Metallic decoration film, metallic interior/exterior member for vehicle, and metallic molded body

Abstract

Provided is a metallic decoration film, having a protective layer, an anchor layer, a metal deposition layer, and a bonding layer. The metal deposition layer comprises indium, the protective layer comprises a first mixed resin layer and a second mixed resin layer, the second mixed resin layer is provided on the anchor layer side, the first mixed resin layer comprises a vinylidene fluoride-based resin and an acrylic acid ester-based resin, the second mixed resin layer comprises a vinylidene fluoride-based resin and an acrylic acid ester-based resin, a solid content concentration ratio (% by mass) of the vinylidene fluoride-based resin to the acrylic acid ester-based resin in the first mixed resin layer is 75:25 to 60:40, and a solid content concentration ratio (% by mass) of the vinylidene fluoride-based resin to the acrylic acid ester-based resin in the second mixed resin layer is 15:85 to 60:40.

Claims

1. A metallic decoration film comprising: a protective layer; an anchor layer; a metal deposition layer; and a bonding layer, wherein: the protective layer, the anchor layer, the metal deposition layer, and the bonding layer are arranged in the stated order; the metal deposition layer comprises indium; the protective layer comprises a first mixed resin layer and a second mixed resin layer; the second mixed resin layer is provided on the anchor layer side; the first mixed resin layer comprises a vinylidene fluoride-based resin and an acrylic acid ester-based resin; the second mixed resin layer comprises a vinylidene fluoride-based resin and an acrylic acid ester-based resin; a solid content concentration ratio (% by mass) of the vinylidene fluoride-based resin to the acrylic acid ester-based resin in the first mixed resin layer is 75:25 to 60:40; a solid content concentration ratio (% by mass) of the vinylidene fluoride-based resin to the acrylic acid ester-based resin in the second mixed resin layer is 15:85 to 60:40; the anchor layer comprises an acrylic polyol resin as a main agent and an isocyanate-based resin as a curing agent; and an adhesion between the second mixed resin layer and the anchor layer is from 2.6 N/15 mm to 3.8 N/15 mm, measured in accordance with a 180-degree peeling test.

2. The metallic decoration film of claim 1, wherein the anchor layer comprises an acryl-based resin.

3. The metallic decoration film of claim 1, wherein the second mixed resin layer comprises an ultraviolet absorber.

4. The metallic decoration film of claim 1, wherein the second mixed resin layer comprises a cross-linked acryl-based fine particle filler.

5. The metallic decoration film of claim 1, the vinylidene fluoride-based resin is polyvinylidene fluoride, and the acrylic acid ester-based resin is polymethyl methacrylate.

6. The metallic decoration film of claim 1, wherein an adherend is provided on the bonding layer.

7. A metallic interior/exterior member for a vehicle, the metallic interior/exterior member comprising the metallic decoration film of claim 1.

8. A metallic molded body comprising the metallic decoration film of claim 1.

9. The metallic decoration film of claim 1, wherein: the bonding layer is in contact with the metal deposition layer; and an adherend is in contact with the bonding layer on a side opposite the metal deposition layer, the adherend having a thickness from 0.3 to 3 mm.

Description

EXAMPLE

(1) Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to these Examples. Unless otherwise limited, % means % by mass, and part means part by mass.

Example 1

(2) A protective layer was prepared which consists of a first mixed resin layer (a concentration ratio (%) of polyvinylidene fluoride to polymethyl methacrylate=75:25, thickness: 13 ?m) and a second mixed resin layer (a concentration ratio (%) of polyvinylidene fluoride to polymethyl methacrylate=20:80, thickness: 27 ?m). Using a gravure coater, an anchor coating agent solution mixed with acrylic polyol-based coating material and an isocyanate-based coating material so as to have 1.3 ?m after drying is applied to the protective layer, which was then dried at 100? C. for 1 minute to form an anchor layer. Next, a metal deposition layer was formed on the anchor layer by a vacuum deposition method so that a thickness of the metal deposition layer made of indium becomes 40 nm. A bonding layer (acrylic resin, thickness: 25 ?m) was bar-coated on the metal deposition layer, and a separator was provided on the bonding layer to produce a film of Example 1.

