JP2022065725A - Method for manufacturing fiber-reinforced resin molded article with hard coat layer - Google Patents

Abstract

To provide a fiber-reinforced resin molded article with a hard coat layer which avoids reduction in durability caused by insufficient durability of an adhesive layer, and therefore has excellent durability.SOLUTION: A method for manufacturing a fiber-reinforced resin molded article 10 with a hard coat layer is provided, including a step of impregnating a reinforcing fiber 31 with a part of a resin 21 for impregnation as a matrix resin 32 thereby forming a fiber-reinforced resin layer 3, and integrating the fiber-reinforced resin layer 3 with the resin film with the hard coat layer through other part of the resin 21 for impregnation.SELECTED DRAWING: Figure 3

Description

The present invention relates to a method for producing a fiber reinforced resin molded product with a hard coat layer and a fiber reinforced resin molded product with a hard coat layer.

In recent years, molding using various fiber reinforced resins typified by carbon fiber reinforced resin (CFRP) and glass fiber reinforced resin (GFRP) as members of sports equipment, automobiles, ships, aircraft, etc. that are subject to large impact and deformation stress. Goods are proposed.

The fiber reinforced resin is manufactured by impregnating reinforced fibers such as carbon fibers and glass fibers with a matrix resin such as a thermoplastic resin or a thermosetting resin and curing them as necessary, and is reinforced by the fibers. As a result, the physical properties are remarkably improved, and the member is relatively lightweight yet tough. Therefore, various molded products using these are positively adopted especially in the field where light weight and high mechanical properties are required.

In a molded product using such a fiber reinforced resin as a base material, in order to improve the scratch resistance, particularly when the molded product is formed in a conspicuous outermost layer instead of a structural member provided inside. It is also widely practiced to provide a hard coat layer on the surface of a base material made of a reinforced resin. Hereinafter, the present specification refers to a general molded product in which a hard coat layer is provided on the surface of at least one of a base material made of a fiber reinforced resin, as described above, and refers to "fiber reinforced with a hard coat layer". It shall be referred to as "resin molded product".

As a method for producing this "fiber-reinforced resin molded product with a hard coat layer", a film obtained by impregnating carbon fibers with a matrix resin (so-called "prepreg", for example, a CFRP sheet disclosed in Patent Document 1) is used. A manufacturing method is widely used in which a resin film with a hard coat layer (see Patent Document 2), which is a base material and has a hard coat layer and an adhesive layer laminated and integrated, is attached to the surface thereof by thermal transfer.

However, in the "fiber reinforced resin molded product with a hard coat layer" manufactured by the above manufacturing method, the durability of the adhesive layer for joining the base material made of the fiber reinforced resin such as "prepreg" and the hard coat layer is durable. Was not always enough. In many cases, this causes a decrease in the durability of the molded product as a whole. At the manufacturing site of the "fiber reinforced resin molded product with a hard coat layer", a new technical means for avoiding the decrease in durability due to such a lack of durability of the adhesive layer has been sought.

Japanese Unexamined Patent Publication No. 10-138354 Japanese Unexamined Patent Publication No. 2014-2084943

It is an object of the present invention to provide a "fiber reinforced resin molded product with a hard coat layer" having excellent durability while avoiding a decrease in durability due to insufficient durability of the adhesive layer.

The present inventors have found that the above problems can be solved by a manufacturing method in which the resin impregnated in the reinforcing fibers contributes to the integration of the fiber-reinforced resin layer and the resin film with the hard coat layer. Has been completed. More specifically, the present invention provides the following.

(1) A method for manufacturing a fiber-reinforced resin molded product with a hard coat layer, in which a part of the impregnated resin is impregnated into the reinforcing fiber as a matrix resin, and the impregnated resin is partially impregnated through the other part of the impregnated resin. A method for producing a fiber-reinforced resin molded product with a hard coat layer, which comprises a step of integrating the fiber-reinforced resin layer and the resin film with a hard coat layer.

According to the method (1) for producing a fiber reinforced resin molded product with a hard coat layer, it is possible to obtain a "fiber reinforced resin molded product with a hard coat layer" having extremely excellent durability as a whole molded product.

(2) The fiber-reinforced resin molded product with a hard coat layer according to (1), wherein the base resin of the impregnated resin and the base resin of the molded substrate film of the resin film with the hard coat layer are the same resin. Production method.

According to the manufacturing method of the fiber-reinforced resin molded product with a hard coat layer of (2), the durability of the fiber-reinforced resin molded product with a hard coat layer is more reliably enjoyed while enjoying the above-mentioned effects of the manufacturing method of (1). It can enhance the sex.

