JP6736451B2 - Method for producing metal vapor deposition film - Google Patents

Description

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

Conventionally, there is known a method of attaching a resin film having a metal thin film layer to an adherend in order to impart a metallic design to the adherend. Documents disclosing prior art relating to a resin film having a metal thin film layer include, for example, Patent Documents 1 and 2.

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

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

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

Examples of the method of forming the metal thin film layer on the resin film include a method of depositing a metal on the resin film serving as the base material. In the metal vapor 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, the base material is generally a polyester film such as polyethylene terephthalate (PET) having high heat resistance. An acrylic film such as polymethylmethacrylate (PMMA) is used.

In recent years, it has been studied to attach a metal vapor deposition film to a three-dimensional curved surface as well as a flat 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 is difficult to break. On the other hand, a polyvinyl chloride film has lower heat resistance than PET, PMMA, etc., and in particular, a polyvinyl chloride film used for decorating an adherend having a three-dimensional curved surface softens from about 60°C. However, it was not suitable for vapor deposition processing. When a polyvinyl chloride film that is easily softened is subjected to vapor deposition processing, the film is softened and bent during processing, which makes it difficult to uniformly apply a metal to the surface of the base material and unevenness may occur.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a metal vapor deposition film having a uniform and thin metal thin film.

The present inventor examined a method of forming a metal vapor deposition film on a substrate made of polyvinyl chloride, and after attaching a supporting film to the substrate, the side of the substrate opposite to the surface on which the supporting film was attached. It has been found that by forming a metal vapor deposition film on the surface, a uniform metal thin film without metal unevenness can be formed even when a polyvinyl chloride film having low heat resistance is used as a substrate. Furthermore, the support film having a specific thickness, and by having a peeling force between the base material and the support film to a certain level or more, the base material is suppressed from bending during vapor deposition processing, and the surface of the base material is suppressed. The present invention has been 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 comprises a step of attaching a support film to one surface of a substrate made of polyvinyl chloride, and a metal vapor deposition on the surface of the base material opposite to the surface on which the support film is attached. The method has a step of forming a film, a step of peeling the support film from the base material after forming 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 is peeled off. The thickness of the support film is 0.1 times or more 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. And

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

The surface roughness of the surface of the substrate opposite to the surface on which the support film 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 and thin metal thin film.

FIG. 3 is a schematic diagram schematically showing the method for producing a metal vapor deposition film of Embodiment 1. 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. 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.

(Embodiment 1)
The method for producing a 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 the surface of the base material opposite to the surface on which the support film is attached. There is 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 is peeled off. The thickness of the support film is 0.1 times or more 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. Characterize. In the present specification, “film” has the same meaning as “sheet”, and the two are not distinguished by the thickness.

The method for producing the metal vapor deposition film of Embodiment 1 will be described below with reference to FIG. FIG. 1 is a schematic diagram schematically showing the method for producing a metal vapor deposition film of Embodiment 1. As shown in (d) of FIG. 1, a metal vapor deposition film 10A manufactured by the method for manufacturing a metal vapor deposition film of Embodiment 1 has a metal vapor deposition film 3, a base material 1 and an adhesive layer 4 laminated in this order. .. The metal vapor deposition film 10A may have a separator 5 on the surface of the pressure-sensitive adhesive layer 4 opposite to the base material 1.

