JPH06344431A - Overhanging or deep drawing molding of fiber reinforced thermoplastic resin and molding method thereof - Google Patents

Abstract

PURPOSE:To provide an overhanging or deep drawing molding wherein moldability and the appearance are excellent and provide the molding method thereof by laminating a thermoplastic resin layer having a melting point higher than the molding temperature of fiber reinforced thermoplastic resin on one or both sides of the layer thereof through an adhesive material. CONSTITUTION:The whole surface of a fiber reinforced thermoplastic resin layer 2 which is not molten or softened at the time of heating is stably covered with a thermoplastic resin layer 3 having a high melting point or high softening point. Exposure of the reinforced fiber is completely prevented. Furthermore, a decorative skin 4 which consists of the heated sheetlike molding material and is correspondent to the use of a molding is overlapped on the surface wherein thermoplastic resin having a high melting point or high softening point is not laminated thereon. The laminate is provided in a molding die 9 and held by clamps 10 in accordance with necessity and pressurized, cooled and solidified. Thereby an overhanging or deep drawing molding 1 of fiber reinforced thermoplastic resin is formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stretched or deep-drawn molded product of a fiber-reinforced thermoplastic resin. INDUSTRIAL APPLICABILITY The molded product of the present invention can be widely used for interior / exterior materials of automobiles, housings for household electric appliances, and industrial parts such as furniture.

[0002]

2. Description of the Related Art Recently, industrial parts manufactured by pressing metal have been replaced by press-molded products of fiber-reinforced thermoplastic resin composed of relatively long reinforcing fibers and thermoplastic resin (matrix resin). Tend to be. The characteristic of the fiber reinforced thermoplastic resin is that the heat-softened fiber reinforced thermoplastic resin sheet material (hereinafter, the fiber reinforced thermoplastic resin sheet material is referred to as sheet material).
It is possible to obtain a complicated molded product by inserting into a room temperature or heated mold and pressurizing and cooling to solidify in a short time. Further, the molded product has high strength and is lightweight. .

A sheet-shaped molding material is manufactured by applying a papermaking technique to uniformly disperse reinforcing fibers and thermoplastic resin powder particles dispersed in a single fiber into a non-woven material. It is manufactured by heating, pressurizing, and cooling and solidifying it as a material (Japanese Patent Publication No. 52-12283 and Japanese Patent Publication No. 55-9119).

Heating the sheet-shaped molding material to a temperature above the softening point or melting point of the thermoplastic resin and subjecting it to overhanging or deep-drawing, which is widely used in metal pressing,
A large product can be molded with a low molding pressure, and since it can be integrally molded with a decorative skin, an excellent effect can be obtained.
However, this method has the following problems.

The stretch forming is a forming method in which a material fixed by a clamp is expanded, that is, the surface area of the material is increased to form a solid. The moldability of overhang molding is
It is evaluated by how deep the molding can be done, and the moldability improves as the elongation of the material increases. Deep drawing is
Since the material moves into the mold to form a solid, the breaking load is important in addition to the amount of elongation of the material. Deep drawing generally enables deeper forming than extrusion forming,
If the breaking load of the material is very small, the material breaks during molding and the moldability decreases. In order to obtain good moldability in overhanging or deep drawing of a fiber-reinforced thermoplastic resin, it is necessary that the heated sheet-shaped molding material has a large elongation amount and a high breaking load.

An example of conventional overhanging or deep drawing of a fiber reinforced thermoplastic resin is shown in FIG. The sheet-shaped molding material 11 is generally heated in the far infrared heating furnace 8 to a temperature equal to or higher than the melting point or softening point of the thermoplastic resin. The heated sheet-shaped molding material is held by a clamp (wrinkle retainer) 10 installed in a molding die 9 and pressed and cooled to solidify to obtain a fiber-reinforced thermoplastic resin overhang or a deep-drawing molded product 12.

In this molding, the elongation at the time of molding decreases as the reinforcing fiber content of the sheet-shaped molding material increases,
Moldability is reduced. A sheet-shaped molding material consisting of reinforcing fibers and thermoplastic resin dispersed in a single fiber weakens the binding force to the reinforcing fibers due to melting or softening of the matrix resin during heating, and spring backs that try to return to the original state of the reinforcing fibers. Expands in the thickness direction. For this reason,
Sheet expansion increases with increasing reinforcing fiber content.
In a heated sheet-shaped molding material, the amount of the thermoplastic resin that is present at the intersections of the reinforcing fibers and plays the role of a binder decreases due to expansion, and the amount of elongation during molding decreases, making it easier to break. Sex decreases.

In a more complicated molded product, a large deformation locally occurs. In the molded product of FIG. 2, the vertical wall portion 13 is deformed more than the horizontal portion 14. Since the matrix resin is melted in the sheet-shaped molding material, the tension during molding is locally applied, and molding failure occurs due to the breakage 15 of the material.

Further, a large number of reinforcing fibers are exposed on the surface of the sheet-shaped molding material expanded by heating, and subsequently, they are pressed, cooled and solidified to be molded, so that the reinforcing fibers remain exposed on the surface of the molded product and the appearance is improved. Degradation occurs (16).

