JP7225943B2 - Fiber reinforced resin molded product with hard coat layer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a fiber-reinforced resin molded product with a hard coat layer.

In recent years, molded products using fiber reinforced resins such as carbon fiber reinforced resin (CFRP) and glass fiber reinforced resin (GFRP) have been used as parts for sports equipment, automobiles, ships, aircraft, etc. that are subjected to large impacts and deformation stress. It has been proposed and is being actively adopted especially in fields where light weight and high mechanical properties are required. This fiber-reinforced resin is manufactured by impregnating carbon fiber or glass fiber with a matrix resin such as a thermoplastic resin or thermosetting resin, and if necessary, hardening it. It is a relatively lightweight yet strong member.

On the other hand, in terms of design, fiber-reinforced resin is often preferred for its elaborate three-dimensional design that makes use of the fine patterns derived from the reinforcing fibers in the fiber-reinforced resin present on its surface (patent Reference 1). In particular, in the fields of automobiles and sporting goods, the demand for various molded products that make the most of such designs is increasing.

In order to improve the scratch resistance of a molded article using such a fiber-reinforced resin as a base material, it is widely practiced to provide a hard coat layer on the surface of the molded article. Such a hard coat layer is usually formed by coating with a curable resin, transferring with a film with a hard coat layer, or adhering a film with the hard coat layer. Moreover, as the above-mentioned film with a hard coat layer, a thermal transfer film in which a hard coat layer and an adhesive layer are laminated and integrated on a substrate film can also be used. (See Patent Document 2).

In this specification, it refers to general molded products in which a hard coat layer is provided on at least one surface of a base material made of carbon fiber reinforced resin or the like, "fiber reinforced resin molding with hard coat layer shall be referred to as “goods”. Incidentally, the reinforcing fibers impregnated with the matrix resin in the "fiber-reinforced resin molded product with a hard coat layer" are not limited to carbon fibers. For example, a molded article having a hard coat layer on the surface of a glass fiber reinforced resin impregnated with a matrix resin using glass fiber instead of carbon fiber also satisfies the requirements of the present invention. It is included in the technical scope of the present invention.

Here, in the process of manufacturing a fiber reinforced resin such as a carbon fiber reinforced resin that constitutes a "fiber reinforced resin molded product with a hard coat layer", voids derived from air bubbles generated in the matrix resin are formed on the surface of the resin. The problem was that it was formed. Since these voids impair the above-mentioned design properties peculiar to fiber resins, it is required to sufficiently remove air bubbles in the matrix resin in the production of fiber reinforced resins.

Conventionally, in the production of fiber-reinforced resins, in many cases, it is essential to carry out a treatment aimed at removing air bubbles generated in the matrix resin by an autoclave method or a relatively simple thermocompression method in a mold. was carried out as a process of In addition, even if such air bubble removal treatment by heating and pressurization is performed, voids derived from air bubbles often remain on the surface of the carbon fiber reinforced resin. A treatment for removing such voids has been carried out from time to time by repeating polishing and painting.

However, the above-described polishing and painting processes for removing voids inevitably increase the manufacturing cost due to the increase in the number of steps, and the difficulty of the polishing work causes deterioration and variation in quality. It could be a problem.

JP-A-10-138354 JP 2014-208493 A JP 2011-102013 A

The present invention provides a fiber reinforced resin molded article with a hard coat layer, which has a hard coat layer on the surface of a carbon fiber reinforced resin base material or the like, in which voids are formed on the surface of the carbon fiber reinforced resin base material or the like during the manufacturing process. It is an object of the present invention to more economically manufacture high-quality fiber-reinforced resin moldings while making the most of the unique design properties of carbon fiber-reinforced resins, etc., by preventing or sufficiently reducing this.

When laminating a hard coat resin base material having a hard coat layer on a carbon fiber reinforced resin base material or the like, the present inventors have found a layer configuration in which a transparent elastic layer having a predetermined thickness is interposed between the two. By doing so, the inventors have found that the above problems can be solved, and have completed the present invention. More specifically, the present invention provides the following.