Below, the manufacturing method of the metal vapor deposition film of Embodiment 1 is demonstrated using FIG. FIG. 1A shows a step of attaching the support film 2 to one surface of the base material 1 made of polyvinyl chloride. The base material 1 is a film made of polyvinyl chloride and has a role of a support for the metal vapor deposition film 10A. By using polyvinyl chloride as the resin component of the base material 1, it is excellent in the shape of the three-dimensional curved surface part when the metal deposition film is attached to the adherend (during molding) at a relatively low temperature (about 130°C). There is an advantage that excellent followability (formability) can be obtained. The term “relatively low temperature” as used herein means that the temperature is lower than the molding temperature (over 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 carried out at a high temperature (500 to 800° C.), but since polyvinyl chloride has a lower heat resistance than PET, PMMA, etc., it easily bends during vapor deposition processing ( The metal cannot be uniformly attached to the surface of the base material 1 and the metal unevenness easily occurs. Therefore, when the vapor deposition process is performed, the support film 2 is temporarily attached to prevent the base material 1 from being softened and bent by heating, and a uniform thin metal film 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 the surface of the base material 1 opposite to the vapor deposition surface when the metal vapor deposition film 3 is formed on the base material 1. The method of attaching the support film 2 to the base material 1 is not particularly limited, and examples thereof include a method of stacking the base material 1, the support film and the support film 2 and laminating 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 calender molding, extrusion molding, and injection molding. Examples of the calender type used for the calender molding include an inverted L type, a Z type, an upright 2-line type, an L-type, and a 3-line inclined type.

FIG. 1B shows a step of forming the metal vapor deposition film 3 on the surface of the base material 1 opposite to the surface on which the support film 2 is attached. Examples of the method for forming the metal vapor deposition film 3 include vapor deposition methods such as a vacuum vapor deposition method, a sputtering method, and an ion plating method. In particular, since vapor deposition processing is performed by heating to a high temperature, it is possible to effectively suppress the occurrence of metal unevenness when using the vacuum vapor deposition method.

The surface roughness of the surface of the base material 1 opposite to the surface on which the support film 2 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. At the time of vapor deposition, the metal enters the irregularities on the surface of the base material 1, and the surface shape of the metal vapor deposition film 3 is affected by the irregular shape existing on the surface of the base material 1 which is the vapor deposition surface. When the flatness of the surface of the substrate 1 is high, the metallic appearance is glossy, and when the flatness of the surface of the substrate 1 is low, the metallic appearance is matte. When the surface roughness exceeds 2.0 μm, the flatness of the surface of the metal vapor deposition film 3 becomes low, which may impair the sharpness of the design of the metal vapor deposition film 10A. The lower limit of the surface roughness of the base material 1 is not particularly limited, and the lower the surface roughness of the base material 1, the better the image clarity. In the present specification, the “surface roughness” means the arithmetic average roughness Ra according to JIS B 0601 (2013).

The surface of the base material 1 opposite to the surface on 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 type of surface treatment include corona discharge treatment, plasma treatment, ozone treatment and the like.

FIG. 1C shows a step of peeling the support film 2 from the base material 1 after forming the metal vapor deposition film 3. Since the support film 2 is peeled off after the metal vapor deposition film 3 is formed, the metal vapor deposition film 10A does not have the support film 2.

The peeling force between the base material 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 is bent to cause metal unevenness. The upper limit of the peeling force is, for example, 0.3 N/25 mm. If the peeling force is more than 0.3 N/25 mm, the adhesive force between the base material 1 and the support film 2 is too high, and therefore the base material 1 is deformed when peeled from the base material 1 after the metal vapor deposition film 3 is formed. There is something to do. The preferable upper limit of the peeling force is 0.2 N/25 mm, and the preferable upper limit is 0.1 N/25 mm. The peeling force can be measured by a method according to JIS Z 0237.

FIG. 1D shows a step of forming the pressure-sensitive adhesive layer 4 on the surface of the base material 1 from which the support film 2 has been peeled off. The method for forming the pressure-sensitive adhesive layer 4 is not particularly limited, and for example, a commercially available pressure-sensitive adhesive sheet may be attached to the surface of the base material 1 from which the support film 2 has been peeled off, or the pressure-sensitive adhesive layer 4 formed on the separator 5 may be used. Alternatively, it may be attached to the surface of the base material 1 from which the support film 2 is peeled off. When the pressure-sensitive adhesive layer 4 formed on the separator 5 is attached, a conventionally known method such as a method of coating the pressure-sensitive adhesive composition on the separator 5 with a bar coater and drying it can be used.

