of formability is “2” (possible), and the evaluation of formability is “2” (possible). It was. When the resin-attached reinforced fiber fabric of Example 3 was placed in a die of a square drawing press and heated under pressure at 260 ° C. and 5 MPa, a box-shaped fiber reinforced resin molded article having a good depth of 50 mm was obtained. I was able to.

[Example 4]
In the fourth embodiment, first, 67.5 tex glass fiber yarns were used as warps and wefts, and woven at a weaving density of 44 warps / 25 mm and 32 wefts / 25 mm to obtain a reinforced fiber fabric. In Example 4, the fiber-opening process was performed with a vibro washer, and the surface treatment of the reinforcing fiber fabric was performed with 3-glycidoxypropyltrimethoxysilane (a kind of epoxysilane). Thereby, the mass W per unit area was 180 g / m ² , the air permeability P was 2 cm ³ / cm ² / s, and a reinforced fiber fabric having epoxy silane attached to the surface was obtained.

Next, a polyamide resin was adhered to the surface of the reinforcing fiber fabric in the same manner as in Example 1. Specifically, the conditions were exactly the same as in Example 1 except that the dot shape had a diameter of 0.88 mm. In Example 4, a polyamide resin was adhered at 77 g / m ² , a reinforcing fiber content was set to 70% by mass, and a resin-attached reinforcing fiber woven fabric having a coverage ratio C of 85% on the surface of the reinforcing fiber woven fabric was obtained. In Example 4, the resin adhesion coefficient A according to the above formula (1) was 126.

Next, the tackiness, formability, and moldability of the resin-attached reinforcing fiber fabric obtained in Example 4 were evaluated under the same conditions as in Example 1. The results are shown in Table 1 below. In Example 4, the evaluation of tackiness was “1” (possible), the evaluation of formability was “2” (possible), and the evaluation of formability was “1” (good). It was. When the resin-attached reinforced fiber fabric of Example 4 was placed in a die of a square drawing press and heated under pressure at 260 ° C. and 5 MPa, a box-shaped fiber reinforced resin molded article having a good depth of 50 mm was obtained. I was able to.

[Example 5]
In Example 5, first, 135 tex glass fiber yarns were used as warps and wefts, and woven at a weaving density of 19 warps / 25 mm and 18 wefts / 25 mm to obtain a reinforced fiber fabric. In Example 5, the reinforcing fiber fabric was surface-treated with 3-glycidoxypropyltrimethoxysilane (a kind of epoxysilane). Thereby, the mass W per unit area was 210 g / m ² , the air permeability P was 70 cm ³ / cm ² / s, and a reinforced fabric with epoxy silane attached to the surface was obtained.

Next, the polyamide resin and Example 1 were completely adhered to the surface of the reinforcing fiber fabric. Specifically, the conditions were exactly the same as in Example 1 except that the diameter of the dot shape was 0.90 mm. In Example 5, 90 g / m ^{2 of} polyamide resin was adhered, the reinforcing fiber content was 70% by mass, and a resin-attached reinforcing fiber woven fabric having a coverage C on the surface of the reinforcing fiber fabric of 88% was obtained. In Example 5, the resin adhesion coefficient A according to the above formula (1) was 132.

Next, the tackiness, formability, and moldability of the resin-adhesion-reinforced fiber fabric obtained in Example 5 were evaluated under the same conditions as in Example 1. The results are shown in Table 2 below. In Example 5, the evaluation of tackiness was “1” (possible), the evaluation of formability was “2” (possible), and the evaluation of moldability was “1” (good). It was. When the resin-attached reinforced fiber fabric of Example 5 was placed in a die of a square drawing press and heated under pressure at 260 ° C. and 5 MPa, a box-shaped fiber reinforced resin molded article having a good depth of 50 mm was obtained. I was able to.

[Example 6]
In Example 6, first, 33.7 tex glass fiber yarns were used as warps and wefts, and woven at a woven density of 30 warps / 25 mm and 30 wefts / 25 mm to obtain a reinforced fiber fabric. In Example 6, the surface treatment of the reinforcing fiber fabric was performed with 3-glycidoxypropyltrimethoxysilane (a kind of epoxy silane). Thereby, the mass W per unit area was 80 g / m ² , the air permeability P was 200 cm ³ / cm ² / s, and a reinforced fiber fabric having epoxy silane attached to the surface was obtained.