(1) A fiber reinforced resin molded article with a hard coat layer, which has a fiber reinforced resin base material and a hard coat layer, wherein the fiber reinforced resin base material is provided on the surface of the side on which the hard coat layer is formed. The fine pattern formed by the reinforcing fibers inside is visibly present, and the hard coat layer uses a curable resin as a main material resin, and is coated on at least one surface of the fiber reinforced resin base material with an elastic layer interposed therebetween. A fiber-reinforced resin molded article with a hard coat layer, wherein the elastic layer is a transparent layer having a thickness of 10 μm or more, the elastic layer being a transparent resin layer having an elastomer as a main material resin.

According to the fiber reinforced resin molded product with a hard coat layer of (1), a fiber reinforced resin molded product with a hard coat layer in which a hard coat layer is provided on the surface of a fiber reinforced resin base material such as a carbon fiber reinforced resin base material. In , by preventing or sufficiently reducing the formation of voids on the surface of the fiber reinforced resin base material during the manufacturing process, a high-quality fiber reinforced resin molded product can be obtained while taking advantage of the unique design of carbon fiber reinforced resin. can be produced more economically.

(2) The fiber-reinforced resin molded product with a hard coat layer according to (1), wherein the main material resin of the elastic layer is either an olefin-based elastomer or a polyester-based elastomer.

In the fiber-reinforced resin molded product with a hard coat layer of (2), the main material resin of the elastic layer in the fiber-reinforced resin molded product with a hard coat layer described in (1) is limited to a specific elastomer. As a result, the effect of the invention (1) for suppressing the generation of voids on the surface of the fiber-reinforced resin base material can be enhanced, and a fiber-reinforced resin molded product with a hard coat layer of higher quality can be obtained with higher accuracy. .

(3) The method for producing a fiber-reinforced resin molded product with a hard coat layer according to (1) or (2), wherein the matrix resin is a thermosetting resin, and the thermosetting resin is uncured. using the fiber reinforced resin temporary molded article in , as a material constituting the fiber reinforced resin base material, the fiber reinforced resin temporary molded article, the material forming the elastic layer, and the material resin forming the hard coat layer A method for producing a fiber-reinforced resin molded product with a hard coat layer, comprising a step of integrating a molded product material laminate obtained by laminating these in this order by heat-pressing in a single or a series of treatments.

In the method for producing a fiber-reinforced resin molded article with a hard coat layer (3), the fiber-reinforced resin temporary molded article in which the matrix resin is in an uncured stage and the hard coat layer are simultaneously treated by a single or a series of treatments. A hardening manufacturing method was employed. As a result, according to the method for manufacturing a fiber-reinforced resin molded article with a hard coat layer of (3), a part of the steps when viewed as an overall process from each raw material to the completion of the product is simplified so that it can be performed collectively. In addition, the formation of voids on the surface of the fiber-reinforced resin substrate can be sufficiently suppressed, so an additional step for removing voids can be eliminated. Therefore, the fiber-reinforced resin molded product with a hard coat layer of (1) or (2) having excellent design properties can be produced with extremely high productivity.

According to the present invention, in a fiber reinforced resin molded product with a hard coat layer, in which a hard coat layer is provided on the surface of a fiber reinforced resin base material such as a carbon fiber reinforced resin base material, the surface of the carbon fiber reinforced resin base material, etc. By preventing or sufficiently reducing the formation of voids during the manufacturing process, it is possible to more economically manufacture high-quality fiber-reinforced resin molded products while taking advantage of the unique design of carbon fiber-reinforced resin. can.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view schematically showing the layer structure of a fiber-reinforced resin molded product with a hard coat layer of the present invention; 1 is a plan view schematically showing a surface aspect of a fiber-reinforced resin molded product with a hard coat layer of the present invention. FIG.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is by no means limited to the following embodiments. The present invention can be implemented with appropriate modifications within the scope of its purpose.

<Fiber-reinforced resin molded product with hard coat layer>
As shown in FIGS. 1 and 2, in the fiber-reinforced resin molded product 10 with a hard coat layer of the present invention, the hard coat layer 1 is a transparent layer having a thickness of 10 μm or more, preferably 12 μm or more. It is a laminate composed of a structure that is joined to the fiber reinforced resin base material 3 with the interposed therebetween. Then, as shown in the figure, in a state where the hard coat layer 1 is integrated with the fiber reinforced resin base material 3 to form the fiber reinforced resin molded product 10 with the hard coat layer, the hard coat layer 1 is It functions as a surface protective layer of the fiber-reinforced resin molded product 10 with a hard coat layer.