Further, after the step of forming the pressure-sensitive adhesive layer 4, there may be a step of attaching the separator 5 to the surface of the pressure-sensitive adhesive layer 4 opposite to the base material 1. In the step of forming the pressure-sensitive adhesive layer 4, when the method of bonding the pressure-sensitive adhesive layer 4 formed on the separator 5 is used, the step of forming the pressure-sensitive adhesive layer 4 also serves as the step of bonding the separator 5. Good.

The above metal vapor deposition film is further subjected to treatments such as cutting and winding into a roll, if 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 another monomer. 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, and preferably 10% by weight or less. If it exceeds 50% by weight, the flex resistance of the substrate 1 may be deteriorated. Among the above polyvinyl chloride, a vinyl chloride homopolymer 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 hardness of the film and the amount of the plasticizer used for adjusting the hardness, and is, for example, 750 to 1300. .. The preferable upper limit of the average degree of polymerization is 1050. When the average degree of polymerization is in the range of 750 to 1300, the moldability at a relatively low temperature is particularly good. On the other hand, if 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, if the average degree of polymerization exceeds 1300, the conformability to the shape of the three-dimensional curved surface portion at the time of molding may be insufficient. In the present specification, the average degree of polymerization of polyvinyl chloride means the average degree of polymerization measured according to JIS K6721 “Test method for vinyl chloride resin”.

The base material 1 may contain a plasticizer. The plasticizer is not particularly limited, and those conventionally blended with vinyl chloride resin can be used, and examples thereof include octyl phthalate (di-2-ethylhexyl phthalate (DOP)), dibutyl phthalate, and phthalic acid. Phthalic acid diesters such as dinonyl and diisononyl phthalate (DINP); Aliphatic dibasic acid diesters such as dioctyl adipate and dioctyl sebacate; Phosphoric acid triesters such as tricresyl phosphate and trioctyl phosphate; Large epoxidation Epoxy plasticizers such as soybean oil and epoxy resin; polymeric polyester plasticizers and the like can be mentioned.

Examples of the high molecular weight polyester plasticizer include polyalkylene glycol diesters such as polyethylene glycol diester of phthalic acid, polypropylene glycol diester, and polyethylene glycol polypropylene glycol diester; polyethylene glycol diester of aliphatic dibasic acid such as adipic acid and sebacic acid. Examples thereof include 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. When the number average molecular weight is less than 350, the plasticizer easily migrates to the adhesive layer 7, which may cause a decrease in adhesive strength. On the other hand, when the number average molecular weight is more than 3,000, the effect of softening the film cannot be sufficiently obtained by adding the plasticizer, and the surface protective layer 8 becomes too hard, so that the film may be broken during molding. is there.

The content of the plasticizer 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. When the content is within the above range, the substrate 1 is unlikely to be deformed by heat, and a more uniform metal thin film can be formed on the surface. When the content is less than 10 parts by weight, the base material 1 becomes too hard, which lowers the moldability and may break the film during 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 likely to bend during vapor deposition processing, and metal unevenness is likely to occur. The more preferable lower limit of the content of the plasticizer is 18 parts by weight, and the more preferable upper limit thereof is 23 parts by weight.

The base material 1 may contain additives such as a stabilizer, an ultraviolet absorber, a colorant, a foaming agent, a lubricant, a modifier, a filler such as inorganic particles and inorganic fibers, and a diluent, if necessary. Good. As these additives, those generally blended with vinyl chloride resin can be used.

Examples of the stabilizer include metal soap 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, barium ricinoleate, and the like. The stabilizers include epoxy stabilizers, barium stabilizers, calcium stabilizers, tin stabilizers, zinc stabilizers, calcium-zinc (Ca-Zn), barium-zinc (Ba). Complex stabilizers such as -Zn type) can also be used.

