JP6666196B2 - Jet-black decorative film, decorative molded product, and method of manufacturing jet-black decorative film - Google Patents

Description

The present invention relates to a jet-black decorative film, a decorative molded product, and a method of manufacturing a jet-black decorative film.

BACKGROUND ART Conventionally, in order to impart a jet-black design to a substrate (adherend), a method has been used in which a black paint is applied to the substrate, and then a clear paint is applied thereon. However, since it takes time and effort to dry the paint, it has been proposed to apply a jet-black decorative film to the substrate. Documents that disclose prior art related to jet-black decorative films include, for example, Patent Documents 1 and 2.

Patent Document 1 discloses a surface film having a predetermined total light transmittance, a pressure-sensitive adhesive layer to which a black dye is added, a metal layer holding film having a metal layer formed on at least one surface, and a transparent or black toned pressure-sensitive adhesive layer. And a jet-black decorative sheet formed by laminating black base sheets in this order. Patent Literature 2 discloses a resin composition that contains a polycarbonate resin, a predetermined amount of an organic black dye, and a predetermined amount of a polyalkylene terephthalate as essential components and performs an organic black dye.

JP 2009-40022 A JP 2012-126776 A

In recent years, it has been studied to attach a jet-black decorative film not only to a flat surface but also to a three-dimensional curved surface. The base film layer, which is the support of the jet-black decorative film, is often made of PET (polyethylene terephthalate), polycarbonate resin, etc. because of its high transparency, but the shape of the base material having a three-dimensional curved surface portion Was difficult to follow. It is also conceivable to apply an ultraviolet (UV) curable resin to the surface of the film and apply UV coating in order to obtain gloss, but the followability was insufficient. For this reason, there has been a demand for a jet-black decorative film having the same appearance as a jet-black painted product and an extensibility that can follow any three-dimensional curved surface.

In addition, if the forming temperature of the film (the temperature at the time of sticking) is increased, the film is softened, so that the followability to the three-dimensional curved surface can be improved. However, when the molding temperature is increased, there is a possibility that the base material may be damaged such as deformation. For this reason, it has been required that the bonding process to the three-dimensional curved surface be performed at a low temperature.

The present invention has been made in view of the above situation, and has a jet-black-tone decorative film, which has the same appearance as jet-black painted products, and is also suitable for sticking to a three-dimensional curved surface portion. An object of the present invention is to provide a decorative molded product obtained by using a decorative film, and a method for producing the jet-black decorative film.

The present inventor studied a method for reproducing the jet-black appearance, and contained a black pigment in an amount of 0.5 parts by weight or more and 10 parts by weight or less in a base film layer having a thickness of 100 μm or more and 300 μm or less. By doing so, I found that deep black can be realized. In addition, the total light transmittance is 80% or more on the base film layer, and by providing a surface film layer of a predetermined thickness, the surface of the film is given a gloss and has an appearance similar to a jet-black painted product. It has been found that a decorative film can be obtained. By using a vinyl chloride resin and a plasticizer for the base film layer and using a vinyl chloride resin or an acrylic resin for the surface film layer, the moldability at a relatively low temperature (about 120 ° C.) is improved. Yes, a jet-black decorative film suitable for sticking to a three-dimensional curved surface is obtained, and even if the jet-black decorative film is stuck to a three-dimensional curved surface, the same appearance as a jet-black painted product can be maintained. Thus, the present invention has been completed.

The jet-black decorative film of the present invention has an adhesive layer, a base film layer, and a surface film layer laminated in this order, and the base film layer contains a vinyl chloride resin, a plasticizer, and a black pigment. The content of the black pigment is 0.5 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin, and the thickness of the base film layer is 100 μm or more and 300 μm or less. Wherein the surface film layer contains a vinyl chloride resin or an acrylic resin, the total light transmittance of the surface film layer is 80% or more, and the surface film layer with respect to the thickness of the base film layer. Is characterized in that the thickness ratio is 0.3 or more and 1.0 or less.

The acrylic resin is preferably polymethyl methacrylate.

The black pigment is preferably carbon black.