(3) The impregnation of a part of the impregnating resin into the reinforcing fiber as a matrix resin, the reinforcing fiber via the other part of the impregnating resin, and the resin film with a hard coat layer. The method for producing a fiber-reinforced resin molded product with a hard coat layer according to (1) or (2), wherein the integration of the above is performed as a single step by a series of treatments.

According to the method (3) for manufacturing a fiber-reinforced resin molded product with a hardcoat layer, a plurality of processes, which were conventionally separate processes, can be integrated into a single process. This makes it possible to further improve the production efficiency while enjoying the above-mentioned effects of the production method (1) or (2).

(4) The method according to any one of (1) to (3), wherein the impregnated resin is injected into an injection molding die and a part of the injected impregnated resin is impregnated into the reinforcing fiber. Manufacturing method of fiber reinforced resin molded product with hard coat layer.

According to the invention of (4), in the production of a fiber-reinforced resin molded product with a hard coat layer by an injection molding die, while enjoying the above-mentioned effect of any of the production methods (1) to (3), gold is used. It is possible to obtain fiber-reinforced resin molded products with a hard coat layer having various shapes within the range of freedom in selecting the shape of the molded product in mold molding.

(5) The other part of the impregnated resin has the reinforcing fiber and the hard coat layer via the intermediate resin layer after forming the intermediate resin layer without impregnating the reinforcing fiber. The method for producing a fiber-reinforced resin molded product with a hard coat layer according to any one of (1) to (4), which integrates with a resin film.

According to the method (5) for manufacturing a fiber-reinforced resin molded product with a hard coat layer, an intermediate resin layer that contributes to adhesion to the hard-coated resin film is integrated on the reinforcing fiber by a resin that impregnates the reinforcing fiber. Can be formed. Thereby, while enjoying the above-mentioned effect of any of the production methods (1) to (4), it is possible to further enhance the adhesion durability between each layer of the fiber-reinforced resin molded product with a hardcoat layer. In addition, the visibility can be adjusted by optimizing the thickness of the intermediate resin layer, and the design of the fiber reinforced resin molded product with a hard coat layer can be further improved by the depth of the design brought about by the reinforcing fibers. You can also.

(6) The fiber with a hard coat layer according to (5), wherein the impregnating resin molded in the form of powder is laminated on the reinforcing fiber, and then a part thereof is melted to impregnate the reinforcing fiber. A method for manufacturing a reinforced resin molded product.

According to the invention of (6), a matrix resin and a resin layer are formed by using a resin molded into a powder as an impregnating resin, such as finely adjusting the addition amount and optimizing the mixing ratio of a plurality of resins. The degree of freedom in adjusting the thickness and chemical properties of the resin to be used is increased. Further, this makes it possible to further enhance the durability of the fiber-reinforced resin molded product with a hard coat layer while enjoying the above-mentioned effect of the production method (5). Furthermore, it can be manufactured by heating and pressurizing with a heat press machine, which is a simpler device, without using a relatively expensive injection molding machine, and a step of forming an impregnated resin into a film in advance. It can also contribute to the improvement of economic efficiency in that it is unnecessary.

(7) The fiber with a hard coat layer according to (5), wherein the impregnating resin molded into a film shape is laminated on the reinforcing fiber, and then a part thereof is melted to impregnate the reinforcing fiber. A method for manufacturing a reinforced resin molded product.

According to the invention of (7), by using a resin formed into a film as an impregnating resin, it is easy to carry out an impregnating resin film that is strictly adjusted to an appropriate amount (optimal thickness). It can be placed on the reinforcing fiber by a simple operation. As a result, while enjoying the above-mentioned effects of the manufacturing method (5), the productivity is enhanced, and the durability of the fiber-reinforced resin molded product with a hard coat layer and the designability by visual recognition of the reinforcing fibers are more reliably performed. It can be improved as intended.

(8) The impregnating resin is any one of polycarbonate, acrylic resin, urethane resin, polypropylene, polyamide, polyimide, polyphenylene sulfide, polyether ether ketone, or acrylonitrile-butadiene-styrene copolymer. The method for producing a fiber-reinforced resin molded product with a hard coat layer according to any one of (1) to (7), which is a mixed resin using any one of them as a base resin.

According to the invention of (8), the above-mentioned effect of the method for producing a fiber-reinforced resin molded product with a hardcourt layer according to (1) to (7) can be more reliably enjoyed.

(9) The method for producing a fiber-reinforced resin molded product with a hard coat layer according to any one of (1) to (8), wherein the reinforcing fiber is carbon fiber.

