JP6734077B2 - Metallic decorative film and decorative molded products - Google Patents

Description

The present invention relates to a metal-tone decorative film and a decorative molded product.

Conventionally, there is known a method of attaching a metal-tone decorative film produced by performing metal vapor deposition on a resin film to a base material in order to impart a metal-like design to the base material (adherend). Documents disclosing the prior art relating to the metallic decorative film include, for example, Patent Documents 1 and 2.

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

Further, in Patent Document 2, (A) (a-1) a biaxially stretched polyethylene terephthalate film, (a-2) an acrylic resin film or (a-3) a polycarbonate resin film, and having a maximum back surface At least one selected from (B) tin, gold and indium on the back surface of the transparent resin film having a height average Rtm of 0.1 to 2.0 μm and a haze value of 0.1 to 4.0%. Disclosed is a metal-finished sheet having a metal deposition layer containing

JP 2012-76353A JP, 2013-18292, A

In recent years, it has been considered to attach a metallic decorative film to a three-dimensional curved surface as well as a flat surface. However, when the shape of the three-dimensional curved surface is complicated, it is difficult to make the metallic decorative film follow the shape of the three-dimensional curved surface without impairing its design. Therefore, there has been a demand for a metal-like decorative film having stretchability that can follow an arbitrary three-dimensional curved surface without impairing the design.

It should be noted that if the molding temperature of the film (temperature at the time of attachment) is increased, the film becomes softer, so that it is possible to improve the followability to the three-dimensional curved surface. However, when the molding temperature is increased, the base material may be damaged by deformation or the like. Further, also on the side of the metal-tone decorative film, there is a possibility that the pre-formed embossed shape may disappear or be deformed due to high temperature. For this reason, it has been required that the attachment process on the three-dimensional curved surface be performed at a low temperature.

The present invention has been made in view of the above-mentioned current situation, and is excellent in designability and is suitable for sticking to a three-dimensional curved surface, and a metal-tone decorative film, and using the metal-tone decorative film. It is intended to provide a decorative molded product obtained.

The present inventor has noticed that a metal-tone decorative film having an excellent metallic luster can be obtained in a configuration in which an indium vapor deposition layer is formed on a base film and the surface of the indium vapor deposition layer is covered with a surface protective film. did. Then, as a result of various studies, by using vinyl chloride resin or acrylic resin as the resin component contained in the base film and the surface protection film, the moldability at a lower temperature (about 130° C.) than that of the conventional one is improved. Therefore, it was found that a metal-tone decorative film suitable for sticking to a three-dimensional curved surface can be obtained. Furthermore, a film containing a vinyl chloride resin or an acrylic resin as a resin component can impart an embossed shape to the surface of the film and can maintain the embossed shape during molding. The present invention has been completed by finding that a metal-like decorative film having a very excellent design can be realized by the synergistic effect of a good metallic luster.

The metal-like decorative film of the present invention is a metal-like decorative film obtained by laminating a surface protective film, an adhesive layer, an indium vapor deposition layer, a base film, an adhesive layer and a separator in that order, and the surface protective film. The film and the base film contain a resin component, and the resin component is a vinyl chloride resin or an acrylic resin.

The surface protective film contains a plasticizer, and the content of the plasticizer is preferably 10 to 25 parts by weight with respect to 100 parts by weight of the resin component.
The thickness of the surface protective film is preferably 40 to 200 μm.

The base film contains a plasticizer, and the content of the plasticizer is preferably 10 to 25 parts by weight with respect to 100 parts by weight of the resin component.
The base film preferably has an arithmetic average roughness of 2.0 μm or less on the surface of the indium vapor deposition layer side.
The thickness of the base film is preferably 50 to 200 μm.

It is preferable that the surface protective film and the base film are stretched by 150% or more without breaking when laminated and subjected to a tensile test at 100°C.
The surface protection film and the base film preferably have a breaking strength of 1 to 30 MPa when laminated and subjected to a tensile test at 100°C.

The decorative molded product of the present invention is a decorative molded product comprising a base material having a three-dimensional curved surface portion and a decorative film covering the three-dimensional curved surface portion, wherein the decorative film is the metal of the present invention. It is characterized in that the above-mentioned separator is peeled from the decorative film, and is attached to the above-mentioned three-dimensional curved surface portion via the above-mentioned adhesive layer.

INDUSTRIAL APPLICABILITY The metal-tone decorative film of the present invention has excellent designability and is suitable for sticking to a three-dimensional curved surface. In addition, the decorative molded product of the present invention is obtained by pasting the metal-like decorative film of the present invention onto a base material including a three-dimensional curved surface portion, which has been difficult to impart a design with a conventional decorative film. As a result, it is possible to give a high-quality design.

It is sectional drawing which showed an example of the metal-like decorative film of this invention typically.