The jet-black decorative film preferably has a tensile strength at 80 ° C. of 1 to 30 MPa.

The above-mentioned jet-black decorative film preferably has an elongation at 80 ° C. of 150% or more.

The decorative molded product of the present invention is a decorative molded product comprising a substrate having a three-dimensional curved surface portion and a decorative film covering the three-dimensional curved surface portion, wherein the decorative film is the jet-black of the present invention. It is a decorative decorative film, characterized by being attached to the three-dimensional curved surface portion via the adhesive layer.

The method for producing a jet-black decorative film of the present invention comprises a step of forming an adhesive layer and a master batch containing a black pigment, a vinyl chloride resin and a plasticizer, and further mixing a vinyl chloride resin. Obtaining a black resin composition, laminating the black resin composition on the adhesive layer, and forming a base film layer, and a vinyl chloride resin or an acrylic resin on the base film layer. Laminating a resin composition containing: and forming a surface film layer, wherein the content of the black pigment is 20 to 25% by weight with respect to the entire master batch, and The content of the black pigment is 0.5 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin, and the thickness of the base film layer is 100 μm or more and 300 μm or less. The total light transmittance of the surface film layer is 80% or more, and the ratio of the thickness of the surface film layer to the thickness of the base film layer is 0.3 or more and 1.0 or less. It is characterized by.

The jet-black decorative film of the present invention has the same appearance as a jet-black painted product, and is suitable for sticking to a three-dimensional curved surface portion. In addition, the decorative molded product of the present invention is affixed with the jet-black decorative film of the present invention to a substrate including a three-dimensional curved surface portion, which has been difficult to impart a design with a conventional decorative film. This makes it possible to provide high-quality black. Furthermore, the method for producing a jet-black decorative film of the present invention can produce a jet-black decorative film having an appearance equivalent to that of a jet-black painted product and suitable for sticking to a three-dimensional curved surface. it can.

It is sectional drawing which showed typically an example of the jet-black decorative film of this invention. It is the schematic diagram which showed an example of the decorative molded article of this invention.

The jet-black decorative film of the present invention has an adhesive layer, a base film layer, and a surface film layer laminated in this order, and the base film layer contains a vinyl chloride resin, a plasticizer, and a black pigment. The content of the black pigment is 0.5 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin, and the thickness of the base film layer is 100 μm or more and 300 μm or less. Wherein the surface film layer contains a vinyl chloride resin or an acrylic resin, the total light transmittance of the surface film layer is 80% or more, and the surface film layer with respect to the thickness of the base film layer. Is characterized in that the thickness ratio is 0.3 or more and 1.0 or less.

FIG. 1 is a sectional view schematically showing an example of the jet-black decorative film of the present invention. In the jet-black decorative film 10 shown in FIG. 1, an adhesive layer 12, a base film layer 13, and a surface film layer 14 are sequentially laminated. Further, the jet-black decorative film 10 may have a separator 11 on the side of the adhesive layer 12 opposite to the base film layer 13.

[separator]
By providing the separator 11, the adhesive layer 12 is prevented from being exposed during production, transportation, and storage of the jet-black decorative film 10, so that the adhesive layer 12 is prevented from deteriorating and the jet-black decorative film 10 10 can be improved in handleability. What is necessary is just to peel off the separator 11 immediately before sticking to a base material.

The separator 11 is not particularly limited, but is preferably a separator that can be easily peeled off without damaging the adhesive layer 12, and may be a release film or release paper. Examples of the release film include a resin film that has been subjected to an easy peeling treatment. Examples of the resin film include films of polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, polypropylene and the like. The easy peeling treatment includes, for example, a method of applying a silicone resin, a fluororesin, or the like to the surface of the resin film that comes into contact with the adhesive layer 12. Examples of the release paper include paper obtained by applying a silicone resin, a fluororesin, or the like to paper such as high-quality paper or glassine paper. The thickness of the separator 11 is preferably from 12 to 200 μm, more preferably from 50 to 150 μm.