When the stabilizer is contained, its 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 adding the stabilizer may not be sufficiently exerted, while if the content is more than 5.0 parts by weight, the stabilizer may bloom (spout). ) May occur.

When the ultraviolet absorbent is contained, its content is preferably 0.3 to 2.0 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 is not so great, while if the content is more than 2.0 parts by weight, the surface of the surface protective layer 8 may be bleeded.

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

[Supporting film]
Examples of the support film 2 include polyester films such as polyethylene terephthalate (PET), acrylic films such as polymethylmethacrylate (PMMA), polycarbonate (PC), and the like. A PET film is preferable because it has excellent heat resistance. The surface of the support film 2 is preferably not subjected to easy peeling treatment. Since the hydrophobicity of the surface of the support film 2 increases when the easily peeling treatment agent is applied, it may be difficult to attach the base film 1 and the support film 2 with a desired peeling force when laminating the base material 1 and the support film 2.

The thickness of the support film 2 is 0.1 times or more the thickness of the base material 1.
If the thickness of the support film 2 is less than 0.1 times the thickness of the base material 1, the base material 1 cannot be sufficiently supported when performing vapor deposition on the surface of the base material 1, and the base material 1 is bent. , Metal unevenness occurs. The upper limit of the thickness of the support film 2 with respect to the thickness of the substrate 1 is not particularly limited, but is preferably 5 times or less, for example. 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 thereof is 4 times, and the further preferable upper limit thereof 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 thereof is 500 μm, the still more preferable upper limit thereof is 250 μm, and the particularly preferable upper limit thereof is 100 μm.

[Metal evaporated 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. The metal vapor deposition film 3 preferably contains aluminum, tin or indium. Since these metals have excellent extensibility, the metal vapor deposition film 3 is unlikely to generate cracks even when the metal vapor deposition 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 an adhesive function, and specifically, acrylic pressure-sensitive adhesive, rubber pressure-sensitive adhesive, silicone pressure-sensitive adhesive. And the like containing an adhesive. Among them, acrylic adhesives are preferably used because they are excellent in tackiness, workability, heat aging resistance, moisture aging resistance, and weather resistance and are 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 method of curing. The cross-linking agent (curing agent) is a compound that chemically reacts or interacts with the functional group in the pressure-sensitive adhesive to cross-link it. As the cross-linking agent, known cross-linking agents such as isocyanate-based curing agents and epoxy-based curing agents can be used.

The pressure-sensitive adhesive composition may further contain a catalyst, a solvent such as a hydrophobic organic solvent, or an inorganic filler, if necessary. Further, the pressure-sensitive adhesive composition, as long as it does not impair the properties required for the metal vapor deposition film of the present invention, if necessary, stabilizers, plasticizers, softeners, fillers, tackifiers, dyes, 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 (converted to dry weight). In other words, the coating amount of the pressure-sensitive adhesive layer 4 obtained by drying the pressure-sensitive adhesive composition is preferably 10 to 90 g/m ² . The adhesive force of the pressure-sensitive adhesive layer 4 can be secured by adjusting the coating amount in the range of 10 to 90 g/m ² . If 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 , part of the pressure-sensitive adhesive layer 4 remains on the surface of the adherend, and adhesive residue tends to occur. The 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 conformability to irregularities on the surface of the base material can be obtained. The more preferable upper limit of the coating amount is 70 g/m ² .

The pressure-sensitive adhesive layer 4 preferably has a thickness of 10 to 60 μm. If the thickness is less than 10 μm, sufficient tackiness may not be obtained in some cases, and if the thickness exceeds 60 μm, the tackiness is not so improved. The 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 pressure-sensitive adhesive layer 4 from being exposed during the production, transportation, and storage of the metal vapor-deposited film 10A, prevent deterioration of the pressure-sensitive adhesive layer 4, and improve the handleability of the metal vapor-deposited film 10A. Become. The separator 5 may be peeled off immediately before being attached to the adherend.

