JP2018070757A - Method for producing metal vapor deposition film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a metal vapor deposition film having a uniform metal thin film.SOLUTION: Provided is a method for producing a metal vapor deposition film comprising: a step where a support film is pasted on either side of a base material made of polyvinyl chloride; a step where a metal vapor deposition film is formed on a face on the side opposite to the face pasted with the support film of the base material; a step where, after the formation of the metal vapor deposition film, the support film is peeled from the base material; and a step where an adhesive layer is formed on a face of the base material from which the support film is peeled. The thickness of the support film is 0.1 time or more to the thickness of the base material, and the peeling force between the base material and the support film is 0.05 N/25 mm or more.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for producing a metal vapor deposited film.

Conventionally, in order to impart a metallic design to an adherend, a method of attaching a resin film having a metal thin film layer to the adherend is known. As literature which disclosed the prior art related to the resin film which has a metal thin film layer, patent document 1 and 2 are mentioned, for example.

Patent Document 1 discloses a metal decorative plate in which an ethylene-vinyl alcohol copolymer film, a metal thin film layer, a thermoplastic resin film, and a metal plate, which have been subjected to easy adhesion treatment, are laminated in this order.

Patent Document 2 discloses that a base material has at least a metal thin film layer and an adhesive layer in this order, and the resin constituting the adhesive layer is a vinyl chloride resin, a vinyl acetate resin, or vinyl chloride / vinyl acetate. A three-dimensional molded decorative film which is a copolymer resin and has an average oxidation of the resin of 1 to 6 mgKOH / g is disclosed.

JP-A-8-34090 JP 2012-76353 A

Examples of the method for forming the metal thin film layer on the resin film include a method in which a metal is vapor-deposited on the resin film serving as a base material. For metal deposition, for example, a metal is vaporized at a high temperature of 500 to 800 ° C. and adhered to the surface of the base material. Therefore, as the base material, a polyester film such as polyethylene terephthalate (PET) generally having high heat resistance is used. An acrylic film such as polymethyl methacrylate (PMMA) is used.

In recent years, it has been studied to attach a metal vapor deposition film not only to a flat surface but also to a three-dimensional curved surface. A polyvinyl chloride film is suitable as a base material for a film to be attached to an adherend having a three-dimensional curved surface because it has good elongation and hardly breaks. On the other hand, the polyvinyl chloride film has lower heat resistance than PET, PMMA, etc., and in particular, the polyvinyl chloride film used for decorating the adherend having a three-dimensional curved surface softens from about 60 ° C. It was not suitable for vapor deposition. When vapor deposition processing is performed on a polyvinyl chloride film that is easily softened, the film softens and bends during processing, so that it is difficult to uniformly apply metal to the substrate surface and unevenness may occur.

This invention is made | formed in view of the said present condition, and aims at providing the manufacturing method of the metal vapor deposition film which has a uniform metal thin film uniformly.

The present inventor has studied a method of forming a metal vapor deposition film on a base material made of polyvinyl chloride, and after pasting a support film on the base material, the side opposite to the surface of the base material on which the support film is pasted It was found that by forming a metal vapor-deposited film on this surface, a uniform metal thin film having no metal unevenness can be formed even when a polyvinyl chloride film having low heat resistance is used as a substrate. Furthermore, the support film has a specific thickness, and the peeling force between the base material and the support film is set to a certain level or more, so that the base material is prevented from being bent during the vapor deposition process. The present invention was completed by finding that a uniform metal thin film can be formed without unevenness.

The method for producing a metal vapor deposition film of the present invention includes a step of attaching a support film to one surface of a substrate made of polyvinyl chloride, and a metal vapor deposition on a surface opposite to the surface of the substrate on which the support film is adhered. A step of forming a film, a step of peeling the support film from the base material after the formation of the metal vapor deposition film, and a step of forming an adhesive layer on the surface of the base material from which the support film has been peeled off. The thickness of the support film is at least 0.1 times the thickness of the base material, and the peel force between the base material and the support film is 0.05 N / 25 mm or more. And

The thickness of the substrate is preferably 50 μm or more and 200 μm or less.

The surface roughness of the surface opposite to the surface on which the support film of the base material is attached is preferably 2.0 μm or less.

The metal vapor deposition film preferably contains aluminum, tin, or indium.

The method for producing a metal vapor deposition film of the present invention can produce a metal vapor deposition film having a uniform metal thin film without unevenness.

It is the schematic which showed the manufacturing method of the metal vapor deposition film of Embodiment 1 typically. It is sectional drawing which showed typically the metal vapor deposition film manufactured by the manufacturing method of the metal vapor deposition film of Embodiment 2. FIG. It is sectional drawing which showed typically the metal vapor deposition film manufactured by the manufacturing method of the metal vapor deposition film of Embodiment 3. FIG.

(Embodiment 1)
The manufacturing method of the metal vapor deposition film of Embodiment 1 includes a step of attaching a support film to one surface of a base material made of polyvinyl chloride, and a metal on a surface opposite to the surface on which the support film of the base material is attached. A step of forming a vapor deposition film, a step of peeling the support film from the base material after the formation of the metal vapor deposition film, and a step of forming an adhesive layer on the surface of the base material from which the support film has been peeled off. And the thickness of the said support film is 0.1 times or more with respect to the thickness of the said base material, and the peeling force of the said base material and the said support film is 0.05 N / 25mm or more. Features. In this specification, “film” is synonymous with “sheet”, and the two are not distinguished by thickness.