According to the invention of (9), a fiber-reinforced resin molded product with a hardcoat layer, which is a lightweight yet tough molded product, enjoys the above-mentioned effect of any of the manufacturing methods (1) to (8). Can be obtained.

(10) A laminate in which a fiber-reinforced resin layer, a resin layer, and a hard coat layer are laminated in this order, and in the thickness direction of a resin base material portion which is a portion of the laminate excluding the hard coat layer. There is a region where the reinforcing fibers are unevenly distributed and a region where the reinforcing fibers do not exist, and the resin base material portion uses the same resin as the base resin, including the matrix resin impregnated by the reinforcing fibers. A fiber-reinforced resin molded product with a hard coat layer, which is formed of a resin composition to be used.

According to the invention of (10), for example, the reinforcing fibers are unevenly distributed only in the region near the center in the thickness direction of the resin base material portion, and the resin base resin constituting the resin base material portion is used. By unifying the same resin, the durability of the resin base material portion of the fiber-reinforced resin molded product with a hard coat layer and the durability of the bonding interface between the hard coat layer and the resin layer can be significantly improved. .. In addition, by intentionally unevenly distributing the reinforcing fibers in any region in the thickness direction of the resin base material portion, the appearance of the reinforcing fibers on the product surface can be freely adjusted with a high degree of freedom in design. It is possible to manufacture a fiber-reinforced resin molded product with a hard coat layer having excellent design.

(11) The fiber-reinforced resin molded product with a hardcoat layer according to (10), wherein the reinforcing fiber is carbon fiber.

According to the invention of (11), the fiber reinforced resin with a hard coat layer, which is a lightweight yet tough molded product, enjoys the above-mentioned effect of the fiber reinforced resin molded product with a hard coat layer according to (10). A molded product can be obtained.

According to the present invention, it is possible to provide a "fiber reinforced resin molded product with a hard coat layer" having excellent durability by avoiding a decrease in durability due to insufficient durability of the adhesive layer.

It is sectional drawing which shows typically the layer structure of the fiber reinforced resin molded article with a hard coat layer of this invention. It is a top view schematically showing the aspect of the surface of the fiber reinforced resin molded article with a hard coat layer of this invention. It is a figure which shows typically the embodiment (the 1st embodiment) of the manufacturing method of the fiber reinforced resin molded article with a hard coat layer of this invention. It is a figure which shows the other embodiment (second embodiment) of the manufacturing method of the fiber reinforced resin molded article with a hard coat layer of this invention schematically.

Hereinafter, embodiments of the present invention will be described. First, the outline of the structure of the "fiber reinforced resin molded product with a hard coat layer" that can be manufactured by the manufacturing method of the present invention will be described. After that, the details of the "method for manufacturing a fiber-reinforced resin molded product with a hard coat layer" of the present invention, which is a preferable manufacturing method for the "fiber-reinforced resin molded product with a hard coat layer", will be described. The present invention is not limited to the following embodiments, and can be carried out with appropriate modifications within the scope of the object.

<Fiber reinforced resin molded product with hard coat layer>
As shown in FIG. 1, the fiber-reinforced resin molded product 10 with a hard coat layer of the present invention has a layer structure in which the hard coat layer 1 is formed on at least one surface of the fiber-reinforced resin layer 3 via the resin layer 2. It is a laminated body made of.

Further, as shown in the figure, the resin layer 2 may be formed on the other surface of the fiber reinforced resin layer 3, that is, the surface opposite to the laminated surface of the hard coat layer 1. Alternatively, the fiber-reinforced resin molded product 10 with a hard coat layer of the present invention has a layer structure (not shown) in which the hard coat layer 1 is formed on both surfaces of the fiber reinforced resin layer 3 via the resin layer 2. You can also do it.

As shown in FIG. 2, the fiber-reinforced resin molded product 10 with a hard coat layer is formed of reinforcing fibers 31 constituting the fiber-reinforced resin layer 3 on the surface on the side where the hard coat layer 1 is formed. It is possible to configure the structure in which the fine pattern is visibly present.

Further, the overall shape of the fiber-reinforced resin molded product 10 with a hard coat layer can be exemplified by a flat film-shaped or plate-shaped molded product as shown in FIG. 1, but is limited to this. It is not something that can be done. The present invention can be applied to molded articles having various shapes depending on the intended use. For example, the present invention can also be applied to the production of fiber-reinforced resin molded products with a hardcourt layer having various shapes including curved surfaces and bent portions.

The fiber-reinforced resin molded product 10 with a hard coat layer is, for example, the body of various airframes such as vehicles and aircraft, other parts for interior and exterior, exterior materials and interior materials of building structures of general houses and public facilities, and the like. It can be widely used for all molded products using reinforced fiber reinforced resin as a base, such as parts for home appliances.

