KR100728847B1 - Display member having metallic luster - Google Patents

Abstract

SUMMARY OF THE INVENTION An object of the present invention is to provide a display member having a metal film which is flexible and has excellent bend surface suitability and durability. The display member having a metal film sequentially includes a base material, a metal layer and a transmissive layer, the display member further comprises an adhesive layer on a side opposite the metal layer of the base material, the metal layer is an indium deposited film provided on the surface of the transmissive layer, The deposited film has a visible light transmittance of 6% or less and a thickness of 600 angstroms or less.

Base material, metal layer, transmission layer, adhesive layer, indium deposited film

Description

DISPLAY MEMBER HAVING METALLIC LUSTER}

The present invention relates to a display member having a metal coating. More particularly, the present invention relates to a flexible display member having a metal coating that can be adapted to various curved surfaces as an outer surface material of automobiles, motorcycles, and the like.

Display members such as emblems attached to the vehicle body of automobiles have been produced so far by plating chromium on a substrate made of a rigid resin such as, for example, ABS resin. However, such display members are made to correspond to the curvature of the adhesive end face because they are generally rigid and have low flexibility because of their rigid substrate. Thus, it was impossible to apply to surfaces with different curvatures. In other words, novel display members having different curvatures corresponding to the adhesive end faces have been produced.

In order to solve this problem, it has been proposed to give flexibility to the entire display member by using a flexible resin as the substrate. For example, Japanese Patent Application Laid-open No. 9-152838 proposes a flexible decorative mark having a glossy color formed by adhering a decorative film provided with a metal deposition layer on a flexible substrate. Since the entire flexible decorative mark is formed of a flexible material, the flexible decorative mark can be applied to each surface of the motor vehicle accordingly.                 

Japanese Patent Application Laid-Open No. 11-50026 is produced by laminating a flexible base layer made of a thermoplastic synthetic resin sheet on the back side of a thermoplastic synthetic resin film having a metal film on its back and punching the laminate into a predetermined shape. A structural member for three-dimensional display is proposed. Such structural members can be adapted to various curved surfaces because the entire structural member is formed of a flexible material.

In the flexible decorative marks disclosed in Japanese Patent Application Laid-open No. 9-152838, tin, chromium, aluminum and silver are listed as the metal constituting the metal deposition layer. However, the following problems arise when using metal as the metal deposition layer. Since the end of the metal deposition layer is exposed at the end of the flexible decorative mark, and tin is essentially soluble in alkali, the end is corroded by acid or alkali and corrosion proceeds into the layer. Since chromium exhibits a darker metal film than in the case of tin, it is therefore impossible to obtain an appearance with an excellent bright metal film, and has a low malleability and, for example, the color of the metal itself in areas where the film extends greatly in the shape of the decorative mark. This changing phenomenon, whitening, occurs. In the case of aluminum, an appearance having an excellent bright metal film can be obtained, but whitening is likely to occur during formation, and corrosion is likely to occur in use. Also in the case of silver, an appearance having an excellent bright metal film can be obtained, but darkening occurs by reaction with sulfur in the air, and similarly to tin, the acid resistance and alkali resistance are low.

In the structural member for three-dimensional display disclosed in Japanese Patent Application Laid-Open No. 11-50026, tin or indium is proposed as a metal because the appearance is damaged by corrosion when aluminum is used as the metal coating. However, when using tin as the metal, the problem of corrosion as described above occurs. And natural climate test, salt water coating test, immersion test and moisture resistance test by the tin deposition layer composed of microstructures that easily break the tin deposit layer itself and combined the major defects such as plastic film cracking and the success of tin aggregation after the immersion test. Happens after such. In addition, in the structural member for three-dimensional display, metal is deposited to have a visible light transmittance of 8 to 17% to form a metal film. However, when the visible light transmittance is higher than 8%, the color of the base layer disposed under the metal luster layer applied to the three-dimensional display member, the color of the adhesive layer disposed under the base layer, or the color of the adhesive end surface can be seen through Due to the influence of these colors, the desired metallic color tone is often not reproduced. Since the three-dimensional display member is manufactured by stacking a base layer on a thermoplastic synthetic resin film having a metallic gloss film to form a laminate and punching the laminate into a desired shape, the cross-sectional shape of the resulting structural member is merely a layer shape and a complex three-dimensional shape. It is impossible to represent the shape. The area of the exposed portion increases at the end, so that the metallic luster layer is susceptible to corrosion.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide a three-dimensional display member which is flexible, has excellent curved surface suitability and durability, and can exhibit various three-dimensional shapes.