The manufacturing method of the metal vapor deposition film of Embodiment 1 is demonstrated below with reference to FIG. FIG. 1 is a schematic view schematically illustrating a method for producing a metal vapor deposition film according to Embodiment 1. As shown in FIG. 1D, the metal vapor deposition film 10 </ b> A produced by the metal vapor deposition film production method of Embodiment 1 is laminated in the order of the metal vapor deposition film 3, the substrate 1, and the adhesive layer 4. . 10 A of metal vapor deposition films may have the separator 5 in the surface on the opposite side to the base material 1 of the adhesive layer 4. FIG.

Below, the manufacturing method of the metal vapor deposition film of Embodiment 1 is demonstrated using FIG. (A) of FIG. 1 represents the process of affixing the support film 2 on one surface of the base material 1 made of polyvinyl chloride. The substrate 1 is a film made of polyvinyl chloride, and has a role of a support for the metal vapor deposited film 10A. By using polyvinyl chloride as the resin component of the substrate 1, it is excellent in the shape of the three-dimensional curved surface portion when a metal vapor deposition film is attached to an adherend at a relatively low temperature (about 130 ° C.). There is an advantage that followability (formability) can be obtained. Here, “relatively low temperature” means that the temperature is lower than the molding temperature (above 130 ° C.) when molding a transparent resin (for example, polyethylene terephthalate) other than polyvinyl chloride and acrylic resin. doing. On the other hand, the vapor deposition of the metal vapor deposition layer 3 is generally performed at a high temperature (500 to 800 ° C.). However, since polyvinyl chloride has low heat resistance compared to PET, PMMA, etc., it is easy to bend during vapor deposition ( It is easy to deform), and the metal cannot be uniformly attached to the surface of the base material 1, and metal unevenness is likely to occur. Therefore, by temporarily attaching the support film 2 during the vapor deposition process, the base material 1 is prevented from being softened and bent by heating, and a uniform metal thin film with no unevenness is formed on the surface of the base material 1. can do. The support film 2 is a film that is attached in advance to a surface opposite to the deposition surface of the substrate 1 when the metal deposition film 3 is formed on the substrate 1. The method for attaching the support film 2 to the substrate 1 is not particularly limited, and examples thereof include a method in which the substrate 1, the support film, and the support film 2 are stacked and laminated at 130 to 170 ° C.

The method for forming the substrate 1 is not particularly limited, and examples thereof include conventionally known molding methods such as calendar molding, extrusion molding, and injection molding. Examples of the calendar format used for the calendar molding include an inverted L shape, a Z shape, an upright two shape, an L shape, and an inclined three shape.

(B) of FIG. 1 represents the process of forming the metal vapor deposition film 3 in the surface on the opposite side to the surface which affixed the support film 2 of the base material 1. FIG. Examples of the method for forming the metal vapor deposition film 3 include vapor deposition methods such as vacuum vapor deposition, sputtering, and ion plating. Especially, since vapor deposition is performed by heating to a high temperature, the occurrence of metal unevenness can be effectively suppressed when the vacuum vapor deposition method is used.

The surface roughness of the surface opposite to the surface on which the support film 2 of the substrate 1 is attached is preferably 2.0 μm or less. The surface of the base material 1 opposite to the surface on which the support film 2 is attached is the surface of the base material 1 on which the metal vapor deposition film 3 is formed. During vapor deposition, the metal enters the irregularities on the surface of the substrate 1, and the surface shape of the metal vapor deposition film 3 is affected by the irregular shape present on the surface of the substrate 1, which is the vapor deposition surface. When the flatness of the surface of the substrate 1 is high, it has a metallic appearance with glossiness, and when the flatness of the surface of the substrate 1 is low, it has a metallic appearance with a matte feeling. If the surface roughness exceeds 2.0 μm, the flatness of the surface of the metal vapor-deposited film 3 is lowered, and the sharpness of the design of the metal vapor-deposited film 10A may be impaired. The lower limit of the surface roughness of the substrate 1 is not particularly limited. The lower the surface roughness, the flatter the surface of the substrate 1 and the better the sharpness. In this specification, “surface roughness” means arithmetic average roughness Ra based on JIS B 0601 (2013).

The surface of the substrate 1 opposite to the surface to which the support film 2 is attached may be subjected to a surface treatment in order to improve the adhesion with the metal vapor deposition film 3. Examples of the surface treatment include corona discharge treatment, plasma treatment, and ozone treatment.

(C) of FIG. 1 represents the process of peeling the support film 2 from the base material 1 after formation of the metal vapor deposition film 3. FIG. Since the support film 2 is peeled after the metal vapor deposition film 3 is formed, the metal vapor deposition film 10 </ b> A does not have the support film 2.

The peeling force between the substrate 1 and the support film 2 is 0.05 N / 25 mm or more. When the peeling force is less than 0.05 N / 25 mm, the support film 2 is peeled off from the base material 1 during the vapor deposition process, and the base material 1 bends to cause metal unevenness. The upper limit of the peeling force is, for example, 0.3 N / 25 mm. When the peeling force exceeds 0.3 N / 25 mm, the adhesive force between the base material 1 and the support film 2 is too high, so that the base material 1 is deformed when peeling from the base material 1 after the metal vapor deposition film 3 is formed. There are things to do. A preferable upper limit of the peeling force is 0.2 N / 25 mm, and a preferable upper limit is 0.1 N / 25 mm. The peeling force can be measured by a method based on JIS Z 0237.