Next, a polyamide resin was adhered to the surface of the reinforcing fiber fabric in the same manner as in Example 1. Specifically, the conditions were exactly the same as in Example 1 except that the diameter of the dot shape was 0.63 mm. In Example 6, a polyamide resin was adhered to 34 g / m ² , a reinforcing fiber content was set to 70% by mass, and a resin-attached reinforcing fiber woven fabric having a coverage ratio C on the surface of the reinforcing fiber fabric of 80% was obtained. In Example 6, the resin adhesion coefficient A according to the above formula (1) was 39.

Next, the tackiness, formability, and moldability of the resin-attached reinforcing fiber fabric obtained in Example 6 were evaluated under the same conditions as in Example 1. The results are shown in Table 2 below. In Example 6, the evaluation of tackiness is “1” (good), the evaluation of formability is “1” (good), and the evaluation of moldability is “1” (good). It was. When the resin-attached reinforced fiber fabric of Example 6 was placed in a die of a square drawing press and heated under pressure at 260 ° C. and 5 MPa, a box-shaped fiber reinforced resin molded article having a good depth of 50 mm was obtained. I was able to.

[Example 7]
In Example 7, in place of the polyamide resin of Example 1, a polyamide resin (copolymerized polyamide, Gritex 2A manufactured by Ems Chemie Japan) having a melting point of 122 ° C. was used, which was exactly the same as Example 1. Under the conditions, a resin-attached reinforcing fiber fabric was obtained. In Example 7, the resin adhesion coefficient A according to the above formula (1) was 66.

Next, the tackiness, formability, and moldability of the resin-attached reinforcing fiber fabric obtained in Example 7 were evaluated under the same conditions as in Example 1. The results are shown in Table 2 below. In Example 7, the evaluation of tackiness was “1” (good), the evaluation of formability was “1” (good), and the evaluation of moldability was “1” (good). It was. Moreover, when the resin-adhesion reinforced fiber fabric of Example 7 was placed in a die of a square drawing press and heated under pressure at 260 ° C. and 5 MPa, a box-shaped fiber reinforced resin molded article having a good depth of 50 mm was obtained. Could get.

[Example 8]
In Example 8, as a reinforcing fiber fabric, a surface-treated carbon fiber fabric (manufactured by Nitto Boseki Co., Ltd.) having a mass W per unit area of 210 g / m ² and an air permeability P of 50 cm ³ / cm ² / s. CF3101) was used. In Example 8, this carbon fiber woven fabric was used, and heat cleaning treatment, fiber opening treatment and surface treatment were not performed, and the coverage C of the surface of the reinforced fiber woven fabric with a thermoplastic resin was set to 65%. Under the same conditions, a resin-attached reinforcing fiber fabric was obtained. In Example 8, the resin adhesion coefficient A according to the higher order formula (1) was 73. In Table 2 below, the carbon fiber is described as “CF”.

Next, the tackiness, formability, and moldability of the resin-attached reinforcing fiber fabric obtained in Example 8 were evaluated under the same conditions as in Example 1. The results are shown in Table 2 below. In Example 8, the evaluation of tackiness is “1” (good), the evaluation of formability is “1” (good), and the evaluation of moldability is “2” (good). It was. When the resin-attached reinforced fiber fabric of Example 8 was placed in a die of a square drawing press and heated under pressure at 260 ° C. and 5 MPa, a box-shaped fiber reinforced resin molded article having a good depth of 50 mm was obtained. I was able to.

[Comparative Example 1]
In Comparative Example 1, a polyamide resin was adhered to the surface of the same reinforcing fiber fabric as in Example 1 as in Example 1. Specifically, the conditions were exactly the same as in Example 1 except that the diameter of the dot shape was 0.55 mm. In Comparative Example 1, a polyamide resin was adhered at 90 g / m ² , a reinforcing fiber content was set to 70% by mass, and a resin-attached reinforced fiber fabric having a coverage C of 40% on the surface of the reinforcing fiber fabric was obtained. In Comparative Example 1, the resin adhesion coefficient A according to the above formula (1) was 29.

Next, the tackiness, formability, and moldability of the resin-adhesion reinforcing fiber fabric obtained in this comparative example were evaluated under the same conditions as in Example 1. The results are shown in Table 3 below. In Comparative Example 1, the evaluation of tackiness was “1” (good), the evaluation of formability was “1” (good), and the evaluation of moldability was “3” (impossible). It was.

