JPH08300373A - Method for producing fiber-reinforced thermoplastic resin foam - Google Patents

Abstract

(57) [Abstract] [Purpose] Manufacture of a fiber-reinforced thermoplastic resin foam that is easy to mold even if it has a complicated cross-sectional shape and that can easily perform good surface decoration. Provide a way. [Structure] A fiber-reinforced thermoplastic resin sheet 1 whose surface is decorated is continuously shaped into a hollow body 2 with its decorated surface 1a facing outward, and its shaping is performed. The foamable thermoplastic resin composition 3 is supplied while being foamed into the hollow body 2 through the opening in the middle, or is foamed after the foaming, and the foaming pressure causes the outer surface of the hollow body 2 to be regulated.
A desired cross-sectional shape is formed along 04.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention comprises a core layer made of a thermoplastic resin foam and a skin layer made of a fiber reinforced thermoplastic resin layer, and the surface of the skin layer is decorated. And a method for producing the fiber-reinforced thermoplastic resin foam.

[0002]

2. Description of the Related Art Conventionally, as a method for producing a fiber-reinforced resin molded product whose surface is decorated, when a fiber-reinforced resin molded product is drawn and molded, a release film having a coating film formed thereon is used.
A method of transferring a coating film onto the surface of a molded body simultaneously with molding of the fiber reinforced resin by drawing the resin into the drawing mold together with the fiber base material impregnated with the resin (JP-A-3-1848).
No. 32) or the like, when the fiber-reinforced resin molded body is pultruded, on the surface of the molded body in the high temperature state, which is pulled out from the mold,
A method of continuously laminating a surface decorative material such as a film or a sheet by pressing it with an adhesive (JP-A-4-32).
No. 3024) is known.

[0003]

However, in order to obtain a molded product having a complicated cross-sectional shape, when the former method is used, the release film is made to follow the complicated cross-sectional shape,
Not only is it difficult to insert it into the mold without wrinkles, but it is also difficult to properly position the film in the area that requires painting. Further, even in the case of using the latter method, it is extremely difficult to laminate a film or sheet-like surface decorative material on the surface of a molded product having a complicated cross-sectional shape drawn from a mold without wrinkling. .

The present invention has been made in view of the above circumstances, and an object thereof is to easily mold a molded product having a complicated cross-sectional shape and to easily perform surface decoration. It is an object of the present invention to provide a method for producing a fiber-reinforced thermoplastic resin foam capable of being manufactured.

[0005]

In order to achieve the above object, the method for producing a fiber-reinforced thermoplastic resin foam of the present invention is applied to the surface as shown in FIGS. The decorated fiber-reinforced thermoplastic resin sheet 1 is continuously shaped into the hollow body 2 so that the decorated surface 1a is on the outside, and the hollow body 2 is foamed inside. It is characterized in that the thermoplastic resin composition 3 is supplied while being foamed, and the foaming pressure causes the outer surface of the hollow body 2 to be shaped into a desired cross-sectional shape along the regulating member 104.

Here, the expandable thermoplastic resin composition 3 is
Instead of supplying while foaming into the hollow body 2 as described above, after supplying the expandable thermoplastic resin composition 3 into the hollow body 2, foaming is performed in the hollow body 2 by heating. Good.

In each of the above methods, the fiber-reinforced thermoplastic resin sheet 1 is regulated by the pressure from the inside.
The film 4 may be preliminarily laminated on the decorated surface 1a of the fiber-reinforced thermoplastic resin sheet 1 in order to avoid damage to the decorated surface when shaping along 04. (See FIG. 4).

Further, by laminating a film 5 having irregularities on the decorative surface of the fiber reinforced thermoplastic resin sheet 1, the foamable thermoplastic resin composition 3 is foamed in the hollow body 2. It is possible to adopt a method in which the outer surface of the hollow body 2 is shaped into a desired cross-sectional shape along with the regulation member by pressure and at the same time, the unevenness of the film 5 is transferred to the decorative surface of the fiber-reinforced thermoplastic resin sheet 1. (See Figure 6).

Furthermore, according to the present invention, a composite sheet 10 composed of a fiber-reinforced thermoplastic resin layer 10a and a foamable thermoplastic resin composition layer 10b whose surface is decorated is provided with a decorative surface. After being continuously shaped into the hollow body 20 so that the outer side of the hollow body 20 is heated, the foamable thermoplastic resin composition on the inner surface side is foamed by heating, and the foaming pressure causes the outer surface of the hollow body 20 to serve as a regulating member. It is possible to adopt a method of forming a desired cross-sectional shape along the line (see FIG. 3).

Also in this case, the surface of the decorated fiber-reinforced thermoplastic resin layer 10a of the composite sheet 10 is
The film 4 for avoiding damage to the decorative surface can be laminated in advance.

Also in the method using the composite sheet 10, the film 5 having irregularities is laminated on the surface of the fiber reinforced thermoplastic resin layer 10a, whereby the foaming property inside the hollow body 20 is improved. A method of transferring the irregularities of the film 5 to the outer surface of the fiber-reinforced thermoplastic resin layer 10a at the same time as shaping the outer surface of the hollow body 20 into a desired cross-sectional shape along the regulating member by the foaming pressure of the thermoplastic resin composition. Can be adopted.

In the above respective methods of the present invention, the fiber-reinforced thermoplastic resin sheet 1 and the composite sheet 10 may be a single layer or may be a laminate of a plurality of layers. The hollow bodies 2 and 20 used in the respective methods of the present invention are
Sheets whose side edges are abutted against each other or overlapped with each other and shaped so that a void is formed inside, as well as those with a slight gap between the side edges Also includes.

The fiber-reinforced thermoplastic resin sheet 1,
Alternatively, as a method of shaping the composite sheet 10 into the hollow body 2 or 20 as described above, a method of gradually bending the sheet with a shoe or roll made of synthetic resin, and a method of gradually bending the sheet It is possible to employ a method in which a die is provided with a sheet passage that is shaped into a hollow body and the sheet is passed through the die.
At the time of shaping into a hollow body, in order to prevent cracking or tearing of the sheet, it is desirable to heat with a far-infrared heater or a hot air blower to shape the thermoplastic resin in a softened state.

Here, the softened state means JIS-K-72.
The state in which the thermoplastic resin is heated to the Vicat softening temperature or higher, which is measured according to 06. Generally, it refers to a state in which the thermoplastic resin begins to deform and is heated to a temperature at which the mechanical properties deteriorate.

The sheet used for shaping into the hollow body 2 or 20 is formed by abutting the side edges of one sheet with each other, by superposing them, or by abutting them with a slight gap, and also by a plurality of sheets. When these are made parallel to each other, these side edges are abutted with each other, or overlapped with each other, or abutted with a slight gap, so that they can be shaped into one hollow body as a whole. Good.

Further, as a method of supplying the foamable thermoplastic resin composition 3 while foaming it into the hollow body 2, the nozzle of the extruder is passed through the opening portion of the hollow body 2 in the process of shaping and the hollow body 2 is opened. A method can be adopted in which the foamable thermoplastic resin composition 3 is extruded from the nozzle while being foamed. In this case, the expandable thermoplastic resin composition 3 containing a decomposable foaming agent or a volatile foaming agent is kneaded in the extruder at a gas generation temperature or higher, and the generated gas is dispersed in the thermoplastic resin to foam. The thermoplastic resin composition 3 is extruded into the hollow body 2 from a nozzle whose temperature is adjusted to a temperature higher than the melting temperature. Alternatively, while kneading the thermoplastic resin at a melting temperature or higher, a gas such as carbon dioxide or nitrogen is injected under pressure to be dispersed in the thermoplastic resin, and the inside of the hollow body 2 is adjusted from a nozzle whose temperature is adjusted to be higher than the melting temperature of the thermoplastic resin. Extrude into.

