JP6965899B2 - Manufacturing method of resin adhesion reinforced fiber woven fabric and fiber reinforced resin molded product - Google Patents

Description

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

In recent years, in various fields such as automobiles and airplanes, it has been studied to replace metal materials with resin materials to reduce the weight of airframes in order to improve fuel efficiency and the like. In particular, a fiber-reinforced resin material containing reinforcing fibers such as glass fiber and carbon fiber is attracting attention as a metal substitute material 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 an internal combustion engine. For example, in the oil pan described in Patent Document 1, a glass fiber reinforcing material is arranged on a flange portion and resin is injected.

Japanese Unexamined Patent Publication No. 7-27289

However, in the prior art described in Patent Document 1 above, although the reinforcing fiber material is partially used, the strength as a product is insufficient. In addition, the step of injecting the resin takes longer than the press molding step usually used for metal materials, and the manufacturing efficiency may decrease. For example, in order to improve the manufacturing efficiency, it is considered possible to solve the problem by processing a resin sheet containing a reinforcing fiber reinforcing material into a desired shape and processing it by press molding. The resin sheet containing the reinforcing material is hard, has insufficient shapeability, is difficult to process into a complicated shape, and is difficult to improve the manufacturing efficiency.

One aspect of the present invention has been made in order to solve such a problem, has moldability and shapeability suitable for press molding, improves handleability, and manufactures a molded product. It is an object of the present invention to provide a resin-adhered reinforced woven fabric capable of improving manufacturing efficiency at the time of production. One aspect of the present invention is to provide a method for producing a fiber-reinforced resin molded product using such a resin-attached reinforced fiber woven fabric.

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

Since the resin adhesion coefficient A according to the above formula (1) is in the range of 35 or more and 135 or less in the resin adhesion reinforcing fiber woven fabric, it has moldability and shapeability suitable for press molding by heating and pressing, and can be handled. It is possible to improve the property and improve the manufacturing efficiency when manufacturing the molded product. Since the tackiness of the resin-adhered reinforced fiber woven fabric is reduced, the handleability can be improved. The tack property is a property that indicates the ease of peeling from the resin-attached reinforcing fiber woven fabric in an overlapping state. For example, if the tackiness is low, the resin-adhered reinforced fiber woven fabric can be easily pulled out from the roll-shaped resin-attached reinforced fiber woven fabric, so that it is easy to handle and the production efficiency at the time of manufacturing the molded product can be improved. In addition, when manufacturing a molded product, it is not necessary to inject resin as in the past, and a molded product can be obtained by press molding by heating and pressurizing, so that the manufacturing time can be shortened and the manufacturing efficiency can be reduced. Can be improved.

The mass W per unit area of the reinforced fiber woven fabric may be in the range of ^{50 g / m 2} or more and 250 g / m ^{2 or less.} As a result, sufficient strength can be secured and sufficient shapeability can be obtained.

The resin adhesion coefficient A may be 35 or more and 95 or less. According to such a resin-adhered reinforced fiber woven fabric, sufficient shapeability can be obtained, and a molded product having a more complicated shape can be manufactured by press molding. It can be improved.

The reinforcing fiber woven fabric may be a glass fiber woven fabric. A silane coupling agent may be attached to the surface of the glass fiber woven fabric. The silane coupling agent may be epoxy silane. When the silane coupling agent is attached to the surface of the glass fiber woven fabric, the impregnation of the glass fiber woven fabric with the thermoplastic resin is improved, and the strength of the molded product of the resin adhesion reinforced fiber woven 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 pressurizing one resin-bonded reinforced fiber woven fabric or a laminate obtained by laminating a plurality of resin-bonded reinforced fiber woven fabrics.

In this method for producing a fiber-reinforced resin molded product, the resin-adhered reinforced fiber woven fabric can be heated and pressed to obtain a molded product, and the production efficiency at the time of producing the molded product can be improved. When manufacturing a molded product, it is not necessary to inject resin as in the past, and a molded product can be obtained by press molding by heating and pressurizing, so that the manufacturing time can be shortened and the manufacturing efficiency can be improved. Can be planned.