[0010]

DISCLOSURE OF THE INVENTION The present invention provides a stretched or deep-drawn molded product of a fiber-reinforced thermoplastic resin excellent in moldability and appearance, and a molding method thereof.

[0011]

Means and Actions for Solving the Problems The gist of the present invention is as follows. (1) The reinforcing fibers dispersed in a single fiber and a reinforcing fiber bundle in which a plurality of reinforcing fibers are bundled and a fiber-reinforced thermoplastic resin layer made of a thermoplastic resin are provided on one or both sides with an adhesive material interposed therebetween. A fiber-reinforced thermoplastic resin overhanging or deep-drawing molded article, characterized in that a thermoplastic resin layer having a melting point or a softening point higher than the molding temperature of the fiber-reinforced thermoplastic resin is laminated.

(2) A thermoplastic resin layer having a melting point or a softening point higher than the molding temperature of the fiber reinforced thermoplastic resin is laminated on one surface of the fiber reinforced thermoplastic resin layer through an adhesive material, and the other surface of the one side is laminated. The fiber-reinforced thermoplastic resin overhanging or deep-drawn molded article according to (1) above, which is obtained by laminating a decorative skin.

(3) The fiber-reinforced thermoplastic resin overhanging or deep-drawn molded article according to (1) or (2), wherein the binder of the reinforcing fiber bundle is a water-insoluble urethane-based or vinyl acetate-based binder.

(4) The fiber-reinforced thermoplastic resin overhanging or deep-drawing according to any one of the above (1) to (3), wherein the fiber-reinforced bundle is a bundle of 10 to 3000 single fibers. Goods.

(5) An adhesive material is provided on one or both sides of a nonwoven material made of a thermoplastic resin and a reinforcing fiber bundle in which a plurality of reinforcing fibers are bundled together and a reinforcing fiber dispersed in a single fiber. A thermoplastic resin film having a melting point or a softening point higher than the molding temperature of the non-woven material, is laminated through heating, pressurizing, and cooling to solidify into a sheet-shaped molding material, and after further heating the sheet-shaped molding material A method for forming a fiber-reinforced thermoplastic resin overhanging or deep-drawing molded article, characterized by performing overhanging or deep-drawing molding.

(6) One side of a non-woven material made of a thermoplastic resin and a reinforcing fiber bundle in which a reinforcing fiber dispersed in a single fiber and a plurality of reinforcing fibers are bundled, and an adhesive material are interposed. A thermoplastic resin film having a melting point or a softening point higher than the molding temperature of the non-woven material is laminated and heated.
After being pressed and cooled to solidify into a sheet-shaped molding material, the sheet-shaped molding material is further heated, and then a decorative skin is superposed on the surface of the sheet-shaped molding material on which the thermoplastic resin film is not laminated, The method for forming a fiber-reinforced thermoplastic resin overhang or deep-draw molded product according to (5) above, which comprises overhanging or deep-drawing.

FIG. 1 shows an example of a fiber-reinforced thermoplastic resin overhanging or deep-drawn molded product of the present invention and a molding method therefor. The fiber-reinforced thermoplastic resin overhanging or deep-drawing molded article 1 of the present invention comprises a fiber-reinforced thermoplastic resin layer 2 and a thermoplastic resin layer 3 having a melting point or a softening point higher than the molding temperature of the fiber-reinforced thermoplastic resin. Accordingly, it is composed of the decorative skin 4.

In the fiber-reinforced thermoplastic resin layer 2, the reinforcing fibers 5 dispersed in a single fiber and the reinforcing fiber bundles 6 in which a plurality of reinforcing fibers are bundled are uniformly dispersed in the thermoplastic resin. Since the thermoplastic resin layer 3 does not melt or soften at the time of molding and covers the entire surface of the fiber-reinforced thermoplastic resin layer 2, the reinforced fibers are prevented from being exposed and a good molded product appearance is obtained. Furthermore, applying a coating to the molded product of the present invention leads to a further improvement in appearance and can be applied to exterior parts such as automobiles and industrial machines. In addition, by superimposing the decorative skin 4 on the heated sheet-shaped molding material and integrally molding the same,
It is possible to efficiently mold a molded product according to the application such as an automobile interior material.

The method for forming the fiber-reinforced thermoplastic resin overhanging or deep-drawing molded article of the present invention will be described below. FIG. 1 shows a method in which a thermoplastic resin layer having a melting point or a softening point higher than the molding temperature of the fiber reinforced thermoplastic resin is provided on one surface, and a decorative skin is provided on the other surface to integrally mold the thermoplastic resin layer.

