JPH10264348A - Decoration forming sheet, its manufacture, and manufacture of fiber-reinforced thermoplastic resin foam using the sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To eliminate erasing of decorating design or convexo-concave pattern even by a forming method including heating and pressurizing steps by laminating a film permeated by an electromagnetic radiation in the state that electromagnetic radiation curable resin is densely interleaved on a surface of a decorative sheet. SOLUTION: The decoration forming sheet is decorated by transferring a decorative sheet to a surface of a molding. And, after the transfer, an outer layer from electromagnetic radiation curable resin is released. To easily release it, a release layer is formed on a surface of the sheet. The manufacturing apparatus of the sheet feeds a film A from a feeder 1, and guides it to a roll coater 3a via a guide bar 2 for regulating tension and position. A decorative sheet B is fed from a feeder 4 in the state that the sheet B is directed upward at its decorative surface, and guided to a roll coater 3b via a guide bar 5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative molding sheet, a method for producing the same, and a method for producing a fiber-reinforced thermoplastic resin foam using the decorative molding sheet.

[0002]

2. Description of the Related Art In recent years, long composite foams having a structure in which the surface of a core material layer made of a synthetic resin foam is covered with a skin layer made of a fiber-reinforced synthetic resin and having an irregular cross section have been used in recent years. It is widely used in materials requiring high strength, for example, interior and exterior building materials and other fields.

[0003] As a method for efficiently producing such a composite foam, a method disclosed in Japanese Patent Application Laid-Open No. 8-118484 is known. According to the production method disclosed in this publication, while continuously forming the fiber-reinforced thermoplastic resin sheet into a hollow body, the foamable thermoplastic resin composition is supplied while being foamed therein, or after being supplied. The surface of the core material layer made of a thermoplastic resin foam is formed by foaming inside the hollow body and guiding the entire body to the outer circumference regulating member to shape the outer peripheral surface of the hollow body into a desired contour shape. Can be continuously obtained with a long fiber-reinforced thermoplastic resin foam covered with a skin layer composed of a fiber-reinforced thermoplastic resin layer and having an irregular cross section.

[0004]

When decorating the surface of a fiber-reinforced thermoplastic resin foam obtained by such a production method, the fiber-reinforced thermoplastic resin foam is molded and then coated on the surface. Method of decorating by gravure printing etc. Method of applying gravure printing on the surface of the fiber reinforced thermoplastic resin sheet in advance Considering the method of laminating and integrating a sheet with a pre-painted pattern on the surface of the fiber reinforced thermoplastic resin sheet However, in the method (1), a part that cannot be printed occurs when the shape of the molded article is complicated, and in the method (2), a problem that the printed pattern flows due to friction with the outer periphery regulating member during molding is particularly complicated. Occurs when the shape or foaming pressure is high.

[0005] Further, when an attempt is made to form an uneven pattern on the surface of a molded fiber-reinforced thermoplastic resin foam,
Even if the irregularities disappear due to friction during molding, or if it is attempted to form irregularities on the surface of the fiber-reinforced thermoplastic resin foam after molding with embossing rolls, it will not be possible to form irregularities if it still has a complicated shape A site occurs.

Heretofore, as a conventional method for producing a decorative sheet for decorating a surface of a molded article with a concavo-convex pattern, a concave portion formed on a roll surface is filled with an electromagnetic radiation-curable resin, By irradiating electromagnetic radiation in a state where the film base material is in contact with the cured resin and curing the electromagnetic radiation cured resin, a release film having an uneven pattern formed on the surface is formed. A method of laminating a transfer layer on an uneven surface (JP-A-4-225000)
No. 2) is known, and by using this technology, a decorative sheet prepared separately for the release film is heated and pressed in a state where the pattern and the irregularities are synchronized. There has been proposed a method of imparting irregularities to a decorative sheet (Japanese Patent Application Laid-Open No. 7-88955).

However, when such a proposed technique is adopted, it is necessary to prepare an embossing roll corresponding to the pattern of the decorative sheet, and it is not possible to perform decoration using a commercially available decorative sheet as it is. There is a problem that it is practically impossible, and special equipment is required to synchronize the pattern and the unevenness.

[0008] Also, Japanese Patent Application Laid-Open No. 2-41242 discloses that
A method is disclosed in which a solid that exhibits the properties of a thermoplastic resin in a non-cured state is applied to a film substrate, embossed on the solid, and then a picture is formed. However, even with this method, it is not possible to perform decoration using a decoration sheet on which a pattern or unevenness is already formed.

It is an object of the present invention to provide a method for continuously heating a composite foam comprising a skin layer comprising a fiber-reinforced thermoplastic resin layer and a core material layer comprising a thermoplastic resin foam. Even by the molding method including the pressing step, the decorative pattern and the uneven pattern do not disappear, and no special equipment is required for the decoration, and the existing or commercially available decorative sheet can be used. It is an object of the present invention to provide a decorative molding sheet that can be used as it is, a method for producing the same, and a method for producing a fiber-reinforced thermoplastic resin foam using the decorative molding sheet.

[0010]

Means for Solving the Problems In order to achieve the above object, the decorative molding sheet of the present invention comprises an electromagnetic radiation curable resin densely coated on the surface of a decorative sheet having a pattern and irregularities formed on the surface. And a structure in which a film that transmits electromagnetic radiation is laminated in a state where the film is interposed.

Here, the decorative molding sheet of the present invention is to decorate the decorative sheet by transferring the decorative sheet to the surface of the molded article. After the transfer, the layer outside the electromagnetic radiation curing resin is peeled off. However, a release layer may be formed on the surface of the decorative sheet in order to facilitate the release (claim 2).

Further, the decorative molding sheet of the present invention has at least one layer in which a plurality of continuous fibers are integrated with a thermoplastic resin in a substantially constant orientation state on the back side of the decorative sheet. The fiber-reinforced thermoplastic resin layer may be laminated (claim 3). With such a configuration, the molding process and the decorating process can be performed by using the above-described continuous production method of the fiber-reinforced thermoplastic resin foam. Can be performed substantially simultaneously.