The metal-like decorative film of the present invention is a metal-like decorative film obtained by laminating a surface protective film, an adhesive layer, an indium vapor deposition layer, a base film, an adhesive layer and a separator in that order, and the surface protective film. The film and the base film contain a resin component, and the resin component is a vinyl chloride resin or an acrylic resin. In the present specification, “film” has the same meaning as “sheet”, and the two are not distinguished by the thickness.

FIG. 1 is a cross-sectional view schematically showing an example of the metallic decorative film of the present invention. The metallic decorative film shown in FIG. 1 is a laminated body in which a surface protection film 11, an adhesive layer 12, an indium vapor deposition layer 13, a base film 14, an adhesive layer 15 and a separator 16 are laminated in this order.

[Surface protection film]
The surface protection film 11 contains a resin component, and the resin component is a vinyl chloride resin or an acrylic resin (polymethylmethacrylate resin). That is, the surface protection film 11 may be what is generally called a polyvinyl chloride film (PVC film) or an acrylic film (PMMA film). The surface protective film 11 has a role of protecting the surface of the indium vapor deposition layer 13, 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 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 other than vinyl chloride resin and acrylic resin (for example, polyethylene terephthalate). doing. High transparency is required from the viewpoint of preventing the metallic gloss obtained by the indium vapor deposition layer 13 from being impaired by the surface protective film 11. In addition, good moldability at a relatively low temperature means that it is excellent in conformability to the shape of the three-dimensional curved surface when the metal decorative film is attached to the base material while heating (during molding), It means that the embossing can give an uneven shape and can maintain the uneven shape during molding. Here, 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, when the unevenness depth of the die is 100 μm, When the uneven depth is 50 μm, the transfer rate is 50%. Moreover, the above-mentioned unevenness depth is a value based on the maximum height (Ry) defined in JIS B 0601 (1994).

The resin component is preferably vinyl chloride resin. Vinyl chloride resin is particularly excellent in moldability at relatively low temperatures. Examples of the vinyl chloride resin 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 cyanide 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 bending resistance of the surface protective film 11 may be deteriorated. Among the above vinyl chloride resins, a vinyl chloride homopolymer is preferable from the viewpoint of obtaining dimensional stability.

The average degree of polymerization of the vinyl chloride resin 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 maintain the embossed shape during molding. 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.

The resin component may be an acrylic resin. Acrylic resins are particularly excellent in transparency and strength. As the acrylic resin, conventionally known ones can be used, and examples thereof include alkyl methacrylate-alkyl acrylate copolymer A, alkyl methacrylate-alkyl acrylate-styrene copolymer B, and mixtures thereof. Used.

The copolymer A is obtained by copolymerizing alkyl methacrylate and alkyl acrylate. The copolymer B is obtained by copolymerizing alkyl methacrylate, alkyl acrylate and styrene. Examples of the method for copolymerizing these include suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization. Further, at the time of polymerization, a chain transfer agent or other polymerization aid may be used if necessary. Various conventionally known chain transfer agents can be used, and mercaptans are particularly preferable.

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 film 11 may contain a plasticizer. The plasticizer is not particularly limited, and those conventionally blended with a vinyl chloride resin or an acrylic resin can be used, and examples thereof include octyl phthalate (di-2-ethylhexyl phthalate (DOP)) and dibutyl phthalate. , Phthalic acid diesters such as dinonyl phthalate; aliphatic dibasic acid diesters such as dioctyl adipate and dioctyl sebacate; phosphoric acid triesters such as tricresyl phosphate and trioctyl phosphate; epoxidized soybean oil and epoxy resin Examples thereof include epoxy plasticizers; polymeric polyester plasticizers and the like.

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 12, which may cause a decrease in adhesive strength. On the other hand, when the number average molecular weight is more than 3000, the effect of softening the film cannot be sufficiently obtained by adding the plasticizer, and the surface protection film 11 becomes too hard, so that the film may be broken during molding. is there.

The content of the plasticizer in the surface protective film 11 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 protection film 11 becomes too hard, and the film may be broken during molding. On the other hand, when the amount is more than 25 parts by weight, the surface protective film 11 becomes too soft, so that the metallic decorative film may be easily peeled from the base material, and the surface protective film 11 may be easily peeled from the base film 14. The content of the plasticizer is more preferably 15 to 25 parts by weight. Since the surface protection film 11 and the base film 14 are laminated, it is preferable that they have basically the same hardness. Therefore, the surface protective film 11 and the base film 14 preferably have the same plasticizer content as long as they have the same thickness.

The surface protective film 11 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. May be. As these additives, those generally blended with vinyl chloride resin or acrylic 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 above-mentioned metallic 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 exceeds 2.0 parts by weight, bleeding may occur on the surface of the surface protective film 11.