The sheet-shaped molding material 7 of the present invention is produced by a papermaking method comprising a reinforcing fiber bundle in which a plurality of reinforcing fibers are bundled together with a reinforcing fiber dispersed in a single fiber and a thermoplastic resin powder granule. It is manufactured by stacking a thermoplastic resin film having a high melting point or a high softening point on one surface of a non-woven material via an adhesive material and heating, pressurizing and cooling to solidify. This sheet-shaped molding material 7 is generally heated in a far-infrared heating furnace 8 to the molding temperature of the fiber-reinforced thermoplastic resin (above the melting point or softening point of the matrix resin). The thermoplastic resin layer 3 having a high melting point or a high softening point does not melt or soften when heated and stably covers the entire surface of the fiber-reinforced thermoplastic resin layer 2 and completely prevents the reinforcing fibers from being exposed. Further, the decorative skin 4 according to the intended use of the molded product is superposed on the surface of the heated sheet-shaped molding material on which the thermoplastic resin having the high melting point or the high softening point is not laminated, and the laminated body is formed into the molding die 9 Clamp 10 if necessary
Then, the fiber-reinforced thermoplastic resin overhanging or deep-drawing molded product 1 of the present invention is molded by holding and pressing and cooling and solidifying.

In the molding method of FIG. 1, a reinforcing fiber bundle in which a plurality of reinforcing fibers are bundled together with a reinforcing fiber dispersed in a single fiber, and a fiber-reinforced thermoplastic resin layer made of a thermoplastic resin have a high melting point on one side. Alternatively, by using the sheet-shaped molding material 7 in which a thermoplastic resin layer having a high softening point is laminated and the decorative skin 4 is overlapped at the time of molding, the moldability of overhanging and deep drawing is significantly improved.

In the conventional molding method, as the content of the reinforcing fibers dispersed in a single fiber increases, the expansion of the heated sheet-shaped molding material increases, and the thermoplastic resin present at the intersections of the reinforcing fibers increases. Since the amount decreases and the elongation of the material decreases, the applicable range of molding has become narrow.

Conventional non-woven materials produced by a papermaking method using reinforcing fibers dispersed in a single fiber and a thermoplastic resin are very bulky (bulk density) because the reinforcing fibers are randomly oriented. Is low). The thickness of the non-woven material is
Although it varies depending on the shape of the reinforced fiber and the papermaking conditions, it has a thickness of about 10 times that of a sheet-shaped molding material from which voids are removed, which is generally used for molding a fiber-reinforced thermoplastic resin. This sheet-shaped molding material has a weak binding force to the reinforcing fibers due to melting or softening of the matrix resin during heating, and greatly expands in the plate thickness direction due to springback to return to the original state of the reinforcing fibers.

In the present invention, by using the reinforcing fiber dispersed in a single fiber and the reinforcing fiber bundle in which a plurality of reinforcing fibers are bundled together, the expansion of the fiber-reinforced thermoplastic resin layer is suppressed and the elongation amount of the material is increased. Solved the problem of the drop. The reinforcing fiber bundle serves to increase the bulk density of the non-woven material without being dispersed into a single fiber during papermaking. In the non-woven material, the fiber dispersion state can be controlled and easily adjusted by the mixing ratio of the reinforcing fiber bundle and the reinforcing fibers dispersed in a single fiber. In the sheet-shaped molding material using this non-woven material, the expansion during heating is suppressed by reducing the springback of the reinforcing fiber, which increases the amount of thermoplastic resin per volume of the heating sheet, and The amount of the thermoplastic resin present at the intersection of is increased. As a result, the contact area of the reinforcing fiber intersection with the resin becomes large, and the intersection can follow the large deformation, so that the elongation amount of the material is increased and the formability is improved.

Further, in the conventional molding method, local deformation in a complicated molded product was associated with a decrease in moldability. In the heated sheet-shaped molding material, the matrix resin was melted or softened, and therefore, when a large local deformation occurred, the material was broken from the portion.

In the present invention, molding proceeds while the thermoplastic resin layer having a high melting point or high softening point and the decorative skin are stretched. The thermoplastic resin layer with a high melting point or high softening point and the decorative skin play a role of retaining the tension during molding and transmitting it to the entire sheet, so local deformation in complicated molded products is mitigated and the material stretches. Increase the amount.

The breaking load of the sheet-shaped molding material of the present invention is
Since the fiber-reinforced thermoplastic resin layer is deformed while being reinforced by the thermoplastic resin layer having a high melting point or high softening point and the decorative skin, it is remarkably improved. The breaking load of the sheet-shaped molding material tends to decrease as the mixing ratio of the reinforced fiber bundles in the fiber-reinforced thermoplastic resin layer increases, but the reinforcing effect is large compared to the breaking load of the conventional sheet-shaped molding material. , Maintain a high level. As a result, both the amount of elongation of the material, which is important in stretch forming, and the breaking load, which is important in deep drawing, are improved, and good formability is obtained.

As the molding material of the present invention, as shown in FIG. 1, in addition to a sheet-shaped molding material in which a thermoplastic resin film having a high melting point or a high softening point is laminated in advance, a molding method prior to heating during molding is used. A thermoplastic resin film with a high melting point or a high softening point is overlaid on one or both sides of the manufactured non-woven material (or sheet) consisting of reinforced fibers, reinforced fiber bundles and thermoplastic resin powder particles through an adhesive material. Alternatively, it can be adjusted by laminating a thermoplastic resin film having a high melting point or a high softening point, which is separately heated via an adhesive material, on one side or both sides of the heated nonwoven material (or sheet).

In the present invention, the molding pressure is generally 100 kgf /
Overhanging or deep drawing is carried out at a cm ² or less. Although FIG. 1 shows the overhanging or deep drawing by the male and female dies, the effect of the overhanging or deep drawing of the present invention can be applied to the molding by vacuum, compressed air, or a combination thereof, and good moldability and The appearance of the molded product is obtained.