On the other hand, as a method for supplying the foamable thermoplastic resin composition 3 into the hollow body 2 before foaming, the nozzle of the extruder is made to face the hollow body 2 in the same manner as in the thermoplastic resin composition. A method of extruding at a temperature above the melting temperature of the resin and below the decomposition temperature of the foaming agent, or a preformed sheet-shaped or pellet-shaped or rod-shaped thermoplastic resin composition containing the foaming agent, or foamed beads continuously. It is possible to employ a method of supplying into the hollow body 2.

Further, a method of supplying the foamable thermoplastic resin composition 3 into the hollow body 2 and then foaming it, or after shaping the composite sheet 10 into the hollow body 20 and then expanding the foamable thermoplastic resin on the inside. Examples of the method of foaming the resin of the layer 10b include a method of inserting the hollow body into a mold heated to a high temperature and a method of blowing hot air inside the hollow body. When hot air is blown into the inside, the structure of the manufacturing apparatus is set to the supply port of the expandable thermoplastic resin composition 3 and the regulating member 1.
It is necessary to provide air piping through the inside of 04 to provide a structure capable of supplying hot air into the inside of the hollow body.

As a method of shaping the hollow bodies 2 and 20 by the foaming pressure of the expandable thermoplastic resin composition, the hollow bodies are inserted into a mold and the foaming pressure of the expandable thermoplastic resin composition is used. A method of pressing the outer surface of the hollow body against the inner surface of the mold,
A method of controlling the outer surface of the hollow body with a roll or a shoe and shaping the foamed thermoplastic resin composition by heating from the surroundings to foam the foamable thermoplastic resin composition can be mentioned. When shaping is performed in the mold, the shaping may be assisted by evacuation or compressed air.

Here, in shaping the hollow bodies 2 and 20 into a desired cross-sectional shape along the regulating member by the foaming pressure of the foamable thermoplastic resin composition on the inside, the foamable thermoplastic resin composition is formed. When the pressure for pressing the hollow body against the regulating member cannot be obtained only by the foaming pressure generated in the foaming operation, a separate pressure may be supplementarily applied to the inside of the hollow body. Including the case of using such auxiliary pressure. When the auxiliary pressure is applied, it is preferable that the structure of the regulating member has a pipe through which gas can be supplied to the inside of the hollow body.

When the hollow bodies 2 and 20 are shaped into a desired cross-sectional shape by the foaming pressure inside, the hollow bodies can be shaped while being spread. That is, it is also possible to shape the outer peripheral length of the molded product to be larger than the outer peripheral length of the hollow body, in this case, in consideration of the expansion of the hollow body, the desired decoration after the expansion. It should be noted that the decoration must be applied to obtain the surface.

Next, as the thermoplastic resin used in the fiber reinforced thermoplastic resin sheet 1 used in each method of the present invention and the fiber reinforced thermoplastic resin layer 10a of the composite sheet 10, polyethylene, polypropylene, polyvinyl chloride,
Polystyrene, polyamide, polyethylene terephthalate, polybutylene terephthalate, polycarbonate,
Polyvinylidene fluoride, polyphenylene sulfide,
Examples thereof include polyphenylene oxide, polyether sulfone, polyether ether ketone, and polymethyl methacrylate. Further, a copolymer or graft resin containing such a thermoplastic resin as a main component, or a blended resin such as chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, vinyl acetate-ethylene copolymer, vinyl acetate- Vinyl chloride copolymer, urethane-vinyl chloride copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, silane-modified polyethylene, acrylic acid-modified polypropylene, maleic acid-modified polyethylene and the like can also be used. Further, a thermoplastic elastomer or a crosslinked thermoplastic resin can also be used. Of these, considering the molding temperature, 120
Polyethylene, polypropylene, polyvinyl chloride, polystyrene, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, vinyl acetate-ethylene copolymer, vinyl acetate-vinyl chloride, which can be molded at a relatively low temperature of up to 250 ° C. It is preferable to use a copolymer, a urethane-vinyl chloride copolymer, an acrylonitrile-butadiene-styrene copolymer, or an acrylonitrile-styrene copolymer.

The thermoplastic resin used in the present invention is
They may be used alone or in combination, and as long as the physical properties are not impaired, dibutyltin malate polymer, organic tin malate such as dibutyltin bis (monoalkylmalate), dibutyltin laurate, monobutyltin fatty acid salt, etc. Organic tin laurate, dioctyl tin sulfide, dibutyl tin 3
Organic tin mercapto-based, such as mercaptopropionate,
Lead stabilizers such as tribasic lead sulfate, basic lead sulfite, heat stabilizers such as metal soaps such as calcium stearate and lead stearate, fatty acid ester wax, low molecular weight polyethylene wax, metal soap, polyhydric alcohol, aliphatic alcohol, Lubricants such as fatty acid amide, acrylic resin,
Processing aids such as olefin resins, plasticizers such as dibutyl phthalate and dioctyl phthalate, antioxidants, UV absorbers, modifiers, additives such as colorants, and talc, mica, calcium carbonate, wood Fillers such as powder and fiber-reinforced thermosetting resin crushed powder may be blended.

Fiber-reinforced thermoplastic resin sheet 1 of the present invention,
And-a fiber-reinforced thermoplastic resin layer 10 of the composite sheet 10
As the fibers used in a, those which are not melt-softened and carbonized by the heat applied in each method of the present invention can be used, and specifically, glass fibers, carbon fibers, silicon / titanium / carbon fibers, boron fibers, Examples include fine metal fibers, organic fibers such as aramid fibers, polyester fibers, and polyamide fibers, and natural fibers such as silk, cotton, and hemp. From the viewpoint of strength and cost, glass fibers and carbon fibers are preferable. The diameter of the filament is preferably 1 to 50 μm, particularly preferably 3 to 30 μm. When the diameter of the filament is smaller than 1 μm, the reinforcing effect by the fiber becomes small, and when it is larger than 50 μm, the contact area between the thermoplastic resin and the fiber becomes smaller than that of the fiber of the same kind and the same weight. However, the reinforcing effect of the fibers becomes small, which is not preferable.

The fiber in the fiber reinforced thermoplastic resin sheet 1 or the fiber reinforced thermoplastic resin layer 10a of the composite sheet 10 is preferably in the range of 5 to 80% by weight, particularly preferably 10 to 50% by weight. When the content of the fibers is less than 5% by weight, the reinforcing effect is small, and when the content of the fibers is more than 80% by weight, the amount of resin binding between the fibers is small, which is rather weak.

Further, the fiber-reinforced thermoplastic resin sheet 1 or the fiber-reinforced thermoplastic resin layer 10a of the composite sheet 10 is used.
The length of the inner fibers is preferably 3 mm or more, and more preferably continuous fibers. The longer the reinforcing fiber, the stronger the strength of the fiber-reinforced thermoplastic resin foam obtained, and the shorter the fiber length is, the smaller the reinforcing effect is. Further, in order to shape the fiber-reinforced thermoplastic resin sheet 1 or the fiber-reinforced thermoplastic resin layer 10a while spreading it, it is preferable that the reinforcing fibers are oriented in the longitudinal direction of the product. That is, it is most preferable that the continuous fibers are oriented in the longitudinal direction of the product.

