JPH09109179A - Film in-molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a film in-molded body of superior durability which maintains a good appearance without generating a release for a long period of time by improving the bonding properties of a film with a base of the film in-molded body. SOLUTION: A synthetic resin film 2 composed of a protective layer 21, a printed layer 22 and a bonding material layer 23 is disposed in a mold, and a synthetic resin material forming a base 1 is injected to integrate the film with the base. As the base 1, ABS resin in which butadiene rubber particles are dispersed in a matrix composed of an acrylonitrile-styrene copolymer or its modified body or its derivative is used, and the molecular-weight distribution (d) of the acrylonitrile-styrene copolymer or its modified body or its derivative forming the matrix is set in the range of 2.18<d<3.05 to improve remarkably the bonding properties of the film 2 with the base 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film-in-molded article which is widely used as an interior material for automobiles such as a console upper panel, a radio case cover and an instrument panel.

[0002]

2. Description of the Related Art A film-in-mold molded body in which the above film and the above base material are integrated by injection molding a synthetic resin material as a base material into a mold in which a film made of a synthetic resin is provided. It is used as an interior material for automobiles such as console upper panels. The film usually has a protective layer and a decorative layer such as a wood grain formed in advance on the surface of the protective layer by printing, painting or vapor deposition, and an adhesive layer formed by coating on the upper surface of the decorative layer. And is bonded to the above base material.

[0003]

However, in the conventional film-in-molded product thus obtained, the adhesion between the film and the substrate is not always sufficient, and the film peels off due to long-term use, and the appearance There was a risk of damaging.

The object of the present invention, therefore, is to improve the adhesion between the film of the film-in-molded product and the substrate and to maintain a good appearance without peeling for a long period of time, which is excellent in durability. To obtain a film-in-molded product.

[0005]

According to a first aspect of the present invention, in a film-in-mold molded article, a film made of a synthetic resin is provided in a mold so that at least a contact surface of the synthetic resin material as a base material with the film is in contact with the film. It is made to adhere to each other in a molten state so that both are integrated. The film has at least a protective layer and an adhesive layer located between the protective layer and the base material, and the base material is butadiene in a matrix composed of an acrylonitrile-styrene copolymer or a modified product or derivative thereof. It is made by dispersing rubber particles. The acrylonitrile-styrene copolymer or its modified product or derivative has a molecular weight distribution d of 2.1.
It is in the range of 8 <d <3.05. (Claim 1).

According to the present invention, the adhesion between the film and the substrate is remarkably improved. The reason for this is not clear, but when a conventional film-in-molded product using the acrylonitrile-butadiene-styrene copolymer as the base material, in which the film 3 was peeled, was examined, it was found that the fracture occurred inside the base material. It turned out that This is because the conventional film-in-mold molded article has a weak matrix of acrylonitrile-styrene copolymer, and the butadiene rubber dispersed therein is deformed by the force during molding and oriented in one direction. It is considered that the fracture occurs along the interface between the particles and the matrix.

On the other hand, in the film-in-molded product of the present invention, the above-mentioned matrix is reinforced by setting the molecular weight distribution of the matrix within the above-mentioned specific range, and this reinforced matrix serves to deform and orient the butadiene rubber particles. It seems that it prevents it and realizes excellent adhesion. In addition, a large molecular weight distribution indicates that the dispersion of the molecular weight is large, and that it is widely contained from low molecular weight to high molecular weight, and this relatively large amount of low molecular weight component increases the fluidity of the base material, It is considered to have the effect of making it easier to contact the film.

The film may have a decorative layer formed between the protective layer and the adhesive layer (claim 2). The molding is performed, for example, by previously disposing the film in a mold and injection-molding the synthetic resin material serving as the base material in the mold (claim 3).

The above-mentioned matrix is specifically acrylonitrile-styrene copolymer, acrylonitrile-α.
-Methyl-styrene copolymer, acrylonitrile-styrene-α-methyl-styrene copolymer, and one selected from acrylonitrile-styrene-N-phenylmaleimide copolymer, or two kinds selected from these copolymers and polycarbonate It consists of the above blend (claim 4).

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION An example in which the film-in-molded product of the present invention is applied to a console upper panel will be described below with reference to the drawings. 1A is a front view of the console upper panel P, and FIG. 1B is a partially enlarged cross-sectional view thereof. In the figure, the console upper panel P
Consists of a base material 1 formed into a predetermined shape and a film 2 formed on the entire upper surface thereof. The film 2 is formed by sequentially laminating a print layer 22 as a decorative layer made of vinyl chloride or the like and a vinyl acetate adhesive layer 23 on the surface of the protective layer 21 made of an acrylic resin or the like on the side of the substrate 1. The printing layer 22 is formed, for example, by performing printing such as wood grain on the surface of the protective layer 21, but any color other than wood grain,
Of course, the shape is also good.