In addition, as shown in FIG. 2, the hard coat layer-attached fiber reinforced resin molded product 10 of the present invention has carbon fibers and the like constituting the fiber reinforced resin base material 3 on the surface on which the hard coat layer 1 is formed. A fine pattern formed by the reinforcing fibers 31 of is visibly present. This fine pattern is formed on the surface of the hard coat layer 1 by the elastic layer 2 and the hard coat layer 1 following the three-dimensional shape (texture) of the reinforcing fibers 31 such as carbon fibers that constitute the fiber-reinforced resin base material 3. It may be a fine three-dimensional pattern formed, or a mode in which the shape of the reinforcing fiber 31 in plan view is visible through the hard coat layer 1 and the elastic layer 2, both of which are transparent layers. It may be a planar pattern.

In addition, as described above, the “transparent layer” in this specification means that the shape of the fine pattern on the outside of one surface of the layer and the outside of the other surface can be visually observed under an illuminance of 300 lux. It refers to a layer having transparency to the extent that it can be visually recognized, and more specifically, refers to a layer having a visible light transmittance of 70% or more, preferably 90% or more.

In addition, in the fiber-reinforced resin molded product 10 with a hard coat layer, in order to improve the visibility of the fine pattern and further improve the design of the molded product, the air surface and the transparent hard coat layer 1 It is more preferable to select the materials so that the difference between the light refractive index at the interface between the hard coat layer 1 and the elastic layer 2, which are both transparent, is minimized.

The overall shape of the fiber-reinforced resin molded product 10 with a hard coat layer is not limited to the flat plate shape shown in FIG. The present invention can be appropriately applied to molded articles of various shapes depending on the application. For example, the present invention can be suitably used when various carbon fiber reinforced resin members molded into shapes including curved surfaces are used as resin substrates with a hard coat layer.

The fiber-reinforced resin molded article 10 with a hard coat layer is, for example, the body of various aircraft such as vehicles and aircraft, other interior and exterior parts, exterior materials and interior materials of building structures of general residences and public facilities, home appliances. It can be widely used for general molded products based on carbon fiber reinforced resin, etc.

[Fiber-reinforced resin substrate]
The fiber reinforced resin base material 3 such as a carbon fiber reinforced resin base material constituting the base portion of the fiber reinforced resin molded product 10 with a hard coat layer is, for example, a matrix resin such as a thermoplastic resin or a thermosetting resin for the carbon fiber. is impregnated with, and optionally cured fiber reinforced resin such as carbon fiber reinforced resin (CFRP) is molded into a desired shape.

The fiber-reinforced resin base material 3 using the carbon fiber as the reinforcing resin is a molded intermediate base material in which the carbon fiber is impregnated with a matrix resin, and generally requires a base material called "prepreg". It can be obtained by laminating and curing according to. In addition, such a fiber-reinforced resin base material 3 can also be configured by laminating a plurality of "prepregs".

(Carbon fiber)
The reinforcing fibers 31 forming the fiber-reinforced resin base material 3 are not particularly limited. When the reinforcing fibers are carbon fibers, that is, when the fiber-reinforced resin base material 3 is a carbon-reinforced resin base material, the carbon fibers are not particularly limited, either. As the carbon fiber constituting the carbon fiber reinforced resin substrate, for example, polyacrylonitrile (PAN)-based carbon fiber, pitch-based carbon fiber, etc., or a mixture thereof can be appropriately selected and used.

Further, the three-dimensional shape (weave) of the reinforcing fibers 31 such as carbon fibers that form a fine pattern visible from the hard coat layer 1 side is represented by a lattice shape as shown in FIG. Examples include, but are not limited to. The three-dimensional shape (texture) of the reinforcing fibers 31 may be any shape such as unidirectional long fibers, bidirectional woven fabrics, multiaxial woven fabrics, nonwoven fabrics, mats, knits, braided cords, and the like. The term "long fiber" as used herein means a single fiber or fiber bundle that is substantially continuous for 10 mm or more.