Examples 2 to 6, Comparative Examples 1 to 6

(3) According to the formulation shown in Table 1, a film was produced by the similar method as in Example 1 except that a concentration ratio of polyvinylidene fluoride to polymethyl methacrylate which both constitute the protective layer was adjusted.

(4) TABLE-US-00001 TABLE 1 First mixed resin layer Second mixed resin layer Evaluation result Thickness Thickness Chemical Adhesion PVDF PMMA (?m) PVDF PMMA (?m) Appearance resistance N/15 mm) Comparative example 1 100 0 31 0 100 7 X ? 0.9 Comparative example 2 80 20 17 20 80 33 X ? 3.4 Example 1 75 25 13 20 80 27 ? ? 3.4 Example 2 70 30 13 20 80 27 ? ? 3.4 Example 3 65 35 13 20 80 27 ? ? 3.4 Example 4 60 40 13 20 80 27 ? ? 3.4 Comparative example 3 50 50 13 20 80 27 ? ? 3.4 Comparative example 4 70 30 13 10 90 27 ? ? 1.1 Example 5 70 30 13 30 70 27 ? ? 2.6 Example 6 70 30 13 60 40 27 ? ? 3.8 Comparative example 5 70 30 13 65 35 27 ? ? 0.7 Comparative example 6 70 30 13 70 30 27 ? ? 1.1

(5) The films obtained in Examples 1 to 6 and Comparative examples 1 to 6 were evaluated for appearance, chemical resistance, and adhesion according to the following methods. The results are shown in Table 1.

(6) <Appearance Evaluation>

(7) Each film was attached to an adherend (a transparent ABS sheet, thickness: 300 ?m). It was heated to a sheet temperature at 140? C. using a tabletop vacuum tester (V. former, manufactured by Rayama Pack Co., Ltd.), and then molded so that a draw ratio became 120%. A metallic luster and cloudiness of the molded film (metallic molded body) were visually evaluated under outdoor sunlight.

(8) (Evaluation Criteria)

(9) ?: The film had a metallic luster and no cloudiness.

(10) ?: The film had a metallic luster and slight cloudiness, which was though within a permissible range.

(11) x: The film had no metallic luster and had cloudiness.

(12) <Chemical Resistance>

(13) Each film was attached to an adherend (an acrylic plate (opaque), Acrylite EX432, manufactured by Mitsubishi Chemical Corporation, thickness: 3 mm), and 0.5 g of a sunscreen cream, Neutrogena (Registered Trademark) Ultra Sheer SPF45 manufactured by Johnson & Johnson K. K. was applied to a 10 cm square area of the film, and the film was placed in a dryer whose temperature was set to be 55? C. for 4 hours. Then, Neutrogena was washed with water to be removed, and appearance of the film surface was evaluated.

(14) (Evaluation Criteria)

(15) ?: The film had no trace of sunscreen cream application.

(16) ?: The film had trace of sunscreen cream application.

(17) <Adhesion>

(18) A vinyl chloride sheet was thermocompression-bonded on the metal deposition layer of each film at 125? C. for 2 seconds, and then cut into a width of 15 mm to produce each sample. Then, a 180-degree peeling test was performed with an autograph (AGX-50kNVD manufactured by Shimadzu Corporation) to measure an adhesion between the second mixed resin layer and the anchor layer.

(19) As shown in Table 1, any of the films of Examples 1 to 6 did not cause cloudiness or the like, or even if they did, cloudiness was within a permissible range, and the films had an excellent metallic appearance. Moreover, the films of Examples 1 to 6 were excellent in chemical resistance and adhesion. On the other hand, the films of Comparative examples 1 and 2, in which a concentration ratio of the vinylidene fluoride-based resin in the first mixed resin layer was large, caused cloudiness and had a poor appearance. Furthermore, in the films of Comparative examples 1, 4 to 6, a concentration ratio of the acrylic acid ester-based resin in the second mixed resin layer was large, and therefore adhesion between the second mixed resin layer and the anchor layer was poor. Furthermore, the film of Comparative example 3, in which the concentration ratio of the vinylidene fluoride-based resin in the first mixed resin layer was small, was inferior in chemical resistance. In addition, in the films of Comparative examples 5 and 6, the concentration ratio of the acrylic acid ester-based resin in the second mixed resin layer was small, and therefore adhesion between the second mixed resin layer and the anchor layer was poor.