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

In the molding step, the resin-attached reinforcing fiber woven fabric can be heated and pressed to form a box shape. Further, in the molding step, the resin-attached reinforcing fiber woven fabric can be heated and pressed to form a box shape to manufacture an oil pan.

According to one aspect of the present invention, it is possible to have moldability corresponding to press molding, improve shapeability and handleability, and improve manufacturing efficiency when manufacturing a molded product. It is possible to provide a method for producing a resin-adhered reinforced fabric and a fiber-reinforced resin molded product.

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

The resin-attached reinforcing fiber woven fabric of the present embodiment has a reinforcing fiber woven fabric. A thermoplastic resin is attached to at least one surface of the reinforcing fiber woven fabric. The woven structure of the reinforced fiber woven fabric is not particularly limited. The woven structure of the reinforced fiber woven fabric may be, for example, a plain weave structure, a twill weave structure, or a satin weave structure. The woven structure of the reinforced fiber woven fabric may be a multiple woven structure such as a double woven structure and a triple woven structure. The weaving structure of the reinforced fiber woven fabric may be a changing structure such as a slanted weaving structure and a ridged weaving structure. The woven structure of the reinforced fiber woven fabric may be a special structure such as a woven fabric structure or a sand grain structure. The woven structure of the reinforced fiber woven fabric may be another woven structure.

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

Reinforcing fiber woven fabrics are not limited to those composed of one type of fiber. The reinforcing fiber woven fabric may be composed of different types of reinforcing fiber yarns, for example, the warp yarn and the weft yarn. The reinforcing fiber woven fabric may contain different types of reinforcing fiber threads as a part of the warp or weft. The warp or weft that constitutes the reinforced fiber woven fabric may be a mixed fiber, a combined yarn, or a combined twist of the reinforcing fiber and the thermoplastic resin fiber made of a thermoplastic resin described later. A part of the warp or weft of the reinforcing fiber woven fabric may contain a thermoplastic resin fiber yarn.

Examples of the silane coupling agent include epoxy silane, amino silane, acrylic silane, methacrylic silane, and cationic silane. The silane coupling agent is preferably epoxysilane. Examples of the epoxysilane include 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane. When the resin-adhered reinforcing fiber woven fabric has a glass fiber woven fabric to which epoxy silane is attached, the moldability becomes particularly excellent.

The thermoplastic resin may be attached to one surface of the reinforcing fiber woven fabric, and the thermoplastic resin may be attached to both sides of the reinforcing fiber woven 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, and polyether ether. Examples thereof include a ketone resin, a polyaryl ether ketone resin, and a liquid crystal polymer (LCP). The thermoplastic resin is preferably a polyamide resin.

The mass W per unit area of the reinforced fiber woven fabric is in the range of ^{25 g / m 2} or more and 400 g / m ^{2 or less.} This unit area is a unit area seen from the thickness direction of the woven fabric. The mass W per unit area of the reinforced fiber woven 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 more, and most preferably 105 g / m ² or more and 215 g / m ² or less.

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

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

The air permeability P of the reinforced fiber woven fabric is in the range of 0.1 cm ³ / cm ² / s or more and 300 cm ³ / cm ² / s or less. The air permeability P of the reinforced fiber woven 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 reinforced fiber woven 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 reinforcing fiber woven fabric ^{is particularly preferably 10 cm 3} / cm ² / s or more and 40 cm ³ / cm ² / s or less, and 12 cm ³ / cm ² / s or more and 30 cm ³ / cm ² / s or less. This is particularly preferable, and 13 cm ³ / cm ² / s or more and 25 cm ³ / cm ² / s or less is particularly preferable, and 14 cm ³ / cm ² / s or more and 24 cm ³ / cm ² / s or less is the most preferable. preferable.

As a method for measuring the air permeability P of the reinforced fiber woven fabric, when the reinforced fiber woven fabric is an inorganic reinforced fiber woven fabric, the resin adhering to the reinforced fiber woven fabric is heated at, for example, 625 ° C. for 1 hour to remove the reinforced fiber woven fabric. The air permeability P of the fiber woven fabric can be measured. When the reinforced fiber woven fabric is an organic reinforced fiber woven fabric, the resin-attached reinforced fiber woven fabric is immersed in a solvent that does not dissolve the organic reinforced fiber but dissolves the resin attached to the reinforced fiber woven fabric, and adheres to the reinforced fiber woven fabric. The air permeability P of the reinforced fiber woven fabric after removing the resin can be measured. The air permeability P of the reinforced fiber woven fabric (particularly the glass fiber woven fabric) can be measured in accordance with JIS R3420.