The thickness of the fiber-reinforced thermoplastic resin sheet 1 or the fiber-reinforced thermoplastic resin layer 10a is 0.1-10.
mm is preferable, and the range of 0.3 to 2 mm is more preferable. When the thickness is less than 0.1 mm, the strength of the fiber-reinforced thermoplastic resin sheet or the same layer is weak, and when it is more than 10 mm, shaping into a hollow body becomes difficult.

As an example of the method for producing the fiber-reinforced thermoplastic resin sheet 1 used in the present invention, a continuous reinforcing fiber bundle is defibrated into filaments and aligned in one direction, and then a film made of a thermoplastic resin is used. A method in which they are overlapped and passed through heating pinch rolls, and a molten thermoplastic resin is allowed to enter between glass filaments to form a sheet can be mentioned.

As another example of the method for producing the fiber reinforced thermoplastic resin sheet 1, continuous reinforced fiber bundles aligned in one direction are drawn into a tank in which the powder thermoplastic resin is flowing, After the powdered thermoplastic resin is attached while the reinforced fiber bundle is disintegrated into filaments, it is passed between heating pinch rolls so that the thermoplastic resin is melted and penetrates between the filaments to form a sheet. Can be mentioned.

Here, when the fiber-reinforced thermoplastic resin sheet 1 is to be obtained by randomly arranging the fibers, the powdered thermoplastic resin obtained as described above is attached. The reinforced fiber bundle was shredded with a rotary cutter, dropped on an endless belt and accumulated, then another endless belt was pressed from above, and it was sandwiched between the upper and lower endless belts while being pressurized and placed in a heating furnace. It is possible to employ a method of impregnating the chopped reinforced fibers with a thermoplastic resin by passing through the sheet, and then passing through a cooling guide roll to form a sheet.

On the other hand, as an example of the method for producing the composite sheet 10 used in the present invention, a foamable thermoplastic resin produced in advance on one surface of the fiber reinforced thermoplastic resin sheet obtained by any of the above methods. A method of heating and fusing the composition sheet can be mentioned.

As another example of the method for producing the composite sheet 10, an unfoamed expandable thermoplastic resin composition is provided on one surface of the fiber-reinforced thermoplastic resin sheet obtained by any one of the above-mentioned methods. Examples include a method of extruding into a sheet form in a molten state and laminating.

Next, as a mode of decorating the surface of the fiber-reinforced thermoplastic resin sheet 1 or the fiber-reinforced thermoplastic resin layer 10a of the composite sheet 10, the fiber-reinforced thermoplastic resin is formed by a method such as printing, transfer, plating or the like. Examples include decoration on the surface of the sheet or the same layer, and three-dimensional decoration that imparts fine irregularities such as embosses and fine irregularities such as wood grain fine grooves. Moreover, you may decorate by laminating the printed thermoplastic resin sheet or film.

Examples of the decoration method by printing include gravure printing, pad printing, screen printing and the like. As the paint used for printing, an organic pigment or an inorganic pigment dissolved or decomposed in an organic solvent can be used, and a paint excellent in adhesiveness to a thermoplastic resin must be used.

The decorating method by transfer is a method of transferring an ink layer printed on a film, paper or the like to a decorated object,
A method called hot stamping involving heating and pressurization at the time of transfer can be adopted, and this method is a method of laminating a paint foil, a metal foil or the like on a body to be decorated by thermocompression bonding.

The method of decoration by plating is to impart conductivity to a decorated object whose surface is roughened by a solvent or machining,
A chemical electroplating method of forming a metal film in a plating solution, a vacuum plating method of depositing a metal forming the metal film in a vacuum and depositing the metal on the surface of the object to be decorated and coating the same can be adopted. .

Before the surface of the fiber reinforced thermoplastic resin sheet 1 (including the fiber reinforced thermoplastic resin sheet which becomes the fiber reinforced thermoplastic resin layer 10a of the composite sheet 10) is decorated by printing, transferring or plating, The produced fiber-reinforced thermoplastic resin sheet may be treated with a commonly used device such as a printing machine or a transfer device. Further, during the production of the fiber-reinforced thermoplastic resin sheet, while the thermoplastic resin of the fiber-reinforced thermoplastic resin sheet is in a molten state, a thermoplastic resin sheet or film that has been decorated by printing in advance is laminated. May be. In addition, if a fiber pattern is visible on the surface of the fiber reinforced thermoplastic resin sheet and the appearance is poor, a synthetic resin sheet or film is adhesively laminated on the surface of the fiber reinforced thermoplastic resin sheet to see the fiber pattern. It may be possible to decorate the surface after the removal.

On the other hand, as a method for decorating the surface of the fiber reinforced thermoplastic resin sheet 1 (including the fiber reinforced thermoplastic resin sheet which becomes the fiber reinforced thermoplastic resin layer 10a of the composite sheet 10) with unevenness, , A method of transferring the unevenness to the sheet surface by pressing a roll having unevenness on the surface to the sheet, a method of adding a filler such as an inorganic filler or glass beads to the thermoplastic resin which is a constituent material of the sheet, the surface It is possible to employ a method of imparting physical unevenness such as rough polishing or etching. When decoration is performed by transferring the irregularities of the roll, it is preferable that the thermoplastic resin of the fiber-reinforced thermoplastic resin sheet is softened.

Next, as the thermoplastic resin of the expandable thermoplastic resin composition 3 used in each method of the present invention or the expandable thermoplastic resin composition layer 10b of the composite sheet 10, the fiber reinforced thermoplastic resin sheet 1 is used. Alternatively, the same thermoplastic resin as that used in the fiber-reinforced thermoplastic resin layer 10a can be used, but a resin that can be heat-sealed to the resin used in the fiber-reinforced thermoplastic resin sheet or the same layer is used. Is desirable. Specifically, it is preferable to use thermoplastic resins of the same type (thermoplastic resins polymerized from the same monomer). As a combination when using different kinds of thermoplastic resins, for example, polyethylene and polypropylene, polyethylene and vinyl acetate-ethylene copolymer, polyethylene and chlorinated polyethylene, polystyrene and acrylonitrile-butadiene-styrene copolymer, polystyrene and. Acrylonitrile-styrene copolymer, polyvinyl chloride and chlorinated polyvinyl chloride, polyvinyl chloride and ethylene-vinyl chloride copolymer, polyvinyl chloride and vinyl acetate-vinyl chloride copolymer, polyvinyl chloride and urethane-vinyl chloride Copolymer, polyvinyl chloride and polymethylmethacrylate, polyvinyl chloride and acrylonitrile-butadiene-styrene copolymer, polybutylene terephthalate and polyethylene terephthalate, acrylonitrile-butadiene-styrene Polymer and an acrylonitrile - styrene copolymer. Also, a combination of the thermoplastic resin and the same type of modified thermoplastic resin can be used. Examples of this include polyethylene and silane-modified polyethylene, polystyrene and acrylic acid-modified polystyrene, polyethylene and maleic acid-modified polyethylene, and the like.

As the foaming agent used in the expandable thermoplastic resin composition 3 or the expandable thermoplastic resin layer 10b, when the foaming agent is supplied while being foamed in the hollow body, it is decomposed by heat to chemically decompose to generate gas. Mold blowing agents and volatile foaming agents that utilize the gasification of volatile liquids can be used. Alternatively, while kneading the thermoplastic resin at a melting temperature or higher, a gas such as carbon dioxide or nitrogen may be injected under pressure to disperse the thermoplastic resin in the thermoplastic resin, and the pressure may be released for foaming. on the other hand,
When foaming after being supplied into the hollow body, so-called foam beads in which a volatile liquid, carbon dioxide, nitrogen, etc. are dissolved and dispersed in a thermoplastic resin can be used.