(20) <Appearance Evaluation on Satin-Like Metallic Molded Body>

Reference Example 1

(21) A protective layer was prepared which consists of a first mixed resin layer (a concentration ratio (%) of polyvinylidene fluoride to polymethyl methacrylate=90:10, comprising 3% by mass of GANZPEARL GM-0105 (particle size: 2 ?m) manufactured by Aica Kogyo Company, Limited, as a fine particle filler, thickness: 17 ?m) and a second mixed resin layer (a concentration ratio (%) of polyvinylidene fluoride to polymethyl methacrylate=0:100, thickness: 33 ?m). Using a gravure coater, an anchor coating agent solution mixed with acrylic polyol-based coating material and an isocyanate-based coating material so as to have 1.3 ?m after drying is applied to the protective layer, which was then dried at 100? C. for 1 minute to form an anchor layer. Next, a metal deposition layer was formed on the anchor layer by a vacuum deposition method so that a thickness of the metal deposition layer made of indium becomes 40 nm. A bonding layer (acrylic resin, thickness: 25 ?m) was bar-coated on the metal deposition layer, and a separator was provided on the bonding layer to produce a film of Reference example 1. Besides, in Reference examples, as the second mixed resin layer, one that does not comprise polyvinylidene fluoride is used so that an evaluation result for an appearance evaluation in the satin-like metallic molded body can be remarkably expressed.

Reference Examples 2 to 14

(22) According to the formulations shown in Table 2, a film was produced by the similar method as in Reference example 1 except that presence/absence, types, particle sizes, and addition amounts of fine particles to be added to the first mixed resin layer and the second mixed resin layer were adjusted. Besides, in Table 2, among the types of fine particles, A is a crosslinked acryl-based fine particle manufactured by Aica Kogyo Company, Limited, and B is a polysiloxane fine particle manufactured by Aica Kogyo Company, Limited. Of the particle sizes, Small represents 2 ?m and Medium represents 3 ?m. Of the addition amounts, Little represents 3% by mass and Much represents 5% by mass.

(23) TABLE-US-00002 TABLE 2 First mixed resin layer Second mixed resin layer Fine particle Fine particle Evaluation Particle Addition Particle Addition result PVDF PMMA Type size amount PVDF PMMA Type size amount Appearance Reference 90 10 A Small Little 0 100 None ? example 1 Reference 90 10 A Medium Little 0 100 ? example 2 Reference 90 10 B Small Much 0 100 ? example 3 Reference 90 10 B Medium Much 0 100 ? example 4 Reference 90 10 None 0 100 A Small Medium ? example 5 Reference 90 10 0 100 A Medium Medium ? example 6 Reference 90 10 0 100 B Small Medium X X example 7 Reference 90 10 0 100 B Medium Medium X X example 8 Reference 90 10 0 100 B Small Little X example 9 Reference 90 10 0 100 B Medium Little X example 10 Reference 90 10 0 100 B Small Medium X X example 11 Reference 90 10 0 100 B Medium Medium X X example 12 Reference 90 10 0 100 B Small Little X example 13 Reference 90 10 0 100 B Medium Little X example 14

(24) Appearance evaluations were performed on the films obtained in Reference examples 1 to 14 according to the following method. The results are shown in Table 2.

(25) <Appearance Evaluation>

(26) Each film was attached to an adherend (a transparent ABS sheet, thickness: 300 ?m). It was heated to a sheet temperature at 140? C. using a tabletop vacuum tester (V. former, manufactured by Rayama Pack Co., Ltd.), and then molded so that a draw ratio became 120%. A metallic luster and cloudiness of the molded film (metallic molded body) were visually evaluated under outdoor sunlight.

(27) (Evaluation Criteria)

(28) ?: The film had an equivalent appearance as a plated satin.

(29) ?: The film had a slightly inferior metallic luster as compared with the plated satin, but had no cloudiness.

(30) ?: The film had an inferior metallic luster as compared with the plated satin, but had no cloudiness.

(31) x: The film had an inferior metallic luster as compared with the plated satin, and had cloudiness.

(32) xx: The film had an inferior metallic luster as compared with the plated satin, and had a strong cloudiness.

(33) As shown in Table 2, the films obtained in Reference examples 5 and 6 comprised a cross-linked acryl-based fine particle as a fine particle, and as a result, could express a satin-like appearance without cloudiness or the like.