[Adhesive layer]
The adhesive layer 12 is not particularly limited as long as it has at least one of an adhesive function (pressure-sensitive adhesive property) and an adhesive function. The adhesive layer 12 has a high initial tack force (stickiness), maintains a wet state even after being adhered to the substrate, and is easy to peel off. It is preferable to have both properties of an adhesive which solidifies after being attached and an adhesive which is hard to peel off, has an excellent initial tack force, and which is hardened and hardly peels off from the substrate after being attached to the substrate. Is also good. The pressure-sensitive adhesive used for the pressure-sensitive adhesive layer 12 is not particularly limited, and may be a pressure-sensitive adhesive that develops adhesion at room temperature, or may be a hot-melt pressure-sensitive adhesive that develops adhesion when heated. Good. The adhesive layer 12 preferably contains a hot-melt adhesive from the viewpoint of use in vacuum / pressure molding. Since the hot melt adhesive does not contain a solvent, it is suitable for attaching the jet-black decorative film 10 by vacuum / pressure molding. Examples of the hot melt adhesive include a polyester hot melt adhesive, an acrylic hot melt adhesive, a rubber hot melt adhesive, and a silicone hot melt adhesive.

The softening temperature of the hot melt adhesive is preferably 60 ° C. or more and 120 ° C. or less. The polyester-based hot melt adhesive is a solvent-based adhesive containing a saturated polyester resin as a main component, and its softening temperature is usually about 60 to 100 ° C. It can be used in combination with the base film layer 13 containing a processable vinyl chloride resin. Examples of the polyester hot melt adhesive include Hibon 7663 manufactured by Hitachi Chemical Co., Ltd.

The thickness of the adhesive layer 12 is preferably 10 to 60 μm. When the thickness is less than 10 μm, sufficient adhesiveness may not be obtained, and when the thickness is more than 60 μm, the adhesiveness is not significantly improved. The more preferable thickness of the adhesive layer 12 is 20 to 50 μm.

[Base film layer]
The base film layer 13 contains a vinyl chloride resin, a plasticizer, and a black pigment. By using a vinyl chloride resin as a resin component of the base film layer 13, when the jet-black decorative film 10 is applied to a base material at a relatively low temperature (about 120 ° C.) (at the time of molding), a three-dimensional curved surface portion is formed. There is an advantage that excellent followability (formability) to the shape can be obtained. Further, the film containing the vinyl chloride resin has good elongation and is hardly broken, so that it can be easily attached to a three-dimensional curved surface portion.

Examples of the vinyl chloride resin include a homopolymer of vinyl chloride and a copolymer of vinyl chloride with another monomer.

Examples of the other monomers include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene and styrene; and (meth) acrylates such as methyl acrylate, ethyl acrylate and methyl methacrylate. Maleic diesters such as dibutyl maleate and diethyl maleate; diesters of fumaric acid 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, preferably 10% by weight or less. If it exceeds 50% by weight, the bending resistance of the surface film layer 14 may be reduced. Among the vinyl chloride resins, a homopolymer of vinyl chloride is preferred from the viewpoint of obtaining dimensional stability.

The average degree of polymerization of the vinyl chloride resin is not particularly limited, but is preferably 750 to 1300, and more preferably 1050. When the average degree of polymerization is in the range of 750 to 1300, moldability at a relatively low temperature is particularly good. On the other hand, if the average degree of polymerization exceeds 1300, the ability to follow the shape of the three-dimensional curved surface portion during molding may be insufficient.

The plasticizer is not particularly limited, and any of the plasticizers conventionally used in vinyl chloride resins can be used. Examples thereof include octyl phthalate (di-2-ethylhexyl phthalate (DOP)), dibutyl phthalate, and phthalate. Phthalic acid diesters such as dinonyl acid; 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 Epoxy plasticizers; high-molecular polyester plasticizers;

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

The number average molecular weight of the plasticizer is preferably from 350 to 3,000. If 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, if the number average molecular weight exceeds 3,000, the effect of softening the film by adding a plasticizer cannot be sufficiently obtained, and the surface film layer 14 becomes too hard, which may cause the film to break during molding. is there.