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

The melting point of the thermoplastic resin is in the range of 70 ° C. or higher and 300 ° C. or lower. 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, the tackiness of the resin-adhered reinforced fiber woven 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 woven fabric to the total mass of the resin-attached reinforcing fiber woven fabric is in the range of 20% by mass or more and 90% by mass or less. This 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 total mass of the resin-bonded reinforced fiber woven fabric to the mass of the reinforced fiber woven fabric is 20% by mass or more, it is possible to avoid insufficient strength of the resin-attached reinforced fiber woven fabric. When the ratio R is 90% by mass or less, it is possible to avoid insufficient penetration of the thermoplastic resin into the reinforcing fiber woven fabric. The total mass T of the resin-adhered reinforcing fiber woven fabric is, for example, the sum of the mass W per unit area of the reinforcing fiber woven fabric and the mass B per unit area of the thermoplastic resin attached to at least one surface of the reinforcing fiber woven fabric. (T = W + B). The ratio R (reinforcing fiber content) is the ratio of the mass B of the reinforcing fiber woven fabric to the total mass T of the resin-attached reinforcing fiber woven fabric (R = B / T).

The coverage C of the surface of the reinforced fiber woven fabric by the thermoplastic resin is in the range of 30% or more and less than 100%. The coverage ratio C is a ratio of the area covered with the thermoplastic resin on the surface of the reinforced fiber woven fabric. The coverage C is preferably 40% or more and 95% or less. 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 preferable, 55% or more and 70% or less is particularly preferable, and 57% or more and 65% or less is most preferable.

When the coverage C is less than 30%, the resin-adhered reinforcing fiber woven fabric does not have sufficient moldability. On the other hand, when the coverage C is 100%, the resin-adhered reinforcing fiber woven fabric is less likely to be deformed and does not have sufficient shapeability.

In the resin-adhered reinforced fiber woven fabric, it is preferable that the resin is evenly adhered to the reinforced fiber woven fabric in order to improve the moldability and shapeability of the resin-attached reinforced fiber woven fabric. For example, the ratio of standard error to the average value (standard error / average value) when at least 20 1 cm × 1 cm square samples are taken out from the resin-attached reinforcing fiber woven fabric and the mass of this 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 reinforced fiber woven fabric has, for example, a dot shape and is evenly dispersed and arranged.

The resin adhesion reinforcing fiber woven fabric has 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)
(Here, W: mass per unit area of the reinforced fiber woven fabric, P: air permeability of the reinforced fiber woven fabric, C: coverage of the surface of the reinforced fiber woven 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 woven fabric. Further, when the resin adhesion coefficient A is 135 or less, the decrease in formability can be suppressed.

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

The fiber-reinforced resin molded product contains a resin-attached reinforced fiber woven fabric, and is obtained by molding the resin-attached reinforced fiber woven fabric. The fiber-reinforced resin molded product is, for example, a product in which a resin-adhered reinforced fiber woven fabric is used as a metal substitute material. The metal substitute material is, for example, an automobile metal substitute material applied to an automobile part. The fiber reinforced resin molded product includes, for example, a box-shaped structure. The fiber-reinforced resin molded product may have a box shape as a whole, or may include a part having a box shape.

An oil pan is mentioned as an example of a fiber reinforced resin molded product which is a component for an automobile and includes a box-shaped structure. The oil pan is, for example, a box-shaped container provided below the crankshaft of an internal combustion engine to store lubricating oil. The oil pan has, for example, an inclined surface at the bottom for collecting the stored lubricating oil in a predetermined place. The oil pan may include a complicated structure or may have a simple structure.