[Fiber reinforced plastic layer]
The fiber reinforced resin layer 3 is made of various types such as carbonized fiber reinforced resin (CFRP) in which reinforced fibers such as carbon fibers are impregnated with a matrix resin such as a thermoplastic resin or a thermosetting resin and cured as necessary. The fiber reinforced resin is molded into a desired shape.

(Reinforcing fiber)
The reinforcing fiber 31 constituting the fiber reinforced resin layer 3 is not particularly limited. For example, polyacrylonitrile (PAN) -based reinforcing fibers, pitch-based reinforcing fibers and the like, or a mixture thereof, glass fibers and the like can be appropriately selected as the reinforcing fibers constituting the fiber-reinforced resin layer.

Further, in particular, when the fiber-reinforced resin molded product 10 with a hard coat layer is produced by the production method of the present invention, it is preferable to use woven carbon fibers woven in a lattice pattern or the like as the fiber-reinforced resin. ..

Further, the fiber-reinforced resin molded product 10 with a hard coat layer is manufactured by the "method for manufacturing a fiber-reinforced resin molded product with a hard coat layer" of the present invention, whereby the reinforcing fiber 31 is a resin excluding the hard coat layer 1. The configuration can be such that it is unevenly distributed only in an arbitrary part of the base material portion in the thickness direction. For example, the reinforcing fibers 31 are unevenly distributed only in the region near the center in the thickness direction of the resin base material portion, and the reinforcing fibers 31 do not exist in the vicinity of both surfaces in the thickness direction of the resin base material portion. In addition, the resin base material portion can be configured to be formed of a resin material using the same resin as a base resin, including the matrix resin 32 impregnated by the reinforcing fibers (Fig.). 4). Alternatively, by intentionally unevenly distributing the reinforcing fibers in any region in the thickness direction of the resin base material portion, the appearance of the reinforcing fibers on the product surface can be freely adjusted, and the hardware is more excellent in design. It is also possible to manufacture a fiber-reinforced resin molded product with a coat layer.

As a typical example of the three-dimensional shape of the reinforcing fiber 31 that can form a fine pattern that can be visually recognized from the side of the hard coat layer 1, a grid-like shape as shown in FIG. 2 can be mentioned. Of course, the above-mentioned fine pattern that contributes to the improvement of design is not limited to the one having such a grid-like shape. The three-dimensional shape of the reinforcing fiber 31 is not particularly limited, and may be any shape, in addition to long fibers aligned in one direction, woven fabrics consisting of two directions or three or more directions, non-woven fabrics, mats, knits, braids, and the like. May be good. Among these, the three-dimensional shape of the reinforcing fiber 31 is preferably the shape of a woven fabric. In other words, in the fiber-reinforced resin base material 4, the reinforcing fibers 31 preferably constitute a woven fabric. In addition, such a woven fabric is formed by weaving carbon yarn made of carbon fiber. Depending on the difference in weaving method, "plain weave" in which warp and weft are woven alternately and "twill weave" in which warp and weft are woven after crossing once instead of alternating are used. The former looks like a checkered pattern due to the reflection of light, is lightweight and has high strength characteristics, and the latter has a unique three-dimensional pattern, although the strength is slightly inferior to that of "plain weave". Each has its own characteristics, such as contributing to the improvement of design by appearing. The manufacturing method of the present invention is particularly advantageous in that the excellent design of the above-mentioned "twill weave" can be more reliably expressed as intended.

Further, the above-mentioned "fine pattern visible from the side of the hard coat layer 1" is more preferably a pattern pattern in which unit patterns having the same or substantially the same shape are regularly repeated. By having at least a part, preferably all of the fine patterns having such a patterning pattern, the design of the fiber-reinforced resin molded product 10 with a hard coat layer can be enhanced. For example, in the case of using a prepreg obtained by impregnating a carbon fiber woven in a lattice pattern with an uncured epoxy resin as the reinforcing fiber 31, the shape of one lattice formed by the carbon fiber is the above-mentioned unit pattern. The entire lattice pattern formed by repeating this corresponds to the above patterning pattern. In the fiber reinforced resin molded product 10 with a hard coat layer of the present invention, the patterning pattern made of such reinforced fibers is intentionally exposed from the side of the hard coat layer 1 so as to have a hard coat layer. The scratch resistance and designability of the fiber-reinforced resin molded product 10 can be enhanced together.