The method for producing a decorative molding sheet according to the present invention comprises:
The surface of the decorative sheet having a pattern and irregularities formed on the surface, and at least one of the surfaces of the film that transmits ultraviolet light, is continuously applied with an electromagnetic radiation curable resin having a viscosity of 10 to 5000 cps, After laminating the sheet and the film with the electromagnetic radiation-curable resin in between, the electromagnetic radiation-curable resin is cured by irradiating electromagnetic radiation from the film-side surface of the laminate (claim). 4).

In the manufacturing method according to the present invention, in the step of irradiating electromagnetic radiation from a film-side surface of a laminate including a decorative sheet, an electromagnetic radiation curable resin, and a film transmitting electromagnetic radiation, It is preferable that the laminate is irradiated with electromagnetic radiation through the convex curved member while pressing the film side surface of the film against a gentle convex curved member capable of transmitting electromagnetic radiation (claim 5).

On the other hand, the method for producing a fiber-reinforced thermoplastic resin foam according to the present invention is directed to the decorative molding sheet according to claim 3,
That is, a decorative molding sheet in which an electromagnetic radiation curing resin and a film that transmits electromagnetic radiation are sequentially laminated on the front side of the decorative sheet, and a fiber reinforced thermoplastic resin layer is laminated on the rear side of the decorative sheet. While forming the hollow body continuously so that the film side is on the outside, while supplying the foamable thermoplastic resin composition to the inner surface while foaming,
The whole is guided to the outer circumference regulating member, and after the outer shape of the hollow body is shaped by changing its shape to a desired cross-sectional shape by the regulating member, the outside including the electromagnetic radiation curable resin layer, or It is characterized by peeling the outside including the peeling layer (claim 6).

Here, in the method for producing a fiber-reinforced thermoplastic resin foam of the present invention, the foamable thermoplastic resin composition is placed inside a hollow body obtained by shaping a decorative molding sheet. Instead of supplying while foaming like
After supplying the expandable thermoplastic resin composition into the hollow body, the resin composition may be foamed inside the hollow body (claim 7).

The decorative molding sheet of the present invention can be used to change the surface condition of a decorative sheet having a surface with a pattern such as a matting process or a wiping process by heating, pressing or the like during processing. Between the film that transmits electromagnetic radiation and the surface of the decorative sheet (pattern side)
The structure employs a structure in which an electromagnetic radiation curable resin is densely interposed, in other words, a structure in which an electromagnetic radiation curable resin in a state where the surface irregularities of the decorative sheet are transferred is interposed between the film and the film. In other words, the three-dimensionally cured electromagnetic radiation curable resin that densely fills the gap between the surface side of the decorative sheet and the film can preserve the transfer state without plasticizing by heating and pressing during processing. The unevenness of the decorative sheet can be protected.

Further, in the method of the present invention for producing a decorative molding sheet having such a structure, the method comprises the steps of:
In order to interpose a liquid electromagnetic radiation-curable resin having a viscosity of 10 to 5000 cps, the interior of the concave portion of the decorative sheet surface is completely filled with the electromagnetic radiation-curable resin, and by irradiating the electromagnetic radiation in that state, the surface has already been exposed. Using a decorative sheet on which irregularities are formed, and therefore using a commercially available decorative sheet, a decorative sheet having a structure in which the electromagnetic radiation curable resin is densely interposed between the surface side and the film, using special equipment You can get without.

In the method for producing a decorative molding sheet according to the present invention, in the method of irradiating electromagnetic radiation from the film-side surface of the laminate comprising the decorative sheet / electromagnetic radiation-cured resin / film as described in claim 5, By irradiating the laminate with electromagnetic radiation through the convex curved member while pressing the surface on the film side against a gentle convex curved member capable of transmitting electromagnetic radiation (see FIG. 1), the film is smoothed. This is preferable because the electromagnetic radiation curable resin can be cured while maintaining the properties.

Here, in the proposed technique described in the above-mentioned publication, when forming irregularities on the film surface with an electromagnetic radiation curable resin, the film is irradiated with electromagnetic radiation from the outside of the roll while pressing the film against a convex curved surface such as a roll. . On the other hand, in producing the decorative molding sheet of the present invention, the decorative sheet itself sometimes uses a material that does not transmit electromagnetic radiation. In order to form like a technique, it is necessary to irradiate the above-mentioned laminate with electromagnetic radiation in a state where the decorative sheet side is in contact with the roll. At that time, when the unevenness level of the decorative sheet is small, there is not much problem. However, when the unevenness level is large, the smoothness on the film side cannot be maintained due to the influence of the state of the uneven surface.
Therefore, as shown in FIG. 1, the film side is irradiated with electromagnetic radiation through the member while pressing the film side against a member formed of a material such as quartz glass that transmits electromagnetic radiation on a convex curved surface such as an R shape. By curing the resin, the resin can be cured while maintaining the smoothness of the film surface without being affected by the unevenness formed on the decorative sheet. The member having the convex curved surface may not rotate itself as shown in FIG. 1, or may have a mechanism that is formed in a cylindrical shape or the like and rotates itself.

Further, the method for producing a fiber-reinforced thermoplastic resin foam according to claims 6 and 7 utilizes the above-mentioned effect of protecting the pattern and unevenness of the electromagnetic radiation-curable resin to make the fiber-reinforced thermoplastic resin foam. In the continuous manufacturing process, it is possible to simultaneously decorate the surface of the molded article, and a fiber-reinforced thermoplastic resin layer is laminated on the back surface of the decorative sheet, and the surface (decoration side) The foamable thermoplastic resin composition is formed inside the decorative molding sheet according to claim 3, wherein the film is laminated with the electromagnetic radiation curable resin interposed therebetween in a continuous manner. Supply while foaming,
Alternatively, since foaming is performed after the supply, the outer periphery of the hollow body is shaped into a desired shape by the regulating member, so that the surface can be decorated simultaneously with continuous molding of the fiber-reinforced thermoplastic resin foam.

The decorative sheet of the present invention and a method for producing the same,
In addition, a specific material or a specific method used in a method for producing a fiber-reinforced thermoplastic resin foam using the decorative sheet can be as shown below.

<About the decorative sheet> All of the commercially available decorative sheets having a picture and irregularities can be used.