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

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

The fiber-reinforced resin molded product is not limited to the one using only the resin-adhered reinforced fiber woven fabric. For example, a fiber-reinforced resin molded product may be molded by heating and pressurizing a laminate obtained by laminating another base material on the resin-adhered surface of the resin-adhered reinforced fiber woven 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, etc.) (Ceramic board), paper (non-combustible paper, honeycomb board) and the like can be used.

As described above, according to the resin adhesion reinforcing fiber woven 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, can be improved in handleability, and can be improved in manufacturing efficiency when manufacturing a molded product. When manufacturing a molded product, it is not necessary to inject resin as in the past, and a molded product can be obtained by press molding by heating and pressurizing, so that the manufacturing time can be shortened and the manufacturing efficiency can be improved. Can be planned.

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 the oil pan, and may have another box-shaped shape, a plate-shaped product, or a molded product having another shape. Further, the fiber-reinforced resin molded product is not limited to the parts for automobiles, and may be parts of other transportation equipment, machines, and structures.

Next, the resin adhesion reinforcing fiber woven fabric according to Examples 1 to 10 and Comparative Examples 1 to 5 will be described.

[Example 1]
In Example 1, first, 135tex glass fiber yarns were used as warp yarns and weft yarns and woven at a weaving density of 19 warp yarns / 25 mm and 18 weft yarns / 25 mm to obtain a reinforced fiber woven fabric. Next, in Example 1, a heat cleaning treatment and a fiber opening treatment with a vibro washer were performed, and a surface treatment was performed with 3-glycidoxypropyltrimethoxysilane (a type of epoxysilane). As a result, a reinforced fiber woven fabric having a mass W of 210 g / m ² per unit area, an air permeability P of 15 cm ³ / cm ² / s, and an epoxy silane attached to the surface was obtained. The mass per unit area of the reinforced fiber woven fabric and the air permeability P of the reinforced fiber woven fabric were measured in accordance with JIS R3420. In Tables 1 to 4 below, glass fibers are referred to 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 attached to the surface of the reinforcing fiber woven fabric. Specifically, using a screen provided with a dot-shaped opening, the polyamide resin is evenly arranged in a diameter of 0.67 mm and 30 dots per 2.54 cm (1 inch), and then heated and fixed to room temperature. By allowing to cool, 90 g / m ^{2 was} attached. 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) (Reinforcing fiber content) R was set to 70% by mass (wt%). As a result, in Example 1, a resin-adhered reinforced fiber woven fabric having a coverage C of 60% on the surface of the reinforced fiber woven fabric was obtained. In Example 1, the resin adhesion coefficient A according to the above formula (1) was 66.

The coverage C on the surface of the reinforced fiber woven fabric is determined by observing the surface of the reinforced fiber woven fabric using a microscope VHX-600 manufactured by Keyence Co., Ltd. and observing the surface of the reinforced fiber woven fabric. Yes, the area of the void portion existing between the reinforcing fiber threads is not included), and the area S2 of the portion where the resin adheres on the surface of the reinforcing fiber woven fabric was determined and determined by S2 / S1. Further, the melting point of the thermoplastic resin can be measured according to JIS K7121.

Immediately after the resin-attached reinforced fiber woven fabric of Example 1 was obtained by heating and fixing the thermoplastic resin and allowing it to cool to room temperature, two sheets of the resin-attached reinforced fiber woven fabric of Example 1 were stacked and pressed, and then peeled off. The tackiness of the resin-adhered reinforced fiber woven fabric was evaluated by the degree of peeling at the time. Here, "1" (possible) is easy when the two resin-attached reinforcing fiber fabrics can be peeled off without sticking, or when the two resin-attached reinforcing fiber fabrics are easily peeled off and there is no resin transfer between the resin-attached reinforcing fiber fabrics. The case where the resin could not be peeled off 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-adhered reinforcing fiber woven fabric obtained in Example 1, 50 mm in the length direction of the test piece was placed on a test table, and 150 mm in the length direction was tested. The shapeability of the resin-adhered reinforced fiber woven fabric was evaluated by measuring the angle from the vertical surface (side wall surface of the test table) when it was hung out of the table. Here, the case where the angle from the vertical plane is 0 ° or more and less than 45 ° (that is, the case where the test piece hangs down greatly) is “1” (good), and the case where the angle is 45 ° or more and less than 70 ° is “2” (. Yes), the case of 70 ° or more and less than 90 ° (when the degree of sagging of the test piece is small) was evaluated as “3” (not possible). The results are shown in Table 1 below.