The thickness of the surface protective film 11 is not particularly limited, but is preferably 40 to 200 μm. When the thickness is less than 40 μm, the metal-like decorative film of the present invention may be too flexible and the workability may be reduced, or the weather resistance may be reduced. On the other hand, if the thickness exceeds 200 μm, the conformability to the shape of the three-dimensional curved surface portion during molding may be insufficient.

The surface of the surface protective film 11 may be subjected to surface processing such as embossing, if necessary. If an embossed shape (irregular shape) is provided on the surface of the surface protection film 11 by embossing, the metal tone decoration of the present invention is achieved by the synergistic effect of improving the texture by the embossing shape and the good metallic luster feeling by the indium vapor deposition layer 13. The design of the film can be greatly improved. 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. In the present invention, since the resin component of the surface protective film 11 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 retained until after molding.

The surface protection film 11 preferably has high transparency in order not to impair the metallic luster of the indium vapor deposition layer 13, and specifically, the total light transmittance is preferably 80% or more. If the total light transmittance is less than 80%, the metallic luster of the indium vapor deposition layer 13 may be impaired. The total light transmittance is more preferably 90% or more. In addition, in this specification, the total light transmittance is a value based on JIS K7375.

The surface protective film 11 preferably has a flat surface in order to obtain high transparency. Specifically, the arithmetic average roughness of the surface (hereinafter, also referred to as “surface roughness”) is 2.0 μm. The following is preferable. In addition, in this specification, the arithmetic mean roughness means the arithmetic mean roughness Ra in accordance with JIS B 0601 (1994). When the surface protection film 11 is embossed, the arithmetic mean 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 arithmetic average roughness may be about 2 to 10 μm.

[Adhesive layer]
The adhesive layer 12 is a layer in which an adhesive for attaching the surface protection film 11 to the surface of the indium vapor deposition layer 13 is hardened. As the above adhesive, one having excellent adhesiveness and transparency is suitable. When the indium vapor deposition layer 13 is formed of indium scattered on the base film 14, the adhesive is preferably one that easily penetrates between the indium particles. In addition, even if the adhesive is stored in a high temperature environment of 60° C. or more (acceleration evaluation test condition) after the metal decorative film is attached to the base material, the adhesive strength may not decrease. preferable.

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 12 is not particularly limited, but is preferably 5 to 25 μm, more preferably 5 to 15 μm.

The adhesive layer 12 preferably has a total light transmittance of 80% or more. If the total light transmittance is less than 80%, the metallic luster of the indium vapor deposition layer 13 may be impaired. The total light transmittance is more preferably 90% or more.

[Indium deposition layer]
The indium deposition layer 13 is a layer for imparting a metallic luster to the appearance of the metal decorative film of the present invention. Examples of the vapor deposition method for forming the indium vapor deposition layer 13 include a vacuum vapor deposition method, a sputtering method, an ion plating method, and the like. Since indium is a metal having a high extensibility, the indium vapor deposition layer 13 does not generate cracks even when the metal-tone decorative film of the present invention is attached to the three-dimensional curved surface portion, It is possible to follow the elongation of the film 14 and the like.

The form of the indium vapor deposition layer 13 is not particularly limited as long as it gives a metallic luster sensation, and indium may not be continuously present to form a film covering the base film 14. May be scattered on the base film 14. The total light transmittance of the indium vapor deposition layer 13 is preferably 5 to 20%. When the total light transmittance is less than 5%, the amount of indium is large, so that the metal-like decorative film becomes hard and the formability deteriorates. When the total light transmittance is more than 20%, the hiding property may be deteriorated, and the appearance of the metallic decorative film may be changed depending on the elongation rate of the metallic decorative film. In particular, when the metal decorative film is stretched by 100% or more, the color of the base film 14 is easily visible from the surface.

[Base film]
The base film 14 contains a resin component, and the resin component is vinyl chloride resin or acrylic resin. The base film 14 has a role as a base material for forming the indium vapor deposition layer 13. By using a vinyl chloride resin or an acrylic resin as the resin component of the base film 14, the three-dimensional curved surface part can be formed when the metal decorative film is attached to the base material (during molding) at a relatively low temperature (about 130° C.). There is an advantage that excellent conformability to a shape (formability) can be obtained. Further, since the vapor deposition of the indium vapor deposition layer 13 is generally performed at a high temperature, the resin component of the base film 14 is required to have high heat resistance. For example, when the base film 14 is deformed by heat during vapor deposition, the amount of indium deposited on the film surface varies. Further, when gas is generated from the base film 14 by heat during vapor deposition, deposition of indium on the film surface is hindered. On the other hand, since both vinyl chloride resin and acrylic resin have high heat resistance, they do not deform or generate gas due to heat during vapor deposition.