That is, the material is not particularly limited. When the electromagnetic radiation-curable resin is made of a material that adheres strongly when it is cured, for example, sheets formed of polyvinyl chloride resin, chlorinated polyvinyl chloride resin, and vinyl chloride copolymer are cured by electromagnetic radiation. It is adhered to the resin, but when using a decorative sheet made of a resin of such a material, a release layer may be formed on the surface thereof. When a fiber-reinforced thermoplastic resin layer is formed on the back side of the decorative sheet, a decorative sheet made of a material that is heat-fused with the thermoplastic resin composition used for the fiber-reinforced thermoplastic resin layer is used. By using these, it is preferable that the lamination can be easily performed by thermocompression bonding, but it is preferable that the non-heat-sealed material be laminated and integrated via an adhesive. Conventionally known thermoplastic resins and synthetic papers such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, chlorinated polyvinyl chloride resin, acrylic resin, nylon, polyethylene terephthalate, aramid, polyphenylene sulfide, fluororesin, thermoplastic elastomer, Cloth, metal stay, etc. are also included.

The height (depth) of the unevenness of the decorative sheet
Is 0.1 μm (the level of unevenness required for matting)
It is 2 mm (the level at which unevenness is recognized from a distance in outdoor use must be 400 μm or more). If it is 0.1 μm or less, the surface state is the same as a mirror surface, and if it exceeds 2 mm, voids are caught in the recessed portions of the unevenness. It is difficult to fill the resin with the electromagnetic radiation curable resin without using it.

<Release Layer> When a decorative sheet made of a material that adheres to the electromagnetic radiation-curable resin is used, the release layer formed on the surface of the decorative sheet is as follows. One that adheres but does not adhere to the electromagnetic radiation curable resin, (2) one that adheres weakly to the decorative sheet surface and adheres strongly to the electromagnetic radiation curable resin,
(3) An electromagnetic radiation curable resin and a decorative sheet that can be weakly adhered to each other can be appropriately selected in some cases. For example, when it is desired to maintain the original surface state of the decorative sheet as it is, (2) and (3) should be selected. When it is desired that the release layer has a function of protecting the decorative sheet surface, What is necessary is just to select 1).

Examples of the resin forming the release layer include a thermosetting resin such as a cellulose derivative, an acrylic resin, a vinyl polymer, and a melamine resin, and an electromagnetic radiation curable resin. The thickness is preferably 0.1 μm to 10 μm. I just need.

<Film> As the material of the film that transmits electromagnetic radiation, any film that is generally commercially available and that can transmit electromagnetic radiation can be used. However, when decorating simultaneously with the molding of the fiber-reinforced thermoplastic resin foam, the film is melt-softened by thermoforming, such as temperature conditions for molding the fiber-reinforced thermoplastic resin foam, and the outer peripheral regulating member Those that cannot be protected because of peeling due to friction or the like cannot be used. Polyester, polyamide,
Acrylic resin, polypropylene, polycarbonate,
Examples include polyimide, polystyrene, and fluorine-based resin. For example, if the main component of the thermoplastic resin used for the fiber-reinforced thermoplastic resin sheet and the foamable thermoplastic resin composition is polyvinyl chloride resin, the molding temperature is about 200
Since it is ° C, as a film which does not melt-soften at that temperature and transmits electromagnetic radiation, a biaxially stretched film of polyethylene terephthalate having heat resistance can be exemplified.

The thickness of the film is 10 to 100.
μm, preferably 20 μm to 60 μm. 10 μm
When it is the following, when used in the continuous production process of the fiber-reinforced thermoplastic resin foam, fine irregularities on the surface of the outer periphery regulating member are picked up, and when it is 100 μm or more, the fiber-reinforced thermoplastic resin foam is molded. There is a problem that the outer contour of the image does not become sharp.

<Regarding Electromagnetic Radiation Curing Resin> Examples of the electromagnetic radiation curing resin include an electron beam curing system and an ultraviolet curing system, and it is preferable to use an ultraviolet curing system whose equipment is relatively inexpensive.

The UV-curable resin composition includes, as main components, UV-polymerizable oligomers such as epoxy acrylate, urethane acrylate, polyester acrylate, and polyether acrylate;
UV-polymerizable monomers such as monofunctional and polyfunctional acrylates for adjusting physical properties such as hardness of the protective layer after curing, and benzoin-based compounds for absorbing and exciting ultraviolet rays to generate radicals and to initiate radical reactions. Contains photo-initiators such as acetophenone and thioxanthone, amine-based and quinone-based photo-initiating assistants that prevent the adverse effects of oxygen, stabilizers for removing free radicals not involved in polymerization, and thermal polymerization inhibitors Use what was done.

As the UV-polymerizable monomer specifically used in each of the constituents to be incorporated into the above composition, isodecyl acrylate, isooctyl acrylate, phenoxyhydroxypropyl acrylate, 1,6-hexanediol Diacrylate and the like. As the photoinitiator, one in which the molecule itself of the photoinitiator is cleaved to initiate a radical is thermally stable and can be suitably used. For example, benzoin ether, α, α-diethoxyacetophenone, 1
-Hydroxycyclohexyl phenyl ketone; and benzophenone, thioxanthone, and xanthone, which are relatively thermally stable, can also be used. As a photoinitiating aid, a relatively high polymer having a tertiary amine in the molecule,
4-diethylaminoisoamylbenzoate and the like.

Further, in order to achieve the object of the present invention,
Even in thermoforming, it is necessary to maintain the unevenness and prevent the pattern from flowing, and the performance required of the resin after curing of the electromagnetic radiation curing resin is that it adheres firmly to the film, The interface does not peel off due to heating, and
The cured resin itself must have viscoelasticity but no plasticity, that is, it must not be deformed by heat. Therefore, the electromagnetic radiation curing resin is three-dimensionally cured,
That is, it is preferable to use a compound containing a polyfunctional oligomer or monomer at a fixed ratio in the composition.