(D) of FIG. 1 represents the process of forming the adhesive layer 4 in the surface which peeled the support film 2 of the base material 1. FIG. The formation method of the adhesive layer 4 is not specifically limited, For example, a commercially available adhesive sheet may be affixed on the surface which peeled the support film 2 of the base material 1, or the adhesive layer 4 formed on the separator 5 is used. The support film 2 of the base material 1 may be bonded to the peeled surface. When the pressure-sensitive adhesive layer 4 formed on the separator 5 is bonded, a conventionally known method such as a method of applying a pressure-sensitive adhesive composition on the separator 5 using a bar coater or the like and drying it can be used.

Furthermore, you may have the process of sticking the separator 5 on the surface on the opposite side to the base material 1 of the adhesive layer 4 after the process of forming the adhesive layer 4. When using the method of bonding the pressure-sensitive adhesive layer 4 formed on the separator 5 in the step of forming the pressure-sensitive adhesive layer 4, the step of forming the pressure-sensitive adhesive layer 4 may also serve as the step of bonding the separator 5. Good.

The metal vapor-deposited film is further subjected to processing such as cutting and winding into a roll as necessary.

Below, the structure of 10 A of metal vapor deposition films manufactured by the manufacturing method of the metal vapor deposition film of Embodiment 1 is demonstrated.

[Base material]
The base material 1 contains polyvinyl chloride as a resin component. Examples of the polyvinyl chloride include a homopolymer of vinyl chloride and a copolymer of vinyl chloride and other monomers. Examples of the other monomer include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene and styrene; (meth) acrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate. Maleic acid diesters such as dibutyl maleate and diethyl maleate; fumaric acid diesters such as dibutyl fumarate and diethyl fumarate; vinyl cyanides such as acrylonitrile and methacrylonitrile; vinyl halides such as vinylidene chloride and vinyl bromide; Examples thereof include vinyl ethers such as methyl vinyl ether and ethyl vinyl ether. These may be used alone or in combination of two or more.

The content of the other monomer in the copolymer is usually 50% by weight or less, preferably 10% by weight or less. If it exceeds 50% by weight, the bending resistance of the substrate 1 may be lowered. Among the polyvinyl chlorides, a homopolymer of vinyl chloride is preferable from the viewpoint of obtaining dimensional stability.

The average degree of polymerization of the polyvinyl chloride is not particularly limited, and is adjusted according to the required film hardness and the amount of plasticizer used for adjusting the hardness, for example, 750 to 1300. . A preferable upper limit of the average degree of polymerization is 1050. When the average polymerization degree is in the range of 750 to 1300, the moldability at a relatively low temperature is particularly good. On the other hand, when the average degree of polymerization is less than 750, it may be difficult to form a metal vapor deposition film on the surface of the substrate 1. On the other hand, when the average degree of polymerization exceeds 1300, the followability to the shape of the three-dimensional curved surface during molding may be insufficient. In this specification, the average degree of polymerization of polyvinyl chloride means the average degree of polymerization measured according to JIS K6721 “Testing method for vinyl chloride resin”.

The base material 1 may contain a plasticizer. The plasticizer is not particularly limited, and those conventionally used in vinyl chloride resins can be used. For example, octyl phthalate (di-2-ethylhexyl phthalate (DOP)), dibutyl phthalate, phthalic acid Phthalic acid diesters such as dinonyl and diisononyl phthalate (DINP); aliphatic dibasic acid diesters such as dioctyl adipate and dioctyl sebacate; phosphate triesters such as tricresyl phosphate and trioctyl phosphate; Mention may be made of epoxy plasticizers such as soybean oil and epoxy resins; polymer polyester plasticizers and the like.

Examples of the polymer polyester plasticizer include polyalkylene glycol diesters such as polyethylene glycol diester, polypropylene glycol diester, and polyethylene glycol polypropylene glycol diester of phthalic acid; polyethylene glycol diesters of aliphatic dibasic acids such as adipic acid and sebacic acid. And polyalkylene glycol diesters such as polypropylene glycol diester and polyethylene glycol polypropylene glycol diester. These may be used alone or in combination of two or more.

The number average molecular weight of the plasticizer is preferably 350 to 3000. If the number average molecular weight is less than 350, the plasticizer tends to migrate to the adhesive layer 7 and may cause a decrease in adhesive strength. On the other hand, if the number average molecular weight exceeds 3000, the effect of softening the film by adding a plasticizer cannot be sufficiently obtained, and the surface protective layer 8 becomes too hard, so that the film may be broken during molding. is there.

The plasticizer content in the substrate 1 is preferably 10 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the resin component. If it is in the range of the said content, the base material 1 cannot change easily with a heat | fever, and can form a uniform metal thin film with the surface. When the content is less than 10 parts by weight, the base material 1 becomes too hard, so that the moldability is deteriorated and the film may be broken at the time of molding. On the other hand, when the amount exceeds 30 parts by weight, the base material 1 becomes too soft, so that the base material 1 is easily bent during vapor deposition and metal unevenness is likely to occur. The minimum with more preferable content of the said plasticizer is 18 weight part, and a more preferable upper limit is 23 weight part.

The substrate 1 may contain additives such as stabilizers, ultraviolet absorbers, colorants, foaming agents, lubricants, modifiers, fillers such as inorganic particles and inorganic fibers, and diluents as necessary. Good. As these additives, those generally used in vinyl chloride resins can be used.