The resin component is preferably vinyl chloride resin, and may be acrylic resin. The vinyl chloride resin or acrylic resin in the base film 14 may be the same as or different from the vinyl chloride resin or acrylic resin in the surface protection film 11 in terms of composition, average molecular weight and the like.

The base film 14 may contain a plasticizer. The plasticizer in the base film 14 may be the same as or different from the plasticizer in the surface protective film 11 in terms of composition, number average molecular weight, and the like.

The content of the plasticizer in the base film 14 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 base film 14 becomes too hard, and the film may be broken during molding. On the other hand, if the amount exceeds 25 parts by weight, the base film 14 becomes too soft, which may result in easy peeling. The content of the plasticizer is more preferably 15 to 20 parts by weight.

The base film 14 contains additives such as a stabilizer, a UV 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 mixed with vinyl chloride resin or acrylic resin can be used, and they may be the same as or different from the additives in the surface protective film 11. ..

The thickness of the base film 14 is not particularly limited, but is preferably 50 to 200 μm. When the thickness is less than 50 μm, the metal-like decorative film of the present invention may be too flexible and the workability may be lowered, or the weather resistance may be lowered. On the other hand, if the thickness exceeds 200 μm, the conformability to the shape of the three-dimensional curved surface portion during molding may be insufficient.

The surface of the base film 14 may be subjected to a surface treatment in order to improve the adhesion with the indium vapor deposition layer 13. Examples of the type of surface treatment include corona discharge treatment, plasma treatment, ozone treatment and the like.

The base film 14 preferably has a flat surface, and specifically, the arithmetic average roughness (Ra) of the surface on the indium vapor deposition layer 13 side is preferably 2.0 μm or less. At the time of vapor deposition, indium enters the irregularities on the surface of the base film 14, and the surface shape of the indium vapor deposition layer 13 is affected by the irregular shape existing on the surface of the base film 14 which is the vapor deposition surface. When the flatness of the surface of the base film 14 is high, the metallic appearance is glossy, and when the flatness of the surface of the base film 14 is low, the metallic appearance is matte. If the arithmetic mean roughness exceeds 2.0 μm, the flatness of the surface of the indium vapor deposition layer 13 becomes low, and the sharpness of the design of the metal decorative film of the present invention may be impaired.

The surface protective film 11 and the base film 14 are preferably stretched by 150% or more without breaking when laminated and subjected to a tensile test at 100°C. When the extension rate at 100° C. is 150% or more, it is suitable for sticking to a three-dimensional curved surface. The elongation rate can be obtained from the following formula by performing a tensile test using a tensile tester in accordance with JIS K 7162. In the following formula, La is the length of the test piece before performing the tensile test, and Lb is the length of the test piece when the test piece breaks in the tensile test.
Expansion rate (%)={(Lb−La)/La}×100

Further, the surface protection film 11 and the base film 14 preferably have a breaking strength of 1 to 30 MPa when laminated and subjected to a tensile test at 100°C. If the breaking strength at 100° C. is 1 to 30 MPa, it is suitable for sticking to a three-dimensional curved surface. If the breaking strength is less than 1 MPa, it may not follow the three-dimensional curved surface and may break. If the breaking strength exceeds 30 MPa, the film may be too hard to follow the three-dimensional curved surface. The breaking strength can be measured by a method according to JIS K7161. Specifically, using a tensile tester, the test piece is left for 1 minute in an environment of 100°C. Then, the test piece is pulled at a measurement temperature of 100° C. at a speed of 200 mm/min, and the tension (MPa) when the sample is broken is measured.

[Adhesive layer]
The pressure-sensitive adhesive layer 15 is not particularly limited as long as it has at least one of an adhesive function (pressure-sensitive adhesive property) and an adhesive function, and specifically, an acrylic adhesive, a rubber adhesive, and a silicone adhesive. Examples include those containing an adhesive such as a system 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 acrylic pressure-sensitive adhesive is a pressure-sensitive adhesive containing an acrylic polymer. Examples of the acrylic polymer include a homopolymer of (meth)acrylic acid alkyl ester or a copolymer thereof.

As the (meth)acrylic acid alkyl ester, for example, an ester obtained from a primary to tertiary alcohol having an alkyl group having 2 to 18, preferably 4 to 12 carbon atoms and acrylic acid or methacrylic acid, and the like. Are listed. Specific examples include methyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and the like. These may be used alone or in combination of two or more.