The separator 5 is not particularly limited, but a separator that can be easily peeled off without damaging the pressure-sensitive adhesive layer 4 is preferable. For example, by applying a silicone resin, a fluororesin, or the like to the surface in contact with the pressure-sensitive adhesive layer 4. Resin film (release film) such as polyester, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, polypropylene, etc. that has been subjected to easy release treatment; paper such as high-quality paper and glassine paper (release paper); between paper and coating layer Examples include laminated films. The thickness of the separator 5 is preferably 12 to 200 μm, 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 0.1 to 0.5 N/25 mm, for example. The lower limit of the peeling force is preferably larger than 0.3 N/25 mm.

[Metal evaporated film]
It is preferable that the metal vapor deposition film 10A has a definition glossiness (Gd value) of 0.5 or more. The sharpness gloss value is a value for evaluating the gloss of the surface of the sample (metal evaporated film 10A), and is a value for evaluating the sharpness of the 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 definition glossiness meter can measure so that the glossiness visually observed and the definition glossiness value match. Specifically, a sample (film) is placed on the bottom of the clarity gloss meter, and a test pattern on which numbers and the like are written is irradiated with light from a light source such as a tungsten lamp and reflected by a plurality of mirror surfaces, The reflected light (pattern image) is made incident on the sample surface. The pattern image is reflected by the sample surface, further reflected by a plurality of other mirror surfaces, and imaged on the observation tube arranged on the observer side. The observer determines the sharpness/glossiness (Gd value) based on the appearance of the image of the formed test pattern. The Gd value is displayed, for example, from 0.1 to 2.0, and the larger the number, the higher the glossiness of the sample surface.

The use of the metal vapor deposition film 10A is not particularly limited, and the metal vapor deposition film 10A can be attached to various adherends and used as a decorative film. According to the above metal vapor deposition film, it is possible to give the adherend a metallic luster equivalent to that of a coated article by a simpler and safer method than coating. Further, since the metal vapor deposition film can decorate even the surface of an adherend having a three-dimensional curved surface portion, which has been difficult to decorate with a conventional decorative film, an adherend having a three-dimensional curved surface portion Especially suitable for decorating.

The material of the adherend is not particularly limited, but if the metal vapor deposition film is attached to a plastic-based adherend such as a resin molded product, a metallic appearance can be obtained while obtaining the advantage of using the plastic-based adherend. Because it is possible, it is highly useful. The type of the adherend is not particularly limited, and examples thereof include a decorative plate, a mobile phone cover, a motorcycle component, and a vehicle interior component.

The method for attaching the above metal vapor deposition film to the adherend is not particularly limited, and examples thereof include lapping, thermoforming, and vacuum forming. As a specific example of the wrapping, there is a method in which the metal vapor deposition film is warmed and softened by a dryer while being attached along the plastic-based adherend. Further, as a specific example of the vacuum forming, a TOM forming machine (manufactured by Fuse Vacuum Co., model number: NGF-0406) is used as a vacuum/pneumatic forming machine, and the heating temperature of the heater is 80 to 140° C. Another example is a method of attaching a metal vapor deposition film. The vacuum forming can effectively prevent air from entering between the metal vapor deposition film and the adherend.

(Embodiment 2)
The method for producing the metal vapor deposition film of the second embodiment is the same as that of the first embodiment, except that the step of forming the primer layer 6 on the base material 1 is performed before the step of forming the metal vapor deposition film 3. 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 according to the second embodiment. As shown in FIG. 2, the metal vapor deposition film 10</b>B produced by the method for producing a metal vapor deposition film of Embodiment 2 has the primer layer 6 between the base material 1 and the metal vapor deposition 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 may be 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 base material 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 deposition film 3, the primer layer 6 is formed by attaching the support film 2 of the base material 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. When the surface roughness of the primer layer 6 exceeds 2.0 μm, the flatness of the surface of the metal vapor deposition film 3 becomes low, which may impair the sharpness of the design of the metal vapor deposition film 10B. The lower limit of the surface roughness of the primer layer 6 is not particularly limited, and the lower the lower the better the sharpness of the metal vapor deposition film 10A is.