(matrix resin)
As the matrix resin 32 constituting the fiber-reinforced resin base material 3, conventionally known resins used as material resins such as "prepreg" can be used without particular limitation. For example, epoxy resin, unsaturated polyester resin, phenol resin, silicone resin, urethane resin, thermosetting resin such as polyimide resin, or thermoplastic resin such as polysulfone, polyethersulfone, polyetherimide, polyimide, and various One selected from thermoplastic elastomers or a combination of two or more thereof can be used as appropriate.

[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"). And this 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 base material 3. It is a layer having a function of providing scratch resistance.

The hard coat layer 1 has the transparency as defined above in order to maintain the design properties peculiar to the carbon fiber reinforced resin base material or the like in the fiber reinforced resin molded article 10 with the hard coat layer. Also a layer.

The thickness of the hard coat layer 1 is preferably 0.5 μm or more and 50 μm or less, more preferably 1.0 μm or more and 10 μm or less. By setting the thickness of the hard coat layer 1 to 10 μm or less, in the fiber reinforced resin molded product 10 with the hard coat layer in which the voids on the surface of the carbon fiber reinforced resin base material etc. are sufficiently reduced, the carbon fiber reinforced resin etc. It is possible to improve the designability by further enhancing the visibility of the design peculiar to .

As the main material resin of the curable resin composition forming such a hard coat layer 1, an ionizing radiation curable resin or a thermosetting resin can be appropriately selected and used.

In this specification, the "main material resin" is a resin having the largest composition ratio among the resin components in the resin layer formed containing the resin, and the composition ratio accounts for 50% by mass or more. We shall refer to the resin. Therefore, the hard coat layer 1 may contain a resin other than the main "material resin", if necessary, in a proportion smaller than that of the "main material resin".

When an ionizing radiation-curable resin is used as the main material resin of the curable resin composition for forming the hard coat layer 1, among polymerizable oligomers and prepolymers conventionally used as ionizing radiation-curable resins, can be appropriately selected from and used. Examples of such polymerizable oligomers and prepolymers include oligomers and prepolymers having radically polymerizable unsaturated groups in the molecule, such as epoxy (meth)acrylate, urethane (meth)acrylate and polyether urethane (meth)acrylates. ) acrylate, caprolactone-based urethane (meth)acrylate, polyester (meth)acrylate-based, polyether (meth)acrylate-based oligomers and prepolymers, and the like can be preferably used.

When an ionizing radiation curable resin is used as the curable resin for forming the hard coat layer 1, the ionizing radiation irradiated to these resins may be an electromagnetic wave or a charged particle beam, which can polymerize or crosslink molecules. such as ultraviolet (UV) or electron beam (EB). In addition, electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams can also be selected.

When a thermosetting resin is used as the main material resin of the curable resin composition for forming the hard coat layer 1, polyester resin, epoxy resin, polyurethane resin, aminoalkyd resin, melamine resin, guanamine resin, urea resin, heat A thermosetting resin such as a curable acrylic resin can be used.

Moreover, the curable resin composition can contain a silicone compound from the viewpoint of improving weather resistance and hard coat properties and obtaining excellent transparency. Examples of silicone compounds include reactive silicone compounds having reactive functional groups such as amino groups, epoxy groups, mercapto groups, carboxy groups, hydroxyl groups, (meth)acryloyl groups, and allyl groups, or those having these reactive functional groups. Any non-reactive silicone compound can be used.

In addition, the curable resin composition forming the hard coat layer 1 preferably further contains a scratch resistant filler and a weather resistant agent in order to improve the hard coat properties and weather resistance. The scratch-resistant filler that can be contained in the hard coat layer 1 includes inorganic and organic fillers. Examples of inorganic substances include inorganic particles such as alumina, silica, kaolinite, iron oxide, diamond, and silicon carbide. be done. Silica particles are one of the preferred inorganic scratch-resistant fillers. This is because the silica particles improve the hard coat properties and do not impair the transparency of the hard coat layer. As the silica particles, it is possible to appropriately select and use from conventionally known silica particles, and colloidal silica particles are also suitable. Colloidal silica particles have little effect on transparency even when the amount added is increased.