Examples of the stabilizer include metal soaps such as fatty acid calcium, fatty acid zinc, and fatty acid barium; hydrotalcite and the like. Examples of the fatty acid component of the metal soap include calcium laurate, calcium stearate, calcium ricinoleate, zinc laurate, zinc ricinoleate, zinc stearate, barium laurate, barium stearate, and barium ricinoleate. In addition, as the stabilizer, epoxy stabilizer; barium stabilizer; calcium stabilizer; tin stabilizer; zinc stabilizer; calcium-zinc-based (Ca-Zn-based), barium-zinc-based (Ba Composite stabilizers such as —Zn-based ”can also be used.

When the stabilizer is contained, the content is preferably 0.3 to 5.0 parts by weight with respect to 100 parts by weight of the resin component. If the content is less than 0.3 parts by weight, the effect of blending the stabilizer may not be sufficiently exerted. On the other hand, if the content exceeds 5.0 parts by weight, the stabilizer is bloomed (spouted). )

Moreover, when the said ultraviolet absorber is contained, the content has preferable 0.3-2.0 weight part with respect to 100 weight part of said resin components. If the content is less than 0.3 parts by weight, there is not much effect. On the other hand, if the content exceeds 2.0 parts by weight, the surface of the surface protective layer 8 may be bleed.

The thickness of the substrate 1 is preferably 50 μm or more and 200 μm or less.
If the thickness of the substrate 1 is less than 50 μm, the metal deposited film 10A becomes too flexible and the workability may be lowered, and the weather resistance may be lowered. On the other hand, if the thickness of the base material 1 exceeds 200 μm, the followability to the shape of the three-dimensional curved surface portion during molding may be insufficient. A more preferable lower limit of the thickness of the substrate 1 is 80 μm, and a more preferable upper limit is 150 μm.

[Support film]
Examples of the support film 2 include polyester films such as polyethylene terephthalate (PET), acrylic films such as polymethyl methacrylate (PMMA), and polycarbonate (PC). A PET film is preferred because of its excellent heat resistance. The surface of the support film 2 is preferably not easily peeled. When the easy-peeling agent is applied, the hydrophobicity of the surface of the support film 2 is increased, so that when the base material 1 and the support film 2 are laminated, it may be difficult to apply with a desired peeling force.

The thickness of the support film 2 is not less than 0.1 times the thickness of the substrate 1.
When the thickness of the support film 2 with respect to the thickness of the base material 1 is less than 0.1 times, the base material 1 cannot be sufficiently supported when vapor deposition is performed on the surface of the base material 1, and the base material 1 is bent. , Metal unevenness occurs. Although the upper limit of the thickness of the support film 2 with respect to the thickness of the base material 1 is not specifically limited, For example, it is preferable that it is 5 times or less. The preferable lower limit of the thickness of the support film 2 with respect to the thickness of the substrate 1 is 0.2 times, the more preferable upper limit is 4 times, and the more preferable upper limit is 3 times.

The thickness of the support film 2 is preferably 5 μm or more and 1000 μm or less. The more preferable lower limit of the thickness of the support film 2 is 10 μm, the more preferable upper limit is 500 μm, the still more preferable upper limit is 250 μm, and the particularly preferable upper limit is 100 μm.

[Metal deposition film]
The metal vapor deposition film 3 is a layer for imparting a metallic luster to the appearance of the metal vapor deposition film 10A. It is preferable that the metal vapor deposition film 3 contains aluminum, tin, or indium. Since these metals are rich in extensibility, the metal vapor-deposited film 3 is unlikely to crack even when the metal vapor-deposited film 10A is attached to the three-dimensional curved surface portion.

[Adhesive layer]
The pressure-sensitive adhesive layer 4 is not particularly limited as long as it has at least one of a pressure-sensitive adhesive function (pressure-sensitive adhesiveness) and a bonding function, and specifically, an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, and a silicone-based pressure-sensitive adhesive. What contains adhesives, such as these, is mentioned. Among them, an acrylic pressure-sensitive adhesive is preferably used because it is excellent in adhesiveness, workability, heat aging resistance, moisture aging resistance, and weather resistance and is relatively inexpensive.

The pressure-sensitive adhesive layer 4 is formed, for example, by coating a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive, a crosslinking agent (curing agent), etc. on a support to form a coating film, and then heating and drying the coating film. It can be formed by a curing method. The crosslinking agent (curing agent) is a compound that undergoes a chemical reaction or interaction with the functional group in the pressure-sensitive adhesive to crosslink. As the crosslinking agent, a known crosslinking agent such as an isocyanate curing agent or an epoxy curing agent can be used.

The pressure-sensitive adhesive composition may further contain a catalyst, a solvent such as a hydrophobic organic solvent, an inorganic filler, or the like as necessary. In addition, the pressure-sensitive adhesive composition includes a stabilizer, a plasticizer, a softener, a filler, a tackifier, a dye, as necessary, as long as the properties required for the metal vapor deposition film of the present invention are not impaired. Various additives such as pigments may be added.

The coating amount of the pressure-sensitive adhesive composition is preferably 10 to 90 g / m ² (in terms of weight when dried). In other words, it is preferable that the coating amount of the pressure-sensitive adhesive layer 4 obtained by drying the pressure-sensitive adhesive composition is 10 to 90 g / m ² . By adjusting the coating amount in the range of 10 to 90 g / m ² , the adhesive strength of the pressure-sensitive adhesive layer 4 can be ensured. When the coating amount is less than 10 g / m ² , the adhesive strength may be insufficient. When the coating amount exceeds 90 g / m ² , a part of the pressure-sensitive adhesive layer 4 remains on the surface of the adherend, and adhesive residue tends to occur. A more preferable lower limit of the coating amount is 50 g / m ² . When the coating amount is 50 g / m ² or more, sufficient followability to the unevenness of the substrate surface can be obtained. A more preferable upper limit of the coating amount is 70 g / m ² .