Next, the resin-adhered reinforced fiber woven fabric obtained in Example 1 was heated to a temperature 20 ° C. higher than the melting point of the thermoplastic resin and pressed at 5 MPa to perform press molding 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-adhered reinforced fiber woven fabric was evaluated. Here, the one in which the glass fiber is impregnated with the thermoplastic resin and becomes transparent is "1" (good), and the glass fiber is not completely transparent, but the resin is sinked, scratched, twisted, and misaligned. The case where none of them could be confirmed was evaluated as "2" (possible), and the case where resin sinking, faintness, eye twist 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 tackiness evaluation is "1" (possible), the shapeability evaluation is "1" (good), and the moldability evaluation is. It was "1" (good). When the resin-adhered reinforced fiber woven fabric of Example 1 was placed in a mold of a square drawing press and heated under pressure at 260 ° C. and 5 MPa, a box-shaped fiber reinforced plastic molded product having a good depth of 50 mm was obtained. I was able to.

[Example 2]
In Example 2, the resin-bonded reinforced fiber woven fabric was subjected to the same conditions as in Example 1 except that the surface of the reinforced fiber woven fabric was treated with 3-aminopropyltriethoxysilane (a type of aminosilane) which is a silane coupling agent. Got In Example 2, the resin adhesion coefficient A according to the above formula (1) was 66.

Next, the resin-adhered reinforcing fiber woven fabric obtained in Example 2 was evaluated for tackiness, shapeability and moldability under exactly the same conditions as in Example 1. The results are shown in Table 1 below. In Example 2, the tackiness evaluation is "1" (possible), the shapeability evaluation is "1" (good), and the moldability evaluation is "2" (possible). rice field. When the resin-adhered reinforced fiber woven fabric of Example 2 was placed in a mold of a square drawing press and heated under pressure at 260 ° C. and 5 MPa, a box-shaped fiber reinforced plastic molded product 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 warp yarns and weft yarns and woven at a weaving density of 57 warp yarns / 25 mm and 53 weft yarns / 25 mm to obtain a reinforced fiber woven fabric. In Example 3, the surface of the reinforcing fiber woven fabric was treated with 3-glycidoxypropyltrimethoxysilane (a type of epoxysilane), which is a silane coupling agent. As a result, a reinforced fiber woven fabric having a mass W of 300 g / m ² per unit area, an air permeability P of 25 cm ³ / cm ² / s, and an epoxy silane attached to the surface was obtained.

Next, the polyamide resin was attached to the surface of the reinforcing fiber woven 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, the polyamide resin was ^{adhered at 129 g / m 2} to make the reinforcing fiber content 70% by mass. In Example 3, a resin-adhered reinforced fiber woven fabric having a coverage C of 70% on the surface of the reinforced fiber woven fabric made of a thermoplastic resin was obtained. In Example 3, the resin adhesion coefficient A according to the above formula (1) was 125.

Next, the resin-adhered reinforcing fiber woven fabric obtained in Example 3 was evaluated for tackiness, shapeability and moldability under exactly the same conditions as in Example 1. The results are shown in Table 1 below. In Example 3, the tackiness evaluation is "1" (possible), the shapeability evaluation is "2" (possible), and the moldability evaluation is "2" (possible). rice field. When the resin-adhered reinforced fiber woven fabric of Example 3 was placed in a mold of a square drawing press and heated under pressure at 260 ° C. and 5 MPa, a box-shaped fiber reinforced plastic molded product having a good depth of 50 mm was obtained. I was able to.

[Example 4]
In the present embodiment 4, first, 67.5 tex glass fiber yarns were used as warp yarns and weft yarns and woven at a weaving density of 44 warp yarns / 25 mm and 32 weft yarns / 25 mm to obtain a reinforced fiber woven fabric. In Example 4, the fiber was opened with a vibro washer, and the surface of the reinforced fiber woven fabric was treated with 3-glycidoxypropyltrimethoxysilane (a type of epoxysilane). As a result, a reinforced fiber woven fabric having a mass W of 180 g / m ² per unit area, an air permeability P of 2 cm ³ / cm ² / s, and an epoxy silane attached to the surface was obtained.

