JP2002355912A - Brilliant laminated film and brilliant molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a brilliant laminated film and a brilliant molded product having stainless steel gloss and excellent in weatherability and corrosion resistance. SOLUTION: In the brilliant laminated film constituted by successively laminating a transparent surface substrate (1), a metal vapor deposition layer 2, an adhesive layer (3) and a backing material (4) and providing a protective substrate (b) on the surface of the transparent surface substrate (1) through an adhesive layer (a), a hue angle (H deg.), at a time when the hue on the side of transparent surface substrate (1) of the laminated film is measured in the L*C*H deg. color specification mode of a hue color-difference meter, is 245-265.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glitter laminate film for decoration and a glitter molded article having metallic luster, weather resistance and corrosion resistance.

[0002]

2. Description of the Related Art Conventionally, there has been a molding for automobile parts as a brilliant molded product.
It is roughly classified into a molding type and a film type using a laminated film. As the latter film type, for example, a metallized layer is formed on the back side of a transparent polyester resin film by vapor deposition of aluminum or sputtering of chromium, and if necessary, bonded to a backing material (for example, vinyl chloride resin), and then molded. It is formed by being applied at the time of molding (for example, at the time of extrusion molding). Then, the metallic luster of the glittering product is obtained by the light reflection of the metallized layer.

[0003] However, the molding using this kind of film uses aluminum or chromium as the metallized layer, so that the luster becomes whitish when aluminum is used, and reverse when chromium is used. There is a problem that the metallic luster is poor because it is shining black. For this reason, there have been many demands for the user's preference for stainless luster, which is an intermediate luster between aluminum luster and chrome luster, among metallic lusters.
Japanese Patent Application Laid-Open No. 9-135257 proposes to solve the above-mentioned problem by molding using a film formed by sputtering a chromium-iron alloy (for example, SUS430).

However, for example, SUS430 is stainless steel in which 18% chromium is alloyed with iron, and most of the components are made of iron, and it is known that corrosion resistance is poor. Further, from the viewpoint of corrosion resistance, it is known that the aluminum vapor-deposited film also has poor corrosion resistance.

On the other hand, sputtering of Hastelloy alloy is disclosed in Japanese Patent Publication No. Hei.
Although it is publicly known from Japanese Patent No. 51134, there is no metal luster for stainless steel luster.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a glitter laminated film having a stainless steel luster, excellent weather resistance and corrosion resistance, and a glitter molded article using the glitter laminated film. And

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the transparent surface substrate (1) in the L ^* C ^* H ° colorimetric mode of the colorimeter. The hue angle (H °) when the color was measured on the side was in the range of 245 to 265, and it was found that the above object can be achieved by using a glittering laminated film having a metal vapor-deposited layer having excellent corrosion resistance. The present invention has been made.

That is, aspects of the present invention are as follows. 1. The transparent surface substrate (1), the metal deposition layer (2), the adhesive layer (3), and the backing material (4) are sequentially laminated, and the transparent surface base is set in the L ^* C ^* H ° colorimetric mode of the colorimeter. The hue angle (H °) when the color of the material (1) is measured is from 245 to 2
65. A glittering laminated film having a range of 65. 2. Thickness 15 to 1 in which the transparent surface substrate (1) has weather resistance
Wherein the metal of the metal deposition layer (2) is a Hastelloy alloy, and the backing material is a polyolefin-based, ABS-based or vinyl chloride-based film having a thickness of 30 to 500 µm ( The glittering laminated film according to 1). 3. (1) or (2), wherein an adhesive layer (a) and a protective substrate (b) having a thickness of 9 to 100 μm are sequentially laminated on the transparent surface substrate (1). The glittering laminated film according to the above. 4. The transparent surface substrate (1), the metal deposition layer (2), the adhesive layer (3), and the backing material (4) are sequentially laminated, and the transparent surface substrate is set in the L ^* C ^* H ° colorimetric mode of the colorimeter. The hue angle (H °) when the color of the material (1) is measured is from 245 to 2
A glittering molded product characterized by using a laminated film having a range of 65. 5. The glitter according to (4), wherein an adhesive layer (a) and a protective substrate (b) having a thickness of 9 to 100 μm are sequentially laminated on the transparent surface substrate (1). Molding.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. However, the present invention is not limited at all by these specific examples. FIG. 1 is a schematic sectional view showing the layer structure of the glittering laminated film of the present invention. The transparent surface substrate (1) is made of, for example, a polyester resin,
An aromatic polyester resin such as polyethylene terephthalate and polybutylene terephthalate, and a copolymer component may be contained. In addition, since weather resistance is required, the sunshine weather meter 200 as a single substrate is used.
ΔE by the 0 hour treatment is preferably at least 3 or less.