As for the thickness of the adhesive layer 4, 10-60 micrometers is preferable. When the thickness is less than 10 μm, sufficient tackiness may not be obtained. When the thickness exceeds 60 μm, the tackiness is not improved so much. A more preferable thickness of the pressure-sensitive adhesive layer 4 is 20 to 40 μm.

[separator]
By providing the separator 5, it is possible to prevent the adhesive layer 4 from being exposed during the production, transportation and storage of the metal vapor-deposited film 10A, thereby preventing deterioration of the pressure-sensitive adhesive layer 4 and improving the handleability of the metal vapor-deposited film 10A. Become. The separator 5 may be peeled off immediately before sticking to the adherend.

Although it does not specifically limit as the separator 5, The thing which can peel easily without damaging the adhesive layer 4 is suitable, For example, by apply | coating a silicone resin, a fluororesin, etc. to the surface which contacts the adhesive layer 4 Resin film (release film) such as polyester, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, and polypropylene that has been subjected to easy release treatment; paper such as high-quality paper and glassine paper (release paper); paper and coating layer A laminated film etc. are mentioned. The thickness of the separator 5 is preferably 12 to 200 μm, and more preferably 50 to 150 μm. The peeling force between the pressure-sensitive adhesive layer 4 and the separator 5 is not particularly limited, but may be, for example, 0.1 to 0.5 N / 25 mm. The lower limit of the peeling force is preferably larger than 0.3 N / 25 mm.

[Metal vapor deposition film]
The metal vapor-deposited film 10A preferably has a clearness glossiness (Gd value) of 0.5 or more. The sharpness and glossiness value is a value for evaluating the gloss of the surface of the sample (metal vapor-deposited film 10A), and is a value for evaluating the sharpness of an image reflected on the surface of the sample. The sharpness and glossiness value can be measured using a sharpness and glossiness meter (for example, PGD-IV manufactured by Japan Color Research Institute). The sharpness gloss meter can measure the glossiness observed with the naked eye and the sharpness glossiness value. Specifically, a sample (film) is placed at the bottom of the sharpness gloss meter, light is irradiated from a light source such as a tungsten lamp to a test pattern on which numbers are described, and reflected by a plurality of mirror surfaces, Reflected light (pattern image) is incident on the sample surface. The pattern image is reflected by the sample surface, and further reflected by a plurality of other mirror surfaces, and formed on an observation tube arranged on the observer side. The observer determines the sharpness and glossiness (Gd value) according to the appearance of the image of the imaged test pattern. The Gd value is displayed as 0.1 to 2.0, for example. The larger the number, the higher the glossiness of the sample surface.

The use of the metal vapor-deposited film 10A is not particularly limited, and can be used as a decorative film by being attached to various adherends. According to the metal vapor-deposited film, it is possible to impart a metallic luster equivalent to a coated product to the adherend by a simpler and safer method than painting. Moreover, since the metal vapor-deposited film can be decorated even on the surface of an adherend having a three-dimensional curved surface, which is difficult to decorate with a conventional decorative film, the adherend having a three-dimensional curved surface. Especially suitable for decorating.

The material of the adherend is not particularly limited, but if the metal vapor-deposited film is attached to a plastic adherend such as a resin molded article, the metal-like appearance is obtained while obtaining the advantage of using the plastic adherend. Because it can be used, the utility value is high. Although the kind of said adherend is not specifically limited, For example, a decorative board, the cover for mobile phones, the components for motorcycles, the interior components for vehicles are mentioned.

The method for attaching the metal vapor-deposited film to the adherend is not particularly limited, and examples thereof include wrapping, thermoforming, and vacuum forming. As a specific example of wrapping, there is a method in which a metal vapor deposition film is warmed and softened with a dryer and is attached along a plastic adherend. Further, as a specific example of vacuum forming, a TOM molding machine (manufactured by Fuse Vacuum Co., Ltd., model number: NGF-0406) is used as a vacuum / pressure forming machine, and the heating temperature of the heater is 80 to 140 ° C. The method of sticking a metal vapor deposition film is mentioned. According to vacuum forming, it can prevent effectively that air enters between a metal vapor deposition film and a to-be-adhered body.

(Embodiment 2)
The manufacturing method of the metal vapor deposition film of Embodiment 2 is the same as that of Embodiment 1 except having the process of forming the primer layer 6 in the base material 1 before the process of forming the said metal vapor deposition film 3. FIG. FIG. 2 is a cross-sectional view schematically showing a metal vapor deposition film produced by the method for producing a metal vapor deposition film of Embodiment 2. As shown in FIG. 2, the metal vapor-deposited film 10 </ b> B produced by the method for producing a metal vapor-deposited film of Embodiment 2 has a primer layer 6 between the substrate 1 and the metal vapor-deposited film 3.

By forming the primer layer 6 between the base material 1 and the metal vapor deposition film 3, the adhesion between the base material 1 and the metal vapor deposition film 3 can be improved. The method for forming the primer layer 6 is not particularly limited, and examples thereof include a bar coating method, a roll coating method, a blade coating method, a reverse coating method, a gravure coating method, and a die coating method.