[Comparative Example 2]
In Comparative Example 2, a polyamide resin was adhered to the surface of the same reinforcing fiber fabric as in Example 1 as in Example 1. Specifically, except that the diameter of the dot shape is 0.82 mm, it is exactly the same as in Example 1, 90 g / m ^{2 of} polyamide resin is adhered, the reinforcing fiber content is 70% by mass, and the reinforcing fiber fabric A resin-adhesive reinforcing fiber woven fabric having a surface coverage C of 90% was obtained. In Comparative Example 2, the resin adhesion coefficient A according to the above formula (1) was 149.

Next, the tackiness, formability, and moldability of the resin-adhesion reinforced fiber fabric obtained in Comparative Example 2 were evaluated under the same conditions as in Example 1. The results are shown in Table 3 below. In Comparative Example 2, the evaluation of tackiness was “1” (possible), the evaluation of formability was “3” (impossible), and the evaluation of moldability was “1” (good). It was.

[Comparative Example 3]
In Comparative Example 3, the same polyamide resin as in Example 1 was applied to the surface of the same reinforcing fiber fabric as in Example 3 except that the dot-shaped diameter was 0.83 mm. Then, 129 g / m ^{2 of} polyamide resin was adhered, the reinforcing fiber content was set to 70% by mass, and a resin-attached reinforcing fiber woven fabric having a coverage C of 75% on the surface of the reinforcing fiber woven fabric was obtained. In Comparative Example 3, the resin adhesion coefficient A according to the above formula (1) was 144.

Next, the tackiness, formability, and moldability of the resin-adhesion reinforcing fiber fabric obtained in Comparative Example 3 were evaluated under the same conditions as in Example 1. The results are shown in Table 3 below. In Comparative Example 3, the evaluation of tackiness was “1” (possible), the evaluation of formability was “3” (impossible), and the evaluation of moldability was “1” (good). It was.

[Comparative Example 4]
In Comparative Example 4, the same polyamide resin as in Example 1 was applied to the surface of the same reinforcing fiber fabric as in Example 4 except that the dot-shaped diameter was 0.91 mm. Then, 77 g / m ^{2 of} polyamide resin was adhered, the reinforcing fiber content was set to 70% by mass, and a resin-attached reinforcing fiber woven fabric having a coverage ratio C of 90% on the surface of the reinforcing fiber woven fabric was obtained. In Comparative Example 4, the resin adhesion coefficient A according to the above formula (1) was 141.

Next, with respect to the resin-adhesion-reinforced fiber fabric obtained in Comparative Example 4, the tackiness, formability, and moldability were evaluated in exactly the same manner as in Example 1. The results are shown in Table 4 below. In Comparative Example 4, the evaluation of tackiness was “1” (possible), the evaluation of formability was “3” (impossible), and the evaluation of moldability was “1” (good). It was.

[Comparative Example 5]
In Comparative Example 5, an ethylene-vinyl acetate copolymer resin (Evaflex EV150 manufactured by Mitsui DuPont Polychemical Co., Ltd.) having a melting point of 61 ° C. was adhered to the surface of the same reinforcing fiber fabric as in Example 1. Specifically, 90 g / m ^{2 of} ethylene-vinyl acetate copolymer resin was adhered under the same conditions as in Example 1 except that the dot shape diameter was 0.67 mm, and the reinforcing fiber content was 70. A resin-attached reinforced fiber fabric having a mass% and a coverage ratio C of 60% on the surface of the reinforced fiber fabric was obtained. In Comparative Example 5, the resin adhesion coefficient A according to the above formula (1) was 66.

Next, with respect to the resin-attached reinforcing fiber fabric obtained in this comparative example, tackiness, shapeability and moldability were evaluated in exactly the same manner as in Example 1. The results are shown in Table 4 below. In Comparative Example 5, the evaluation of tackiness was “2” (impossible), the evaluation of formability was “1” (good), and the evaluation of moldability was “1” (good). It was.