<Method of Coating Electromagnetic Radiation-Curable Resin> The electromagnetic radiation-curable resin is adjusted by a blending ratio of oligomer / monomer so that the viscosity becomes 10 to 5000 cps in a temperature range to be applied. The most suitable one is selected from conventionally known coating techniques such as a contact coater, a rod coater, a draw coater, and an extrusion coating in accordance with the resin viscosity to be used and the level of unevenness of the decorative sheet. For example, a knife coater or a contact coater is preferably used when the depth of the recess is 200 μm or less, and a draw coater is preferably used when the depth is more than the above. After applying the electromagnetic radiation curable resin to the film with such a coating machine, the decorative sheet may be laminated, or vice versa, and when using a draw coater, the film and the decorative sheet are respectively corresponded. It is also possible to supply on a roll which performs electromagnetic radiation curing resin between the film and the decorative sheet. In any case, the coating must be applied so that no voids are trapped in the gap between the film and the decorative sheet. When a void is involved, when the resin is cured by electromagnetic radiation in a subsequent step, the decorative sheet surface of the void portion is deformed, and the original surface state of the decorative sheet cannot be maintained. .

<Method of Curing Electromagnetic Radiation-Curable Resin> As a specific method for curing the electromagnetic radiation-curable film, a laminate obtained by applying and laminating an electromagnetic radiation-curable resin between a decorative sheet and a film may be used. There is a method in which the resin is continuously supplied to an electromagnetic radiation irradiating apparatus, and the electromagnetic radiation curable resin is cured by irradiating the film with the electromagnetic radiation. Examples of the electromagnetic radiation to be irradiated include ultraviolet rays, electron beams, and the like. Irradiation sources and irradiation devices may be conventionally known ones. Regarding irradiation time and output, the electromagnetic radiation curable resin to be used is used. Will be adjusted by

For example, low-pressure / high-pressure mercury lamps, metal halide lamps, pulse xenon lamps, and electrodeless discharge lamps are used as the irradiation source as the ultraviolet irradiation device. A known electron beam accelerator such as a variable-voltage type is used.

<Regarding Fiber-Reinforced Thermoplastic Resin Layer> Types of Thermoplastic Resin Types of thermoplastic resin used for the fiber-reinforced thermoplastic resin layer laminated on the back side of the decorative sheet in the decorative molding sheet of the present invention. Is not particularly limited, for example, polyvinyl chloride, chlorinated polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyamide, polycarbonate, polyphenylene sulfide, polysulfone, polyether sulfone, polyphenylene oxide, polyvinylidene fluoride, polyether ether ketone, polymethyl Examples include methacrylates and thermoplastic elastomers. Further, copolymers and graft resins containing the above-mentioned thermoplastic resin as a main component, for example, ethylene-vinyl chloride copolymer, vinyl acetate-vinyl chloride copolymer, silane-modified polyethylene, and acrylic acid-modified polypropylene can be used.

The above-mentioned thermoplastic resins may be used alone or in combination, that is, as a polymer alloy. Heat stabilizers, plasticizers, lubricants, antioxidants, ultraviolet absorbers, pigments, inorganic fillers , Additives such as reinforcing short fibers, fillers, processing aids, modifiers and the like may be added.

Conditions for Thermoplastic Resin in Fiber Reinforced Thermoplastic Layer In the present invention, the thermoplastic resin used for the fiber reinforced thermoplastic resin layer has a high melt viscosity of 1 × 10 ⁵ to 1 × 10 ⁷ poise. By using the thermoplastic resin, it is possible to suppress unevenness in the thickness of the fiber-reinforced thermoplastic resin layer even when a cross-section changes inside a drawing die or the like as an outer periphery regulating member for shaping the hollow body. Thus, a fiber-reinforced thermoplastic resin layer having excellent moldability is obtained, which is preferable.

When the viscosity of the thermoplastic resin is 1 × 10 ⁵ poise or less, the thickness of the reinforcing layer becomes uneven due to the pressure of the foamed resin, and when the viscosity is 1 × 10 ⁷ poise or more, the cross-sectional shape of the product becomes a simple cross-sectional shape. Then, it can be molded, but if it has a complicated shape, it will be difficult to shape it with the pressure of the foamed resin, and the moldability will be poor.

Further, in a drawing die as an outer periphery regulating member, the fiber-reinforced thermoplastic resin layer may be stretched. In such a case, it is preferable to use a thermoplastic resin having high stretchability. Crosslinking treatment may be performed to improve elongation.

Further, the fiber-reinforced thermoplastic resin layer is required to have airtightness, and this airtightness is determined by the volume ratio of the reinforcing fiber in the fiber-reinforced thermoplastic resin layer, the adhesion between the reinforcing fiber and the thermoplastic resin, and the like. Depending on the degree of the cross-sectional change and elongation change described above,
In order to impart airtightness, a layer made of only a thermoplastic resin having excellent stretchability and airtightness may be separately provided in the fiber-reinforced thermoplastic resin.

Types of Reinforcing Fibers In the present invention, the reinforcing fibers used in the fiber-reinforced thermoplastic resin layer include, for example, inorganic fibers such as glass fibers, carbon fibers, silicon fibers, and boron fibers, polyester fibers, aramid fibers, vinylon, and the like. Organic synthetic fibers, iron, metal fibers such as titanium, and natural fibers such as silk, cotton, hemp, etc., all fibers that can be used as reinforcing fibers can be used, and a single type of these fibers, Alternatively, a plurality of types of mixed fibers different from each other may be used.

The fiber preferably has a diameter of 1 to 50 μm, particularly 3 to 25 μm in order to maintain the impact resistance of the obtained fiber-reinforced thermoplastic resin layer and not to impair the surface smoothness. Should be at least one layer integrated with the resin in a substantially constant orientation, and the others have a length of 1
It is preferable to use long fibers or continuous fibers of 0 μm or more.

In order to obtain a reinforcing effect and airtightness, it is preferable that the fibers are sufficiently impregnated with a thermoplastic resin between filaments and held. Therefore, in order to enhance the adhesiveness between the fiber and the resin, the fiber may be subjected to a surface treatment conventionally applied to the glass fiber or a pretreatment for improving the affinity between the fiber and the resin.

Morphology of Reinforcing Fibers The fiber morphology inside the fiber reinforced thermoplastic resin layer is at least one as described above, and the other particularly if it has a layer in which continuous fibers are arranged in a substantially constant direction. There is no limitation, for example, a state in which long fibers are randomly oriented, a mat shape in which long fibers are entangled with each other, a strand shape in which continuous fibers are bundled, a cross shape in which fibers are woven in two and three dimensions, and a continuous shape. One in which each filament is dispersed in the thermoplastic resin and is aligned in the longitudinal direction of the sheet.