The content of the reinforcing fibers and the reinforcing fiber bundles in the fiber-reinforced thermoplastic resin layer is 5% by volume or more at which a good reinforcing effect of the reinforcing fibers and the reinforcing fiber bundles is exhibited, and the reinforcing fibers and the reinforcing fiber bundles and the thermoplastic resin are contained. It is preferable to be 40% by volume or less, which can be adhered to and can sufficiently express mechanical properties.

As the reinforcing fibers dispersed in a single fiber,
In addition to glass fibers, carbon fibers, and metal fibers, inorganic fibers, organic fibers, and a mixture thereof may be used depending on the application.
The shape of the reinforcing fiber is preferably 3 μm or more from the viewpoint of easy handling and economical, and 30 μm or less in order to express sufficient strength, and the fiber length is 3 mm or more from the viewpoint of strength development, and is uniform. It is desirable to set the thickness to 50 mm or less, which allows various dispersion. In addition, the reinforcing fiber is preferably subjected to a surface treatment with a water-soluble polymer, a wetting agent, etc. in order to improve hydrophilicity for the purpose of good dispersion in water, and further adheres to a thermoplastic resin for the purpose of expressing strength. In order to improve the property, it is desirable to perform surface treatment with a silane coupling agent or the like.

The reinforcing fiber bundle must be tightly bundled with a water-insoluble urethane type or vinyl acetate type binder in order to suppress fiber dispersion during papermaking. It is desirable to add a silane coupling agent or the like to the sizing agent for the purpose of developing strength. The reinforcing fiber to be bundled has the same shape as the reinforcing fiber dispersed in a single fiber, but the preferable range of the number of bundles is 10 to 3000.
As the number of bundles of the reinforcing fiber bundle increases, the effect of increasing the bulk density of the non-woven material is exhibited, but the denseness of the fiber dispersion state is lost and the strength of the molded product is reduced.

A preferable range of the mixing ratio of the reinforcing fiber bundle and the reinforcing fiber is 5/95 to 95/5 of reinforcing fiber bundle / reinforcing fiber.
Is. When the mixing ratio is 5/95 or more, the effect of increasing the bulk density of the non-woven material appears, and when it exceeds 95/5, the denseness of the fiber dispersion state is lost and the strength of the molded product decreases.

In the present invention, according to the shape of the molded product and the molding method (moldability required for the sheet-shaped molding material), and the fiber content (expanded state) of the fiber-reinforced thermoplastic resin layer, the bundle of reinforcing fiber bundles is bundled. It is desirable to manufacture the non-woven material by appropriately setting the number and mixing ratio.

The thermoplastic resin includes polyethylene, polypropylene, polystyrene, styrene-butadiene-acrylonitrile copolymer, styrene-acrylonitrile copolymer, polymethylmethacrylate, polyamide, polycarbonate, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polyphenylene oxide, It is a resin such as polyvinylidene fluoride, polysulfone, polyphenylene sulfide, etc., and crystalline resin is preferable because it is easy to exert the reinforcing effect by the reinforcing fiber such as glass fiber, and among the crystalline resins, polyolefin such as polyethylene and polypropylene is preferable. used. further,
Plasticizers, heat stabilizers, light stabilizers, which are commonly used in these, including mixtures of two or more of these,
Fillers, dyes and pigments, impact resistance agents, extenders, nucleating agents, processing aids and the like can also be added. The shape of the thermoplastic resin is appropriately selected from pellets, powders, flakes, and fibrous shapes.

The thermoplastic resin having a high melting point or a high softening point to be laminated on the fiber reinforced thermoplastic resin is preferably used in the form of a film because it is easy to handle and is melted or softened at a temperature higher than the molding temperature of the fiber reinforced thermoplastic resin. You have to choose what to start with. It is desirable to select a thermoplastic resin having a melting point or softening point higher by 30 ° C. or more than the matrix resin of the fiber reinforced thermoplastic resin layer. When a thermoplastic resin having a difference in melting point or softening point from the matrix resin of the fiber reinforced thermoplastic resin layer of less than 30 ° C. is selected, it overlaps with the molding temperature of the fiber reinforced thermoplastic resin to melt the thermoplastic resin layer. Alternatively, since the phenomenon of softening and exposing of the reinforcing fibers to the surface of the molded product occurs, the effect of the present invention cannot be expected.

When polyolefin is used as the matrix resin of the fiber reinforced thermoplastic resin layer, polyamide, polyester, polycarbonate, polymethylmethacrylate, etc. are selected from the viewpoint of difference in melting point or softening point with polyolefin, moldability into film and the like. It is preferable to select a thermoplastic resin.

When it is necessary to improve the designability, heat resistance, surface hardness, abrasion resistance, etc. by coloring or coating the surface layer, a mixture with a different resin, or a plasticizer generally used for these, heat stability It is also possible to use a film to which agents, light stabilizers, fillers, dyes and pigments, impact resistance agents, extenders, nucleating agents, processing aids, etc. are added, and multilayer films of different resins may be used.