(Matrix resin)
As the matrix resin 32 constituting the fiber reinforced resin layer 3, various known resins conventionally used as the material resin of "prepreg" can be used without particular limitation. Examples of the matrix resin 32 include thermoplastic resins such as epoxy resin, unsaturated polyester resin, phenol resin, silicone resin, urethane resin, and polyimide resin, or polysulfone, polyethersulfone, polyetherimide, polyimide, polycarbonate, and the like. A selected type from thermoplastic resins such as polypropylene and polyamide and various thermoplastic elastomers, or a combination of two or more of them can be appropriately used.

[Hard coat layer]
The hard coat layer 1 is a layer made of a resin composition containing a curable resin (hereinafter, also referred to as “curable resin composition”). The hard coat layer 1 is mainly used as a surface protective layer of the fiber reinforced resin molded product 10 with a hard coat layer in which the hard coat layer 1 is bonded to the fiber reinforced resin layer 3, and has good scratch resistance on the outermost surface thereof. It is a layer having a function of providing sex. It should be noted that this hard coat layer can also impart general antifouling and antifog properties to the fiber reinforced resin molded product with the hard coat layer.

The hard coat layer 1 is a "layer that transmits visible light" as defined above in order to retain the design characteristics peculiar to the fiber reinforced resin layer in the fiber reinforced resin molded product 10 with the hard coat layer. But it is also.

As the base resin of the curable resin composition forming such a hard coat layer 1, a thermosetting resin or an ionizing radiation curable resin can be appropriately selected and used. In the present specification, the "base resin" is a resin having the largest composition ratio in the resin component in the resin layer formed containing the resin, and occupies a ratio of 50% by mass or more in the same composition ratio. I shall say that. Therefore, a resin other than the main "material resin" may be mixed in the hard coat layer 1 in a smaller proportion than the "base resin", if necessary.

When a thermosetting resin is used as the base resin of the curable resin composition for forming the hard coat layer 1, a polyester resin, an epoxy resin, a polyurethane resin, an aminoalkyd resin, a melamine resin, a guanamine resin, a urea resin, and a thermosetting resin are used. Acrylic resin, silicone resin and the like can be used.

When an ionized thermosetting resin is used as the base resin of the curable resin composition for forming the hard coat layer 1, it is selected from the polymerizable oligomers and prepolymers conventionally used as resins having ionizing and radiation curable properties. It can be appropriately selected and used. Examples of such polymerizable oligomers and prepolymers include oligomers and prepolymers having radically polymerizable unsaturated groups in their molecules, such as epoxy (meth) acrylate-based, urethane (meth) acrylate-based and polyether-based urethane (meth). ) An acrylate, a caprolactone-based urethane (meth) acrylate, a polyester (meth) acrylate-based oligomer, a polyether (meth) acrylate-based oligomer, a prepolymer, or the like can be preferably used.

It is also possible to use a silicone resin as the base resin of the curable resin composition for forming the hard coat layer, but the silicone resin has little stretch of the resin at the time of molding, and is suitable for moldability. Often lacking. On the other hand, the acrylic resin or the urethane resin has a relatively large stretchability, so that it has excellent moldability, and particularly when it is accompanied by curved surface molding, it exhibits a particular advantage.

When an ionizing radiation curable resin is used as the curable resin for forming the hard coat layer 1, the ionizing radiation irradiating these resins is an energy quantum capable of polymerizing or cross-linking molecules among electromagnetic waves or charged particle beams. For example, an electromagnetic wave (UV) or an electron beam (EB) can be selected. In addition, electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion rays can also be selected.

[Resin layer]
As described above, in the fiber reinforced resin molded product 10 with a hard coat layer, the resin layer 2 arranged on at least one surface of the fiber reinforced resin layer 3 or both surfaces of the fiber reinforced resin layer 3 is a hard coat layer. As long as there is no inconvenience depending on the use, form, manufacturing and processing method of the fiber-reinforced resin molded product 10, it can be formed by using various conventionally known resin films without particular limitation. As a specific example, the resin layer 2 includes an acrylic resin, a polyester resin, a polycarbonate resin, an acrylonitrile / butadiene / styrene copolymer, an acrylonitrile / styrene / (meth) acrylate copolymer, and a (meth) acrylate / acrylonitrile. It is preferable that the resin layer uses one resin selected from the butadiene / styrene copolymer as the base resin.

The thickness of the resin layer 2 is not particularly limited. However, the resin layer 2 located between the fiber reinforced resin layer 3 and the hard coat layer 1 (the resin layer arranged at this position is referred to as an "intermediate resin layer" in the present specification) is 10 μm or more. It is preferably 1000 μm or less, and more preferably 100 μm or more and 500 μm or less. In order to sufficiently ensure the durability at the bonding interface between the fiber reinforced resin layer 3 and the hard coat layer 1, the thickness of this layer is preferably within the above range. Further, by adjusting the thickness of the intermediate resin layer to an arbitrary thickness within the above range, the above-mentioned "fine pattern visible from the side of the hard coat layer 1" in the fiber reinforced resin molded product 10 with a hard coat layer. It is also possible to improve the design by adjusting the appearance of the fabric to a desired mode, including the sense of depth.