Further, the fiber reinforced thermoplastic resin layer may be a laminate of a plurality of layers obtained by laminating layers made of these various forms of fibers. Conditions for the fiber-reinforced thermoplastic resin layer In addition to the above conditions, the thickness of the fiber-reinforced thermoplastic resin layer forming the skin layer of the fiber-reinforced thermoplastic resin foam is not particularly limited. There is no effect, and when it is thick, shaping becomes difficult, so the thickness is 0.1 to 5 m.
m is preferable. If the amount of fibers in the fiber-reinforced thermoplastic resin layer is small, a sufficient reinforcing effect and molding stability cannot be obtained, and if it is large, the thermoplastic resin cannot be impregnated and fusion becomes difficult. Since the airtightness is reduced, the content is preferably set to 5 to 70% by volume.

Further, since the fiber-reinforced thermoplastic resin layer bears almost all of the shear resistance generated during molding,
In the molding temperature range, the tensile strength in the longitudinal direction, the elastic modulus, it is necessary to be designed in accordance with the above-mentioned shear resistance level, as an example, the fiber-reinforced thermoplastic resin layer mentioned in Examples described later, The tensile strength and the modulus of elasticity were 50 MPa and 5 GPa or more, respectively, and the fiber-reinforced thermoplastic resin layer could be formed stably without being distorted in the longitudinal direction and without being broken during molding.

Method for Producing Fiber Reinforced Thermoplastic Resin Layer The fiber reinforced thermoplastic resin layer in the present invention is produced, for example, as a fiber reinforced thermoplastic resin sheet, but the production method is not particularly limited. For example, it can be manufactured as follows.

In order to obtain a fiber-reinforced thermoplastic resin sheet having a fiber form arranged in one direction, a powdery thermoplastic resin is placed inside a fluidized tank, and a porous resin is provided at the bottom of the tank. The fiber is brought into a fluidized state by jetting air from the plate, a plurality of fiber bundles guided by guide rolls are passed through the plate to form a thermoplastic resin-adhered fiber bundle, and then the fibers are heated by passing through a heating roll. It is impregnated with a plastic resin and passed through a cooling roll to obtain a desired fiber-reinforced thermoplastic resin sheet.

When a fiber-reinforced thermoplastic resin sheet having a layer in which fibers are randomly arranged is to be obtained, the layer is made of a thermoplastic resin-adhered fiber bundle obtained by the same method as described above. Was cut by a rotary cutter, dropped on an endless belt, accumulated, and then passed through a heating furnace by applying pressure while being sandwiched between another endless belt provided above the endless belt. It can be obtained by impregnating a fiber with a thermoplastic resin and then passing the fiber through a cooling guide roll.

On the other hand, when a resin having a low viscosity is used, a fiber reinforced thermoplastic resin sheet can be obtained by directly impregnating a thermoplastic resin in a molten state into a fiber base material.
At this time, it is necessary that the thermoplastic resin does not drop by its own weight during melting after being composited. Therefore, after complexing, it is necessary to increase the melt viscosity by polymerizing or modifying the thermoplastic resin by a crosslinking treatment or the like.

Further, in order to obtain the decorative molding sheet by laminating a fiber-reinforced thermoplastic resin layer on the back side of the decorative sheet of the decorative forming sheet of claim 1 or 2, the laminating method is used. Is not particularly limited. (1) At least one of the above two layers is heat-fused as long as the decorative sheet and the thermoplastic resin used for the fiber-reinforced thermoplastic resin layer can be heat-fused to each other. It is possible to adopt a method in which the thermoplastic resin used for the decorative sheet and the fiber-reinforced thermoplastic resin layer is thermally fused to each other by heating to a temperature at which the decorative sheet and the fiber-reinforced thermoplastic resin layer can be bonded to each other. If it is impossible resin, it is also possible to bond and laminate by applying an adhesive to the interface between these two layers.

<Regarding the Thermoplastic Resin Foam Layer> Conditions for the Thermoplastic Resin Used for the Thermoplastic Resin Foam Layer In the method for producing a fiber-reinforced thermoplastic resin foam according to the invention of claims 6 and 7, the core material is used. As the thermoplastic resin used for the thermoplastic resin foam layer to be a layer, any resin that can be continuously molded as a foam can be basically used, but it is used for a fiber-reinforced thermoplastic resin layer. It is preferable to use a resin having heat-fusibility with a thermoplastic resin. However, any material can be used as long as it is not easily separated from the fiber-reinforced thermoplastic resin layer and the foam layer after being joined via an adhesive layer, and solidified by heating and cooling during molding. In the molding temperature range, it is preferable that the resin is in a plasticized state together with the fiber-reinforced thermoplastic resin layer, and has a lower viscosity than that of the thermoplastic resin of the fiber-reinforced thermoplastic resin layer and is easy to flow. Further, depending on the product use, the foam itself may be hard or soft.

Conditions for the thermoplastic resin foam layer The conditions for the thermoplastic resin foam layer are as follows:
5 times to 30 times is preferable, and a more preferable range is 1.5 times to 5 times. When the expansion ratio is less than 1.5 times, it is difficult to change the cross-section, and when the expansion ratio is 30 times or more, the foam cells are broken by heating during molding, and the airtightness and the foaming pressure can be maintained. Disappears.

<Method of shaping decorative molding sheet with fiber-reinforced thermoplastic resin layer into a hollow shape> A decorative molding sheet in which a fiber-reinforced thermoplastic resin layer is laminated on the back side of the decorative sheet is used. The method of shaping into a hollow body is not particularly limited. For example, in addition to the method using a mold described later in the examples, a method of gradually bending with a synthetic resin shoe or roll or the like Is mentioned. When shaping into a hollow body, shaping is performed while heating the thermoplastic resin in a softened state by heating with a far infrared heater or a blower.

The term "hollow body" as used in the present invention means not only a sheet whose ends are abutted or simply overlapped and shaped, but also one end of a decorative molding sheet. In the area provided only with the fiber reinforced thermoplastic resin layer without partially providing the decorative sheet, and formed in a hollow body by overlapping with the other end in the area only with the fiber reinforced thermoplastic resin layer You may.