Decomposition type foaming agents include azodicarbonamide, azobisisobutyronitrile, N, N'-dinitrosopentamethylenetetramine, pp'-oxybisbenzenesulfonyl hydrazide, barium azodicarboxylate, and trihydrazinotriazine. , P-toluenesulfonyl hydrazide, sodium bicarbonate, ammonium carbonate and the like.

Examples of the volatile type blowing agent include aliphatic hydrocarbons such as propane, butane, pentane, hexane and heptane, carbonized aliphatic hydrocarbons such as methyl chloride and methylene dichloride, and 1,1-dichloro-1-fluoro. Ethane, 2,
2-dichloro-1,1,1-trifluoroethane, 1,
Fluorocarbon gas such as 1,1,2-tetrafluoroethane can be used.

The amount of the foaming agent to be blended must be appropriately adjusted because the amount of gas generated varies depending on the type of the foaming agent, but it is 0.5 to 15 per 100 parts by weight of the thermoplastic resin.
It is preferable to blend in the range of parts by weight. If the blending amount of the foaming agent is too small, a foamed molded article cannot be obtained. On the other hand, if the blending amount of the foaming agent is too large, cells are broken and a dense cell cannot be obtained. For example, when a thermoplastic resin foam having a foaming ratio of 10 times is produced using azodicarbonamide, resin 10
It is suitable to mix 5 to 7.5 parts by weight with respect to 0 parts by weight.

The expansion ratio of the internal foam layer (core material layer) of the molded product obtained by foaming the expandable thermoplastic resin composition 3 or the expandable thermoplastic resin layer 10b is the strength and specific gravity required for the product. Although it is appropriately selected depending on the kind of the thermoplastic resin used, a range of 1.2 to 20 times is preferable, and a range of 2 to 10 times is particularly preferable. When the expansion ratio is 1.2 times or less, the effect of reducing the weight by foaming is small, and when the expansion ratio is 20 times or more, the strength becomes very weak.

In the present invention, when the fiber reinforced thermoplastic resin sheet 1 or the composite sheet 10 is shaped along the regulating member by the pressure from the inside, the decorative surface is damaged, that is, the decorative surface is damaged. The material of the film 4 to be preliminarily laminated on the decorative surface is hollow, for the purpose of avoiding wearing, peeling due to melting of the coating material for printing, or failure to obtain a desired pattern. It may be any one that can be shaped by following the shaping of the body, and specifically, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyamide, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyphenylene sulfide, chlorinated poly. Examples thereof include vinyl chloride. The thickness of the film is preferably 5 to 100 μm,
10 to 60 μm is a particularly preferable range. When it is thinner than 5 μm, the strength is weak, and when it is thicker than 100 μm, it becomes difficult to shape the fiber-reinforced thermoplastic resin sheet or the composite sheet in conformity with the shape.

The film 4 laminated on the decorative surface may be peeled off from the surface of the product after the production of the fiber-reinforced thermoplastic resin foam or may be used as it is, but it is peeled off after the production and used. In this case, in order to facilitate the peeling, it is preferable to provide a peeling layer between the film 4 and the decorative surface.

The peeling layer is a layer for peeling the film 4 for the purpose of protecting the decorative surface from the decorative surface without damaging the decoration, and is made of a resin having weak adhesiveness.
Specifically, an acrylic resin having a weak cohesive force, a low molecular weight and a small number of polar groups can be used, and a weight ratio of a raw material methacrylate monomer to another monomer and a lubricant to be blended as necessary. The peelability is adjusted by the amount of
Specifically, a resin obtained by modifying polymethyl methacrylate with ethyl acrylate, butyl acrylate, hydroxyethyl methacrylate, or the like can be used.

As a method for obtaining a fiber-reinforced thermoplastic resin sheet in which the protective film 4 is laminated on the decorative surface as described above, it is efficient to use a thermal transfer film in which an ink layer, a release layer and a film are laminated. Is. That is, a thermal transfer film is laminated on a fiber reinforced thermoplastic resin sheet, and an ink layer is adhered to the fiber reinforced thermoplastic resin sheet surface by appropriately applying heat and pressure, thereby decorating the surface of the fiber reinforced thermoplastic resin sheet. In addition to the above, the film may be used in the subsequent step after the shaping into the hollow body while being laminated on the fiber reinforced thermoplastic resin sheet without being peeled off.

Here, as the ink layer of the thermal transfer film as described above, a commonly used ink layer can be used. For example, an acrylic resin or a blend resin of an acrylic resin and a vinyl acetate-vinyl chloride copolymer, A metallic pigment or the like can be used. The ink layer may be provided with an adhesive layer such as an acrylic-vinyl acetate copolymer or a low molecular weight acrylic resin in order to enhance the adhesiveness with the fiber reinforced thermoplastic resin sheet. Further, an ink layer made of a thermosetting resin or an ultraviolet curable resin, or a hard coat layer for protecting the ink layer may be provided.

On the other hand, an uneven film 5 laminated on the decorative surface 1a of the fiber-reinforced thermoplastic resin sheet 1 or the surface of the fiber-reinforced thermoplastic resin layer 10a of the composite sheet 10.
As a method of obtaining the film, a method of adding a filler such as an inorganic filler or glass beads to the film raw material at the time of forming the film, or a thermosetting urethane resin or melamine resin is applied to the convex portion of the film by gravure printing on the film surface. It is possible to employ a method of working or a method of roughening or roughening the surface to physically make the surface uneven.

[0051]

The present invention uses a fiber-reinforced thermoplastic resin sheet or composite sheet whose surface is decorated, shapes this into a hollow body, and foams the expandable thermoplastic resin composition therein. By the pressure, the outer surface of the hollow body is shaped into a desired shape along the regulating member, and the fiber-reinforced thermoplastic resin sheet or the fiber-reinforced thermoplastic resin layer to be the skin layer of the molded body is formed. Since is already decorated before shaping, it is possible to easily manufacture a molded product having a complicated cross-sectional shape and surface decoration.
That is, since the decoration is performed in the form of a sheet, the decoration process is facilitated, and the subsequent shaping process is performed using such a decorated sheet, so that the molded body is intricately involved. Even if there is a portion or a protrusion having a small surface area, these surfaces can be decorated without omission.

If a film for protecting the decorative surface is laminated on the decorative surface of the fiber reinforced thermoplastic resin sheet or the composite sheet, the decorative surface is not damaged by contact with the shaping regulating member. Suppressed.

Further, in the state where a film having irregularities is laminated on a fiber reinforced thermoplastic resin sheet or a composite sheet,
Through the hollow body with the film on the outside, when performing shaping and uneven transfer along the regulating member on the outer surface of the hollow body by the foaming pressure of the foamable thermoplastic resin composition inside, the above decoration In addition to surface protection, unevenness is added to the surface simultaneously with shaping.

[0054]

According to the present invention, a fiber-reinforced thermoplastic resin sheet or composite sheet whose surface has been decorated in advance is shaped into a hollow body, and the foamable thermoplastic resin composition foaming pressure inside the hollow body causes Since the shape and the expandable thermoplastic resin inside the shape are shaped, the decoration process is greatly simplified compared to the case where the surface is decorated after being shaped into the cross-sectional shape of the product. Not only can it be performed, but even for a product having a complicated cross-sectional shape, it is possible to easily decorate the entire surface of the product without leakage, and there is no fear of defective decoration.