The content of the plasticizer in the base film layer 13 is preferably 10 parts by weight or more and 25 parts by weight or less based on 100 parts by weight of the vinyl chloride resin. If 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 layer 13 becomes too hard, and the film may be broken during molding. On the other hand, if it exceeds 25 parts by weight, the jet-black decorative film 10 may not easily penetrate the edge of the substrate because the base film layer 13 becomes too soft, and may be easily peeled off. A more preferred lower limit of the content of the plasticizer is 15 parts by weight, and a more preferred upper limit is 23 parts by weight.

The black pigment is added to color the base film layer 13 black. Since pigments are more excellent in weather resistance than dyes, the jet-black decorative film 10 can be used in a wide range of usage environments by using pigments as coloring agents.

The black pigment is preferably an inorganic pigment. Among them, carbon black is more preferable. Carbon black is preferably used because it is easily available among black pigments and the color tone can be easily adjusted depending on the primary average particle diameter and the like. Note that aniline black, which is a dye, has higher jet-blackness than carbon black, but is inferior in weather resistance. Therefore, carbon black is preferable.

The primary average particle diameter of the black pigment is preferably 10 nm or more and 20 nm or less. When the primary average particle diameter of the black pigment is within the above range, the dispersibility is excellent, and a more excellent jet-black tone can be obtained. Within the above range, the smaller the primary average particle diameter is, the higher the dispersibility is, so that the jet blackness tends to be further increased. If the primary average particle size exceeds 20 nm, jet-blackness may be poor and may become whitish. In addition, the primary average particle diameter refers to the average particle diameter of non-aggregated primary particles.

The content of the black pigment is 0.5 parts by weight or more and 10 parts by weight or less based on 100 parts by weight of the vinyl chloride resin. When the content of the black pigment is less than 0.5 parts by weight, the concealability of the jet-black decorative film 10 is low, and when the jet-black decorative film 10 is attached to a substrate having a three-dimensional curved surface portion, The color of the material is transparent. Further, when the jet-black decorative film 10 is bent, the jet-black color cannot be maintained. On the other hand, when the content of the black pigment exceeds 10 parts by weight, even when the content of the black pigment is increased, the jet-tone color difference of the jet-black decorative film 10 becomes almost invisible. Further, when the content of the black pigment is excessively increased, the black pigment is aggregated and appears as a foreign substance on the film surface, which causes poor appearance.

The base film layer 13 may further contain a pigment other than black. Examples of the pigment other than black include a red pigment and a blue pigment. By containing these pigments, it is possible to adjust the jet-black tint.

The base film layer 13 may contain additives such as a stabilizer, an ultraviolet absorber, a lubricant, a modifier, a filler such as inorganic particles and inorganic fibers, and a diluent, if necessary. As these additives, those generally blended with a vinyl chloride resin can be used.

Examples of the stabilizer include metal soaps such as fatty acid calcium, fatty acid zinc, and fatty acid barium; and hydrotalcite. 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. Examples of the stabilizer include an epoxy stabilizer; a barium stabilizer; a calcium stabilizer; a tin stabilizer; a zinc stabilizer; a calcium-zinc (Ca-Zn), a barium-zinc (Ba). -Zn-based) composite stabilizers can also be used.

When the stabilizer is contained, the content is preferably 0.3 to 5.0 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content is less than 0.3 parts by weight, the effect of blending the stabilizer may not be sufficiently exerted. On the other hand, if the content exceeds 5.0 parts by weight, the stabilizer may not be bloomed. ).

When the ultraviolet absorbent is contained, the content is preferably 0.3 to 2.0 parts by weight based on 100 parts by weight of the vinyl chloride resin. When the content is less than 0.3 part by weight, the effect is not so large. On the other hand, when the content exceeds 2.0 parts by weight, the surface of the base film layer 13 may bleed.