According to the present invention, the above object is a display member having a metal film sequentially comprising a substrate, a metal layer and a transmission layer, the display member further comprising an adhesive layer on the side opposite to the metal layer of the substrate, wherein the metal layer is a transmission layer. An indium deposited film provided on the surface of the film, and the indium deposited film can be obtained by a display member having a metal film having a visible light transmittance of 6% or less and a thickness of 600 Angstrom or less.

As a result of various studies on the metal constituting the metal layer, according to the display member of the present invention, the highest durability such as weather resistance, salt water resistance, acid resistance, alkali resistance, water resistance and moisture resistance can be obtained by the use of indium and The desired metal color tone can be reproduced, and furthermore, the corrosion resistance can be improved by adjusting the visible light transmittance of the metal layer to 6% or less and the thickness to 600 angstroms or less. The entire three-dimensional display member can be made flexible, and flexion surface suitability can be obtained by using a flexible thermoplastic resin as the substrate, and in addition, the three-dimensional appearance can be obtained by forming the substrate by injection molding. have.

1 is a cross-sectional view showing one embodiment of a display member having a metal film according to the present invention.

2 is a cross-sectional view showing another embodiment of a display member having a metal film according to the present invention.

1 is a cross-sectional view showing a preferred embodiment of a display member according to the present invention. Fig. 2 is a sectional view showing another preferred embodiment of the display member according to the present invention. As shown in Fig. 1, the display member 1 sequentially includes a substrate, a metal layer 3, and a transmission layer 2 formed of a flexible resin having a predetermined three-dimensional shape, and the display member is formed of a substrate. The adhesive layer 5 is further included on the side opposite to the metal layer 3.

As the material constituting the transmission layer 2, a thermoplastic resin which is colorless or colored, transparent and flexible is required. For example, flexible vinyl chloride resins, fluorine resins, urethane resins, silicone resins, polyester resins and olefinic resins such as polyethylene, polypropylene and ionomer resins can be used. The thickness of the transmissive layer 2 is preferably in the range of approximately 10 to 150 mu m, and when the thickness is less than 10 mu m, it is likely to be broken in the formation step of the display member described later. On the other hand, it is not required that the thickness exceed 150 m because of the forming step and the configuration of the display member. The transmissive layer 2 is colorless and transmissive, and the appearance of an excellent metallic film of deposited indium deposited on its backside in the display member can be obtained. Since indium has a bright silver color, a desired color different from that of indium itself (for example, gold) can be represented by coloring the transmission layer 2 by incorporation of a transmission pigment. Since chromium conventionally used as the metal layer has a dark color, the desired color may not appear even when a transparent pigment is incorporated in the transmission layer 2.

Various additives such as ultraviolet absorbers, photostabilizers and antioxidants can be incorporated into the transmission layer 2 to improve performance under the conditions of use of the display member. In order to improve the film forming treatment capability of the permeable layer 2, leveling agents such as silicone resins, fluorine resins and acrylic resins, lubricants and auxiliary film forming agents may be incorporated. The permeable layer 2 may be composed of not only a single resin but also a composite membrane formed of a combination of resins of different materials. In order to improve the adhesion of the indium deposited film, which will be described later, a primer such as a urethane resin, a silicone resin, an epoxy resin, and a polyester resin may be coated in advance. In addition, the surface to be deposited may be pre-plasma treated or corona treated.