When a decorative molding sheet having a fiber-reinforced thermoplastic resin layer is formed into a hollow body, a plurality of sheets are used, and their ends are overlapped with each other to form one hollow body as a whole. It may be shaped on the body.

Further, as a matter of course, the decorative sheet only needs to be laminated to the fiber-reinforced thermoplastic resin layer only on the portion requiring decorating, and the decorative sheet covers the entire surface of the hollow body. Need not be stacked.

[0060]

EXAMPLES Examples in which the present invention is applied to actually produce decorative molding sheets and fiber-reinforced thermoplastic resin foams will be described together with comparative examples.

Example 1 A decorative molding sheet having an electromagnetic radiation curable resin interposed between a decorative sheet and a film was produced by the following method.

As a film transmitting electromagnetic radiation,
Polyethylene terephthalate film (manufactured by Teijin: TYP
E = SC, thickness 38 μm, inner surface corona treated product). This film is hereinafter referred to as film A.

As the decorative sheet, a decorative sheet having a wood grain pattern having an uneven surface was used. Specifically, it is a commercially available decorative sheet having a fluorine resin layer on the surface of a soft vinyl chloride resin sheet (manufactured by Toppan Printing Co., Ltd .: product name TOOPAN Super EX, eye pattern, recess depth = 50 to 90 μm) Hereinafter, this decorative sheet is referred to as a decorative sheet B.

As the electromagnetic radiation curing resin, a resin composition (viscosity = 500 cps / 25 ° C.) having the composition shown in the following Table 1 and being cured by ultraviolet rays was used. Hereinafter, this resin composition is referred to as resin composition C.

[0065]

[Table 1]

Using a manufacturing apparatus having the structure shown in FIG. 1, a decorative molding sheet was manufactured in the following procedure. That is, the above-mentioned film A is fed from the feeding machine 1,
It guided to the roll coater 3a through the guide bar 2 which can adjust a tension and a position. On the other hand, the decorative sheet B is fed out from the feeding machine 4 with its decorative surface (irregular surface) facing upward, and the guide bar 5 is provided.
To the roll coater 3b. The film A and the decorative sheet B having passed through the roll coaters 3a and 3b were laminated on each other with the decorative surface of the decorative sheet B facing the film A side. Prior to the lamination, the resin composition C was applied to the corona-treated surface of the film A at a rate of 30 g / m ² by the application device 6 arranged on the roll coater 3a. As a result, the film A and the decorative sheet B are mutually laminated with the resin composition C interposed therebetween. This laminate is hereinafter referred to as a laminate sheet D1. Here, the resin composition C has a viscosity of 5 as described above.
Since the resin composition C has a low viscosity of 00 cps, in this laminating step, the resin composition C is densely placed between the film A and the decorative sheet B including the concaves and convexes formed on the decorative surface of the decorative sheet B. I was full.

A curing furnace 7 is disposed below the roll coaters 3a and 3b. In the curing furnace 7, there is provided a curved surface member 8 formed by processing a member that transmits ultraviolet rays such as quartz to a radius of curvature of 1000 mm. , A high-pressure mercury lamp (1) arranged at a distance of 100 mm from the concave curved surface side (inner surface side) of the curved surface member 8.
60 W / cm) is accommodated.

The laminated sheet D1 filled with the resin composition C between the film A and the decorative sheet C via the roll coaters 3a and 3b was guided into the curing furnace 7 via the guide bar. In the curing furnace 7, the laminated sheet D1 is
The guide was guided by a plurality of guide bars so as to be transported while being pressed along the convex curved surface side (outer peripheral surface side) of the curved surface member 8. Then, ultraviolet light from an ultraviolet irradiation device 9 was irradiated from the concave side of the curved surface member 8. This allows
While the laminated sheet D1 is transported while being pressed against the curved member 8, the resin composition C in the laminated sheet D1 is cured by being irradiated with ultraviolet rays through the curved member 8 and the film A that transmit ultraviolet rays, and cured. The decorative molding sheet D2 is obtained.
The decorative molding sheet D2 after curing of the resin composition C is
It was guided between a pair of take-up rolls 10 by a guide bar, taken up at a take-up speed of 5 m / min, and taken up by a winder 11.

The decorative molding sheet D2 thus obtained, as shown in a schematic cross-sectional view in FIG. 2, is such that the resin composition C also fills the concave portions formed on the decorative sheet B, and The layer made of the resin composition C was formed with a thickness of 30 μm.

(Example 2) A fiber-reinforced thermoplastic resin sheet was laminated on the decorative molding sheet D2 obtained in Example 1 to produce a decorative molding sheet F with a fiber-reinforced thermoplastic resin layer. Using the sheet F, a fiber-reinforced thermoplastic resin foam was produced.

Production of Fiber Reinforced Thermoplastic Resin Sheet Glass fiber bundle (manufactured by Nitto Boseki Co., Ltd .: 4400 g / km,
Twelve fibers (diameter: 23 μm) are aligned and the following [Table 2]
The polyvinyl chloride resin powder having the composition shown in (1) was drawn into a tank in which air was flowing by air, and the polyvinyl chloride resin powder was attached to the glass filaments while breaking the glass fiber bundle into filament units. In a state where the glass fibers to which the polyvinyl chloride resin is attached are aligned in a plane, 220 °
Heating was performed while applying pressure at 10 kg / cm with a pinch roll heated to C, thereby melting the polyvinyl chloride resin and infiltrating between the glass fibers. Then, it was cooled with a cooling pinch roll, and a glass fiber reinforced polyvinyl chloride sheet having a width of 100 mm and the same thickness as a glass fiber reinforced polyvinyl chloride sheet having a width of 170 mm and a thickness of 0.5 mm (hereinafter, referred to as a fiber reinforced sheet E1). A vinyl chloride sheet (this sheet is hereinafter referred to as a fiber reinforced sheet E2) was obtained.

[0072]

[Table 2]

Lamination of Fiber Reinforced Thermoplastic Resin Sheet and Decorative Forming Sheet The above fiber reinforced sheet E1 was heated to 170 ° C., and the 160 mm wide decorative forming sheet obtained in Example 1 was provided at the center thereof. By laminating D2 with a pinch roll and heat-sealing, as shown in a schematic sectional view in FIG.
A decorative molding sheet F obtained by laminating and fusion-bonding the fiber-reinforced sheet E1 and the decorative molding sheet D2 was obtained.