The thickness of the base film layer 13 is 100 μm or more and 300 μm or less. If the thickness is less than 100 μm, a sufficient jet-black color cannot be maintained when the jet-black decorative film 10 is attached to a substrate. On the other hand, if the thickness exceeds 300 μm, the ability to follow the shape of the three-dimensional curved surface during molding becomes insufficient. A preferred lower limit of the thickness is 150 μm, and a preferred upper limit is 250 μm.

[Surface film layer]
The surface film layer 14 contains a vinyl chloride resin or an acrylic resin. That is, the surface film layer 14 may be what is generally called a polyvinyl chloride film (PVC film) or an acrylic film. By using a vinyl chloride resin or an acrylic resin for the surface film layer 14, high transparency and good moldability at a relatively low temperature (about 120 ° C.) can be obtained. Here, “relatively low temperature” means that the temperature is lower than the molding temperature when molding a transparent resin (for example, polyethylene terephthalate) other than the vinyl chloride resin and the acrylic resin. By superimposing on the black base film layer 13, gloss can be imparted to the surface of the jet-black decorative film 10, so that the surface film layer 14 is required to have high transparency. In addition, good moldability at a relatively low temperature means that, when the jet-black decorative film 10 is applied to a substrate while being heated (at the time of molding), it has excellent followability to the shape of a three-dimensional curved surface portion. Point.

The surface film layer 14 may contain a plasticizer. The content of the plasticizer in the surface film layer 14 is preferably 10 parts by weight or more and 25 parts by weight or less based on 100 parts by weight of the vinyl chloride resin. A preferred lower limit of the content of the plasticizer is 15 parts by weight, and a preferred upper limit is 23 parts by weight. The plasticizer in the surface film layer 14 may be the same as or different from the plasticizer in the base film layer 13 in terms of composition, number average molecular weight, content, and the like.

The vinyl chloride resin used for the surface film layer 14 may be the same as or different from the vinyl chloride resin in the base film layer 13 in terms of composition, average molecular weight, and the like.

Examples of the acrylic resin include alkyl acrylate polymers. Among them, polymethyl methacrylate (PMMA) is preferable from the viewpoint that calenderability is advantageous. The acrylic resin may be a homopolymer of PMMA, or may contain another acrylic resin as long as the effects of the present invention are not impaired.

The surface film layer 14 may contain additives such as stabilizers, ultraviolet absorbers, lubricants, modifiers, fillers such as inorganic particles and inorganic fibers, and diluents, as necessary. As these additives, those generally blended with a vinyl chloride resin or an acrylic resin can be used.

The thickness of the surface film layer 14 is preferably 30 μm or more and 150 μm or less. When the thickness of the surface film layer 14 is within the above range, the moldability is excellent and the base film layer 13 can be followed, so that the appearance equivalent to the jet-black painted product can be maintained even after the decorative molding. . If the thickness of the surface film layer 14 is less than 30 μm, a uniform film may not be formed when calendering is used. On the other hand, if the thickness of the surface film layer 14 exceeds 150 μm, it is necessary to increase the processing temperature for decorative molding. Examples of commercially available acrylic films include Acryprene HBS006 manufactured by Mitsubishi Rayon Co., Ltd.

The total light transmittance of the surface film layer 14 is 80% or more. By arranging the surface film layer 14 having a total light transmittance of 80% or more on the base film layer 13, the surface can be made glossy and the black color of the base film layer 13 can be made more prominent. If the total light transmittance is less than 80%, the luster of the surface of the jet-black decorative film 10 becomes insufficient. A preferable lower limit of the total light transmittance is 85%. The total light transmittance is measured by a method according to JIS K 7105. The surface film layer 14 preferably has a flat surface in order to obtain high transparency. However, if the total light transmittance is 80% or more, the surface film layer 14 is sufficient as the surface film layer 14 used in the present invention. It can be determined that it has excellent surface smoothness.

The ratio of the thickness of the surface film layer 14 to the thickness of the base film layer 13 is 0.3 or more and 1.0 or less. If the above ratio is less than 0.3, the thickness of the surface film becomes thin when following a three-dimensional curved surface shape, and the gloss becomes insufficient. On the other hand, when the above ratio exceeds 1.0, the thickness of the surface film layer 14 becomes large, and the moldability becomes insufficient. In particular, the bite into the end of the curved base material becomes insufficient. A preferred lower limit of the thickness ratio is 0.5, and a preferred upper limit is 0.8.