Moreover, the curable resin composition forming the hard coat layer 1 preferably contains a weather resistance improving agent in order to obtain excellent weather resistance. Weather resistant agents include UV absorbers, light stabilizers, and the like. UV absorbers absorb harmful UV rays and improve the long-term weather resistance and stability of carbon fiber reinforced resin molded products with a hard coat layer. Also, the light stabilizer itself hardly absorbs ultraviolet rays, but it is said that stabilization can be obtained by efficiently trapping harmful free radicals generated by ultraviolet rays. Preferred examples of the UV absorber include inorganic compounds such as titanium dioxide, cerium oxide, and zinc oxide, and organic UV absorbers such as benzotriazole and triazine compounds. Among them, triazine UV absorbers are preferred. As the light stabilizer, for example, a hindered amine light stabilizer (HALS) is preferably used.

Further, the curable resin composition forming the hard coat layer 1 may contain various additives as long as the performance thereof is not impaired. Various additives include, for example, polymerization inhibitors, cross-linking agents, antistatic agents, adhesion improvers, antioxidants, leveling agents, thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, solvents and the like.

[Elastic layer]
The elastic layer 2 is an elastic layer made of a resin composition containing various elastomers (hereinafter also referred to as "elastomer composition") and has a thickness of 10 μm or more, preferably 12 μm or more. The elastic layer 2 follows and fills in the irregularities on the surface of the fiber-reinforced resin substrate 3, exhibits adhesiveness to the surface, and prevents the formation of the above-described voids on the surface of the fiber-reinforced resin substrate 3. Alternatively, it is a layer that expresses a function of sufficiently reducing it. The thickness of the elastic layer is preferably 1000 μm or less from the viewpoint of weight reduction.

The elastic layer 2 also has the above-specified shape in order to retain the design properties peculiar to the fiber-reinforced resin base material such as the carbon fiber-reinforced resin base material in the fiber-reinforced resin molded product 10 with the hard coat layer. It is a layer having transparency.

As the elastomer used as the main material resin of the elastomer composition, both thermoplastic elastomers and thermosetting elastomers can be used as long as they are "elastic materials" generally called "elastomers". Specific examples of the elastomer used as the main material resin of the elastomer composition forming the elastic layer 2 include polyethylene resin, polypropylene resin, polybutene resin, ethylene-propylene copolymer resin, and ethylene-propylene-butene copolymer resin. Various olefin-based elastomers based on any of the above, or polyester-based elastomers, styrene-based elastomers, vinyl chloride-based elastomers, chlorinated polyethylene-based elastomers, chlorosulfonated ethylene-based elastomers, polyurethane-based elastomers, polyamide-based elastomers, Silicone rubber-based elastomers, acrylic rubber-based elastomers, fluororubber-based elastomers, and the like can be mentioned. Among these, an olefin-based elastomer or a polyester-based elastomer can be particularly preferably used as the main material resin of the elastomer composition forming the elastic layer 2 .

At the interface between the hard coat layer 1 and the elastic layer 2, an adhesive layer (not shown) is separately provided to maintain the necessary adhesion between the hard coat layer 1 and the elastic layer 2. may be In particular, when the hard coat layer 1 is formed on the surface of the fiber-reinforced resin base material 3 using the above-described thermal transfer film (see Patent Document 2), the adhesive layer derived from the thermal transfer film is attached to the hard coat layer as a result. It is arranged between the hard coat layer 1 and the elastic layer 2 in the fiber-reinforced resin molded product 10 . When this layer arranged as an adhesive layer is a "layer having elasticity" like the elastic layer 2, this adhesive layer is also regarded as part of the elastic layer, and the thickness of the adhesive layer is also included. The thickness is regarded as the thickness of the elastic layer of the fiber-reinforced resin molded article with the hard coat layer. The term "elastic layer" as used above refers to a layer that is elastically deformed by an external force at room temperature of about 25°C.