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

(Embodiment 3)
The method for producing a metal vapor deposition film of the second embodiment is the same as that of the first embodiment except that the method includes the step of forming the surface protective layer 8 on the surface of the metal vapor deposition film 3 opposite to the base material 1. 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 according to the third embodiment. As shown in FIG. 3, the metal vapor deposition film 10C produced by the method for producing a metal vapor deposition film of Embodiment 3 has an adhesive layer 7 and a surface protective layer on the surface of the metal vapor deposition film 3 opposite to the base material 1. 8, the surface protection layer 8, the adhesive layer 7, the metal vapor deposition film 3, the substrate 1 and the pressure-sensitive adhesive layer 4 may be laminated in this order. The metal vapor deposition film 10C may also have a primer layer between the base material 1 and the metal vapor deposition film 3, similarly to the metal vapor deposition film 10B.

Examples of the step of forming the surface protective layer 8 include a method of forming an adhesive layer on the surface of the metal vapor deposition film 3 opposite to the base material 1 and laminating the surface protective layer 8 on the adhesive layer. To be The surface protective layer 8 can be produced by a conventionally known molding method such as calender molding, extrusion molding, injection molding or the like. Examples of the calender type used for the calender molding include an inverted L type, a Z type, an upright 2-line type, an L-type, and a 3-line inclined type.

[Adhesive layer]
The adhesive layer 7 is a layer in which an adhesive for attaching the surface protective layer 8 to the surface of the metal vapor deposition film 3 is hardened. As the above adhesive, one having excellent adhesiveness and transparency is suitable. Even when the adhesive is stored in a high temperature environment of 60° C. or higher (acceleration evaluation test condition) after the metal vapor deposition 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. The thickness of the adhesive layer 7 is not particularly limited, but is preferably 5 to 25 μm, more preferably 5 to 15 μm. 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 protection layer]
The surface protective layer 8 contains a resin component, and the resin component is preferably polyvinyl chloride or acrylic resin (polymethylmethacrylate resin). The surface protective layer 8 has a role of protecting the surface of the metal vapor deposition film 3, but by using a vinyl chloride resin or an acrylic resin as a resin component, high transparency and a relatively low temperature (about 130° C.) can be obtained. It is possible to obtain good moldability. The high transparency is required from the viewpoint of preventing the metallic glossy feeling obtained by the metal vapor deposition film 3 from being impaired by the surface protective layer 8. In addition, good moldability at relatively low temperatures means that it is excellent in conformability to the shape of the three-dimensional curved surface when the metal deposition film is attached to the substrate while heating (during molding), and embossed. It means that an uneven shape can be imparted and the uneven shape can be maintained during molding.

The resin component is preferably polyvinyl chloride, and may be 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 above-mentioned acrylic resin in the surface protective layer 8, a conventionally known one can be used. For example, alkyl methacrylate-alkyl acrylate copolymer A, alkyl methacrylate-alkyl acrylate-styrene copolymer B , A mixture thereof or the like is used. Acrylic resins are particularly excellent in transparency and strength.

Alkyl methacrylate, which is a monomer component of the copolymer A and the copolymer B, is not particularly limited, and examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, and hexyl methacrylate. , 2-ethylhexyl methacrylate and the like can be mentioned. Above all, it is preferable to use methyl methacrylate as the monomer component of each of the copolymer A and the copolymer B, from the viewpoint of calender processability being 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, and examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate. , 2-ethylhexyl acrylate, and the like. Among them, both of the monomer components of the copolymer A and the copolymer B are acrylic acid 2 which is an alkyl acrylate having a large number of carbon atoms in the alkyl moiety from the viewpoint that the flexibility can be improved. Preference is given to using ethylhexyl. These may be used alone or in combination of two or more.