<Manufacturing method of fiber reinforced resin molded product with hard coat layer>
The "method for manufacturing a fiber-reinforced resin molded product with a hard coat layer (hereinafter, also referred to as" the manufacturing method for the present invention ")" of the present invention uses a "impregnated resin" such as an acrylic resin to partially use a part thereof. The fiber reinforced resin layer is formed by impregnating the reinforcing fibers, and the other part of the "impregnated resin" contributes to the bonding between the "resin film with a hard coat layer" and the fiber reinforced resin layer. It is a manufacturing method characterized by making it.

Here, the above-mentioned "impregnated resin" in the "manufacturing method of the present invention" is a fiber-reinforced resin molded product with a hard coat layer manufactured by the manufacturing method by impregnating various reinforcing fibers. , Refers to the resin that constitutes the fiber reinforced resin layer.

In the "manufacturing method of the present invention", this "impregnated resin" not only functions as a resin for forming the matrix resin of the fiber-reinforced resin layer as in the case of the conventional manufacturing method, but also has the same function. A part of the resin (surplus part that does not invade the reinforcing fibers) functions as a resin constituting a resin layer that contributes to the bonding between the "resin film with a hard coat layer" and the fiber-reinforced resin layer.

As an example, in the production method of the present invention, an intermediate resin layer having an appropriate thickness is formed by a surplus portion of the above-mentioned impregnating resin that does not impregnate the reinforcing fibers, and then the fibers are passed through the intermediate resin layer. It can be a step of integrating the reinforced resin layer and the resin film with the hard coat layer.

Further, the "impregnation resin" used in the production method of the present invention is, for example, a "fiber reinforced resin" by impregnating various reinforcing fibers in the fiber reinforced resin molded product 10 with a hard coat layer described above. It is required that the resin can be formed as a "layer" and is also suitable as a resin for forming a resin layer. And, as long as such a requirement is satisfied, various resins can actually be selected.

Specific examples of the resin that can be used as the "impregnated resin" in the production method of the present invention include acrylic resin, polyester resin, polycarbonate, polysulfone, polyethersulfone, polyetherimide, polyimide, polycarbonate, polypropylene, and the like. One resin selected from thermoplastic resins such as polyamide, polyphenylene sulfide, polyether ether ketone, and acrylonitrile / butadiene / styrene copolymer synthetic resin, or two or more kinds selected from these thermoplastic resins. A mixed resin made of a combination of resins, one resin selected from thermosetting resins such as epoxy resin, unsaturated polyester resin, phenol resin, silicone resin, urethane resin, and polyimide resin, or the above-mentioned thermoplasticity. A mixed resin composed of a combination of two or more kinds of resins selected from the resins can be appropriately selected and used.

In the production method of the present invention, the above-mentioned various resins can be appropriately selected and used as the "impregnated resin", but the hard coat is used as the base resin of the curable resin composition for forming the hard coat layer 1. When the layer resin is an acrylic resin or a urethane resin, it is particularly preferable to use an acrylic resin, a polycarbonate, an acrylonitrile / butadiene / styrene copolymer synthetic resin, or a urethane resin among the above resins. .. Polycarbonate is also preferable in that it is inexpensive, and acrylic resin is more expensive than polycarbonate, but is superior in terms of performance such as weather resistance and abrasion resistance. Further, regarding the polycarbonate and the acrylic resin, the film and the pellets for injection are generally easily available, and can be particularly preferably used as the "impregnated resin" for the production method of the present invention.

Further, in the present specification, the "resin film with a hard coat layer" refers to a film-like member in which a hard coat layer is formed on the surface of a molded substrate film made of, for example, polycarbonate or the like. The "resin film with a hard coat layer" used in the manufacturing method of the present invention has a molded substrate film that is thermocompression bonded to the resin selected as the "impregnation resin" described above, without interposing other adhesive resins or the like. Any resin that can be bonded to is sufficient.

Further, the molded substrate film of the resin film with a hard coat layer is preferably a resin film using the same resin as the base resin of the "impregnation resin" as the base resin. In the present specification, the "resin film using the same resin as a certain resin as a base resin" naturally includes "a resin film made of the same resin as the resin", and the same as used herein. Naturally, the resin also includes polymers of the same type having different molecular weights and three-dimensional structures.