In addition to the surface film layer 14, the base film layer 13, the adhesive layer 12 and the separator 11, the jet-black decorative film 10 of the present invention may be provided with another layer such as a primer layer. .
From the viewpoint of obtaining a jet-black appearance with a simpler configuration, other layers are not interposed between the adhesive layer 12, the base film layer 13, and the surface film layer 14, and the adhesive layer 12 and the base layer are not interposed. The film layer 13 is preferably in contact, and the base film layer 13 and the surface film layer 14 are preferably in contact.

The jet-black decorative film 10 preferably has a tensile strength at 80 ° C. of 1 to 30 MPa. If the tensile strength at 80 ° C. is 1 to 30 MPa, it is suitable for sticking to a three-dimensional curved surface portion. If the tensile strength is less than 1 MPa, it may not be able to follow the three-dimensional curved surface portion and may be broken. If the tensile strength exceeds 30 MPa, there is a possibility that the film cannot follow the three-dimensional curved surface portion because the film is hard. The tensile strength can be measured by a method according to JIS K7161. Specifically, the test piece of the jet-black decorative film 10 is left under an environment of 80 ° C. for 1 minute using a tensile tester. Thereafter, the test piece is pulled at a measurement temperature of 80 ° C. at a speed of 200 mm / min, and the strength when the sample is cut (ruptured) is measured.

The jet-black decorative film 10 preferably has an elongation at 80 ° C. of 150% or more. When the elongation is 150% or more, it is possible to sufficiently follow the shape of the substrate having the cubic curved surface portion. A preferred upper limit of the elongation at 80 ° C. is 500%. If the elongation percentage at 80 ° C. exceeds 500%, the stiffness of the jet-black decorative film 10 becomes insufficient, and there is a possibility that the jet-black decorative film 10 hangs during heating and becomes difficult to process. Moreover, after sticking to a base material, there is a possibility that the jet-black decorative film 10 may float or be easily peeled off. The expansion rate can be obtained by the following equation (1). In the following formula (1), La is the length of the test piece before the tensile test is performed, and Lb is the length of the test piece when the test piece breaks in the tensile test.
Elongation rate (%) = {(Lb−La) / La} × 100 (1)

The jet-black decorative film of the present invention can be manufactured by using a manufacturing method in which a black pigment is added as a master batch when a base film layer is formed. That is, a step of forming an adhesive layer, a step of obtaining a black resin composition by further mixing a vinyl chloride-based resin with a master batch containing a black pigment, a vinyl chloride-based resin, and a plasticizer, Laminating a black resin composition on the adhesive layer, forming a base film layer, laminating a resin composition containing a vinyl chloride resin or an acrylic resin on the base film layer, the surface Forming a film layer, wherein the content of the black pigment is 20 to 25% by weight based on the entire master batch, and the content of the black pigment in the black resin composition is a vinyl chloride-based resin. 0.5 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the resin, the thickness of the base film layer is 100 μm or more and 300 μm or less, and The transmittance is 80% or more, and the ratio of the thickness of the surface film layer to the thickness of the base film layer is 0.3 or more and 1.0 or less. This is one embodiment of the present invention.

The step of forming the adhesive layer 12 is not particularly limited. For example, a conventionally known method such as a method of applying a pressure-sensitive adhesive composition directly on the separator 11 using a bar coater or the like and drying the same is used. Can be used. When the adhesive layer 12 contains a hot-melt adhesive, for example, the adhesive layer 12 may be formed by applying a hot-melt applicator or the like on the separator 11, or after once applying to a separately prepared support. And may be formed by transfer.

The master batch is prepared, for example, using a known kneader such as a kneader, a Banbury mixer, a single-screw kneading extruder, a twin-screw kneading extruder, or the like, and melt-kneading a black pigment, a vinyl chloride resin, and a plasticizer. can do. By processing the black pigment into a masterbatch in advance and forming the base film layer 13, the black pigment can be prevented from aggregating in the base film layer 13 and can be uniformly dispersed in the base film layer 13. .