The metal layer 3 can be formed on one main surface of the transmissive layer 2 by indium deposition by a heating method such as a high frequency dielectric heating using a conventional vacuum vapor deposition apparatus for plastic films and an electron beam method. It is essential that the visible light transmittance of the metal layer 3 is 6% or less. When the visible light transmittance exceeds 6%, the substrate disposed under the lower laminate is seen through the metal layer 3, and the desired metal film is hard to appear. The thickness of the metal layer 3 is 600 angstroms or less, preferably in the range of 300 to 600 angstroms. Although the predetermined metal film does not change even if the thickness is larger than 600 angstroms, the cost increases because indium itself is an expensive substrate. When the thickness exceeds 600 angstroms, the corrosion resistance is reduced. On the other hand, when the thickness is less than 300 angstroms, the substrate disposed under the lower laminate is seen through the indium deposited layer 3, and the appearance is degraded.

The substrate 14 constitutes a main part of the structure of the three-dimensional display member. Thus, the substrate is preferably composed of a flexible resin in order to flexibly produce the entire three-dimensional display material. As the flexible resin, thermoplastic resins such as vinyl chloride resin, urethane resin and thermoplastic elastomer can be used. The substrate 4 is applied to the die layer 2 with the metal layer 3 as an indium deposited film, and the aforementioned metal layer 3 is subjected to the above-described method using an injection molding method such as hot melt injection molding and two-component mixed reaction injection molding. It can be provided in a predetermined three-dimensional shape by injecting one resin. Optionally, a preform having a predetermined shape formed from the above-mentioned flexible resin by injection molding may be contact-bonded with the layer 2 having the metal layer 3. In the display material of the present invention, since the substrate 4 is injection molded in this manner, it is possible to exhibit a complicated design that is difficult to exhibit by punching. The exposure of the metal layer 3 is reduced as much as possible by the coating of the layer 2 with the metal layer so as to coat the end of the substrate 4 so as to prevent the risk of corrosion of the metal layer 2. The thickness of the substrate 4 varies depending on the design of the display material required, but is in the range of approximately 0.5 to 10 mm when used in the emblem product for general automotive exteriors. In order to improve performance, various additives such as ultraviolet absorbers, light stabilizers and antioxidants can be incorporated into the resins used for the substrate 4.

In this way, the substrate 4 can be in direct contact bonding with the layer 2 having the metal layer 3, but the adhesive resin layer 7 made of polyamide, nylon, polyurethane, vinyl chloride or vinyl acetate resin 7 As shown in FIG. 2, between the metal layer 3 and the substrate 4 to protect the metal layer 3 and / or to improve adhesion to the substrate in the forming step after the providing step of the metal layer 3. Can be provided. The thickness of the adhesive resin layer 7 is preferably in the range of 2 to 100 mu m. When the thickness is smaller than 2 mu m, the adhesion is lowered. On the other hand, when the thickness is larger than 100 mu m, a predetermined effect is not obtained and the material becomes useless. In addition, the resulting overall three-dimensional display member is thickened, and has a low processing capacity.

As the lower laminate of the base layer 4, that is, the adhesive layer provided on the side opposite to the metal layer 3, for example, an acrylic adhesive, a rubber adhesive or a silicone adhesive can be used. In addition, a double coated tape having a bubble layer such as an acrylic bubble tape, a urethane bubble tape, or the like can be used. The thickness of the adhesive layer 5 is generally in the range of approximately 0.1 to 1.2 mm. When the thickness is less than 0.1 mm, it becomes difficult to adhere to the adhesive end. Even if the thickness exceeds 0.5 mm, the effect of improving adhesion is not obtained, and the material becomes useless. In addition, the resulting entire display member is thickened and has a reduced processing capacity. In order to protect the adhesive layer 5, a release paper or release film 6 on which one surface is released is generally provided. The adhesive layer 5 and the release paper 6 can be provided at the same time by preparing the adhesive layer and release paper separately, and the coated adhesive layer is provided on the release surface of the release paper and dried on the adhesive layer having the substrate 4. Are stacked.