The copolymerizable monomer used in the synthesis of the copolymer has at least one unsaturated double bond involved in the copolymerization reaction in the molecule, and also has a carboxyl group [eg (meth)acrylic acid, Itaconic acid, maleic acid, maleic anhydride, etc.], hydroxyl group [eg (meth)acrylic acid hydroxyethyl ester, (meth)acrylic acid hydroxypropyl ester etc.], sulfoxyl group [eg styrene sulfonic acid, allyl sulfonic acid, (Meth)acrylic acid sulfopropyl ester, (meth)acryloyloxynaphthalenesulfonic acid, acrylamidomethylpropanesulfonic acid, etc.], amino group [eg (meth)acrylic acid aminoethyl ester, (meth)acrylic acid dimethylaminoethyl ester, (Meth)acrylic acid tert-butylaminoethyl ester, etc.], amide group [for example, (meth)acrylamide, dimethyl(meth)acrylamide, N-butylacrylamide, N-methylol(meth)acrylamide, N-methylolpropane (meth)] Acrylamide, etc., alkoxyl groups [eg (meth)acrylic acid methoxyethyl ester, (meth)acrylic acid ethoxyethyl ester, (meth)acrylic acid methoxyethylene glycol ester, (meth)acrylic acid methoxydiethylene glycol ester, (meth)acrylic Acid methoxy polyethylene glycol ester, (meth)acrylic acid methoxy polyethylene glycol ester, (meth)acrylic acid tetrahydrofurfuryl ester and the like]. These may be used alone or in combination of two or more.

Examples of other copolymerizable monomers include (meth)acrylonitrile, vinyl acetate, vinyl propionate, N-vinyl-2-pyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine. , Vinylpyrrole, vinylimidazole, vinylcaprolactam, vinyloxazole, vinylmorpholine and the like. These may be used alone or in combination of two or more.

As the acrylic pressure-sensitive adhesive, a polymer obtained by polymerizing an alkyl (meth)acrylate at a ratio of 40% by weight or more is preferable. In particular, a copolymerization weight obtained by copolymerizing 50 to 98 wt% of one or more (meth)acrylic acid alkyl ester with 2 to 50 wt% of one or more copolymerizable monomers. Coalescence is preferred.

The weight average molecular weight of the acrylic pressure-sensitive adhesive is preferably 600,000 to 1,000,000. When the weight average molecular weight is in the range of 600,000 to 1,000,000, it is advantageous in that sufficient adhesive force can be exhibited. On the other hand, if the weight average molecular weight is less than 600,000, adhesive residue may occur. On the other hand, if the weight average molecular weight is more than 1 million, the wettability is lowered to exhibit a desired adhesive force. Can be difficult. The weight average molecular weight of the acrylic pressure-sensitive adhesive is more preferably 700,000 to 900,000.

The weight average molecular weight (Mw) of the acrylic pressure-sensitive adhesive is a polystyrene-converted measurement value by GPC (gel permeation chromatograph) measurement. The measurement conditions are as follows.
Device name: HLC-8120 (manufactured by Tosoh Corporation)
Column: G7000HXL 7.8 mm ID x 30 cm 1 piece GMHXL 7.8 mm ID x 30 cm 2 pieces G2500HXL 7.8 mm ID x 30 cm 1 piece (Tosoh Corporation)
Dilute with tetrahydrofuran so that the sample concentration is 1.5 mg/ml. Mobile phase solvent: Tetrahydrofuran flow rate: 1.0 ml/min
Column temperature: 40°C

The pressure-sensitive adhesive layer 15 is formed, for example, by applying a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive, a cross-linking agent (curing agent) or the like on a support to form a coating film, and then applying the coating film. It can be formed by a method of curing by heating and drying. 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 isocyanate curing agent is a compound having an isocyanate group, and specific examples thereof include, for example, tolylene diisocyanate, xylylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hydrogenation. Compounds having two isocyanate groups in the molecule such as diphenylmethane diisocyanate; compounds obtained by addition reaction of these with polyhydric alcohols such as trimethylolpropane and pentaerythritol; and polyether polyols, polyester polyols, acrylic polyols , A polybutadiene polyol, a polyisoprene polyol, and the like, and a compound having two or more isocyanate groups in the urethane prepolymer type molecule that has been subjected to an addition reaction.
Among them, a compound obtained by addition-reacting a compound having two isocyanate groups in the molecule with a polyhydric alcohol is preferable, and a compound obtained by addition-reacting tolylene diisocyanate or diphenylmethane diisocyanate with a polyhydric alcohol is more preferable.

The epoxy curing agent is a compound having an epoxy group, and specific examples thereof include bisphenol A epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, and glycerin triglycidyl ether. , 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, diamine glycidyl amine, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis( Examples thereof include compounds having two or more epoxy groups in the molecule such as N,N'-diamineglycidylaminomethyl)cyclohexane.

When the crosslinking agent is contained, its content is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight (solid content) of the adhesive. If the content is less than 0.05 parts by weight, the crosslink density is low, the cohesive force of the adhesive layer 15 is insufficient, and adhesive residue may occur. If the above content exceeds 10 parts by weight, the adhesive strength may decrease. The content is more preferably 0.1 to 3 parts by weight. When both the isocyanate curing agent and the epoxy curing agent are used, the above content means the total amount of the isocyanate curing agent and the epoxy curing agent.