Next, the polyamide resin was attached to the surface of the reinforcing fiber woven 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 0.88 mm. In Example 4, a polyamide resin was ^{adhered at 77 g / m 2} to obtain a resin-adhered reinforced fiber woven fabric having a reinforcing fiber content of 70% by mass and a coverage C on the surface of the reinforced fiber woven fabric of 85%. In Example 4, the resin adhesion coefficient A according to the above formula (1) was 126.

Next, the resin-adhered reinforcing fiber woven fabric obtained in Example 4 was evaluated for tackiness, shapeability and moldability under exactly the same conditions as in Example 1. The results are shown in Table 1 below. In Example 4, the tackiness evaluation was "1" (possible), the shapeability evaluation was "2" (possible), and the moldability evaluation was "1" (good). rice field. The resin-adhered reinforced fiber woven fabric of Example 4 was placed in a mold of a square drawing press and heated under pressure at 260 ° C. and 5 MPa to obtain a box-shaped fiber reinforced plastic molded product having a good depth of 50 mm. I was able to.

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

Next, the polyamide resin as in Example 1 was completely adhered to the surface of the reinforcing fiber woven 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, a polyamide resin was ^{adhered at 90 g / m 2} to obtain a resin-adhered reinforced fiber woven fabric having a reinforcing fiber content of 70% by mass and a coverage C of 88% on the surface of the reinforced fiber woven fabric. In Example 5, the resin adhesion coefficient A according to the above formula (1) was 132.

Next, the resin-adhered reinforcing fiber woven fabric obtained in Example 5 was evaluated for tackiness, shapeability and moldability under exactly the same conditions as in Example 1. The results are shown in Table 2 below. In Example 5, the tackiness evaluation was "1" (possible), the shapeability evaluation was "2" (possible), and the moldability evaluation was "1" (good). rice field. When the resin-adhered reinforced fiber woven fabric of Example 5 was placed in a mold of a square drawing press and heated under pressure at 260 ° C. and 5 MPa, a box-shaped fiber reinforced plastic molded product 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 warp yarns and weft yarns and woven at a weaving density of 30 warp yarns / 25 mm and 30 weft yarns / 25 mm to obtain a reinforced fiber woven fabric. In Example 6, the surface of the reinforcing fiber woven fabric was treated with 3-glycidoxypropyltrimethoxysilane (a type of epoxysilane). As a result, a reinforced fiber woven fabric having a mass W of 80 g / m ² per unit area, an air permeability P of 200 cm ³ / cm ² / s, and an epoxy silane attached to the surface was obtained.

Next, the polyamide resin was attached to the surface of the reinforcing fiber woven 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 at 34 g / m 2} to obtain a resin-adhered reinforced fiber woven fabric having a reinforcing fiber content of 70% by mass and a coverage C of 80% on the surface of the reinforced fiber woven fabric. In Example 6, the resin adhesion coefficient A according to the above formula (1) was 39.

Next, the resin-adhered reinforcing fiber woven fabric obtained in Example 6 was evaluated for tackiness, shapeability and moldability under exactly the same conditions as in Example 1. The results are shown in Table 2 below. In Example 6, the tackiness evaluation was "1" (possible), the shapeability evaluation was "1" (good), and the moldability evaluation was "1" (good). rice field. The resin-adhered reinforced fiber woven fabric of Example 6 was placed in a mold of a square drawing press and heated under pressure at 260 ° C. and 5 MPa to obtain a box-shaped fiber reinforced plastic molded product having a good depth of 50 mm. I was able to.

[Example 7]
In Example 7, the same as in Example 1 except that a polyamide resin having a melting point of 122 ° C. (copolymerized polyamide, Griltex2A manufactured by Ems-Chemie Japan) was used instead of the polyamide resin of Example 1. Under the conditions, a resin-adhered reinforcing fiber woven fabric was obtained. In Example 7, the resin adhesion coefficient A according to the above formula (1) was 66.