The thickness of the thermoplastic resin film is appropriately selected within the range of 0.01 to 1 mm depending on the application. When the film thickness is less than 0.01 mm, the unevenness of the reinforcing fibers affects the surface of the molded product, and when it exceeds 1 mm, the strength per plate thickness of the molded product decreases and the economical efficiency deteriorates. Further, a thermoplastic resin film added with an inorganic filler can also be used. As the inorganic filler to be added, particulate fillers such as calcium carbonate and talc, flaky fillers such as mica, fibrous fillers such as chopped glass fibers and rock wool fibers are used. The inorganic filler is preferably surface-treated with a silane coupling agent or the like in order to improve the adhesiveness with the thermoplastic resin. The kind of the inorganic filler is appropriately selected according to the application, and a mixture of two or more kinds of the inorganic filler may be added. The amount of the inorganic filler added is preferably 30% by volume or less, which allows stable film formation.

The thermoplastic resin layer having a high melting point or a high softening point needs to be bonded to the fiber reinforced thermoplastic resin layer by some method. The adhesive material used in the present invention is an adhesive resin or the like, or an adhesive or the like used for film lamination.

When polyolefin is used as the matrix resin of the fiber reinforced thermoplastic resin layer, it is graft-modified with unsaturated carboxylic acid or its derivative (acid anhydride, ester, amide, imide, metal salt, etc.) as the adhesive resin. Ethylene copolymer graft-modified with polypropylene, unsaturated carboxylic acid or its derivatives (ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene-acrylic acid copolymer, etc.)
Alternatively, a hydrocarbon elastomer (butyl rubber or the like) added thereto may be mentioned, and a mixture of two or more of these may also be used.

The adhesive resin is provided between the high melting point or high softening point thermoplastic resin layer and the fiber reinforced thermoplastic resin layer,
It melts together with the matrix resin of the fiber reinforced thermoplastic resin layer and is fixed by cooling. The adhesive resin is preferably used in the form of a film because it is easy to handle, and its thickness is preferably 5 to 500 μm, more preferably 10 to 100 μm in view of the adhesive effect and economy.

By using a multilayer film obtained by previously laminating a thermoplastic resin film having a high melting point or a high softening point and an adhesive resin film, the handling property in the molding process is improved. The multilayer film is manufactured by a general extrusion lamination method such as extrusion lamination, coextrusion lamination, or lamination with an adhesive. For example, polyamide / maleic anhydride modified polypropylene extruded laminated film, polyamide / maleic anhydride modified polypropylene coextruded laminated film, polyamide / maleic anhydride modified polypropylene / polypropylene coextruded laminated film, polyamide / adhesive / polypropylene dry film Laminate films and the like can be mentioned.

In the present invention, a thermoplastic resin layer containing an inorganic filler and a dye / pigment, a fiber reinforced thermoplastic resin layer, a transparent or translucent high melting point or high softening point thermoplastic resin layer and an adhesive material layer. If it is provided between the two, it improves the design of the molded product. As the inorganic filler, it is common to use a particulate filler such as calcium carbonate or talc, and the thermoplastic resin is generally the same as the matrix resin of the fiber reinforced thermoplastic resin layer. Also in this case, it is preferable to use it in the form of a film because it is easy to handle, and by setting the thickness to 0.1 to 1 mm, desired designability can be improved. The addition amount of the inorganic filler and the dye / pigment is preferably 30% by volume or less, which allows stable film formation.

Since the thermoplastic resin layer containing the inorganic filler and the dye / pigment has an increased melt viscosity, it is possible to stably cover the fiber-reinforced thermoplastic resin layer even in a heated sheet material. Since it works to hide the reinforcing fibers, the design of the molded product is further improved.

The decorative skins are woven fabrics made of natural and synthetic fibers as breathable skins, non-woven fabrics obtained by needle punching, raised woven fabrics, knitted fabrics, flocked fabrics, and smooth or non-breathable skins. A plastic sheet or film having a textured surface such as cloth or leather pattern, a metal sheet mixed with metal powder, or a metal coated plastic sheet or film is used. Moreover, polyethylene foam, ethylene-propylene copolymer foam, ethylene-vinyl acetate copolymer foam, and these decorative skins,
It is also possible to use a laminate of porous sheets such as urethane foam. The decorative skin and the fiber-reinforced thermoplastic resin layer are joined by fusing the decorative skin, bonding with a hot-melt type adhesive resin film or an adhesive.

[0047]

The present invention will be described in detail with reference to the following examples. Example 1 A glass fiber having a diameter of 10 μm and a length of 13 mm which was surface-treated with a water-soluble polymer, a wetting agent, and a silane coupling agent as a reinforcing fiber, a silane coupling agent as a reinforcing fiber bundle, and a diameter of 10 μm with a urethane binder. A glass fiber bundle in which 67 pieces of 13 mm glass fibers are bundled, and spherical pellets with a diameter of 3 mm as a thermoplastic resin are mechanically crushed, and the crushed product is sieved to 70 mesh (opening diameter 0.21).
A polypropylene powder (melting point: 165 ° C.) classified from 2 mm) to 10 mesh (opening diameter 1.7 mm) was used.