Foamable thermoplastic resin composition The composition shown in the following Table 3 containing polyvinyl chloride as a main component was used as the foamable thermoplastic resin composition G. At the time of compounding, the resin temperature was 100 ° C using a super mixer.
I went to C.

[0075]

[Table 3]

An apparatus and a mold for producing a fiber-reinforced thermoplastic resin foam are provided by:
FIG. 4 is a schematic sectional view.

The decorative forming sheet F was wound around one sheet feeding machine 101, and the fiber reinforced sheet E2 was wound around the other sheet feeding machine 102. The decorative molding sheet F fed from the sheet feeding machine 101 is:
It is inserted between an extrusion die 104 mounted on the extruder 103 and a die 105 having a shape surrounding the outer periphery thereof. FIG. 5 shows a state in which the extrusion mold 104 and the mold 105
A gap that can pass through in a shape as shown in a cross-sectional view of the decorative molding sheet F at a location indicated by XX ′ in FIG. Although not shown, the decorative molding sheet F is provided on the downstream side (left side in the figure) of the extrusion die 104.
And a hot-air heating device for heating and softening the sheet F of the shaping jig.

Further, an introduction hole 1051 for introducing the fiber reinforced sheet E2 is formed below the mold 105, and the fiber reinforced sheet E2 introduced from the introduction hole 1051 is formed into a shape shown in FIG. As shown in FIG. 6, a cross-sectional view taken along the line YY 'in FIG. 4 is placed on the decorative forming sheet F so as to cover the opening of the shaped decorative forming sheet F. The two sheets F and E2 form a hollow body T as a whole. In addition, the fiber reinforced sheet E2 and the decorative molding sheet F overlap each other with a width of 5 mm on the folded portions formed on both sides of the opening of the decorative molding sheet F. Although not shown, a hot air heating device for heating and softening the fiber reinforced sheet E2 to be introduced into the introduction hole 1051 at the preceding stage is provided below the mold 105.

The extrusion mold 104 includes a horizontal core mold 1041 for shaping the decorative molding sheet F into the shape shown in FIG. 5 in cooperation with the mold 105, and a right angle from the core mold 1041. And has a vertical portion 1042 which is connected to the extruder 103 through the opening of the decorative molding sheet F, and opens toward the inside of the hollow body T through the whole thereof. A plurality of circular resin flow paths 1043 are formed in parallel. Then, the foamable resin composition G supplied from the extruder 103 via the resin flow path 1043 can be extruded into the hollow body T.

A shaping die 107 is provided downstream of the extrusion die 104 and the die 105. The cross-sectional shape of the shaping die 107 is the same as the cross-sectional shape of the hollow body T shown in FIG. 6 at its upstream end (the joint portion with the extrusion die 104 and the die 105), but at the downstream end. 7, the cross-sectional shape of the product at the location indicated by ZZ 'in FIG. 4 is the same as the final cross-sectional shape of the product, during which the cross-sectional shape gradually changes.

The shaping mold 107 and the above-described mold 1
05 can be heated to a desired temperature by heaters 107a and 105a provided on the respective outer peripheral surfaces.

On the downstream side of the shaping mold 107, a heat insulating material 10
The cooling mold 109 is connected through the connection 8. The cross-sectional shape of the heat insulating material 108 and the cooling mold 109 is the shape of the shaping mold 1.
07 is exactly the same as the shape at the downstream end. And
On the downstream side of the cooling mold 109, a take-off machine 110 for taking out a molded product is provided.

Production of Fiber-Reinforced Thermoplastic Foam In the above-described production apparatus and mold, with the extrusion mold 104 temperature-controlled to 170 ° C., the decorative molding sheet F
Is heated and softened to 100 ° C. by a hot air heating device, and shaped into a shape shown in FIG. 5 by a shaping jig, and an upstream opening is formed in a gap formed between the extrusion mold 104 and the mold 105. While passing through it through the insertion hole 10 of the mold 105.
To 51, a fiber reinforced sheet E2 heated and softened to 100 ° C. by a hot air heating device was inserted, and the hollow body T shown in FIG. at the same time,
Inside the hollow body T, 205 inside the extruder 103
The foamable resin composition G heated and kneaded to a temperature
Extruded while foaming through 43. Thereafter, the entirety of the hollow body T and the resin composition G inside the hollow body T are rotated by 180 °
C is introduced into the shaping mold 107 heated to C, and is taken out by the take-off machine 110 while pressing the outer peripheral surface of the hollow body T against the inner circumferential surface of the shaping mold 107 by the foaming pressure of the foamable resin composition G. The shape of the film A and the resin composition C on the surface side of the decorative molding sheet F are further separated by gradually changing the cross-section to form the shape shown in FIG. As a result, a fiber having an irregular cross-sectional shape comprising a skin layer made of a fiber-reinforced thermoplastic resin and a core material layer made of a thermoplastic resin foam, in which the decorative sheet B is arranged in a region indicated by a chain line in FIG. A reinforced thermoplastic resin foam was obtained.

It was confirmed that the decorative sheet B on the surface of the fiber-reinforced thermoplastic resin foam had the original surface condition preserved as it was. (Embodiment 3) The decorative molding sheet F and the fiber reinforced sheet E2 are formed into the same hollow body T as described above by using the same manufacturing apparatus and mold as in Embodiment 2, and extruded into the hollow body T. The foaming resin composition G heated and kneaded at 180 ° C. is supplied without foaming inside the molding machine 103,
7 was heated to 220 ° C. to heat and foam the resin composition G, and the foaming pressure was used to form the whole into exactly the same shape as in Example 1, followed by cooling with the cooling mold 109 and further cooling. By peeling the film A and the resin composition C, the same fiber-reinforced thermoplastic resin foam as in Example 2 was obtained. With respect to the decorative sheet B on the surface of the fiber-reinforced thermoplastic resin foam produced in Example 3, it was confirmed that the original surface state was preserved as it was.

(Comparative Example 1) An attempt was made to thermocompression-bond the decorative sheet B directly to the fiber-reinforced thermoplastic resin sheet E1,
When both were heated to a temperature (150 ° C.) at which they could be thermally fused to each other and pressed at a linear pressure of 0.5 kg / cm, all the irregularities on the surface of the decorative sheet B had disappeared.