The content of the black pigment is 20 to 25% by weight based on the entire master batch. When the content is less than 20% by weight, the resulting jet-black decorative film 10 has a low concealing property, and when the jet-black decorative film 10 is attached to a substrate having a three-dimensional curved surface, May be transparent. On the other hand, if the content exceeds 25% by weight, the black pigment may be aggregated and cannot be uniformly dispersed.

The content of the vinyl chloride resin with respect to the entire masterbatch may be 25 to 30% by weight. Further, the content of the plasticizer with respect to the entire master batch may be 45 to 50% by weight.

The method for producing a jet-black decorative film of the present invention has a step of further mixing a vinyl chloride resin with the master batch to obtain a black resin composition. The master batch is further mixed with a vinyl chloride resin, so that the content of the black pigment is 0.5 parts by weight or more and 10 parts by weight or less based on 100 parts by weight of the vinyl chloride resin. A resin composition can be obtained. In the black resin composition, the content of the plasticizer may be 10 parts by weight or more and 25 parts by weight or less based on 100 parts by weight of the vinyl chloride resin. By using the black resin composition, the above-described base film layer 13 can be formed.

The method for producing a jet-black decorative film of the present invention includes a step of laminating the black resin composition on the adhesive layer to form a base film layer. In the above step, for example, the black resin composition is formed into a film by a conventionally known molding method such as calender molding, extrusion molding, or injection molding, and the obtained film is laminated on the adhesive layer 12. Method. Examples of the calendar format used for the calender molding include an inverted L-shape, a Z-shape, an upright two-shape, an L-shape, and an inclined three-shape.

The method for producing a jet-black decorative film of the present invention includes a step of laminating a resin composition containing a vinyl chloride resin or an acrylic resin on the base film layer to form a surface film layer. As the above step, for example, a method of forming the resin composition into a film by a conventionally known molding method such as calender molding, extrusion molding, or injection molding, and laminating the obtained film on the base film layer 13 may be used. No. Examples of the calendar format used for the calender molding include an inverted L-shape, a Z-shape, an upright two-shape, an L-shape, and an inclined three-shape. By such a method, the jet-black decorative film 10 of the present invention can be manufactured. The jet-black decorative film 10 of the present invention is further subjected to processing such as cutting and winding into a roll as required.

The application of the jet-black decorative film 10 of the present invention is not particularly limited, and can be used by sticking to various substrates. According to the jet-black decorative film 10 of the present invention, the base material can be given the same appearance as the jet-black painted product in a simpler and safer method than painting. Further, since the jet-black decorative film 10 can be decorated even on the surface of a substrate having a three-dimensional curved surface, which is difficult to decorate with a conventional decorative film, the substrate having a three-dimensional curved surface Especially suitable for decorating. That is, a decorative molded article comprising a substrate having a three-dimensional curved surface portion and a decorative film covering the three-dimensional curved surface portion, wherein the decorative film is the jet-black decorative film, A decorative molded product attached to the three-dimensional curved surface portion via an adhesive layer is also one embodiment of the present invention.

The material of the base material is not particularly limited. For example, resins such as polycarbonate resin, acrylic resin, styrene resin, ABS (acrylonitrile-butadiene-styrene) resin; metals such as iron, copper, and aluminum; and alloys And the like. Above all, if the jet-black decorative film 10 is affixed to the resin substrate, the jet-black appearance can be obtained while obtaining the advantage of using the resin substrate, so that the utility value is high. The type of the base material is not particularly limited, and examples thereof include building materials such as covers for mobile phones, parts for motorcycles, interior parts for vehicles, and wall surfaces of buildings.

As a method of attaching the jet-black decorative film 10 to the base material, after the separator 11 is peeled off, for example, the base material is formed by vacuum forming, pressure forming, vacuum / pressure forming, in-mold forming, film insert forming, laminating, or the like. Can be pasted on. Above all, vacuum / pressure molding is preferably used. Specifically, a TOM molding machine (NGF-0406, manufactured by Fuse Vacuum Co., Ltd.) was used as a vacuum / pressure molding machine, and the base material was coated with a jet-black decorative film 10 at a heater heating temperature of 80 to 140 ° C. Paste.