By preliminarily laminating the film on the decorative surface of the sheet, there is no risk of the decorative surface being damaged during shaping, and if the film is made to have irregularities, the above-mentioned is possible. In addition to each effect, by the foaming pressure of the expandable thermoplastic resin composition to be the core material layer, it is possible to perform decoration such as embossing on the surface simultaneously with shaping,
There is also an advantage that efficient decoration can be performed.

[0056]

EXAMPLES Hereinafter, examples of actually producing a fiber-reinforced thermoplastic resin foam using each method of the present invention will be described together with comparative examples. <Example 1> Production of fiber-reinforced thermoplastic resin sheet 1 Glass fiber bundle (glass roving manufactured by Nitto Boseki, 4400)
g / km, fiber diameter 23 μm) 4 pieces are aligned and drawn into a tank in which powder of polyvinyl chloride resin having the composition shown in [Table 1] below is flowing by air, and a glass fiber bundle is taken as a filament unit. While solving the above, polyvinyl chloride resin powder was attached. In a state where the glass fibers to which the polyvinyl chloride resin is attached are aligned in a plane, glass cloth (glass cloth manufactured by Nitto Boseki Co., Ltd., 96 g / m ² ) is overlaid to form 220 °
While heating with a pinch roll heated to C at a pressure of 10 kg / cm ² , the polyvinyl chloride resin was melted and penetrated between the glass fibers. Then cool with a cooling pinch roll, trim to a width of 100 mm, thickness 0.4 mm
Glass fiber reinforced polyvinyl chloride resin sheet (hereinafter, this sheet is referred to as fiber reinforced thermoplastic resin sheet 11)
I got

[0057]

[Table 1]

On one side of the above fiber reinforced thermoplastic resin sheet 11, a brown color is entirely coated by gravure printing, and a black line with a grain of wood is further printed, as shown in the sectional view of FIG. 2 (A). A fiber-reinforced thermoplastic resin sheet 1 having a decorative surface 1a on one surface (hereinafter, this sheet is referred to as a fiber-reinforced thermoplastic resin sheet 1A) was obtained.

Foamable thermoplastic resin composition 3 A composition containing polyvinyl chloride as a main component and having a composition shown in the following [Table 2] was used. The mixing was performed using a super mixer until the resin temperature reached 100 ° C.

[0060]

[Table 2]

Mold and Manufacturing Apparatus As shown in the schematic sectional view of FIG.
01, extruder 102, extrusion die 103, shaping die 10
4. The cooling die 105 and the product take-up machine 106 are mainly configured.

The above-mentioned fiber reinforced thermoplastic resin sheet 1A was wound around the sheet feeding machine 101 so that it could be fed out and fed rightward in the drawing. In FIG. 1, the left side is called the upstream side and the right side is called the downstream side.

The extrusion die 103 is composed of an outer die 103a and a core die 103b, and a space for passing the fiber reinforced thermoplastic resin sheet 1A is provided between them. This void opens in an inverted U shape on the upstream end surface of the mold 103, and gradually changes to a cylindrical shape toward the downstream side,
By guiding and passing the fiber-reinforced thermoplastic resin sheet 1A into the voids, the fiber-reinforced thermoplastic resin sheet 1 is obtained.
A is gradually formed into a cylindrical shape, and eventually both side edges thereof are butted against each other to form a hollow body 2 having a diameter of 31.8 mm and a perfect circular cross section.

Further, the core die 103b of the extrusion die 103
Is connected to the extruder 102 at the lower end of the bend, where the upstream end of the fiber-reinforced thermoplastic resin sheet 1A passes through an opening part that is completely formed into the hollow body 2 and is bent downward. There is. This core mold 103b has an extruder 1
02, and a resin flow channel 103c having a diameter of 5 mm, which is open in the hollow body 2 at the downstream end face, is formed, and is supplied from the extruder 102 through this resin flow channel 103c. The expandable thermoplastic resin composition 3 shown can be extruded into the hollow body 2 that has been shaped.

In the shaping die 104, the cross-sectional shape of the inner surface is a perfect circle having a diameter of 31.8 mm at the upstream end surface portion and the final product cross-section shown in FIG. 2 (E) at the downstream end surface portion. It has the same cross-sectional shape and dimensions, but gradually changes between its ends.

The cross-sectional shape of the cooling mold 105 is exactly the same as the cross-sectional shape of the shaping mold 104 at the end face on the downstream side. Manufacture of Fiber Reinforced Thermoplastic Resin Foam With the extrusion die 103 temperature-controlled at 170 ° C., the fiber reinforced thermoplastic resin sheet 1A is opened from the opening of the upstream end face thereof as shown in FIG. 2 (B). The decorative surface 1a is placed in an inverted U-shaped cross section so that the decorative surface 1a is on the outside, and the molded surface is inserted into the mold 103 and continuously shaped into the hollow body 2 as shown in FIG. The foamable thermoplastic resin composition 3 was extruded into the hollow body 2 through the resin flow channel 103c while foaming. This state is shown in FIG.
Shown in After extruding the expandable thermoplastic resin composition 3, 16
It is introduced into the shaping die 104 heated to 0 ° C., and the outer surface of the hollow body 2 is pressed against the inner surface of the shaping die 104 by the foaming pressure of the expandable thermoplastic resin composition 3 to form a shape. After shaping into a cross-sectional shape equal to the cross-sectional shape of the inner surface of the mold 104, it is cooled by a cooling mold 105, and as shown in FIG. 2 (E), a fiber around the core material layer P made of a thermoplastic resin foam. A fiber-reinforced thermoplastic resin foam having a modified cross-section was obtained, which was covered with a skin layer S made of a reinforced thermoplastic resin, and the outer peripheral surface of the skin layer S became a decorative surface 1a.

This fiber-reinforced thermoplastic resin foam is shown in FIG.
It was confirmed that the print decoration applied to the original fiber-reinforced thermoplastic resin sheet 1A was present on the entire surface of a to h shown in (E) without being impaired. <Example 2> The production of the fiber-reinforced thermoplastic resin sheet 1, the expandable thermoplastic resin composition 3, the mold and the production apparatus were the same as in Example 1.

Production of Fiber Reinforced Thermoplastic Resin Foam Extrusion die 10 heated to 170 ° C. as in Example 1.
3, the fiber-reinforced thermoplastic resin sheet 1A is introduced into the hollow body 2 with a U-shaped cross section so that the decorative surface 1a is on the outside, and the hollow body 2 is filled with the resin flow. Road 103
The expandable thermoplastic resin composition 3 was extruded via c without foaming. Then, the shaping die 1 heated to 220 ° C
No. 04, the foamable thermoplastic resin composition 3 is foamed, and the foaming pressure of the foamable thermoplastic resin composition 3 causes the outer surface of the hollow body 2 to be shaped.
4 and the inner surface of the cooling mold 105 were subjected to shaping and cooling to obtain a fiber-reinforced thermoplastic resin foam having exactly the same shape and structure as shown in FIG. 2 (E).

It was confirmed that this fiber-reinforced thermoplastic resin foam had decorative printing applied to the entire surfaces a to h as in Example 1. <Example 3> Production of composite sheet 10 A sheet-shaped mold in which the expandable thermoplastic resin composition 3 containing polyvinyl chloride as a main component shown in Table 2 was temperature-controlled from an extruder to 165 ° C. While extruding without foaming through it, by laminating it on the surface opposite to the decorative surface 1a of the fiber-reinforced thermoplastic resin sheet 1A produced in the above-mentioned Example 1, a cross-sectional view is shown in FIG. 3 (A). In addition, a fiber-reinforced thermoplastic resin layer 1 having a decorative surface 1a on the surface
0a and a foamable thermoplastic resin composition layer 10b (hereinafter, this sheet is referred to as a composite sheet 10A).
Called).