The substrate 1 is made of ABS resin.
The ABS resin has a structure in which butadiene rubber particles are dispersed in an AS resin matrix. As the AS resin constituting the matrix, other than the acrylonitrile-styrene copolymer, a modified product thereof, that is, a copolymer or blend of other monomers or polymers for the purpose of improving the physical properties of the polymer itself is used. For example, in order to have heat resistance, α-methylstyrene or N
-Copolymerization of phenylmaleimide or blending of polycarbonate (PC) for improving heat resistance and fluidity. Also, a derivative of an acrylonitrile-styrene copolymer can be used as the matrix. More specifically, acrylonitrile-styrene copolymer, acrylonitrile-α-methyl-styrene copolymer, acrylonitrile-styrene-α-methyl-styrene copolymer, and acrylonitrile-styrene-
One kind selected from N-phenylmaleimide copolymers or a blend of two or more kinds selected from these copolymers and polycarbonate is preferably used.

Further, in the present invention, the molecular weight distribution d of the AS resin constituting the matrix is made to satisfy the following formula (1), 2.18 <d <3.05 (1). The molecular weight distribution d is represented by the following formula (2)
It is represented by Molecular weight distribution d = weight average molecular weight Mw / number average molecular weight Mn (2) Here, a large molecular weight distribution d means that the molecular weight distribution is wide, that is, a wide range of low to high molecular weight components is contained. This means that in the present invention, by setting this in a specific range, the adhesion with the film 2 can be greatly improved. When the molecular weight distribution d is 2.18 or less, there are few low molecular weight components, it is difficult to fuse at the film interface, and it is difficult to secure sufficient adhesiveness. Further, when the molecular weight distribution d is 3.05 or more, the strength of the matrix decreases.

When the console upper panel having the above-mentioned structure is manufactured by film-in-mold molding, first, the surface of the protective layer 21 forming the film 2 is preliminarily printed with a grain tone by a known method, and this printed layer is formed. An adhesive that will become the adhesive layer 23 is applied to the surface of the surface 22 and dried. Then, the film 2 is placed in the mold with the adhesive layer 23 facing up,
The film 14 is brought into close contact with the mold surface by heating and vacuuming. Then, with the film 2 being sucked, the substrate 1
The ABS resin to be formed is melted and injection-molded to be integrated with the film 2. At this time, the temperature of the ABS resin is
Usually, the temperature is set to 240 ° C. or higher, and in order to prevent the orientation of butadiene, it is generally preferable that the temperature of the ABS resin is high. After that, the molded body is taken out of the mold, and the excess film on the outer periphery and the holes is removed to obtain the console upper panel shown in FIG.

The ABS resin used as the base material 1 does not necessarily have to be injection-molded, and at least the surface of the film 2 that comes into contact with the adhesive layer 23 is placed in a molten state in a mold and both are pressure-bonded. You can do it. Further, the decorative layer of the film 2 does not necessarily have to be provided.

[0015]

EXAMPLES As shown in Table 1 below, as a base material 1, acrylonitrile-α-methyl-styrene copolymer, acrylonitrile-styrene-N-phenylmaleimide copolymer, and acrylonitrile-styrene copolymer and polycarbonate were used. The blended product was used to fabricate the console upper panel shown in FIG. Blending of the ABS resin used, molecular weight distribution d of AS resin used as matrix
Is shown in Table 1. In Table 1, the composition and molecular weight distribution d in the case of the polycarbonate blend relate to the ABS resin. Further, for measuring the molecular weight distribution d, a gel permeation chromatography (GPC) device (manufactured by Tosoh Corporation, CC
Using a PM type high performance liquid chromatograph, the molecular weight in terms of polystyrene was measured under the following measurement conditions. Column: shodex KF80M manufactured by Showa Denko KK
× 2 Detector: Waters 991J type photodiode array Solvent: THF

As the film 2, a wood grain print layer 2 made of vinyl chloride is formed on the surface of a protective layer 21 made of an acrylic resin.
Using an acrylic film (film thickness 110 μm) on which 2 (film thickness 2 μm) was formed by printing, a vinyl acetate adhesive was applied on the upper surface of the print layer 22 and dried to form an adhesive layer 23.
The characteristics of the acrylic film used here were as follows. Pencil hardness 2H Transmittance 92.6% Extension 500% at 120 ° C Light resistance Fade meter (83 ° C) 1000H No abnormality

[0017]

[Table 1]

Then, the film 2 was placed in the mold with the adhesive layer 23 facing upward, heated for several seconds with a heater, and then vacuumed to bring the film 2 into close contact with the mold surface. AB having various molecular weight distributions shown in Table 1 while sucking the film 2
The S resin was injected and integrally molded with the film 2. The setting of ABS resin at this time is shown in Table 1. The temperature was set to 243 ° C or 280 ° C. After that, the molded body was taken out from the mold, and the outer periphery and the hole were trimmed.

A cross-cut evaluation test (JIS D 0202) was conducted on each of the obtained molded products to examine the adhesion between the substrate 1 and the film 2, and the results are shown in Tables 2 and 3. The cross-cut evaluation test result shows that the number of peeling was 0 in 100 specimens.
The values are shown as ◯, less than 10 as Δ, and 10 or more as x.