Next, the resin-adhered reinforcing fiber woven fabric obtained in Example 7 was evaluated for tackiness, shapeability and moldability under exactly the same conditions as in Example 1. The results are shown in Table 2 below. In Example 7, the tackiness evaluation was "1" (possible), the shapeability evaluation was "1" (good), and the moldability evaluation was "1" (good). rice field. Further, when the resin-adhered reinforced fiber woven fabric of Example 7 was placed in a mold of a square drawing press and pressurized and heated under the conditions of 260 ° C. and 5 MPa, a box-shaped fiber reinforced plastic molded product having a good depth of 50 mm was obtained. I was able to get.

[Example 8]
In Example 8, the surface-treated carbon fiber woven fabric (manufactured by Nitto Boseki Co., Ltd.) has a mass W of 210 g / m ² per unit area and a breathability P of 50 cm ³ / cm ^{2 / s as the reinforced fiber woven fabric.} 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 the thermoplastic resin was set to 65%. Under the same conditions, a resin-attached reinforced fiber woven fabric was obtained. In Example 8, the resin adhesion coefficient A according to the superordinate formula (1) was 73. In Table 2 below, carbon fibers are listed as "CF".

Next, the resin-adhered reinforcing fiber woven fabric obtained in Example 8 was evaluated for tackiness, shapeability and moldability under exactly the same conditions as in Example 1. The results are shown in Table 2 below. In Example 8, the tackiness evaluation is "1" (possible), the shapeability evaluation is "1" (good), and the moldability evaluation is "2" (possible). rice field. The resin-adhered reinforced fiber woven fabric of Example 8 was placed in a mold of a square drawing press and heated under pressure at 260 ° C. and 5 MPa to obtain a box-shaped fiber reinforced plastic molded product having a good depth of 50 mm. I was able to.

[Comparative Example 1]
In Comparative Example 1, the polyamide resin was adhered to the surface of the same reinforcing fiber woven 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} to obtain a resin-adhered reinforced fiber woven fabric having a reinforcing fiber content of 70% by mass and a coverage C of 40% on the surface of the reinforced fiber woven fabric. In Comparative Example 1, the resin adhesion coefficient A according to the above formula (1) was 29.

Next, the resin-adhered reinforcing fiber woven fabric obtained in this comparative example was evaluated for tackiness, shapeability and moldability under exactly the same conditions as in Example 1. The results are shown in Table 3 below. In Comparative Example 1, the tackiness evaluation was "1" (possible), the shapeability evaluation was "1" (good), and the moldability evaluation was "3" (impossible). rice field.

[Comparative Example 2]
In Comparative Example 2, the polyamide resin was adhered to the surface of the same reinforcing fiber woven fabric as in Example 1 as in Example 1. Specifically, the same as in Example 1 except that the diameter of the dot shape is 0.82 mm, the polyamide resin is ^{adhered at 90 g / m 2} , the reinforcing fiber content is 70% by mass, and the reinforcing fiber woven fabric is used. A resin-adhered reinforced 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 resin-adhered reinforcing fiber woven fabric obtained in Comparative Example 2 was evaluated for tackiness, shapeability and moldability under exactly the same conditions as in Example 1. The results are shown in Table 3 below. In Comparative Example 2, the tackiness evaluation was "1" (possible), the shapeability evaluation was "3" (impossible), and the moldability evaluation was "1" (good). rice field.

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

Next, the resin-adhered reinforcing fiber woven fabric obtained in Comparative Example 3 was evaluated for tackiness, shapeability and moldability under exactly the same conditions as in Example 1. The results are shown in Table 3 below. In Comparative Example 3, the tackiness evaluation was "1" (possible), the shapeability evaluation was "3" (impossible), and the moldability evaluation was "1" (good). rice field.

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

Next, the resin-adhered reinforcing fiber woven fabric obtained in Comparative Example 4 was made exactly the same as in Example 1 to evaluate tackiness, shapeability and moldability. The results are shown in Table 4 below. In Comparative Example 4, the tackiness evaluation was "1" (possible), the shapeability evaluation was "3" (impossible), and the moldability evaluation was "1" (good). rice field.