Mold and Manufacturing Apparatus The same one as shown in Example 1 was used. Production of Fiber Reinforced Thermoplastic Resin Foam Extrusion die 103 whose temperature was adjusted to 170 ° C.
As shown in (B), the composite sheet 10A is bent and introduced into an inverted U shape so that the decorative surface 1a is located on the outer side, and after being shaped into the hollow body 20 as shown in FIG. The foamable thermoplastic resin layer 10 is guided to the shaping mold 104 heated to ° C.
The resin of b is foamed, and the foaming pressure presses the outer surface of the hollow body 20 against the inner surfaces of the shaping die 104 and the cooling die 105 to cool after shaping, as shown in FIG. A fiber-reinforced thermoplastic resin foam having the same structure and shape as the one obtained was obtained.

It was confirmed that this fiber-reinforced thermoplastic resin foam had decorative printing applied to the entire surfaces a to h as in Examples 1 and 2. <Example 4> Production of fiber-reinforced thermoplastic resin sheet 1 Glass fiber bundle (glass roving manufactured by Nitto Boseki, 4400)
20 pieces (kg / km, fiber diameter 23 μm) are aligned and drawn into a tank in which a powdered resin whose main component is polyvinyl chloride having the composition shown in [Table 1] is flowing to draw a glass fiber bundle. The powder resin was attached while unraveling into filament units. In a state where the glass fibers to which the resin powder has adhered are aligned in a plane, glass cloth (glass cloth manufactured by Nitto Boseki Co., Ltd., 96 g / m ² ) is piled up and applied with a pinch roll heated to 220 ° C. at 10 kg / cm ² . Heat while pressing,
The polyvinyl chloride resin was melted and penetrated between the glass fibers. Next, on the surface on which the glass cloth is not laminated,
Soft vinyl chloride sheets (Wiping processed wood grain made by Ando Sangyo, thickness 0.2 mm, width 110 mm) are stacked, introduced into a cooling pinch roll, and while being cooled, the soft vinyl chloride sheets are heat-sealed and laminated to decorate one side. After the application, trimming was performed to obtain a fiber-reinforced thermoplastic resin sheet 1 having a thickness of 0.6 mm and a width of 100 mm (hereinafter, this sheet is referred to as a fiber-reinforced thermoplastic resin sheet 1B).

The expandable thermoplastic resin composition 3, the mold and the manufacturing apparatus were the same as in Example 1. Production of Fiber Reinforced Thermoplastic Resin Foam The same as Example 1 except that the above fiber reinforced thermoplastic resin sheet 1B is used instead of the fiber reinforced thermoplastic resin sheet 1A in Example 1, and FIG. The same fiber-reinforced thermoplastic resin foam as shown in 1 was obtained.

The fiber-reinforced thermoplastic resin foam obtained is
The decoration with the soft vinyl chloride sheet was present on the entire surface of a to h of FIG. 2 (E) without being impaired. <Example 5> Production of Fiber Reinforced Thermoplastic Resin Sheet 1 Glass fiber bundle (glass roving manufactured by Nitto Boseki, 4400)
g / km, fiber diameter 23 μm) 20 pieces are aligned and drawn into the tank where the resin powder containing polyvinyl chloride as the main component shown in [Table 1] is flowing by air, and the glass fiber bundle is fractionated. The resin powder was attached while being broken into units. With the glass fibers to which the resin powder adheres aligned in a plane, glass cloth (glass cloth manufactured by Nitto Boseki Co., Ltd., 96 g / m ² ) is layered and heated at 220 ° C with a pinch roll at 10 kg / cm ² . The mixture was heated under pressure to melt the polyvinyl chloride resin and penetrate it between the glass fibers. Next, a thermal transfer film (a 25 μm-thick polyethylene terephthalate film with a modified acrylic resin release layer, and a color ink layer in which 50 parts by weight of vinyl acetate resin was added to 100 parts by weight of acrylic resin were sequentially laminated on the surface not laminated with glass cloth. The heat transfer film is laminated while being cooled, and then trimmed to a thickness of 0.43 mm and a width of 100 mm.
As shown in the schematic cross-sectional view of FIG. 4, a fiber reinforced thermoplastic resin sheet 1 (hereinafter, a polyethylene terephthalate film 4 of a thermal transfer film is laminated on the outermost surface layer on one side)
This sheet was obtained as a fiber-reinforced thermoplastic resin sheet 1C). The thermal transfer film was obtained by laminating a release layer and a color ink layer on a polyethylene terephthalate film 4 manufactured in advance using a gravure printing machine.

The expandable thermoplastic resin composition 3, the mold and the manufacturing apparatus were the same as in Example 1. Manufacture of Fiber Reinforced Thermoplastic Resin Foam Into an extrusion die 103 whose temperature is adjusted to 170 ° C., the above fiber reinforced thermoplastic resin sheet 1C is bent and inserted into an inverted U shape so that the film 4 is on the outside. After forming a hollow body in the mold 103, the foamable thermoplastic resin composition 3 was extruded while foaming the foamable thermoplastic resin composition 3. 160 ° C after extrusion
It is introduced into the shaping die 104 that has been heated to, and the outer surface of the hollow body, that is, the outer surface of the film 4, is pressed against the inner surface of the shaping die 104 by the foaming pressure of the expandable thermoplastic resin composition 3 to perform shaping. After cooling with the cooling mold 105, the film 4 is peeled off from the surface of the molded product to obtain the same shape as that shown in FIG.
A fiber reinforced thermoplastic resin foam having a structure was obtained. It was confirmed that the entire surface of the obtained product was decorated by thermal transfer. <Example 6> The fiber-reinforced thermoplastic resin sheet 1, the expandable thermoplastic resin composition 3, the mold, and the manufacturing apparatus were the same as in Example 5.

Manufacture of Fiber Reinforced Thermoplastic Resin Foam Body: The above-mentioned fiber reinforced thermoplastic resin sheet 1C is bent and inserted into an inverted U-shape so that the film 4 is on the outside in an extrusion die 103 whose temperature is adjusted to 170 ° C. Then, after forming a hollow body in the mold 103, the expandable thermoplastic resin composition 3 was extruded inside the mold without being foamed. After the composition 3 is extruded, it is introduced into the shaping die 104 heated to 220 ° C. to foam the expandable thermoplastic resin composition 3, and the foaming pressure causes the laminated surface of the film 4 of the hollow body to move. Shaped mold 10
4 and the inner surface of the cooling die 105 to perform shaping and cooling, and then peel off the film 4 from the surface of the molded product to form a fiber-reinforced thermoplastic resin foam having the shape and structure of FIG. 2 (E). Got the body Example 5 was applied to the entire surface of the obtained product.
It was confirmed that decoration was performed by thermal transfer in the same manner as in. <Example 7> Production of Composite Sheet 10 On the surface of the fiber-reinforced thermoplastic resin sheet 1C obtained in Example 5 opposite to the laminated surface of the transfer film, the expandable thermoplastic resin having the composition shown in [Table 2] is formed. The composition was transferred from the extruder 16
Extruded through a sheet-shaped mold whose temperature was adjusted to 5 ° C. without foaming, and as shown in the schematic cross-sectional view of FIG. 5, a fiber-reinforced thermoplastic resin layer 10a ′ and a polyethylene terephthalate film 4 laminated on the surface and A composite sheet 10 (hereinafter, referred to as a composite sheet 10B) including the expandable thermoplastic resin composition layer 10b was obtained.