The adhesive composition may further contain a catalyst. Examples of the catalyst include the catalysts used in the reaction of the above-mentioned cross-linking agent, and examples thereof include organotin compounds such as di-n-butyltin dilaurate, dimethyltin dilaurate, dibutyltin oxide and octane tin; organotitanium compounds; organic compounds. Zirconium compounds; carboxylic acid tin salts; carboxylic acid bismuth salts; amine catalysts such as triethylenediamine.

The adhesive composition may further contain a solvent such as a hydrophobic organic solvent. Examples of the hydrophobic organic solvent include ethyl acetate, toluene, hexane, mineral oil, petroleum ether and the like.

The adhesive composition may further contain an inorganic filler. By blending the above-mentioned inorganic filler, the hiding property of the substrate can be improved. Examples of the inorganic filler include titanium oxide, kaolin, bentonite, calcium carbonate, talc, carbon black, iron oxide, titanium oxide/antimony oxide/nickel oxide solid solution, aluminum hydroxide, magnesium hydroxide and the like. Of these, titanium oxide is preferable. This is because it is white and has excellent hiding power.

The content of the inorganic filler is preferably 3 to 30 parts by weight with respect to 100 parts by weight of the adhesive. If the content is less than 3 parts by weight, sufficient adhesiveness may not be imparted to the adhesive layer 15, whereas if the content exceeds 30 parts by weight, the adhesive layer 15 may be insufficient. May have insufficient tackiness.

The average particle diameter of the inorganic filler is preferably 0.05 to 5 μm. If the average particle size is less than 0.05 μm, the dispersibility may be poor. On the other hand, if the average particle size is more than 5 μm, the hiding power and the adhesive strength may be reduced. Here, the average particle diameter of the inorganic filler is a median particle diameter (50% volume particle diameter).

In the adhesive composition, the stabilizer, the plasticizer, the softening agent, the filler, and the tackifier may be added, if necessary, to the extent that they do not impair the properties required for the metal decorative film of the present invention. Various additives such as agents, dyes and pigments may be added.

The coating amount of the adhesive composition is preferably 10 to 90 g/m ² (dry weight conversion). In other words, it is preferable that the coating amount of the adhesive layer 15 obtained by drying the adhesive composition is 10 to 90 g/m ² . By adjusting the coating amount in the range of 10 to 90 g/m ² , it is possible to secure the adhesive force of the adhesive layer 15. If the coating amount is less than 10 g/m ² , the adhesive strength may be insufficient. If the coating amount exceeds 90 g/m ² , adhesive residue is likely to occur on the adhesive layer 15. 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 thickness of the adhesive layer 15 is preferably 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 adhesive layer 15 is 20 to 40 μm.

[separator]
By providing the separator 16, the adhesive layer 15 is prevented from being exposed during the production, transportation and storage of the metal decorative film of the present invention, so that the adhesive layer 15 is prevented from being deteriorated and the adhesive layer 15 of the present invention is provided. It is possible to improve the handleability of the metallic decorative film. The separator 16 may be peeled off immediately before being attached to the base material.

The separator 16 is not particularly limited, but a separator that can be easily peeled off without damaging the adhesive layer 15 is preferable. For example, a silicone resin, a fluororesin, or the like may be provided on the surface in contact with the adhesive layer 15. A resin film (release film) made of polyester, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, polypropylene, etc., which has been subjected to an easy-release treatment by applying; paper such as high-quality paper or glassine paper (release paper); paper And a coating layer. The thickness of the separator 16 is preferably 12 to 200 μm, more preferably 50 to 150 μm.

In addition to the surface protection film 11, the adhesive layer 12, the indium vapor deposition layer 13, the base film 14, the adhesive layer 15 and the separator 16, the metal tone decorative film of the present invention includes, for example, other primer layers and the like. Layers may be provided.

The metal-tone decorative film of the present invention can be manufactured by utilizing a conventionally known manufacturing method. The surface protection film 11 and the base film 14 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.

The indium vapor deposition layer 13 can be formed on the base film 14 by using a vapor deposition method such as a vacuum vapor deposition method, a sputtering method, an ion plating method, or the like. The adhesive layer 12 may be formed by, for example, applying an adhesive on the surface protection film 11, bonding the adhesive to the indium vapor deposition layer 13 formed on the base film 14, and then curing the adhesive. it can.

The method for forming the tacky-adhesive layer 15 is not particularly limited, and for example, a conventionally known method such as a method in which the tacky-adhesive composition is directly applied onto the separator 16 using a bar coater or the like and dried. Can be used. In this case, the adhesive layer 15 formed on the separator 16 is attached to the base film 14 to produce the metal decorative film of the present invention. The metal-tone decorative film of the present invention is further subjected to treatments such as cutting and winding into a roll, if necessary.