[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 attached to the surface of the same reinforcing fiber woven fabric as in Example 1. Specifically, under exactly the same conditions as in Example 1 except that the diameter of the dot shape is 0.67 mm, an ethylene-vinyl acetate copolymer resin is ^{adhered at 90 g / m 2} and the reinforcing fiber content is 70. A resin-adhered reinforced fiber woven fabric having a coating ratio C on the surface of the reinforced fiber woven fabric was 60% by mass. In Comparative Example 5, the resin adhesion coefficient A according to the above formula (1) was 66.

Next, the resin-adhered reinforcing fiber woven fabric obtained in this comparative example was made exactly the same as in Example 1 and the tackiness, shapeability and moldability were evaluated. The results are shown in Table 4 below. In Comparative Example 5, the tackiness evaluation was "2" (impossible), the shapeability evaluation was "1" (good), and the moldability evaluation was "1" (good). rice field.

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

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

In Examples 9 and 10, "strongly integrated" means a resin-adhered reinforced fiber woven fabric in accordance with the test method standard "Film material quality and performance test method" of the Japan Film Structure Association. When the adhesive strength of the aluminum foil or the vinyl chloride resin sheet is measured with respect to the resin, it means that the aluminum foil or the vinyl chloride resin sheet cannot be peeled off from the resin adhesion reinforced fiber woven fabric and is in a state of being damaged.

Claims (11)

A resin-adhered reinforced fiber woven fabric in which a thermoplastic resin is attached to at least one surface of the reinforced fiber woven fabric.
The mass W per unit area of the reinforcing fiber woven fabric is in the range of ^{25 g / m 2} or more and 400 g / m ^{2 or less.}
The air permeability P of the reinforced fiber woven fabric is in the range of 7 cm ³ / cm ² / s or more and 300 cm ³ / cm ² / s or less.
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 woven fabric to the total mass of the resin-attached reinforcing fiber woven fabric is in the range of 20% by mass or more and 90% by mass or less.
The coverage C of the surface of the reinforcing fiber woven fabric by the thermoplastic resin is in the range of 30% or more and 95% or less.
A resin adhesion reinforcing fiber woven fabric in which the resin adhesion coefficient A represented by the following formula (1) is in the range of 35 or more and 135 or less.
A = W × (C / 100) ² / P ^0.05 … (1) The resin-adhered reinforcing fiber woven fabric according to claim 1, wherein the mass W per unit area of the reinforcing fiber woven fabric ^{is in the range of 50 g / m 2} or more and 250 g / m ^{2 or less.} The resin adhesion reinforcing fiber woven fabric according to claim 1 or 2, wherein the resin adhesion coefficient A is 35 or more and 85 or less. The resin-adhered reinforcing fiber woven fabric according to any one of claims 1 to 3, wherein the reinforcing fiber woven fabric is a glass fiber woven fabric. The resin-adhered reinforcing fiber woven fabric according to claim 4, wherein the silane coupling agent is attached to the surface of the glass fiber woven fabric. The resin-adhered reinforcing fiber woven fabric according to claim 5, wherein the silane coupling agent is epoxysilane. Fiber reinforced including a molding step of heating and pressurizing one piece of the resin-bonded reinforced fiber woven fabric according to any one of claims 1 to 6 or a laminate obtained by laminating a plurality of the resin-attached reinforced fiber woven fabrics. A method for manufacturing a resin molded product. The method for producing a fiber-reinforced resin molded product according to claim 7, wherein in the molding step, the resin-adhered reinforcing fiber woven fabric is adopted as a metal substitute material, and the resin-attached reinforced fiber woven fabric is heated and pressed. The method for producing a fiber-reinforced resin molded product according to claim 8, wherein in the molding step, the resin-attached reinforced fiber woven fabric is adopted as a metal substitute material for an automobile, and the resin-attached reinforced fiber woven fabric is heated and pressed. The method for producing a fiber-reinforced resin molded product according to any one of claims 7 to 9, wherein in the molding step, the resin-adhered reinforcing fiber woven fabric is heated and pressed to form a box shape. The method for producing a fiber-reinforced resin molded product according to claim 10, wherein in the molding step, the resin-adhered reinforcing fiber woven fabric is heated and pressed to form a box shape to produce an oil pan.