Specifically, in the production method of the present invention, as the "resin film with a hard coat layer", the molded substrate film is a polycarbonate or acrylic resin, or a resin using either of them as a base resin. Moreover, a resin having a common base resin as the "impregnated resin" or a "resin film with a hard coat layer" having a resin film made of the same resin as a molded substrate film can be preferably used. The "resin film with a hard coat layer" includes a "thermal transfer film (as an example, a thermal transfer film disclosed in Patent Document 2)" including a structure in which a hard coat layer is laminated on an acrylic adhesive resin layer. Can also be used.

The curable resin forming the hard coat layer of the “resin film with a hard coat layer” is not particularly limited. Any resin may be appropriately selected from the various curable resins described above according to the surface protection performance required for the "fiber-reinforced resin molded product with a hard coat layer" manufactured by the production of the present invention.

[First Embodiment]
The impregnation of a part of the "impregnated resin" in the "manufacturing method of the present invention" into the reinforcing fiber as a matrix resin, and the fiber reinforced resin layer via another part of the "impregnated resin". The integration with the resin film with a hard coat layer is preferably an embodiment in which these are performed as a single step by a series of treatments. This embodiment can be performed, as an example, in the manner shown in FIG.

In the embodiment shown in FIG. 3, first, a resin film with a hard coat layer is placed on the inner bottom surface of an injection molding die 20 for molding a fiber reinforced resin molded product 10 with a hard coat layer on the side of the hard coat layer 1. Is arranged toward the inner bottom surface side of the injection molding die 20.

Then, next, the reinforcing fiber 31 is placed on the resin film with the hard coat layer. The reinforcing fiber 31 is preferably a member that has been previously molded into a woven fabric, such as carbon fibers woven in a lattice pattern.

Then, the reinforcing fibers 31 are placed on the molded substrate film of the resin film having the hard coat layer 1 mounted on the inner bottom surface of the injection molding die 20 to be reinforced. The impregnating resin 21 is injected from the side of the fiber 31. Also in this case, as described above, it is preferable that the impregnating resin 21 and the molded substrate film of the resin film with the hard coat layer are resins having a common base resin or the same resin.

By injecting the impregnating resin 21 into the injection molding mold 20 in this way, the impregnating resin 21 is impregnated into the reinforcing fiber 31 as the matrix resin 32, and the hard coat layer 1 is formed on the outermost surface. The process of forming the resin layer 22 that contributes to the integration with the hard-coated resin film having the hard coat layer by the injected impregnated resin 21 is performed as a single step by a series of processes. By this series of treatments, it is possible to manufacture a fiber-reinforced resin molded product 10 with a hard coat layer, which has excellent durability of the resin substrate portion.

[Second Embodiment]
As an embodiment of the "manufacturing method of the present invention", a series of steps from the formation of a reinforcing fiber layer by a part of the "impregnated resin" to the formation of an intermediate resin layer by another part of the "impregnated resin". After that, the steps of integrating the fiber-reinforced resin layer and the resin film with the hard coat layer via the intermediate resin layer formed by a part of the "impregnated resin" are sequentially performed. You can also do it. This embodiment can be performed, as an example, in the manner shown in FIG.

In the embodiment shown in FIG. 4, first, the reinforcing fiber 31 is placed on the inner bottom surface of the heat press machine 30 for molding the fiber-reinforced resin molded product 10 with a hard coat layer, and the reinforcing fiber 31 is formed into a powder on the inner bottom surface. The impregnated resin 21p is further laminated (see FIG. 4 (1)). Even in this case, it is preferable that the reinforcing fiber 31 is a member that is previously formed into a woven fabric such as carbon fibers woven in a lattice pattern.

Then, by heating with a hot press machine 30, the impregnation resin 21p is melted and a part thereof is impregnated into the reinforcing fiber 31 as a matrix resin 32 to form the fiber reinforced resin layer 3. At this time, as a series of treatments, the resin layer 2 is formed on at least one surface or both surfaces of the fiber reinforced resin layer 3 by the other part of the impregnating resin 21p (FIG. 4 (2). )reference).

After the resin layer 2 (intermediate resin layer) is formed by the above-mentioned series of treatments, a resin film with a hard coat layer containing the hard coat layer 1 is laminated on the same layer, and these are integrally heat-bonded. (See Fig. 4 (3)). After this integration, the molded substrate film 23 of the resin film with the hard coat layer forms the resin layer 2 (intermediate resin layer) together with the resin layer formed of the impregnating resin 21p. Even in this case, the impregnating resin 21p and the molded substrate film 23 of the resin film with the hard coat layer are also preferably resins having a common base resin or the same resin.