[0010] The thickness of the transparent surface substrate (1) is 15 to 10
0 μm is preferred, more preferably 25 to 75 μm,
When the thickness is reduced, performance such as weather resistance becomes a problem, and when the thickness is increased, the cost increases. Further, the surface side of the base material may be subjected to a lubricating treatment in order to improve the processability, and the metal deposition surface side may be subjected to a primer treatment.

As a method for forming the metal thin film of the metal deposition layer (2), a physical film formation method such as a sputtering method, an electron beam evaporation method, and an ion plating method is preferably used. The thickness of the metal deposition layer is preferably in the range of 150 to 750 °, more preferably 200 to 5 °.
Desirably, it is 00 °. If it is 750 ° or more, cracks are easily generated in the metal deposition layer, which is not preferable from the viewpoints of appearance, manufacturing, and cost. On the other hand, 150Å
In the following, the intended glitter film cannot be obtained.

As for the metal species, for example, Hastello
Not only alloy but also color difference meter L ^*C^*H ° color mode
Angle when the color of the transparent surface substrate (1) side is measured by using
If (H °) is in the range of 245 to 265,
Preferably, if within the range of 250 to 260,
Metal species can also be used. However, corrosion resistance,
Hastelloy alloy that needs weatherability, water resistance, heat resistance, etc.
It is generally known that they have excellent corrosion resistance and the like. C
As the stelloy alloy, for example, C-22 can be mentioned.

The adhesive layer (3) is a layer for bonding the metal deposition layer (2) and the backing material (4), and can be applied by a dry laminator. As the adhesive, a two-component polyurethane adhesive or the like can be used.
Heat resistance, water resistance and the like are required, and a heat stabilizer and the like are added as necessary. It is desirable that the thickness after coating and drying is 1 to 10 μm, more preferably 2 to 7 μm. If it is 1 μm or less, satisfactory adhesive strength cannot be obtained, and if it is 10 μm or more, it is not preferable from the viewpoint of manufacturing and cost.

The backing material (4) is selected from the viewpoint of adhesiveness to a material used for attaching or covering the glittering laminated film of the present invention. For example, when a vinyl chloride resin is used in extrusion molding, a vinyl chloride resin film is also used as a backing material. As materials, besides vinyl chloride resin,
Due to the recent effects of non-vinylation, among polyolefin resins, particularly polypropylene resins and resins containing copolymer components have been used, and in addition, ABS resins and the like may be used as polymer alloy resins. Since heat resistance, water resistance and the like are required as required performance, a heat stabilizer and the like may be contained.

The thickness of the backing material is 30 to 500 μm,
Preferably, it is 50 to 300 μm, and if it is 30 μm or less, the adhesion performance is not satisfactory, and if it is 500 μm or more, it is not preferable from the viewpoint of manufacturing and cost. Further, the backing material may be subjected to a primer treatment on the side opposite to the metal-deposited layer in order to improve the adhesion to a material used in the post-processing.

The protective substrate (b) is for the purpose of preventing the transparent surface substrate (1) from being damaged during a post-processing step or during transportation and storage, and comprises a polyester resin film or a polyester containing a copolymer component. A base resin film or a polypropylene resin film can be used. The thickness of the protective substrate is 9 to 100 μm, more preferably 12 to 100 μm.
If the thickness is 75 μm and the thickness is 9 μm or less, the protection performance cannot be satisfied.
If it is 100 μm or more, it is not preferable from the viewpoint of cost.