The alkyl methacrylate as a monomer component of the copolymer A and the alkyl methacrylate as a 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. The acrylic resin may contain another acrylic resin as long as the effect of the present invention is not impaired.

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, number average molecular weight and the like. The content of the plasticizer 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. When the content is less than 10 parts by weight, the surface protective layer 8 becomes too hard, and the film may be broken during molding. On the other hand, when the amount exceeds 25 parts by weight, the surface protective layer 8 becomes too soft, so that the metal vapor deposition film is likely to be 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. Since the surface protection layer 8 and the base material 1 are laminated, it is preferable that they have basically the same hardness. Therefore, the surface protective layer 8 and the substrate 1 preferably have the same plasticizer content as long as they have the same thickness.

The surface protective layer 8 contains a stabilizer, an ultraviolet absorber, a colorant, a foaming agent, a lubricant, a modifier, a filler such as inorganic particles or inorganic fibers, and an additive such as a diluent, if necessary. Good. As these additives, those generally blended with vinyl chloride resin or acrylic resin can be used, and they may be the same as or different from the additives in the substrate 1.

The thickness of the surface protective layer 8 is not particularly limited, but is preferably 40 to 200 μm, more preferably 50 to 100 μm. 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, if necessary. If an embossed shape (irregular shape) is given to the surface of the surface protective layer 8 by embossing, the design of the metal vapor deposition film is improved by the synergistic effect of improving the texture due to the embossing shape and the good metallic luster feeling of the metal vapor deposition film 3. Can be greatly increased. Although it is possible to perform embossing on a conventional decorative film, it is difficult to maintain the uneven shape during the forming into a curved shape, and the designability is greatly deteriorated. When the resin component of the surface protective layer 8 is vinyl chloride resin or acrylic resin, the embossed shape can be maintained during molding into a curved shape, and the design is retained until after molding.

It is preferable that the transfer rate is 60% or more for imparting the uneven shape by embossing. 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 die (for example, embossing roll). For example, the unevenness depth of the die is 100 μm, and When the uneven depth is 50 μm, the transfer rate is 50%. The above-mentioned unevenness depth is a value based on the maximum height roughness (Ry) defined in JIS B 0601 (2013).

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

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

(Example 1)
A polyvinyl chloride (PVC) film used as a base material was produced by the following procedure. 20 parts by weight of diisononyl phthalate (DINP) as a plasticizer was added 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 calender to produce a PVC film. It should be noted 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 superposed on the base material as a supporting film and laminated by laminating at 150 to 160° C. The PET film used was not subjected to easy peeling treatment. The surface roughness of the surface of the base material opposite to the surface on which the support film was attached was 1.2 μm. The surface roughness was measured by a method according to JIS B 0601 (2013). The peeling force between the base material and the support film was 0.06 N/25 mm. The peeling force was measured by a method based on JIS Z 0237.

Then, an aluminum (Al) vapor deposition layer was formed on the surface of the base material opposite to the surface on which the support film was attached by a vacuum vapor deposition method.

In addition, on one surface of a separator (biaxially stretched polyester (PET) film, "Lumirror (registered trademark)" manufactured by Toray Industries, Inc.) having a thickness of 100 μm, a pressure-sensitive adhesive having a dry thickness of 40 μm with a comma bar coater A solution (manufactured by Hitachi Chemical Polymer Co., Ltd., "Hybon 7663") was applied to form a coating film. The solvent in the coating film was removed by heating and drying the coating film in a drying oven at 80° C. for 1 minute to obtain an adhesive layer.