In the second embodiment of the manufacturing method of the present invention, a resin film with a hard coat layer including the hard coat layer 1 is previously formed in the form of powder with respect to the reinforcing fibers 31 in the step of FIG. 4 (1). The hard coat can also be obtained by placing it in advance on the side opposite to the laminated surface of the impregnated resin 21p (lower side of the reinforcing fiber 31 in FIG. 4 (1)) and then performing the same steps as described above. The layered fiber reinforced resin molded product 10 can be manufactured. By performing such a step, it is possible to obtain a fiber-reinforced resin molded product with a hard coat layer having a structure in which the reinforcing fibers 31 are unevenly distributed in the vicinity of the outer surface on the hard coat layer side.

Further, in this embodiment, instead of the impregnating resin 21p formed in the form of powder, the impregnating resin formed in the form of a film is used, and the fiber reinforced resin with a hard coat layer is molded by the same procedure. It is also possible to manufacture products.

As a specific method for integrating the fiber-reinforced resin layer and the resin film with a hardcoat layer by heat treatment as described above, a press molding method, an autoclave molding method, a bagging molding method, a wrapping tape method and an internal pressure molding method are used. Etc. can be adopted as appropriate.

1 Hard coat layer 2, 22 Resin layer 21 Immersion resin 23 Molded substrate film of resin film with hard coat layer 3 Fiber reinforced resin layer 31 Reinforced fiber 32 Matrix resin 10 Fiber reinforced resin molded product with hard coat layer 20 Injection molding gold Mold 30 heat press machine

Claims (11)

It is a manufacturing method of fiber reinforced resin molded products with a hard coat layer.
A part of the impregnating resin is impregnated into the reinforcing fiber as a matrix resin to form a fiber reinforced resin layer.
Including a step of integrating the fiber-reinforced resin layer and the resin film with a hardcoat layer via another part of the impregnating resin.
A method for manufacturing a fiber-reinforced resin molded product with a hard coat layer. The base resin of the impregnating resin and the base resin of the molded substrate film of the resin film with the hard coat layer are the same resin.
The method for producing a fiber-reinforced resin molded product with a hardcourt layer according to claim 1. The impregnation of the reinforcing fiber as a matrix resin of a part of the impregnation resin,
The integration of the reinforcing fiber and the resin film with the hardcoat layer via the other part of the impregnating resin is performed as a single step by a series of treatments.
The method for producing a fiber-reinforced resin molded product with a hardcourt layer according to claim 1 or 2. The impregnated resin is injected into an injection molding die, and a part of the injected impregnated resin is impregnated into the reinforcing fiber.
The method for producing a fiber-reinforced resin molded product with a hardcoat layer according to any one of claims 1 to 3. The other part of the impregnated resin forms an intermediate resin layer without impregnating the reinforcing fibers, and then the reinforcing fibers and the resin film with a hard coat layer are formed via the intermediate resin layer. To integrate
The method for producing a fiber-reinforced resin molded product with a hardcourt layer according to claim 1 or 2. After laminating the impregnating resin molded in powder form on the reinforcing fiber, a part of the impregnating resin is melted to impregnate the reinforcing fiber.
The method for producing a fiber-reinforced resin molded product with a hardcoat layer according to any one of claims 1 to 5. After laminating the impregnating resin molded into a film shape on the reinforcing fiber, a part of the impregnating resin is melted to impregnate the reinforcing fiber.
The method for producing a fiber-reinforced resin molded product with a hardcoat layer according to any one of claims 1 to 5. Whether the impregnating resin is either polycarbonate, acrylic resin, urethane resin, polypropylene, polyamide, polyimide, polyphenylen sulphide, polyetheretherketone, or acrylonitrile-butadiene-styrene copolymer, or , A mixed resin using any of them as a base resin,
The method for producing a fiber-reinforced resin molded product with a hardcoat layer according to any one of claims 1 to 7. The reinforcing fiber is carbon fiber.
The method for producing a fiber-reinforced resin molded product with a hardcoat layer according to any one of claims 1 to 8. It is a laminated body in which a fiber reinforced resin layer, a resin layer, and a hard coat layer are laminated in this order.
In the thickness direction of the resin base material portion, which is a portion of the laminate excluding the hard coat layer, there is a region where the reinforcing fibers are unevenly distributed and a region where the reinforcing fibers do not exist.
The resin base material portion is formed of a resin composition using the same resin as a base resin, including the matrix resin impregnated by the reinforcing fibers.
Fiber reinforced resin molded product with hard coat layer. The reinforcing fiber is carbon fiber.
The fiber-reinforced resin molded product with a hard coat layer according to claim 10.

Images