The adhesive layer (a) is a layer for adhering the protective substrate (b) and the transparent surface substrate (1). The adhesive layer (a) does not easily peel off from the protective substrate (b). Transparent surface substrate (1)
Means that the adhesive does not peel off during the processing step, but needs an adhesive strength that can be easily peeled off when necessary.
There are two processing methods for the adhesive layer (a) as described below, and the material used varies depending on the processing method, but either processing method can be adopted.

The first method is to use a polyethylene resin as an adhesive material by extrusion lamination.
The protective base material (b) is subjected to corona treatment and anchor coat treatment as necessary, and the protective base material (b) and the transparent surface base material (1) are laminated by a melt-extruded polyethylene resin film. A film is obtained. In this case, the thickness of the polyethylene resin film is 1
5 to 30 μm is preferred.

The second method is dry lamination,
This is a method of using an adhesive as an adhesive material. After applying a corona treatment to the protective substrate (b) as required, for example, an acrylic adhesive is applied with a dry laminator, dried, and then the transparent surface substrate ( By laminating with 1), a laminated film is obtained. In this case, the thickness of the adhesive is 1 to
5 μm is preferred. In addition, for the molding process, there are cases where only extrusion molding or injection molding is performed, and cases where terminal molding is performed after extrusion molding is performed, and injection molding is performed after vacuum molding is performed. In some cases.

Hereinafter, the present invention will be described with reference to examples.

Example 1 As a transparent surface substrate (1), a polyester film having a thickness of 50 μm (Tefle manufactured by Teijin Dupont Co., Ltd.)
x) and a Hastelloy alloy (C
-22; main component Ni, Mo 12.5 to 14.5%, Cr
20.0 to 22.5%, W2.5 to 3.5%, Fe4 to
(6%, etc.), a metallized layer having a thickness of 350 ° was formed, and a two-part curable urethane-based adhesive was applied to the surface thereof by a dry laminator and dried to form an adhesive layer having a thickness of 4 μm. This was adhered to a corona-treated surface of a polypropylene resin film having a thickness of 150 μm as a backing material to produce a glittering laminated film.

[0021]

Example 2 A glittering laminated film was produced in the same manner as in Example 1 except that a soft vinyl chloride resin (thickness: 150 μm) was used as a backing material.

[0022]

Comparative Example 1 A glittering laminated film was produced in the same manner as in Example 1 except that a metallized layer was formed by sputtering of Cr.

[0023]

Comparative Example 2 A glittering laminated film was produced in the same manner as in Example 1 except that a metallized layer was formed by sputtering of Cr and a soft vinyl chloride resin (thickness: 150 μm) was used as a backing material.

[0024]

Comparative Example 3 For comparison, a metal plate for SUS molding (SUS430M) was obtained and used as a sample for evaluation. (The design surface was used as the evaluation surface.) The glittering laminated films and comparative samples of Examples 1 and 2 and Comparative Examples 1, 2, and 3 were measured by the following evaluation items and evaluation methods. Table 1 shows the results of the comparative evaluation.
As for the initial peel strength and the heat resistance, Examples 1 and 2 and Comparative Examples 1 and 2 showed good results, but the hue angle was different between Examples 1 and 2 and Comparative Examples 1 and 2. The values of Examples 1 and 2 are close to those of Comparative Example 3.

Evaluation Items and Evaluation Method [Thickness] Five points in the width direction were measured with a thickness gauge, and the average value was obtained (unit: μm). [Initial Peeling Strength] The interlayer peeling strength of the laminated film was measured using a sample width of 25 mm, 180 ° peeling, and a tensile speed of 50 mm / m.
In was measured in, and the average value at five points in the width direction was obtained. (Unit m
N / 25mm width)

[80 ° C. hot strength] The initial peel strength was measured in the same manner as in the method of measuring the initial peel strength except that it was measured in an atmosphere of 80 ° C. (Unit: mN / 25 mm width) [Breaking strength] Sample width 25 mm, chuck distance 100 m
m, measured at a tensile strength of 50 mm / min, and taken as an average value at five points in the width direction. (Unit MPa)