On the outermost surface of the display member thus obtained, i.e., the transmissive layer 2, a transparent coating layer 9 made of acrylic resin or fluorine resin can be provided to prevent scratches and to improve weather resistance. The thickness of the transparent coating layer is preferably in the range of 10 to 60 μm. When the thickness is less than 10 mu m, a desirable protective effect cannot be obtained. On the other hand, even if the thickness exceeds 60 mu m, the desired effect cannot be obtained, and the material becomes useless. In addition, the resulting overall display member is thick and has low processing capacity. Depending on the design requirements, a color layer 8 having a desired shape can be provided to the surface by digital printing, screen printing, spray coating and hot stamp transfer. The thickness of the color layer is preferably in the range of 2 to 50 μm. When the thickness is less than 2 μm, the improvement of the desired color effect cannot be obtained. On the other hand, even if the thickness exceeds 50 mu m, the desired effect cannot be obtained, and the material becomes useless. In addition, the resulting overall display member is thick and has low processing capacity. In the case where the color layer 8 is provided, the aforementioned transparent coating layer 9 is required to protect the color layer 8. At the outermost surface of the display member, a known surface protection tape can be applied to protect the surface during storage, movement and application of the adhesive end.

Yes

Example 1

Polyester polyol (trade name Desmophine 670 manufactured by SUMITOMO BYER URETHANE Co., Ltd.) and yellowing-free type polyisocyanate [Sumitomo Bayer urethane] SUMIJULE N3300, manufactured by SUMITOMO BYER URETHANE Co., Ltd., was mixed in the same amount, and then the mixture was injected to produce a permeable polyester urethane membrane having a thickness of 50 μm. do. Indium is vacuum deposited to form a laminated film on the surface of the polyester urethane film to a thickness of approximately 400 angstroms. The visible light transmittance of the laminated film is measured according to JIS A 5759. As a result, it is 5%. The laminated film is placed in a die for in-mold decorating so that an indium deposition layer is placed on the injection resin side, and the same amount of polyurethane resin and dicyclohexylmethane-4, 4-diisocyanate prepolymer A predetermined amount of liquid resin prepared by mixing two portions of polyester polyol of (4-diisocyanate prepolymer) is injected into the die. The polyester polyol reacts with dicyclohexylmethane-4, 4-diisocyanate prepolymer to form a substrate, and then the die is opened to obtain an interposed preform. Acrylic foam tape # 4215, manufactured by SUMITOMO 3M Co., Ltd., is placed on the lower surface of the base resin of the interposed preform. Finally, the unnecessary laminated film, the burr of the base resin, and the unnecessary acrylic bubble tape are trimmed to obtain the display member of the present invention.

Example 2

Fluorine resin (trade name YHV200P (TFE: HFP: VDF = 40:20:40) manufactured by DYNEON Co.) was colorless and injected to produce a 30 μm thick permeate fluorine-based membrane. Indium is vacuum deposited on one surface of the film to a thickness of approximately 400 angstroms to form a laminated film. The visible light transmittance of the laminated film is measured according to JIS A 5759. As a result, it is 5%. Using the same steps and materials as in Example 1, the display member of the present invention is manufactured.

Indium is deposited on one surface of a colorless, transmissive polyester urethane film having a thickness of 50 μm, prepared in Example 1 to a thickness of approximately 500 Angstroms to form a laminated film. The visible light transmittance of the laminated film is measured according to JIS A 5759 so that it is 2%. Using the same steps and materials as in Example 1, a display member was manufactured.