The adhesive layer is preferably a two-layer adhesive layer in which a primer layer and a heat seal layer are arranged in order from the hard coat layer side (see Patent Document 2). The primer layer is a layer provided to suppress the occurrence of blocking phenomenon during the production process and storage, and to prevent deterioration of the winding shape of the film and damage to the film, and is a resin composition containing a binder resin and an antiblocking agent. Consists of The thickness of the primer layer is preferably 1-3 μm. On the other hand, the heat seal layer is a layer provided for stably maintaining the adhesiveness of the hard coat layer 1 to other substrates. For example, it can be formed using heat-sealable resins such as acrylic resins, vinyl chloride-vinyl acetate copolymers, polyamide resins, polyester resins, chlorinated polypropylene, chlorinated rubber, urethane resins, epoxy resins, and styrene resins. . As for the thickness of the heat seal layer, it is preferably thicker than the primer layer and has a thickness of 1 to 5 μm.

[Method for producing fiber-reinforced resin molded product with hard coat layer]
The fiber-reinforced resin molded article with a hard coat layer of the present invention can be produced by a conventionally known method for producing a molded article with a hard coat layer, or by various production methods based thereon. However, according to the manufacturing method described in detail below, the fiber-reinforced resin molded product with a hard coat layer of the present invention having excellent design properties and good quality can be manufactured with particularly high productivity.

(Lamination process)
The lamination step is a step of obtaining a laminate in which a hard coat layer is laminated on the surface of a fiber-reinforced resin substrate via an elastic layer. However, in the manufacturing method of the present invention, the matrix resin constituting the fiber reinforced resin base material is a thermosetting resin, and the thermosetting resin is in an uncured stage "carbon fiber reinforced resin temporary molded article ” as a material for obtaining the laminate. Then, this laminate obtained using the above materials is used as a "molded article material laminate" that constitutes a fiber reinforced resin molded article with a hard coat layer, and this is subjected to the next integral molding step. Each material is integrally molded.

(Integrated molding process)
In the integrated molding step, the above-mentioned "molded article material laminate" obtained in the lamination step is molded under heat and pressure to join the hard coat layer and the fiber reinforced resin substrate via the elastic layer. This is the process of integral molding. This heat and pressure molding is a process of integrally molding a molded product material laminate comprising a hard coat layer, an elastic layer, and a carbon fiber reinforced resin base material by heat and pressure bonding in a single or a series of processes. be. By carrying out heat and pressure molding of the "molded product material laminate" in this way, the integration molding process and the curing of the matrix resin, which are usually performed separately, can proceed simultaneously, thereby improving productivity. be able to.

Specific methods for the above-mentioned heat and pressure molding include press molding, autoclave molding, bagging molding, wrapping tape, and internal pressure molding. A press molding method is preferable from the viewpoint of enhancing adhesion. The molding temperature (or curing time) in the heat and pressure molding method may be appropriately selected according to the selected matrix resin. A temperature of 220° C. is preferred. If the molding temperature is too low, a sufficient rapid curability may not be obtained. Further, although the pressure for molding by press molding varies depending on the thickness of the prepreg, etc., a pressure of 0.1 to 1 MPa is usually preferable. If the molding pressure is too low, the heat may not be sufficiently conducted to the inside of the prepreg, and the prepreg may become partially uncured or warped. Conversely, if the temperature is too high, the resin may flow out to the surroundings before it hardens, and voids may occur in the carbon fiber reinforced resin.