[Elongation] The elongation was measured at a sample width of 25 mm, a distance between chucks of 100 mm, and a tensile strength of 50 mm / min. (Unit%) [Thermal shrinkage] A sample of 10 cm square was collected and measured at 135 ° C.
After treatment in an oven for 30 minutes, the length in the MD direction was measured, and the average value was obtained at three points in the width direction. (Heat resistance) After heat treatment at 80 ° C. for 400 hours, it was measured according to the measurement method of initial peel strength. (Unit mN / 25m
m width)

[Lightness] Color difference meter CR manufactured by Minolta Co., Ltd.
Using -321, the color was measured in the L ^* C ^* H ° colorimetric mode (average value of n = 10). [Saturation] Using a colorimeter CR-321 manufactured by Minolta Co., Ltd., the color was measured in the L ^* C ^* H ° colorimetric mode (n = 10).
Average). [Hue angle] Color-difference meter CR-321 manufactured by Minolta Co., Ltd.
Was used to measure the color in the L ^* C ^* H ° colorimetric mode (n =
10 average). (Unit °)

[0029]

Example 3 As a protective substrate (b), a polyester film having a thickness of 25 μm (Tefle manufactured by Teijin Dupont Co., Ltd.)
x), which has been subjected to corona treatment and anchor coating treatment, and has a thickness of 50 as a transparent surface substrate (1).
μm polyester film (manufactured by Teijin DuPont)
Teflex) and a melt-extruded polyethylene resin film (thickness: 20 μm) to obtain a laminated film. A glittering laminated film was produced in the same manner as in Example 1 except that this laminated film was used as the transparent surface substrate (1). A sample having a width of 25 mm and a length of 100 mm was prepared from the glittering laminated film with the protective base material (b), and the protective base material (b) was peeled off by hand. According to the measurement method of the initial peel strength, when the strength of the portion easy to peel was measured,
The strength was 90 mN / 25 mm width.

[0030]

[Table 1]

[0031]

The brilliant laminated film of the present invention has a higher stainless steel gloss than conventional ones, and is excellent in weather resistance and corrosion resistance, contributing to the production of a SUS molding film currently used. can do.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing a layer configuration of a glittering laminated film of the present invention. The protective substrate (b) and the adhesive layer (a) are protective portions, and are finally removed and removed.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Koichi Shoko 2102 Hiratsuka, Oaza, Ageo-shi, Saitama Asahi Kasei Pax Co., Ltd. (72) Inventor Seinosuke Mizuno 1-8-8 Kameido, Koto-ku, Tokyo Mitsui Life 9F Kameido Building (72) Inventor Masahiro Nakai 6-12-1, Ayase, Adachi-ku, Tokyo F-term (reference) 4F100 AB01B AB31B AK03D AK07 AK15D AK41A AK51 AK74D AR00D AR00E BA04 BA05 BA07 BA10A BA10D BA10E CB00H EC36 E02B02E JL09A JN01A JN24 YY00A YY00D YY00E

Claims (5)

[Claims] 1. A transparent surface substrate (1), a metal deposition layer (2), an adhesive layer (3), and a backing material (4) which are sequentially laminated, and a colorimetric L ^* C ^* H ° colorimeter. Hue angle (H °) when color is measured on the transparent surface substrate (1) side in mode
Is in the range of 245 to 265. 2. The transparent surface substrate (1) is a polyester film having a weather resistance of 15 to 100 μm in thickness,
The metal of the metal deposition layer (2) is a Hastelloy alloy, and the backing material is a polyolefin-based material having a thickness of 30 to 500 μm;
The glittering laminated film according to claim 1, which is an ABS-based or vinyl chloride-based film. 3. An adhesive layer (a) and a protective substrate (b) having a thickness of 9 to 100 μm are sequentially laminated on the transparent surface substrate (1). The glittering laminated film according to claim 2. 4. A transparent surface substrate (1), a metal deposition layer (2), an adhesive layer (3), and a backing material (4) which are sequentially laminated, and a colorimetric L ^* C ^* H ° colorimeter. Hue angle (H °) when color is measured on the transparent surface substrate (1) side in mode
Wherein a laminated film having a range of 245 to 265 is used. 5. The method according to claim 4, wherein an adhesive layer (a) and a protective substrate (b) having a thickness of 9 to 100 μm are sequentially laminated on the transparent surface substrate (1). The glittering molded article according to the above.