The application of the metallic decorative film of the present invention is not particularly limited, and it can be used by being attached to various base materials. According to the metal-tone decorative film of the present invention, a metallic luster similar to that of a coated product can be imparted to a substrate by a simpler and safer method than coating. Further, the metal-like decorative film of the present invention has a three-dimensional curved surface portion because it can be decorated even on the surface of a base material having a three-dimensional curved surface portion which is difficult to decorate with a conventional decorative film. It is particularly suitable for decorating substrates. That is, a decorative molded product comprising a base material having a three-dimensional curved surface portion and a decorative film covering the three-dimensional curved surface portion, wherein the decorative film is the metal-tone decorative film of the present invention to the separator. The decorative molded product which is obtained by peeling off the adhesive and is attached to the three-dimensional curved surface portion via the adhesive layer is also an aspect of the present invention.

The material of the base material is not particularly limited, but if the metal-like decorative film of the present invention is attached to a plastic-based base material such as a resin molded product, the appearance of a metal-like appearance can be obtained while obtaining the advantage of using the plastic-based base material. Since it can be obtained, it has high utility value. The type of the base material is not particularly limited, but examples thereof include a mobile phone cover, a motorcycle part, and a vehicle interior part.

The method of sticking the metal decorative film of the present invention to the substrate 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-like decorative film is warmed and softened by a dryer while being attached along the plastic base material. 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 a heating temperature of the heater is 80 to 140° C. The method of sticking a metal tone decorative film is mentioned. By vacuum forming, it is possible to effectively prevent air from entering between the metallic decorative film and the base material.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the present specification, "part" means "part by weight" and "%" means "% by weight" unless otherwise specified.

(Example 1)
A polyvinyl chloride (PVC) film used as a surface protection film and a base film was prepared by the following procedure.
15 parts by weight of bis(2-ethylhexyl) phthalate ("DOP" manufactured by J-Plus Co.) as a plasticizer was added to 100 parts by weight of PVC having an average polymerization degree 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.

Then, an indium (In) vapor deposition layer having a total light transmittance of about 10% was formed on one surface of the base film by a vacuum vapor deposition method. Further, a polyester polyurethane adhesive (“Vylon (registered trademark) 50AS” manufactured by Toyobo Co., Ltd.) was coated on one surface of the surface protective film with a comma bar coater so that the dry thickness was 10 μm. Then, the indium vapor deposition layer formed on the base film and the adhesive coated on the surface protection film are in a direction in which they are in contact with each other, and the base film and the surface protection film are bonded by pressure bonding with a nip roll, and laminated. Got the body

In addition, a separator (biaxially stretched polyester (PET) film, "Lumirror (registered trademark)" manufactured by Toray Industries, Inc.) having a thickness of 100 μm is adhered to one surface of the separator with a comma bar coater so that the dry thickness is 40 μm. A coating solution was formed by applying a binder solution ("Hybon 7663" manufactured by Hitachi Chemical Polymer Co., Ltd.). 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 separator and the laminate were bonded together via the adhesive layer, and the adhesive layer formed on the separator was transferred to the laminate side. Thereby, the metal-tone decorative film of Example 1 was obtained. The constitution of the metallic decorative film of Example 1 is shown in Table 1 below.

(Examples 2 to 10, reference examples and comparative examples 1 to 3)
In the same manner as in Example 1, a metallic decorative film having the constitution shown in Table 1 below was produced. The adhesive layer was the same in all Examples, Reference Examples and Comparative Examples. In Example 8, a PMMA film (Acryprene (registered trademark) HBS006 manufactured by Mitsubishi Rayon Co., Ltd.) was used as the surface protection film. In Comparative Example 2, a PET film (Lumirror (registered trademark) H10 manufactured by Toray Industries, Inc.) was used as the surface protection film.
In the reference example, the surface roughness of the surface protective film is remarkably larger than that of the example.

(Evaluation test)
With respect to the metallic decorative films produced in Examples, Reference Examples and Comparative Examples, (1) gloss value, (2) embossing workability, (3) curved surface formability, and (4 ) The breaking strength at 100°C was evaluated. The results are shown in Table 1 below.