[0020]

[Table 2]

[0021]

[Table 3]

Further, the terminal was resistant to peeling and the IZOD impact value was examined, and the results are shown in Tables 2 and 3 together. The terminal resistance to peeling was evaluated by measuring the resistance to peeling when the film 2 was peeled from the edge in three grades of ◯, Δ, and ×. The evaluation method is shown below. ○ No peeling △ Peeling near the terminal × Peeling near the center of the product

As is apparent from the table, in Examples 1 to 4 in which the molecular weight distribution is within the range of the present invention, peeling did not occur at all in the cross-cut evaluation test regardless of the resin temperature. Further, it can be seen that the terminal has good resistance to peeling and good IZOD impact value, and is superior in adhesiveness and resistant to impact as compared with the comparative example.

2 and 3 show TEM (transmission electron microscope) photographs of the cross sections of the molded articles of Example 1 and Comparative Example 1 described above (magnification: 10,000 times). In the figure, the protective layer 21, the print layer 22, the adhesive layer 23, and the base material 1 are shown in order from the top layer. In the base material 1 as the bottom layer, butadiene rubber particles are dispersed in a matrix of AS resin. There is. As shown in the figure, in the molded body of Example 1, the butadiene rubber particles dispersed in the matrix of the AS resin are spherical, whereas in the molded body of Comparative Example 1, the butadiene rubber particles are different in pressure during molding. It can be seen that it deforms and has an elliptical shape that is long in the left-right direction.

4 and 5 show TEM photographs of the bonded portions of the molded articles of Example 1 and Comparative Example 1 after the cross-cut evaluation test (magnification: 10,000 times). As is clear from the comparison of the figures, the molded body of Example 1 does not peel at all, whereas the molded body of Comparative Example 1 has fractured in the lowermost base material 1. This is because, in the molded body of Comparative Example 1, the butadiene rubber particles were oriented in the left and right directions as shown in FIG. 3, so that the breakage easily proceeded along the interface between the butadiene rubber particles and the matrix, and peeling occurred. It is considered to be a thing.

As described above, the film-in-molded product of the present invention has excellent adhesion between the film and the substrate, and does not peel even after long-term use. Therefore, it is preferably used for interior materials such as console upper panels of automobiles,
It exhibits high durability over a long period of time and has an excellent appearance.

[Brief description of the drawings]

FIG. 1 (a) is a front view of a console upper panel of an automobile showing an embodiment of the present invention, and FIG. 1 (b) is a sectional view taken along line Ib-Ib of FIG. 1 (a).

FIG. 2 is a photomicrograph (magnification: 10000 times) showing the structure of the cross section of the molded body of Example 1.

FIG. 3 is a micrograph (magnification: 10,000 times) showing a structure of a cross section of a molded body of Comparative Example 1.

FIG. 4 is a micrograph (magnification: 10000) showing the structure of the cross section of the bonded part of the molded body of Example 1 after the cross-cut evaluation test.
Times).

FIG. 5 is a micrograph showing a structure of a cross section of an adhesive part of a molded body of Comparative Example 1 after a cross-cut evaluation test (magnification: 10,000).
Times).

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base material 2 Film 21 Protective layer 22 Printing layer (decoration layer) 23 Adhesive layer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasushi Iwata Aichi Prefecture Nishikasugai-gun Kasuga-cho Ochiai letter Nagachibata No. 1 in Toyoda Gosei Co., Ltd. (72) Inventor Yama ▲ Saki ▼ Chiho Aichi Prefecture Kasugai-gun Ochiai letter Nagahata No. 1 in Toyoda Gosei Co., Ltd. (72) Inventor Tomoko Miyake Ochiai, Kasuga-cho, Nishikasugai-gun, Aichi Nagahata No. 1 Toyoda Gosei Co., Ltd. (72) Inventor Ken Watanabe, Kasuga-cho, Nishi-Kasugai-gun, Aichi Pref. No. 1 within Toyoda Gosei Co., Ltd.

Claims (4)

[Claims] 1. In a mold, a synthetic resin material as a base material is brought into close contact with a film made of a synthetic resin in a state where at least a contact surface with the film is melted,
A film-in-mold molded body in which the both are integrated, wherein the film has at least a protective layer and an adhesive layer located between the protective layer and the base material, and the base material is an acrylonitrile-styrene copolymer. The butadiene rubber particles are dispersed in a matrix composed of a polymer or a modified product or derivative thereof, and the acrylonitrile-styrene copolymer serving as the matrix or a modified product or derivative thereof has a molecular weight distribution d of 2.18 <d <. 3.05
The film-in-mold molded body is characterized by: 2. The film-in-molded article according to claim 1, wherein the film has a decorative layer formed between the protective layer and the adhesive layer. 3. The film-in-molded product according to claim 1, which is obtained by injection-molding a synthetic resin material serving as the base material in a mold in which the film is arranged in advance. 4. The matrix is acrylonitrile-styrene copolymer, acrylonitrile-α-methyl-
Styrene copolymer, acrylonitrile-styrene-α-
The film-in according to any one of claims 1 to 3, comprising one selected from a methyl-styrene copolymer and an acrylonitrile-styrene-N-phenylmaleimide copolymer, or a blend of two or more selected from these copolymers and a polycarbonate. Molded body.