The step of forming the primer layer 6 may be before the step of attaching the support film 2 or between the step of attaching the support film 2 and the step of forming the metal vapor deposition film 3. May be. When the step of forming the primer layer 6 is before the step of attaching the support film 2, the support film 2 is attached to the surface of the substrate 1 opposite to the surface on which the primer layer 6 is formed. When the step of forming the primer layer 6 is between the step of attaching the support film 2 and the step of forming the metal vapor-deposited film 3, the primer layer 6 has attached the support film 2 of the substrate 1 It is formed on the surface opposite to the surface.

The surface roughness of the primer layer 6 is preferably 2.0 μm or less. If the surface roughness of the primer layer 6 exceeds 2.0 μm, the flatness of the surface of the metal vapor-deposited film 3 is lowered, and the sharpness of the design of the metal vapor-deposited film 10B may be impaired. The lower limit of the surface roughness of the primer layer 6 is not particularly limited. The lower the surface roughness, the better the visibility of the metal vapor-deposited film 10A.

[Primer layer]
The primer layer 6 is a layer that improves the adhesion between the substrate 1 and the metal vapor deposition film 3. The primer layer 6 is not particularly limited, and may contain, for example, an acrylic urethane type, polyvinyl chloride type, vinyl chloride / vinyl acetate copolymer type, butyral type resin, or the like.

(Embodiment 3)
The manufacturing method of the metal vapor deposition film of Embodiment 2 is the same as that of Embodiment 1 except having the process of forming the surface protective layer 8 in the surface on the opposite side to the base material 1 of the metal vapor deposition film 3. FIG. FIG. 3 is a cross-sectional view schematically showing a metal vapor deposition film produced by the method for producing a metal vapor deposition film of Embodiment 3. As shown in FIG. 3, the metal vapor-deposited film 10 </ b> C produced by the method for producing a metal vapor-deposited film of Embodiment 3 has an adhesive layer 7 and a surface protective layer on the surface of the metal vapor-deposited film 3 opposite to the substrate 1. 8, and the surface protective layer 8, the adhesive layer 7, the metal vapor deposition film 3, the base material 1, and the pressure-sensitive adhesive layer 4 may be laminated in this order. 10 C of metal vapor deposition films may also have a primer layer between the base material 1 and the metal vapor deposition film 3, like the metal vapor deposition film 10B.

The step of forming the surface protective layer 8 includes, for example, a method of forming an adhesive layer on the surface of the metal vapor-deposited film 3 on the side opposite to the substrate 1 and laminating the surface protective layer 8 on the adhesive layer. It is done. The surface protective layer 8 can be produced by a conventionally known molding method such as calendar molding, extrusion molding, injection molding or the like. Examples of the calendar format used for the calendar molding include an inverted L shape, a Z shape, an upright two shape, an L shape, and an inclined three shape.

[Adhesive layer]
The adhesive layer 7 is a layer obtained by curing an adhesive for attaching the surface protective layer 8 to the surface of the metal vapor deposition film 3. As the adhesive, those having excellent adhesiveness and transparency are suitable. Even when the adhesive is stored in a high-temperature environment of 60 ° C. or higher (conditions for accelerated evaluation test) after the metal vapor-deposited film is attached to the adherend, it is preferable that the adhesive strength does not decrease.

The adhesive is not particularly limited, and for example, a polyester polyurethane adhesive, an acrylic resin adhesive, a rubber adhesive, a polyester resin adhesive, or the like can be used. Although the thickness of the adhesive bond layer 7 is not specifically limited, It is preferable that it is 5-25 micrometers, and it is more preferable that it is 5-15 micrometers. The adhesive layer 7 preferably has a total light transmittance of 80% or more. If the total light transmittance is less than 80%, the metallic luster of the metal vapor deposition film 3 may be impaired. The total light transmittance is more preferably 90% or more.

[Surface protective layer]
The surface protective layer 8 contains a resin component, and the resin component is preferably polyvinyl chloride or an acrylic resin (polymethyl methacrylate resin). The surface protective layer 8 has a role of protecting the surface of the metal vapor-deposited film 3, but by using a vinyl chloride resin or an acrylic resin as a resin component, it has high transparency and a relatively low temperature (about 130 ° C.). Good moldability can be obtained. High transparency is calculated | required from a viewpoint which prevents that the metallic luster obtained by the metal vapor deposition film 3 is impaired for the surface protective layer 8. FIG. In addition, good moldability at a relatively low temperature means that the metal vapor deposition film has excellent followability to the shape of the three-dimensional curved surface when it is attached to the substrate while heating (at the time of molding), and embossing It means that the concave / convex shape can be imparted and the concave / convex shape can be maintained during molding.

The resin component is preferably polyvinyl chloride, and may be an acrylic resin. The polyvinyl chloride in the surface protective layer 8 may be the same as or different from the polyvinyl chloride in the substrate 1 in terms of composition and average molecular weight.

As the acrylic resin in the surface protective layer 8, conventionally known ones can be used. For example, alkyl methacrylate-alkyl acrylate copolymer A, alkyl methacrylate-alkyl acrylate-styrene copolymer B Or a mixture thereof. Acrylic resins are particularly excellent in transparency and strength.

The alkyl methacrylate that is a monomer component of the copolymer A and the copolymer B is not particularly limited. For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate And 2-ethylhexyl methacrylate and the like. Among these, it is preferable to use methyl methacrylate as the monomer component of the copolymer A and the copolymer B from the viewpoint that the calendar processability is advantageous. These may be used alone or in combination of two or more.