10% by weight of glass fiber (4.
4% by volume), glass fiber bundle 20% by weight (8.8% by volume)
A non-woven material having a composition of polypropylene and 70% by weight (86.8% by volume) and a basis weight (weight per area) of 2000 g / m ² was produced.

As the high melting point thermoplastic resin film and the hot melt type adhesive resin film, a polyamide (nylon 66: melting point 265 ° C.) film (thickness 80 μm
m) and a modified polypropylene film (thickness 30 μm) grafted with maleic anhydride were laminated in advance.

A multilayer film is laminated so that the adhesive resin film is in contact with one surface of the non-woven material, and a stainless steel plate having a smooth surface (board thickness 2
mm) are stacked and inserted into a heating press machine whose temperature is set to 210 ° C., and the temperature of the central portion of the nonwoven material is increased to about 190 ° C. or more under a pressure of 2 kgf / cm ² by about 5 mm. Preheated for a minute. At this temperature, polypropylene and the adhesive resin were sufficiently melted, and polyamide was not melted. Then, pressurize at a pressure of 5 kgf / cm ² for 3 minutes, insert the laminate into a cooling press machine, pressurize at a pressure of 5 kgf / cm ² for about 5 minutes to cool and solidify, remove the end plate, and remove the plate thickness. A 1.9 mm sheet-shaped molding material was molded.

The molding evaluation shown in FIG. 3 was performed as a quantitative evaluation of the overhanging and deep drawing formability. The sheet-shaped molding material 7 was cut into 210 × 210 mm and heated in a far infrared heating furnace for 3 minutes. At this time, the surface temperature of the sheet-shaped molding material was about 200 ° C, and the polypropylene of the fiber-reinforced thermoplastic resin layer was melted, but it was confirmed that the polyamide layer was not melted and the exposure of the glass fiber was completely suppressed. Was done.
It was confirmed that many glass fibers were exposed on the surface on which the polyamide film was not laminated.

The heated sheet-shaped molding material 7 is
The punch 18 side was placed on a stand 17 with a hole of 50 mm cut out so that the surface of the punch 18 was not laminated with polyamide film, and was fixed by a flat plate clamp 10 with a hole of 150 mm diameter cut out like the stand. . Subsequently, the sheet-shaped molding material fixed by the clamp is overhanged by the punch 18 having a diameter of 50 mm, and the overhang amount of the sheet-shaped molding material (downward amount of the punch) and the load at the time of molding by the load cell 19 installed in the punch. Was measured. Using the amount of overhang at maximum load as an index of overhang formability,
Further, the deep load formability was evaluated using the maximum load as the breaking load of the material.

The appearance of the molded product was evaluated by measuring the surface roughness of the polyamide layer and measuring the center line average roughness (Ra). The results are shown in Table 1.

Example 2 Using the glass fiber, glass fiber bundle and polypropylene powder of Example 1, a glass fiber 20 was produced by a papermaking method.
% By weight (8.8% by volume), 10% by weight of glass fiber bundle
(4.4% by volume) and 70% by weight of polypropylene (86.
A non-woven material having a composition of 8% by volume and a basis weight of 2000 g / m ² was produced. The multilayer film of Example 1 was laminated on both sides of the non-woven material so that the adhesive resin side was in contact with each other, and a sheet-shaped molding material having a plate thickness of 2.0 mm was molded in the same manner as in Example 1.

Using this sheet-shaped molding material, Example 1
The moldability was evaluated in the same manner as in. The appearance of the molded product was evaluated by measuring the surface roughness and measuring the center line average roughness (Ra). The results are shown in Table 1.

Example 3 On both sides of the nonwoven material of Example 1, the multilayer film of Example 1 was laminated so that the adhesive resin side was in contact, and as in Example 1, a sheet-like molding material having a plate thickness of 2.0 mm. Was molded.

Using this sheet-shaped molding material, Example 1
The moldability was evaluated in the same manner as in. The appearance of the molded product was evaluated by measuring the surface roughness and measuring the center line average roughness (Ra). The results are shown in Table 1.

Example 4 The moldability in integral molding of the sheet-shaped molding material of Example 1 and the decorative skin was evaluated. As a decorative skin,
A multilayer skin was used in which a 0.5 mm thick polyvinyl chloride film having a skin pattern and a 3 mm ethylene-propylene copolymer foam (melting point 137 ° C., expansion ratio 15 times) were laminated.

The sheet-shaped molding material was heated in the same manner as in Example 1, and a multilayer skin was laminated so that the foam was in contact with the surface of the heated sheet-shaped molding material on which the polyamide film was not laminated. The moldability was evaluated by fixing with a pedestal and clamp so that was on the punch side.
The appearance of the molded product was evaluated by measuring the surface roughness of the polyamide layer and measuring the center line average roughness (Ra). The results are shown in Table 1.

Example 5 The moldability in the integral molding of the sheet-shaped molding material and the decorative skin of Example 1 was evaluated. As a decorative skin,
A polyester fiber non-woven fabric having a basis weight of 230 g / m ² was used. An ethylene-vinyl acetate copolymer film having a thickness of 20 μm was used as the adhesive resin film.