[Creation of carbon fiber reinforced resin molded article sample with hard coat layer]
Carbon fiber reinforced resin molded product samples with a hard coat layer of Examples and Comparative Examples were prepared by the above-described method for producing a carbon fiber reinforced resin molded product with a hard coat layer according to the present invention. The following materials were used to prepare the materials. The size of each plate-shaped sample was 100 mm×50 mm.
(Carbon fiber reinforced resin base material)
A prepreg (thickness: 200 μm) obtained by impregnating uncured epoxy resin into carbon fibers woven in a grid pattern was used as a carbon fiber reinforced resin substrate (“carbon fiber reinforced resin temporary molding”).
(elastic layer)
An elastomer film obtained by forming an elastomer composition having a polyester resin-based thermoplastic elastomer ("Hytrel HTD-741H" (manufactured by DuPont Toray) as a main material resin into a film having a thickness of 12 μm or 3 μm. , was used as a material for forming the "elastic layer" in each sample.
(Hard coat transfer film)
Total thickness including a 3-μm-thick hard coat layer made of a urethane acrylate-based oligomer as a main material and cured by electron beam irradiation on a 50-μm-thick polyethylene terephthalate film, and a 3-μm-thick elastic adhesive layer. A hard coat transfer film having a thickness of 6 μm was used.
(Lamination process)
The carbon fiber reinforced resin substrate (carbon fiber reinforced resin temporary molded product), the elastomer film, and the hard coat transfer film were sequentially laminated to obtain a "molded product material laminate" constituting each sample. However, in the examples, an elastomer film with a thickness of 12 μm was used, and in Comparative Example 1, an elastomer film with a thickness of 3 μm was used. In Comparative Example 2, the hard coat transfer film was laminated directly on the carbon fiber reinforced resin substrate without the elastomer film interposed therebetween. The adhesive layer derived from the hard coat transfer film was regarded as part of the elastic layer, and the thickness including the thickness of the adhesive layer (3 μm) was regarded as the thickness of the elastic layer of each sample.

(Integrated molding process)
Each molded product material laminate was integrally molded by heat and pressure molding (curing temperature: 130 ° C., curing time: 2 hours, pressure: 0.49 MPa), and carbon fiber reinforced resin molding with a hard coat layer of Examples and Comparative Examples A quality sample was obtained.

Each sample obtained by the above method was evaluated for designability based on the following evaluation method. Table 1 shows the results.

<Method for evaluating designability>
The surface appearance of each sample of Examples and Comparative Examples having a size of 100 mm×50 mm was visually confirmed and evaluated according to the following criteria. In any sample, the pattern following the three-dimensional shape of the carbon fiber was visible when viewed from the hard coat layer side.
Good: The number of visible voids (excluding concave portions that are part of the pattern) was 0 or more and 2 or less when visually observed from the hard coat layer side.
Δ: The number of visible voids (excluding concave portions that are part of the pattern) was 3 or more and 5 or less when visually observed from the hard coat layer side.
x: The number of visible voids (excluding concave portions that are part of the pattern) was 6 or more when visually observed from the hard coat layer side.

From Table 1, according to the carbon fiber reinforced resin molded product with a hard coat layer of the present invention, by preventing or sufficiently reducing the formation of voids on the surface of the carbon fiber reinforced resin substrate during the manufacturing process, carbon It can be seen that high-quality carbon fiber reinforced resin molded products can be produced more economically while taking advantage of the unique design properties of fiber reinforced resin.

REFERENCE SIGNS LIST 1 hard coat layer 2 elastic layer 3 fiber reinforced resin substrate 31 reinforcing fiber 32 matrix resin 10 fiber reinforced resin molded product with hard coat layer

Claims (3)

A fiber-reinforced resin molded product with a hard coat layer, comprising a fiber-reinforced resin base material and a hard coat layer,
A fine pattern formed by the reinforcing fibers in the fiber-reinforced resin base material is visibly present on the surface on which the hard coat layer is formed,
The hard coat layer is a transparent resin layer containing a curable resin as a main material resin and laminated on at least one surface of the fiber reinforced resin substrate via an elastic layer,
The elastic layer is a transparent layer having a thickness of 10 μm or more and having an elastomer as a main resin material.
Fiber reinforced resin molded product with hard coat layer. 2. The fiber-reinforced resin molded product with a hard coat layer according to claim 1, wherein the main material resin of said elastic layer is either an olefin-based elastomer or a polyester-based elastomer. A method for producing a fiber-reinforced resin molded product with a hard coat layer according to claim 1 or 2,
The matrix resin is a thermosetting resin, and a fiber reinforced resin temporary molded article in which the thermosetting resin is in an uncured stage is used as a material constituting the fiber reinforced resin base material,
A molded product material laminate obtained by laminating the fiber-reinforced resin temporary molded product, the material forming the elastic layer, and the material resin forming the hard coat layer in this order is subjected to a single or a series of treatments. comprising a step of heat-pressing and integrating by
A method for producing a fiber-reinforced resin molded product with a hard coat layer.

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