The alkyl acrylate that is a monomer component of the copolymer A and the copolymer B is not particularly limited. For example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate And 2-ethylhexyl acrylate. Among them, the monomer components of the copolymer A and the copolymer B are both acrylic acid 2 which is an alkyl acrylate having a large number of carbon atoms in the alkyl portion from the viewpoint of improving the flexibility. It is preferable to use ethylhexyl. These may be used alone or in combination of two or more.

The alkyl methacrylate as the monomer component of the copolymer A and the alkyl methacrylate as the monomer component of the copolymer B may be the same or different. Similarly, the alkyl acrylate as the monomer component of the copolymer A and the alkyl acrylate as the monomer component of the copolymer B may be the same or different. In addition, the said acrylic resin may contain another acrylic resin in the range which does not inhibit the effect of this invention.

The surface protective layer 8 may contain a plasticizer. The plasticizer in the surface protective layer 8 may be the same as or different from the plasticizer in the substrate 1 in terms of composition and number average molecular weight. The plasticizer content in the surface protective layer 8 is preferably 10 to 25 parts by weight with respect to 100 parts by weight of the resin component. When the content is within the above range, the moldability at a relatively low temperature is particularly good. If the content is less than 10 parts by weight, the surface protective layer 8 becomes too hard, and the film may be torn during molding. On the other hand, when the amount exceeds 25 parts by weight, the surface protective layer 8 becomes too soft, whereby the metal vapor deposition film is easily peeled off from the adherend, and the surface protective layer 8 may be easily peeled off from the substrate 1. The content of the plasticizer is more preferably 15 to 25 parts by weight. In addition, since the surface protective layer 8 and the base material 1 are laminated | stacked, it is preferable that it is fundamentally the same hardness. Therefore, if the surface protective layer 8 and the base material 1 have the same thickness, the plasticizer content is preferably the same.

The surface protective layer 8 contains additives such as stabilizers, ultraviolet absorbers, colorants, foaming agents, lubricants, modifiers, fillers such as inorganic particles and inorganic fibers, and diluents as necessary. Also good. As these additives, those generally blended with a vinyl chloride resin or an acrylic resin can be used, and they may be the same as or different from the additives in the substrate 1.

Although the thickness of the surface protective layer 8 is not specifically limited, It is preferable that it is 40-200 micrometers, and it is more preferable that it is 50-100 micrometers. The total light transmittance of the surface protective layer 8 is preferably 80% or more. If the total light transmittance is less than 80%, the metallic luster of the metal vapor deposition film 3 may be impaired. The total light transmittance is more preferably 90% or more.

The surface of the surface protective layer 8 may be subjected to surface processing such as embossing as necessary. If an embossed shape (irregular shape) is imparted to the surface of the surface protective layer 8 by embossing, the design of the metal deposited film can be improved by the synergistic effect of improving the texture due to the embossed shape and the good metallic luster of the metal deposited film 3. Can be greatly increased. Although it was possible to emboss the conventional decorative film, it was difficult to maintain the uneven shape during molding into a curved surface shape, and the design was greatly reduced. When the resin component of the surface protective layer 8 is a vinyl chloride resin or an acrylic resin, the embossed shape can be maintained during molding into a curved surface shape, and the design is maintained until after molding.

It is preferable that the unevenness by embossing has a transfer rate of 60% or more. The transfer rate indicates the ratio of the depth of the unevenness transferred to the film to the depth of the unevenness provided on the embossing mold (for example, an embossing roll). For example, the unevenness depth of the mold is 100 μm, When the uneven depth is 50 μm, the transfer rate is 50%. Moreover, the said uneven | corrugated depth is a value based on the maximum height roughness (Ry) prescribed | regulated to JISB0601 (2013).

The surface protective layer 8 preferably has an outermost surface roughness of 2.0 μm or less. When embossing is performed on the surface protective layer 8, the surface roughness can be reduced to 2.0 μm or less by embossing with a mirror surface roll. When embossing is performed with a roll having an uneven shape, the surface roughness may be about 2.0 to 10 μm.

EXAMPLES Hereinafter, although an Example is hung up and demonstrated in more detail about this invention, this invention is not limited only to these Examples.

Example 1
A polyvinyl chloride (PVC) film used as a substrate was produced by the following procedure. 20 parts by weight of diisononyl phthalate (DINP) was added as a plasticizer to 100 parts by weight of PVC having an average degree of polymerization of 1000 to obtain a PVC compound. The obtained PVC compound was melt-kneaded with a Banbury mixer, and then molded into a sheet having a thickness of 50 μm with an inverted L-shaped calendar to produce a PVC film. Note that additives such as a heat stabilizer, an antioxidant, and a pigment for coloring may be added to the PVC compound.

Next, a polyethylene terephthalate (PET) film having a thickness of 12 μm was stacked on the substrate as a support film, and was laminated by laminating at 150 to 160 ° C. The PET film was not subjected to easy peeling treatment. The surface roughness of the surface opposite to the surface on which the support film of the base material was attached was 1.2 μm. The surface roughness was measured by a method based on JIS B 0601 (2013). Moreover, the peeling force of a base material and a support film was 0.06 N / 25mm. The said peeling force was measured by the method based on JISZ0237.

Then, the aluminum (Al) vapor deposition layer was formed in the surface on the opposite side to the surface which affixed the support film of the base material by the vacuum evaporation method.