The sheet-shaped molding material was heated in the same manner as in Example 1, and the adhesive resin film and the polyester fiber non-woven fabric were superposed on the surface of the heated sheet-shaped molding material on which the polyamide film was not laminated to form a polyamide layer. The moldability was evaluated by fixing with a pedestal and clamp so that was on the punch side. The appearance of the molded product was evaluated by measuring the surface roughness of the polyamide layer and measuring the center line average roughness (Ra). The result
The results are shown in Table 1.

Comparative Example 1 Using the glass fiber and polypropylene powder of Example 1, 30% by weight (13.2% by volume) of glass fiber and 70% by weight (86.8% by volume) of polypropylene were prepared by a papermaking method. A non-woven material having a composition and a basis weight of 2000 g / m ² was produced. No glass fiber bundles were used in this non-woven material, and it showed a property that was extremely bulky as compared with the non-woven materials of Examples. Without laminating the film on the non-woven material, a sheet-shaped molding material having a plate thickness of 1.8 mm was molded in the same manner as in Example 1.

Using this sheet-shaped molding material, Example 1
The moldability was evaluated in the same manner as in. It was confirmed that many glass fibers were exposed on the surface of the heated sheet-shaped molding material. The appearance of the molded product was evaluated by measuring the surface roughness and measuring the center line average roughness (Ra). The results are shown in Table 1.

Comparative Example 2 The non-woven material of Example 1 was subjected to no film lamination to Example 1.
A sheet-shaped molding material having a plate thickness of 1.8 mm was molded in the same manner as in.
Using this sheet-shaped molding material, the moldability was evaluated in the same manner as in Example 1. It was confirmed that many glass fibers were exposed on the surface of the heated sheet-shaped molding material. The appearance of the molded product was evaluated by measuring the surface roughness and measuring the center line average roughness (Ra). The results are shown in Table 1.

Comparative Example 3 Polypropylene films (thickness: 200 μm) were laminated on both sides of the non-woven material of Comparative Example 1, and a sheet-like molding material having a plate thickness of 2.2 mm was molded in the same manner as in Example 1. Further, using this sheet-shaped molding material, the moldability was evaluated in the same manner as in Example 1. The surface of the heated sheet material is
Exposure of many glass fibers was confirmed. The appearance of the molded product is
The surface roughness was measured and evaluated by the center line average roughness (Ra).
The results are shown in Table 1.

Comparative Example 4 The multilayer film of Example 1 was laminated on both sides of the non-woven material of Comparative Example 1 so that the adhesive resin side was in contact, and as in Example 1, a sheet-like molding material having a plate thickness of 2.0 mm. Was molded. Using this sheet-shaped molding material, the moldability was evaluated in the same manner as in Example 1. The appearance of the molded product was evaluated by measuring the surface roughness and measuring the center line average roughness (Ra). The results are shown in Table 1.

Comparative Example 5 The sheet-like molding material of Comparative Example 1 and the multilayer decorative skin of Example 4 were used to evaluate the moldability in integral skin molding in the same manner as in Example 4. The appearance of the molded product was evaluated by measuring the surface roughness of the molded product on which the decorative skin was not laminated and measuring the center line average roughness (Ra). The results are shown in Table 1.

[0068]

[Table 1]

In the example, the elongation amount of the material, which is important for the stretch formability, and the breaking load of the material, which is important for the deep drawability, were improved compared to the comparative example, and it was confirmed that the formability was improved. It was

Comparative Examples 1 and 2 show the effect of the mixing ratio of the glass fiber bundle in the sheet-shaped molding material. As the mixing ratio of the glass fiber bundles increased, the expansion of the sheet-shaped molding material during heating was suppressed, and it was confirmed that the amount of overhang and the maximum load were reduced.

In the present invention, the decrease of the maximum load is compensated by the lamination of the resin layer having a high melting point or the high softening point and the decorative skin. The unmelted polyamide layer and the decorative skin are stretched and bulged out, and both play a role of transmitting tension to the entire sheet. Since the molten fiber-reinforced thermoplastic resin layer is deformed while being reinforced by both, local breakage is less likely to occur. As a result, local deformation is alleviated, the amount of overhang is further increased, and the maximum load is increased by the deformation resistance of the polyamide layer and the decorative skin.

Examples 2 and 3 and Comparative Examples 2 and 4 show the combined effect of mixing the glass fiber bundles in the fiber reinforced thermoplastic resin layer and laminating the resin layer having a high melting point or a high softening point. . In the examples, it was recognized that the amount of overhang was remarkably improved by increasing the mixing ratio of the glass fiber bundles and reinforcing the polyamide layer. The maximum load decreases as the mixing ratio of the glass fiber bundles increases, but shows a higher level than the material in which the polyamide layer is not laminated due to the reinforcement of the polyamide layer.

In Comparative Example 3, the formability of a sheet-shaped molding material in which the same polypropylene film as the matrix resin of the fiber reinforced thermoplastic resin layer was laminated was evaluated. In this case, since the laminated film melts when heated, no improvement in moldability and appearance of the molded product was obtained.

When the polyamide layer has one side (comparison between Example 1 and Comparative Example 2), the moldability is obviously improved even when integrally molded with the decorative skin (Comparison between Examples 4 and 5 and Comparative Example 5). Improvement was noted.