Comparative Example 2 Decorative sheet B having a width of 160 mm
Is bonded to the central portion of the fiber reinforced sheet E1 with an adhesive, and the other is made of the fiber reinforced thermoplastic resin foam under exactly the same conditions using the same manufacturing apparatus and mold as in Example 2. Was manufactured.

The decorative sheet B disposed on the obtained fiber-reinforced thermoplastic resin foam had all the patterns on the surface thereof flow, and the decorative sheet B was partially peeled off. (Comparative Example 3) A laminated body obtained by laminating the film A on the design side of the decorative sheet B was used as a fiber-reinforced sheet E1 having a width of 160 mm.
A fiber reinforced thermoplastic resin foam was manufactured using exactly the same manufacturing equipment and mold as in Example 2 and using exactly what was fused and integrated at 150 ° C. After that, the film A was peeled off.

Although there was almost no flow of the pattern on the surface of the decorative sheet B, the irregularities had completely disappeared.

[0089]

According to the present invention, a film that transmits electromagnetic radiation is disposed on the surface side of a decorative sheet having a pattern and irregularities formed on the surface, and an electromagnetic radiation curable resin is densely placed between the two. This structure uses a commercially available decorative sheet as it is, and irradiates electromagnetic radiation from the film side by interposing a relatively low-viscosity electromagnetic radiation curable resin between the film and the film. The decorative sheet can be easily obtained by doing so, without providing special equipment, and without deteriorating the initial surface state of the decorative sheet even in heating and pressure molding, the decorative sheet can be used as a base material of the molded article. A decorative molding sheet that can be firmly bonded by heat fusion is obtained.

Also, by using a fiber-reinforced thermoplastic resin layer laminated on the surface of the decorative molding sheet opposite to the film, the foamed resin layer is covered with the fiber-reinforced thermoplastic resin layer. The surface can be decorated simultaneously with the continuous molding process of the fiber-reinforced thermoplastic resin foam, which has a lightweight, high-strength and complex irregular cross-sectional shape, and any area of the surface can be decorated It has become possible to manufacture the molded article very efficiently.

[Brief description of the drawings]

FIG. 1 is a configuration diagram of an apparatus for manufacturing a decorative molding sheet according to a first embodiment of the present invention.

FIG. 2 is a schematic cross-sectional view showing the structure of a decorative molding sheet obtained in Example 1 of the present invention.

FIG. 3 is a schematic cross-sectional view showing the structure of a decorative molding sheet F manufactured in Example 2 of the present invention.

FIG. 4 is a schematic cross-sectional view showing a configuration of a manufacturing apparatus and a mold of a fiber-reinforced thermoplastic resin foam of Examples 2 and 3 of the present invention.

FIG. 5 is a cross-sectional view of the decorative molding sheet F at a location indicated by XX ′ in FIG. 3;

FIG. 6 is a cross-sectional view of the hollow body T at a location indicated by YY ′ in FIG.

FIG. 7 is a cross-sectional view of the molded product at a location indicated by ZZ 'in FIG. 3 (final cross-sectional view of the product).

[Explanation of symbols]

 1, 4 Sheet feeding machine 3a, 3b Roll coater 6 Coating device 7 Curing furnace 8 Curved surface member 9 Ultraviolet irradiation device 101, 102 Sheet feeding machine 103 Extruder 104 Extrusion mold 1041 Core mold portion 1042 Vertical portion 1043 Resin flow path 105 Mold 1051 Introducing hole 107 Shaping mold 109 Cooling mold 110 Take-off machine T Hollow body

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // B29K 105: 04

Claims (7)

[Claims] 1. A decorative molding sheet in which a film that transmits ultraviolet light is laminated on a surface side of a decorative sheet having a pattern and irregularities formed on the surface thereof in a state where an electromagnetic radiation-curable resin is densely interposed. . 2. The decorative molding sheet according to claim 1, wherein a release layer is formed on the surface of the decorative sheet. 3. A fiber-reinforced thermoplastic resin layer having at least one layer in which a plurality of continuous fibers are integrated with a thermoplastic resin in a substantially constant orientation state is laminated on the back side of the decorative sheet. 3. The method according to claim 1, wherein
The decorative molding sheet according to 1. 4. The viscosity of at least one of the front side of the decorative sheet having a pattern and irregularities formed on the surface and one side of a film that transmits ultraviolet light has a viscosity of 10 to 500.
After continuously applying an electromagnetic radiation curable resin of 0 cps, laminating the sheet and the film with the electromagnetic radiation curable resin interposed therebetween, and irradiating electromagnetic radiation from the film side surface of the laminate, the electromagnetic radiation curable resin is applied. A method for producing a decorative molding sheet, comprising curing a cured resin. 5. When irradiating the electromagnetic radiation-curable resin with electromagnetic radiation from the film-side surface of the laminate, the film-side surface of the laminate is formed into a gently convex curved member capable of transmitting electromagnetic radiation. The method for producing a decorative molding sheet according to claim 4, wherein the laminate is irradiated with electromagnetic radiation through the convex curved member while being pressed. 6. The decorative molding sheet according to claim 3,
While continuously shaping the hollow body so that the film side is on the outside, the foamable thermoplastic resin composition is supplied while being foamed on the inner surface thereof, and the whole is guided to the outer periphery regulating member, and the regulating member is provided. After shaping by changing the outer shape of the hollow body to the desired cross-sectional shape by
A method for producing a fiber-reinforced thermoplastic resin foam, characterized by peeling the outside including the electromagnetic radiation-curable resin layer or the outside including the release layer. 7. The decorative molding sheet according to claim 3,
While continuously forming the hollow body so that the film side is on the outside, while supplying the expandable thermoplastic resin composition therein, the resin composition is foamed inside the hollow body, and the whole To the outer periphery regulating member, and after shaping by changing the outer contour of the hollow body to a desired cross-sectional shape by the regulating member, including the layer of the electromagnetic radiation curable resin, or the outer layer. A method for producing a fiber-reinforced thermoplastic resin foam, characterized in that the outer surface of the fiber-reinforced thermoplastic resin foam is peeled off.