In addition, a pressure-sensitive adhesive is applied on one surface of a separator (biaxially stretched polyester (PET) film, “Lumirror (registered trademark)” manufactured by Toray Industries, Inc.) with a comma bar coater to a dry thickness of 40 μm. A solution (“Hybon 7663” manufactured by Hitachi Chemical Co., Ltd.) was applied to form a coating film. The said coating film was heat-dried at 80 degreeC for 1 minute in the drying furnace, the solvent in a coating film was removed, and the adhesive layer was obtained.

Next, the support film is peeled from the base material, and the separator and the laminate are bonded to the surface of the base material from which the support film has been peeled, with the pressure-sensitive adhesive layer formed on the separator. Transferred to the substrate side. Thereby, the metal vapor deposition film of Example 1 was obtained. The structure of the metal vapor deposition film of Example 1 is shown in Table 1 below. In Table 1, the surface roughness on the metal vapor deposition surface side of the substrate is the surface roughness of the surface opposite to the surface on which the support film of the substrate is attached.

(Examples 2-9 and Comparative Examples 1-3)
In the same manner as in Example 1, metal deposited films having the configurations shown in Table 1 below were produced. In Comparative Example 3, a metal vapor deposition film was formed without attaching a support film to the substrate.

(Evaluation test)
About the metal vapor deposition film produced by the Example and the comparative example, the following method evaluated (1) the presence or absence of a metal nonuniformity, (2) the presence or absence of a stripe type, and (3) visibility by the following method. Moreover, comprehensive evaluation was performed from the result of said (1)-(3). Comprehensive evaluation made x when the metal unevenness of the above (1) occurs, and ○ when the metal unevenness does not occur at least. Furthermore, the case where all of the above (1) to (3) were good was marked as ◎. The results of (1) are shown in Table 1 below.

(1) Presence / absence of metal unevenness The presence / absence of metal unevenness in the metal vapor-deposited film was obtained by visually observing the surface of the metal vapor-deposited film. The result was determined according to the following criteria. The metal unevenness is an appearance defect that occurs when the base material is bent and the thickness of the metal vapor deposition film is different. For example, in the range of about 10 cm, the density of the metal is generated.
(Criteria)
Existence: No metal unevenness was observed visually. No metal unevenness was observed visually.

(2) Presence / absence of streak type Presence / absence of the streaky type of the metal-deposited film was observed visually on the surface of the metal-deposited film. The result was determined according to the following criteria. The above streak type is an appearance defect that occurs when the base material is deformed and the metal accumulates in the valleys, and metal streaks are generated in a linear shape over the flow direction of the film, for example, 2 to 3 m. To do.
(Criteria)
Existence: No streak type was visually observed None: No streak type was observed visually

(3) Sharpness The sharpness of the metal-deposited film was evaluated according to the following measurement conditions and criteria.
(Measurement condition)
Using a sharpness gloss meter (manufactured by Japan Color Research Institute, PGD-IV), the test pattern reflected on the surface of the metal vapor-deposited film is visually observed, and the sharpness glossiness depends on how the test pattern is visible. (Gd value) was determined.
(Criteria)
If the sharpness / glossiness was 0.5 or more, it was qualified, and if it was less than 0.5, it was unsuitable.

As can be seen from Table 1, in Examples 1 to 9, metal unevenness did not occur, and a metal vapor deposition film having a uniform metal thin film without unevenness was obtained. Further, in Examples 1 to 8, neither metal unevenness nor streak type occurred. Furthermore, in Examples 1-6, 8, and 9, since the surface opposite to the surface on which the support film of the substrate was attached was flat, a uniform metal thin film could be formed on the surface of the substrate, A metal-deposited film excellent in sharpness was obtained. However, in Example 8, since the content of the plasticizer contained in the substrate was small, the moldability was slightly inferior.

On the other hand, in Comparative Example 1, since the thickness of the support film was smaller than the thickness of the base material, the base material was bent during the vapor deposition process, and a uniform metal thin film could not be formed. In Comparative Example 2, since the peeling force between the base material and the support film was weak, the support film was peeled off during the vapor deposition process, and the base material was bent and a uniform metal thin film could not be formed. In Comparative Example 3, since the metal vapor deposition film was formed without attaching the support film to the base material, the base material was bent during the vapor deposition processing, and metal unevenness occurred.

DESCRIPTION OF SYMBOLS 1 Base material 2 Support film 3 Metal vapor deposition film 4 Adhesive layer 5 Separator 6 Primer layer 7 Adhesive layer 8 Surface protective layer 10A, 10B, 10C Metal vapor deposition film

Claims (4)

A step of attaching a support film to one surface of a substrate made of polyvinyl chloride;
Forming a metal vapor-deposited film on the surface opposite to the surface to which the support film of the substrate is attached;
After the formation of the metal vapor deposition film, the step of peeling the support film from the substrate;
Forming a pressure-sensitive adhesive layer on the surface from which the support film of the substrate has been peeled,
The thickness of the support film is at least 0.1 times the thickness of the base material,
The method for producing a metal-deposited film, wherein a peeling force between the substrate and the support film is 0.05 N / 25 mm or more. The thickness of the said base material is 50 micrometers or more and 200 micrometers or less, The manufacturing method of the metal vapor deposition film of Claim 1 characterized by the above-mentioned. The method for producing a metal vapor-deposited film according to claim 1 or 2, wherein the surface roughness of the surface opposite to the surface on which the support film of the substrate is attached is 2.0 µm or less. The said metal vapor deposition film contains aluminum, tin, or indium, The manufacturing method of the metal vapor deposition film in any one of Claims 1-3 characterized by the above-mentioned.

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