The appearance of the molded products compared by the center line average roughness is
It was confirmed that the polyamide layer was significantly improved by the lamination. In the examples, the surface of the heated sheet-shaped molding material was covered with the polyamide layer, and the exposure of the glass fiber was suppressed. Since the molded product is frozen in this state and molded, a good appearance can be obtained.

[0076]

INDUSTRIAL APPLICABILITY In the fiber-reinforced thermoplastic resin overhanging or deep-drawing molded article of the present invention, expansion of the fiber-reinforced thermoplastic resin layer is suppressed by using a reinforcing fiber bundle in which a plurality of reinforcing fibers are bundled together, and as a reinforcing layer. Good moldability can be obtained by applying a thermoplastic resin layer having a high melting point or a high softening point and a decorative skin. Further, the thermoplastic resin layer having a high melting point or a high softening point prevents the reinforcing fibers from being exposed, and a good appearance of the molded product can be obtained.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of a fiber-reinforced thermoplastic resin overhanging or deep-drawn molded product of the present invention and a molding method thereof.

FIG. 2 is a schematic view showing an example of a conventional fiber-reinforced thermoplastic resin overhanging or deep-drawing molded product and its molding method.

FIG. 3 is a schematic diagram showing an overhang test method performed in Examples.

[Explanation of symbols]

1 Fiber Reinforced Thermoplastic Resin Overhang or Deep Drawing Molded Product 2 of the Present Invention 2 Fiber Reinforced Thermoplastic Resin Layer 3 High Melting Point or High Softening Point Thermoplastic Resin Layer 4 Decorative Skin 5 Reinforcing Fiber Dispersed in Single Fiber 6 Multiple Reinforced fiber bundles in which reinforcing fibers of a book are bundled 7 Sheet-shaped molding material of the present invention 8 Far-infrared heating furnace 9 Mold 10 Clamp 11 Conventional sheet-shaped molding material 12 Conventional fiber-reinforced thermoplastic resin overhang or deep-drawing molded product 13 Vertical wall part of molded product 14 Horizontal part 15 Breakage of material 16 Exposed reinforcing fiber 17 Stand 18 Punch 19 Load cell

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Takao Kimura 1 Toho-cho, Yokkaichi-shi, Mie Prefecture Yokkaichi Research Institute, Mitsubishi Petrochemical Co., Ltd. (72) Kensuke Ohno 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Petrochemical Incorporated company Yokkaichi Research Institute

Claims (6)

[Claims] 1. A fiber-reinforced thermoplastic resin layer composed of a thermoplastic resin and a reinforcing fiber bundle in which a plurality of reinforcing fibers are bundled together and a reinforcing fiber dispersed in a single fiber, on one side or both sides,
A fiber-reinforced thermoplastic resin overhang or deep-draw molded product, characterized in that a thermoplastic resin layer having a melting point or a softening point higher than the molding temperature of the fiber-reinforced thermoplastic resin is laminated via an adhesive material. 2. A thermoplastic resin layer having a melting point or a softening point higher than the molding temperature of the fiber reinforced thermoplastic resin is laminated on one surface of the fiber reinforced thermoplastic resin layer with an adhesive material interposed between the one surface and the other surface. The fiber-reinforced thermoplastic resin overhanging or deep-drawing molded article according to claim 1, wherein decorative skins are laminated. 3. The fiber-reinforced thermoplastic resin overhanging or deep-drawn molded article according to claim 1, wherein the binder of the reinforcing fiber bundle is a water-insoluble urethane-based or vinyl acetate-based binder. 4. The fiber-reinforced thermoplastic resin overhang or deep-draw molding according to claim 1, wherein the reinforcing fiber bundle is a bundle of 10 to 3000 single fibers. 5. A non-woven material made of a thermoplastic resin and a reinforcing fiber bundle in which a reinforcing fiber dispersed in a single fiber and a plurality of reinforcing fibers are bundled and a thermoplastic resin are used on one or both sides with an adhesive material interposed therebetween. And by laminating a thermoplastic resin film having a melting point or a softening point higher than the molding temperature of the non-woven material,
Molding of a fiber-reinforced thermoplastic resin overhanging or deep-drawing product characterized by heating, pressurizing, and cooling to solidify into a sheet-like forming material, and further heating the sheet-like forming material and then performing overhanging or deep-drawing molding Method. 6. A non-woven material produced by a papermaking method, which comprises a reinforcing fiber bundle in which a plurality of reinforcing fibers are bundled together and a reinforcing fiber dispersed in a single fiber, and a thermoplastic resin are bonded to one side of the nonwoven material through an adhesive material. A thermoplastic resin film having a melting point or softening point higher than the molding temperature of the nonwoven material is laminated, heated, pressed and cooled to solidify into a sheet-shaped molding material, and the sheet-shaped molding material is further heated. The fiber-reinforced thermoplastic resin overhanging or deep-drawing according to claim 5, wherein a decorative skin is superposed on the surface of the sheet-shaped molding material on which the plastic resin film is not laminated, and the overhanging or deep-drawing is performed. Molding method.