[Example 9]
A laminate obtained by laminating an aluminum foil (thickness 100 μm, weight 250 g / m ² , manufactured by Toyo Aluminum Co., Ltd.) on the resin adhesion surface of the resin adhesion reinforcing fiber fabric obtained in Example 7 is thermoplastic. Heating was performed at a temperature 20 ° C. higher than the melting point of the resin, pressurizing was performed at 5 MPa, and press molding was performed to prepare a fiber-reinforced resin molded product. In the obtained fiber reinforced resin molded product, the aluminum foil and the fiber reinforced resin flat plate derived from the resin-adhesion reinforced fiber fabric were firmly integrated.

[Example 10]
From the melting point of the thermoplastic resin, a laminate obtained by laminating a vinyl chloride resin sheet (thickness 250 μm, weight 300 g / m ² ) on the resin adhesion surface of the resin adhesion reinforcing fiber fabric obtained in Example 7 was used. A fiber reinforced resin molded article was prepared by heating to a temperature 20 ° C. and pressurizing by pressurizing at 5 MPa. In the obtained fiber reinforced resin molded product, the vinyl chloride resin sheet and the fiber reinforced resin flat plate derived from the resin-adhesion reinforced fiber fabric were firmly integrated.

In Example 9 and Example 10, “strongly integrated” means that the resin-bonded reinforced fiber fabric conforms to the Japan Membrane Structure Association Test Method Standard “Membrane Material Quality and Performance Test Method”. When the adhesive strength of the aluminum foil or the vinyl chloride resin sheet is measured, it means that the aluminum foil or the vinyl chloride resin sheet cannot be peeled off from the resin-adhesive reinforcing fiber fabric and is in a damaged state.

Claims (11)

A resin-attached reinforcing fiber fabric in which a thermoplastic resin is attached to at least one surface of the reinforcing fiber fabric,
The mass W per unit area of the reinforcing fiber fabric is in the range of 25 g / m ^{2 to} 400 g / m ² ,
The air permeability P of the reinforcing fiber fabric is in the range of 0.1 cm ³ / cm ² / s to 300 cm ³ / cm ² / s,
The melting point of the thermoplastic resin is in the range of 70 ° C. or higher and 300 ° C. or lower,
The ratio of the mass of the reinforcing fiber fabric to the total mass of the resin-attached reinforcing fiber fabric is in the range of 20% by mass to 90% by mass,
The coverage C of the reinforcing fiber fabric surface with the thermoplastic resin is in the range of 30% or more and less than 100%,
Resin adhesion reinforcing fiber woven fabric having a resin adhesion coefficient A represented by the following formula (1) in the range of 35 or more and 135 or less.
A = W × (C / 100) ² / P ^0.05 (1) The resin-attached reinforcing fiber woven fabric according to claim 1, wherein a mass W per unit area of the reinforcing fiber woven fabric is in a range of 50 g / m ^{2 to} 250 g / m ² . The resin adhesion reinforcing fiber fabric according to claim 1 or 2, wherein the resin adhesion coefficient A is 35 or more and 95 or less. The resin-attached reinforcing fiber fabric according to any one of claims 1 to 3, wherein the reinforcing fiber fabric is a glass fiber fabric. The resin-attached reinforcing fiber woven fabric according to claim 4, wherein a silane coupling agent is attached to a surface of the glass fiber woven fabric. The resin-attached reinforcing fiber fabric according to claim 5, wherein the silane coupling agent is epoxy silane. A fiber reinforcement comprising a molding step of heating and pressurizing one sheet of the resin-bonded reinforcing fiber fabric according to any one of claims 1 to 6 or a laminate of a plurality of the resin-bonded reinforcing fiber fabrics. Manufacturing method of resin molded product. The method for producing a fiber-reinforced resin molded article according to claim 7, wherein, in the molding step, the resin-adhesion-reinforced fiber fabric is adopted as a metal substitute material, and the resin-adhesion-reinforced fiber fabric is heated and pressurized. The method for producing a fiber-reinforced resin molded article according to claim 8, wherein, in the molding step, the resin-adhesion-reinforced fiber fabric is adopted as a metal substitute material for automobiles, and the resin-adhesion-reinforced fiber fabric is heated and pressurized. The method for producing a fiber-reinforced resin molded article according to any one of claims 7 to 9, wherein, in the molding step, the resin-adhesion-reinforced fiber fabric is heated and pressed to form a box shape. The method for producing a fiber-reinforced resin molded article according to claim 10, wherein in the molding step, the resin-adhesion-reinforced fiber fabric is heated and pressed to form a box shape to produce an oil pan.