The mold and manufacturing apparatus were the same as in Example 1. Manufacture of Fiber Reinforced Thermoplastic Resin Foam A composite sheet 10B is bent and inserted into an inverted U shape so that the film 4 is on the outside, and is inserted into an extrusion mold 103 whose temperature is adjusted to 170 ° C. After forming into a shape, 2
The resin of the expandable thermoplastic resin composition layer 10b is foamed by introducing it into the shaping mold 104 heated to 20 ° C., and the foaming pressure causes the outer surface (film 4) of the hollow body to be shaped.
Also, by pressing against the cooling mold 105 to perform shaping and cooling, by peeling off the film 4 on the surface of the molded product,
A fiber-reinforced thermoplastic resin foam having the shape and structure shown in FIG. 2 (E) was obtained. Examples 5 and 6 were formed on the entire surface of the obtained product.
It was confirmed that decoration was performed by thermal transfer in the same manner as in. <Example 8> Production of fiber-reinforced thermoplastic resin sheet 1 Glass fiber bundle (glass roving manufactured by Nitto Boseki, 4400)
g / km, fiber diameter 23 μm) 20 pieces are aligned and drawn into the tank where the resin powder containing polyvinyl chloride as the main component shown in [Table 1] is flowing by air, and the glass fiber bundle is fractionated. The resin powder was attached while being broken into units. With the glass fibers to which the resin powder adheres aligned in a plane, glass cloth (glass cloth manufactured by Nitto Boseki Co., Ltd., 96 g / m ² ) is layered and heated at 220 ° C with a pinch roll at 10 kg / cm ² . The mixture was heated under pressure to melt the polyvinyl chloride resin and penetrate it between the glass fibers. Then, on the surface not laminated with the glass cloth, a thermal transfer film (polyethylene terephthalate film having a thickness of 25 μm, polyurethane resin pitch layer, modified acrylic resin peeling layer, color obtained by adding 50 parts by weight of vinyl acetate resin to 100 parts by weight of acrylic resin) An ink layer is sequentially laminated.The polyurethane resin pitch layer has 4000 mm / m of convex streaks having a length of 5 mm, a width of 0.5 mm and a height of 0.1 mm.
² ) were randomly placed), introduced into a cooling pinch roll, laminated with a thermal transfer film while being cooled, and then trimmed to have a thickness of 0.43 mm and a width of 100 mm, as shown in a schematic sectional view in FIG. In addition, a fiber reinforced thermoplastic resin sheet 1 (hereinafter, this sheet is referred to as fiber reinforced thermoplastic resin 1D) in which a polyethylene terephthalate film of a thermal transfer film and an uneven film 5 composed of a polyurethane resin pitch layer are laminated on the outermost surface layer on one side Obtained. The thermal transfer film was obtained by laminating a polyurethane resin pitch layer, a release layer, and a color ink layer on a polyethylene terephthalate film produced in advance using a gravure printing machine.

The expandable thermoplastic resin composition 3, the mold and the manufacturing apparatus were the same as in Example 1. Manufacture of Fiber Reinforced Thermoplastic Resin Foam A fiber reinforced thermoplastic resin sheet 1D is inserted into an extrusion mold 103 whose temperature is adjusted to 170 ° C. by bending it into an inverted U shape so that the concavo-convex film 5 is on the outside. After shaping into a hollow body in 103, the expandable thermoplastic resin composition 3 was extruded while foaming. After this extrusion, 160
After being introduced into the shaping die 104 heated to ° C, the outer surface of the hollow body is pressed against the shaping die 104 by the foaming pressure to perform shaping, and then cooled by the cooling die 105, the molded product after cooling. The concavo-convex film 5 was peeled off from the surface of to obtain a fiber-reinforced thermoplastic resin foam having the same shape and structure as in FIG. 2 (E).

The obtained fiber-reinforced thermoplastic resin foam is decorated with the color ink layer of the thermal transfer film over the entire surface thereof, and the unevenness of the polyurethane resin pitch layer of the uneven film 5 is transferred. It was confirmed that embossing was applied. <Example 9> The production of the fiber-reinforced thermoplastic resin sheet 1, the expandable thermoplastic resin composition 3, the mold and the production apparatus were the same as in Example 8.

Manufacture of Fiber Reinforced Thermoplastic Resin Foam A fiber reinforced thermoplastic resin sheet 1D is bent and inserted into an inverted U-shape so that the concavo-convex film 5 is on the outside in an extrusion die 103 whose temperature is adjusted to 170 ° C. After being shaped into a hollow body in the mold 103, the expandable thermoplastic resin composition 3 was extruded therein without foaming. 220 ° after extrusion
It is introduced into the shaping die 104 heated to C to foam the expandable thermoplastic resin composition 3, and the foaming pressure pushes the outer surface of the hollow body against the inner surfaces of the shaping die 104 and the cooling die 105. After shaping and cooling, the concavo-convex film 5 was peeled from the surface of the molded product to obtain a fiber-reinforced thermoplastic resin foam having the same shape and structure as in FIG. 2 (E).

The obtained fiber reinforced thermoplastic resin foam was decorated with the color ink layer of the thermal transfer film over the entire surface in the same manner as in Example 8, and the unevenness of the uneven film 5 was embossed by the transfer. It was confirmed that decoration was applied. <Example 10> Production of composite sheet 10 Fiber-reinforced thermoplastic resin sheet 1 produced in Example 8
On the surface opposite to the laminated surface of the thermal transfer film D, [Table 2]
The extrudable thermoplastic resin composition having the composition shown in (1) was extruded from the extruder through a sheet-shaped mold whose temperature was adjusted to 165 ° C. without foaming, and polyethylene was formed on the surface as shown in the schematic cross-sectional view of FIG. 7. A composite sheet 10 including a fiber-reinforced thermoplastic resin layer 10a ″ in which a concavo-convex film 5 including a terephthalate film and a polyurethane resin pitch layer is laminated, and a foamable thermoplastic resin composition layer 10b.
(Hereinafter, this sheet is referred to as composite sheet 10C).

The mold and manufacturing apparatus were the same as in Example 1. Manufacture of Fiber Reinforced Thermoplastic Resin Foam A composite sheet 10C is bent and inserted into an inverted U-shape so that the uneven film 5 is on the outside in an extrusion mold 103 whose temperature is adjusted to 170 ° C. After being shaped into a shaped body, it is introduced into the shaping die 104 heated to 220 ° C. to foam the resin of the expandable thermoplastic resin composition layer 10b, and the outer surface of the hollow shaped body is shaped by the foaming pressure. After being pressed against the inner surfaces of the mold 104 and the cooling mold 105 to perform shaping and cooling, the concavo-convex film 5 is peeled off from the surface of the molded product, and as shown in FIG.
A fiber-reinforced thermoplastic resin foam having the same shape and structure as (E) was obtained.

This fiber-reinforced thermoplastic resin foam was decorated with the color ink layer of the thermal transfer film over the entire surface, and the unevenness of the uneven film 5 was embossed by the transfer, as in Examples 8 and 9. It was confirmed that the decoration was applied. Comparative Example 1 Production of Fiber Reinforced Thermoplastic Resin Sheet The fiber reinforced thermoplastic resin 11 produced in the production process of the fiber reinforced thermoplastic resin sheet 1A in Example 1 before decoration by printing was used.