Comparative Example 1

Aluminum was deposited on one surface of a colorless, transmissive polyester urethane film having a thickness of 50 μm, prepared in Example 1 to a thickness of approximately 500 Angstroms to form a laminate. Using the same steps and materials as in Example 1, a display member was manufactured.

Comparative Example 2

Chromium was deposited on one surface of a colorless, transmissive polyester urethane film having a thickness of 50 μm, prepared in Example 1 to a thickness of approximately 500 Angstroms. Using the same steps and materials as in Example 1, a display member was manufactured.

Comparative Example 3

Tin is deposited on one surface of a colorless, transmissive polyester urethane film having a thickness of 50 μm, prepared in Example 1 to a thickness of approximately 500 Angstroms to form a laminated film. Using the same steps and materials as in Example 1, a display member was manufactured.

Comparative Example 4

Indium is deposited on one surface of a colorless, transmissive polyester urethane film having a thickness of 50 μm, prepared in Example 1 to a thickness of approximately 200 Angstroms to form a laminate. The visible light transmittance of the laminated film is measured according to JIS A 5759. As a result, it is 11%. The laminated film thus obtained has an outer appearance with a metal film, but is seen as a whole and is not suitable for use as the three-dimensional display member of the present invention.

Comparative Example 5

Indium is deposited on one surface of a colorless, transmissive polyester urethane film having a thickness of 50 μm, prepared in Example 1 to a thickness of approximately 650 Angstroms to form a laminated film. Using the same steps and materials as in Example 1, a display member was manufactured.

The appearance of the three-dimensional display members thus produced is compared. The results are summarized in Table 1.

Table 1

Deposited metal Exterior Whitening of Formation Example 1 indium Excellent metal film Does not occur Example 2 indium Excellent metal film Does not occur Example 3 indium Excellent metal film Does not occur Comparative Example 1 aluminum Excellent metal film Slightly whitening occurs Comparative Example 2 chrome Dark color tone Whitening outbreak Comparative Example 3 Remark Excellent metal film Does not occur Comparative Example 4 indium Excellent metal film but high permeability (Not performed) Comparative Example 5 indium Excellent metal film Does not occur

Next, the three-dimensional display members are subjected to various tests as described later. The results are shown in Table 2.

Test procedure

Outdoor exposure: The three-dimensional display members are exposed in a 45 ° direction southward from Shizuoka, Fuji, for one year.

Acid Resistance: Three-dimensional display members are immersed in sulfuric acid hydroxide solution (0.05 mol / liter) at 20 ° C. for 24 hours.                 

Alkali Resistance: The three-dimensional display members are immersed in sodium hydroxide solution (0.1 mol / liter) at 20 ° C. for 8 hours.

Salt spray resistance: 5% aqueous sodium chloride solution is sprayed on the three-dimensional display members at 40 ° C. for 336 hours.

Water resistance: Three-dimensional display members are immersed in water at 40 ° C. for 168 hours.

Moisture Resistance: The three-dimensional display members are allowed to withstand in the atmosphere under 50% RH 95% RH for 168 hours.

Evaluation procedure

Appearance: Evaluate the visible appearance.

Adhesion: Evaluated by the Checkers Taping Method (8.5.2) of adhesion (8.5) as defined in JIS K5400. Checker has a length of 2 mm. For corroded test specimens, the adhesion test is performed where there is no corrosion.

Evaluation standard

Exterior:

A: No change is observed in the initial appearance.

B: Corrosion is found at the end.

C: Corrosion proceeds from the end into the display member.

Adhesion: The evaluation score is based on the evaluation criteria of the checker taping method (8.5.2) of adhesion (8.5) as defined in JIS K5400.

10 points: No peeling off.                 

8 points | pieces: It peels at the ratio of 5% or less.

6 points | pieces: It peels at the ratio of 5 to 15%.

4 points | pieces: It peels at the ratio of 15 to 35%.

2 points | pieces: It peels at the ratio of 35-65%.

0 points | pieces: Peel more than 65%.