(1) Gloss value The gloss value of the surface of the metal decorative film on the surface protective film side was measured. A black specular glass plate having a refractive index of 1.567 was used as a reference for the gloss value. The measurement conditions and criteria are shown below.
(Measurement condition)
The gloss value (glossiness) at a measurement angle of 60° was measured using a gloss measuring instrument and evaluated according to the following criteria. The gloss measuring device is not particularly limited as long as it can measure reflected light at an incident angle of 60° and a light receiving angle of 60° according to JIS K 7105. For example, a digital variable angle gloss meter manufactured by Nippon Denshoku Industries Co., Ltd. VG-1D etc. are mentioned.
(Criteria)
◯: Gloss value is 85 or more ×: Gloss value is less than 85

(2) Embossing property An embossing shape was given to the surface of the surface protective film using an embossing roll under the following processing conditions. The formed embossed shape was confirmed, and the result was judged according to the following criteria.
(Processing conditions)
Maximum height of unevenness on embossing roll surface Ry: 80±20 μm
Material of embossing roll: Temperature of iron embossing roll: Normal temperature Film temperature when passing through embossing roll: Range of 150 to 200°C Pressure: 20±10 (N)
(Criteria)
◯: Transfer rate is 60% or more ×: Transfer rate is less than 60%

(3) Formability into curved surface shape The separator was peeled off from the metal-like decorative film and attached to a substrate having a three-dimensional curved surface portion. For the attachment, a TOM molding machine (Fuse Vacuum Co., Ltd., model number: NGF-0406) was used as a vacuum/compressed air molding machine. Based on whether or not the metal-tone decorative film stretches 100% or more within the set temperature range (80 to 140° C.) and follows the shape of the three-dimensional curved surface portion, it was determined according to the following criteria.
(Criteria)
◯: Can be molded in the set temperature range △: Can be molded in the set temperature range, but film breakage occurred at the edge of the substrate, or the film did not penetrate to the edge of the substrate ×: Cannot be molded in the set temperature range

(4) Breaking strength at 100° C. The same surface protection film and base film as those used in the production of the metallic decorative film were cut into a length of 15 cm and a width of 2.5 cm, respectively, and laminated to form a test piece. did. After leaving the test piece for 1 minute in an environment of 100° C., a tensile test was performed by a method according to JIS K7162. Specifically, using a tensile tester (manufactured by Shimadzu Corporation, AG-100NXplus), the measurement temperature was 100° C. and the tensile speed was 200 mm/min.

As can be seen from Table 1, the metallic decorative films of Examples 1 to 10 had good results in terms of gloss value, embossability, formability into curved surface shape, and breaking strength at 100°C. .. However, the metal-tone decorative film of Example 9 contained a small amount of the plasticizer in the surface protective film, and the metal-tone decorated film of Example 10 contained a large amount of the plasticizer in the surface protective film. Was slightly inferior in moldability to a curved shape. Further, the metal-tone decorative film of Reference Example had a low gloss value because the surface protection film had a large surface roughness.

On the other hand, the metal-tone decorative film of Comparative Example 1 was inferior in formability into a curved shape because aluminum (Al) was used in the metal vapor deposition layer. The metal decorative films of Comparative Examples 2 and 3 used polyethylene terephthalate (PET) as the surface protection film or the base film, and thus were inferior in both embossability and moldability into a curved shape.

11 Surface Protective Film 12 Adhesive Layer 13 Indium Deposition Layer 14 Base Film 15 Adhesive Layer 16 Separator

Claims (8)

A surface decorative film, an adhesive layer, an indium vapor deposition layer, a base film, a tacky adhesive layer and a metal-like decorative film in which a separator is laminated in order,
The surface protection film and the base film contain a resin component, and have a breaking strength of 1 to 30 MPa when laminated and subjected to a tensile test at 100°C.
The resin component is a vinyl chloride resin or an acrylic resin, which is a metal-like decorative film. The surface protective film contains a plasticizer,
Content of the said plasticizer is 10-25 weight part with respect to 100 weight part of the said resin components, The metal tone decorative film of Claim 1 characterized by the above-mentioned. The metal decorative film according to claim 1 or 2, wherein the surface protection film has a thickness of 40 to 200 µm. The base film contains a plasticizer,
Content of the said plasticizer is 10-25 weight part with respect to 100 weight part of the said resin components, The metal-like decorative film in any one of Claims 1-3 characterized by the above-mentioned. The metal film according to any one of claims 1 to 4, wherein the base film has an arithmetic average roughness of 2.0 µm or less on a surface on the side of the vapor deposition layer of indium. The thickness of the said base film is 50-200 micrometers, The metal-like decorating film in any one of Claims 1-5 characterized by the above-mentioned. 7. The surface protective film and the base film, when laminated and subjected to a tensile test at 100[deg.] C., are stretched by 150% or more without breakage. The metallic decorative film described. A decorative molded product comprising a base material having a three-dimensional curved surface portion and a decorative film covering the three-dimensional curved surface portion,
The decorative film is from metallic decorative film according to any one of claims 1 to 7 obtained by peeling off the separator, affixed to the three-dimensional curved surface portion through said adhesive layer A decorated molded product characterized by being.

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