The expandable thermoplastic resin composition, the mold and the manufacturing apparatus were the same as in Example 1. Production of Fiber Reinforced Thermoplastic Resin Foam The same as Example 1 except that the fiber reinforced thermoplastic resin sheet 1A in Example 1 is used instead of the fiber reinforced thermoplastic resin sheet 1A, and is shown in FIG. A fiber-reinforced thermoplastic resin foam having the same shape and structure as the one obtained was obtained.

Decoration of Molded Article The surface of the fiber-reinforced thermoplastic resin foam obtained was painted by spraying the brown color paint used in the gravure printing of Example 1 from four directions. . Next, a wood-tone black line was printed by gravure printing. After printing, when observing the surface of the product, d, e,
The f, g, and h faces could be printed with a urethane rubber roll having a width of 50 mm and a diameter of 100 mm, but black lines could not be printed on the a, b, and c faces. Comparative Example 2 The production of the fiber reinforced thermoplastic resin sheet, the expandable thermoplastic resin composition, the mold and the production apparatus, and the production of the fiber reinforced thermoplastic resin foam were the same as those of Comparative Example 1.

Decoration of Molded Article A vinyl acetate resin adhesive was applied to the back surface of the soft vinyl chloride sheet used in Example 4 and continuously stuck to the surface of the obtained fiber-reinforced thermoplastic resin foam. Diameter 3mm, width 5
mm roll, a, b, c, shown in FIG.
The above sheets were stuck in the order of d, e, f, g and h faces, but voids remained between the soft vinyl chloride sheet and the fiber reinforced thermoplastic resin foam, and wrinkles were formed, which was good. It was not possible to obtain a good surface decoration state. Comparative Example 3 The production of the fiber-reinforced thermoplastic resin sheet, the expandable thermoplastic resin composition, the mold and the production apparatus, and the production of the fiber-reinforced thermoplastic resin foam were the same as those of Comparative Example 1.

Decoration of Molded Article While heating the surface of the obtained fiber-reinforced thermoplastic resin foam to 190 ° C. with a far infrared heater,
The thermal transfer films used in Example 5 were continuously laminated.
Using a roll having a diameter of 3 mm and a width of 5 mm, the heat transfer films were laminated in the order of the a, b, c, d, e, f, g, and h faces shown in FIG. 2 (E). Some voids remained between the reinforced thermoplastic resin foam and wrinkles. Lamination of thermal transfer film,
After cooling, the film was peeled off from the surface of the fiber reinforced thermoplastic resin foam, and a molded product with decoration by transfer was obtained. However, the transferred state on the a side was poor, and the b and c faces could not be transferred at all. No good surface decoration was obtained. Comparative Example 4 The production of the fiber-reinforced thermoplastic resin sheet, the expandable thermoplastic resin composition, the mold and the production apparatus, and the production of the expandable thermoplastic resin foam were the same as in Comparative Example 1.

Decoration of Molded Article While heating the surface of the obtained fiber-reinforced thermoplastic resin foam to 190 ° C. with a far infrared heater,
The thermal transfer films used in Example 8 were continuously laminated.
Using a roll having a diameter of 3 mm and a width of 5 mm, the heat transfer films were laminated in the order of the a, b, c, d, e, f, g, and h faces shown in FIG. 2 (E). Some voids remained between the reinforced thermoplastic resin foam and wrinkles. Lamination of thermal transfer film,
After cooling, the film was peeled off from the surface of the fiber reinforced thermoplastic resin foam, and a molded product with decoration by transfer was obtained. However, the transferred state on the a side was poor, and printing by thermal transfer was also embossed on the b and c faces. However, no good surface decoration was obtained.

[Brief description of drawings]

FIG. 1 is a schematic sectional view showing an example of a mold and a manufacturing apparatus according to an embodiment of the present invention.

FIG. 2 is a schematic diagram showing a material and a cross-sectional shape of a molded product in each step in Example 1 of the present invention.

FIG. 3 is a schematic diagram showing a cross-sectional shape of a material in each step in Example 3 of the present invention.

FIG. 4 is a schematic sectional view of a fiber-reinforced thermoplastic resin sheet 1C used in Example 5 of the present invention.

FIG. 5 is a schematic cross-sectional view of a composite sheet 10B in which the films used in Example 7 of the present invention are laminated.

FIG. 6 is a schematic sectional view of a fiber-reinforced thermoplastic resin sheet 1D used in Example 8 of the present invention.

FIG. 7 is a schematic cross-sectional view of a composite sheet 10C on which a concavo-convex film used in Example 10 of the present invention is laminated.

[Explanation of symbols]

1, 1A, 1C, 1D Fiber reinforced thermoplastic resin sheet 1a Decorative surface 2,20 Hollow body 3 Expandable thermoplastic resin composition 4 Film (polyethylene terephthalate film) 5 Concavo-convex film (polyethylene terephthalate film and polyurethane resin chip layer) ) 10, 10A to 10C composite sheet 10a, 10a 'fiber reinforced thermoplastic resin layer 10b foamable thermoplastic resin layer 101 sheet feeding machine 102 extruder 103 extrusion die 104 shaping die 105 cooling die 106 take-up machine

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area B29K 105: 08 B29L 9:00

Claims (7)

[Claims] 1. A hollow body in which a fiber-reinforced thermoplastic resin sheet whose surface is decorated is continuously formed into a hollow body such that the decorated surface is on the outside. A method for producing a fiber-reinforced thermoplastic resin foam, in which a foamable thermoplastic resin composition is supplied while foaming, and the foaming pressure causes the outer surface of the hollow body to be shaped into a desired cross-sectional shape along a regulating member. 2. A hollow fiber body, wherein a fiber-reinforced thermoplastic resin sheet whose surface is decorated is continuously formed into a hollow body so that the decorated surface is on the outside. After the foamable thermoplastic resin composition is supplied to the foam, the foamable thermoplastic resin composition is foamed in the hollow body by heating, and the foaming pressure causes the outer surface of the hollow body to follow the regulating member to have a desired cross-sectional shape. A method for producing a fiber-reinforced thermoplastic resin foam, which is shaped into. 3. The fiber-reinforced thermoplastic resin foam according to claim 1, wherein a film is previously laminated on the decorated surface of the fiber-reinforced thermoplastic resin sheet. Manufacturing method. 4. A film having irregularities is previously laminated on the decorated surface of the fiber-reinforced thermoplastic resin sheet, and the foaming pressure of the foamable thermoplastic resin composition in the hollow body is applied. The outer surface of the hollow body is formed into a desired cross-sectional shape along the regulation member, and at the same time, the unevenness of the film is transferred to the outer surface of the fiber-reinforced thermoplastic resin sheet. A method for producing a fiber-reinforced thermoplastic resin foam. 5. A composite sheet comprising a fiber-reinforced thermoplastic resin layer whose surface is decorated and a foamable thermoplastic resin composition layer is continuously formed so that the decorated surface is on the outside. After shaping into a hollow body, the foamable thermoplastic resin composition on the inner surface side is foamed by heating, and by the foaming pressure, the hollow body outer surface is shaped into a desired cross-sectional shape along the regulating member,
A method for producing a fiber-reinforced thermoplastic resin foam. 6. The decorated surface of the composite sheet,
Characterized by laminating films in advance,
The method for producing the fiber-reinforced thermoplastic resin foam according to claim 5. 7. The decorative surface of the composite sheet,
By laminating a film having irregularities in advance, by the foaming pressure of the expandable thermoplastic resin composition in the hollow body, the outer surface of the hollow body is shaped into a desired cross-sectional shape along the regulating member, and at the same time, The method for producing a fiber-reinforced thermoplastic resin foam according to claim 5, wherein the irregularities are transferred to the outer surface of the fiber-reinforced thermoplastic resin layer.