[Table 2]

Outdoor exposure Acid resistance Alkali resistant Brine Spray Resistant Exterior adhesion Exterior adhesion Exterior adhesion Example 1 A 10 A A A 10 Example 2 A 10 A A A 10 Example 3 A 10 A A A 10 Comparative Example 1 C 10 C C B 10 Comparative Example 2 A 10 A A A 10 Comparative Example 3 B 4 B C B 4 Comparative Example 5 C 10 C B C 10

Water resistance Moisture resistance Exterior adhesion Exterior adhesion Example 1 A 10 A 10 Example 2 A 10 A 10 Example 3 A 10 A 10 Comparative Example 1 A 10 A 10 Comparative Example 2 A 10 A 10 Comparative Example 3 A 0 A 0 Comparative Example 5 A 10 A 10

According to the present invention, by forming a metal layer by vapor deposition of indium and adjusting the thickness of the metal layer to a predetermined thickness, the display member of the present invention is flexible and has excellent bending surface suitability and durability and can exhibit various shapes. Can be obtained.

Claims (18)

It is a flexible display member which has a metal film containing a base material, a metal layer, and a transmission layer sequentially, The display member includes a first adhesive layer on a side opposite to the metal layer of the substrate, the metal layer is an indium deposited film provided on the surface of the transmissive layer, and the indium deposited film has a visible light transmittance of 6% or less and a thickness of 600 angstroms or less. A flexible display member having a metal film having. The flexible display member according to claim 1, wherein the base material is a predetermined three-dimensional shape formed of a flexible resin and the transmission layer has a metal film formed of a thermoplastic resin. The flexible display member according to claim 2, wherein the substrate has a metal coating comprising vinyl chloride resin, urethane resin, thermoplastic elastomer, or a combination thereof. The flexible display member according to claim 2, wherein the permeable layer has a metal film comprising vinyl chloride resin, fluorine resin, urethane resin, silicone resin, polyester resin, polyethylene, polypropylene, ionomer resin, or a combination thereof. The flexible display member of claim 1, wherein the substrate has a metal film having a thickness in the range of approximately 0.5 to 10 mm.  The flexible display member of claim 1, wherein the transmissive layer has a metal film having a thickness in the range of 10 to 150 μm. The flexible display member of claim 1, wherein the first adhesive layer has a metal coating comprising an acrylic adhesive, a rubber adhesive, or a silicone adhesive. The flexible display member of claim 1, wherein the first adhesive layer has a metal coating comprising an acrylic foam tape or a urethane foam tape. The flexible display member of claim 1, wherein the first adhesive layer has a metal film having a thickness in the range of 0.1 to 1.2 mm. The flexible display member according to any one of claims 1 to 9, further comprising a metal film further comprising a second adhesive layer between the metal layer and the substrate. The method of claim 1, further comprising a second adhesive layer between the metal layer and the substrate, wherein the second adhesive layer comprises a polyamide, nylon, polyurethane, vinyl chloride, or vinyl acetate resin. Flexible display member having a metal film. The flexible display member according to claim 1, further comprising a second adhesive layer between the metal layer and the substrate, wherein the second adhesive layer has a metal coating having a thickness in the range of 2 to 100 μm. . The flexible display member according to any one of claims 1 to 9, wherein the indium deposited film has a metal film having a thickness of 300 angstroms or more. The flexible display member according to any one of claims 1 to 9, further comprising a metal film further comprising a color layer in the transparent resin layer. The flexible display member according to any one of claims 1 to 9, further comprising a metal film further comprising a transparent coating layer on the transparent resin layer. The flexible display member according to any one of claims 1 to 9, wherein the transparent resin layer has a metal coating containing a pigment. The flexible display member of claim 1, wherein the end of the display member has a metal coating coated to prevent the risk of corrosion of the metal layer. The flexible display member of claim 1, further comprising a metal film further comprising a release liner on the first adhesive layer.

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