Next, the support film is peeled from the base material, the surface of the base material from which the support film is peeled off, the separator and the laminate are attached via an adhesive layer to form a 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 of the metal deposition surface side of the substrate is the surface roughness of the surface of the substrate opposite to the surface on which the support film is attached.

(Examples 2-9 and Comparative Examples 1-3)
In the same manner as in Example 1, a metal vapor deposition film having the constitution shown in Table 1 below was produced. In Comparative Example 3, the metal vapor deposition film was formed without attaching the supporting film to the base material.

(Evaluation test)
With respect to the vapor-deposited metal films produced in the examples and comparative examples, (1) presence or absence of metal unevenness, (2) presence or absence of streaks, and (3) sharpness were evaluated as appearance evaluations by the following methods. In addition, comprehensive evaluation was performed from the results of (1) to (3) above. In the comprehensive evaluation, the case where the metal unevenness in the above (1) occurred was evaluated as x, and the case where at least the metal unevenness did not occur was evaluated as o. Furthermore, the case where all of the above (1) to (3) were good was marked with ⊚. The above (1) result is shown in Table 1 below.

(1) Presence or absence of metal unevenness The presence or absence of metal unevenness of the metal vapor deposition film was visually observed on the surface of the metal vapor deposition film. The result was judged according to the following criteria. The metal unevenness is a defective appearance caused by the bending of the base material and the difference in the thickness of the metal vapor deposition film, and the light and shade of the metal occurs in the range of about 10 cm, for example.
(Criteria)
Yes: No metal unevenness was visually observed No: No metal unevenness was visually observed

(2) Presence or absence of streak type The presence or absence of streak type in the metal vapor deposition film was visually observed on the surface of the metal vapor deposition film. The result was judged according to the following criteria. The above-mentioned streak type is a defective appearance that occurs when the base material is deformed and metal is accumulated in the valley portions, and linear streak is generated in the film flow direction, for example, over 2 to 3 m. To do.
(Criteria)
Yes: No streak was visually observed No: No streak was visually observed

(3) Sharpness The sharpness of the metal vapor deposition film was evaluated under the following measurement conditions and criteria.
(Measurement condition)
Using a sharpness gloss meter (PGD-IV, manufactured by Japan Color Research Institute), visually observe the test pattern reflected on the surface of the metal deposition film, and determine the sharpness of the test pattern according to how the test pattern looks. (Gd value) was determined.
(Criteria)
If the sharpness/glossiness was 0.5 or more, it was determined as conforming, and if it was less than 0.5, it was determined as not conforming.

As can be seen from Table 1, in Examples 1 to 9, no metal unevenness was generated and a metal vapor deposition film having a uniform metal thin film was obtained. Furthermore, in Examples 1 to 8, neither metal unevenness nor streak formation occurred. Furthermore, in Examples 1 to 6, 8 and 9, since the surface of the base material opposite to the surface on which the support film was attached was flat, it was possible to form a more uniform metal thin film on the surface of the base material. A metal-deposited film having excellent image clarity was obtained. However, since the content of the plasticizer contained in the base material was small in Example 8, 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 layers 10A, 10B, 10C Metal vapor deposition film

Claims (4)

A step of attaching a support film to one surface of a base material made of polyvinyl chloride,
A step of forming a metal vapor deposition film on the surface opposite to the surface on which the support film of the base material is attached,
After forming the metal vapor deposition film, a step of peeling the support film from the substrate,
A step of forming a pressure-sensitive adhesive layer on the surface of the base material from which the support film is peeled off,
The thickness of the support film is 0.1 times or more the thickness of the substrate,
The peeling force between the base material and the support film is 0.05 N/25 mm or more. The method for producing a metal deposition film according to claim 1, wherein the substrate has a thickness of 50 μm or more and 200 μm or less. The surface roughness of the surface of the base material opposite to the surface on which the support film is attached is 2.0 μm or less, and the method for producing a metal vapor deposition film according to claim 1 or 2. 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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