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

(Example 1)
[Formation of adhesive layer]
On one side of a 100 μm thick separator (Lumirror, manufactured by Toray Industries, Inc.), using a comma bar coater, a hot melt adhesive (Hybon 7663, manufactured by Hitachi Chemical Polymer Co., Ltd.) was applied to a dry thickness of 40 μm. Coating was performed to form a coating film. The coating film was heated and dried in a drying oven at 80 ° C. for 1 minute to remove the solvent in the coating film and form an adhesive layer.

[Formation of base film layer]
First, a master batch containing a black pigment was prepared. Using a Banbury mixer, 25% by weight of a black pigment, 25% by weight of polyvinyl chloride having an average degree of polymerization of 1000, and 50% by weight of bis (2-ethylhexyl) phthalate (DOP) as a plasticizer, based on the total weight of the master batch. % Was melt-kneaded to produce a master batch. As the black pigment, carbon black having a primary average particle diameter of 13 nm was used.

Next, 5 parts by weight of the obtained master batch and 100 parts by weight of polyvinyl chloride having an average degree of polymerization of 1000 are added, and the mixture is melt-kneaded for 3 to 5 minutes using a Banbury mixer, and 100 parts by weight of polyvinyl chloride having an average degree of polymerization of 1000 is added. Parts, a black resin composition containing 15 parts by weight of a plasticizer and 5 parts by weight of a black pigment was obtained. The obtained black resin composition was processed into a film by calendering and laminated on the above-mentioned adhesive layer to form a base film layer having a thickness of 100 μm.

[Formation of surface film layer]
100 parts by weight of polyvinyl chloride having an average degree of polymerization of 1000 and 15 parts by weight of DOP (manufactured by J-Plus) as a plasticizer were melt-kneaded with a Banbury mixer for 3 to 5 minutes to obtain a PVC compound. The obtained PVC compound was processed into a film by calendering and laminated on the base film layer to form a surface film layer having a thickness of 80 μm.

Thus, the jet-black decorative film of Example 1 was obtained. The structure of the jet-black decorative film of Example 1 is shown in Table 1 below.

(Example 2)
In Example 2, the jet-black decorative film of Example 2 was produced in the same manner as in Example 1, except that a film containing an acrylic resin was used as the surface film layer. As the surface film layer, a polymethyl methacrylate (PMMA) film (Acryprene HBS006 manufactured by Mitsubishi Rayon Co., Ltd.) was used as a film containing an acrylic resin. The PMMA film had a total light transmittance of 93% and a thickness of 50 μm. The PMMA film was laminated on the base film layer by thermal lamination to form a surface film layer. Thus, a jet-black decorative film of Example 2 was obtained. The structure of the jet-black decorative film of Example 2 is shown in Table 1 below.

(Examples 3 to 8 and Comparative Examples 1 to 7)
In the same manner as in Example 1, jet-black decorative films having the configurations shown in Tables 1 and 2 below were produced. The same adhesive layer as in Example 1 was used.

(Evaluation test)
For the jet-black decorative films produced in the examples and comparative examples, the following methods were used to (1) tensile strength, (2) elongation, (3) appearance before molding, (4) appearance after molding, and (5) Formability to a curved surface shape was evaluated. The results are shown in Tables 1 and 2 below.

(1) Tensile strength The jet-black decorative film was cut into a length of 15 cm and a width of 2.5 cm, and left at 80 ° C. for 1 minute. Thereafter, the separator was peeled off to obtain a test piece. Using a tensile testing machine (manufactured by Shimadzu Corporation, AG-100NXplus), a tensile test was performed according to a method based on JIS K7162, and the tensile strength (MPa) when the test piece was broken was measured. The measurement temperature was 80 ° C., and the tensile speed was 200 mm / min. If the tensile strength is 1 to 30 MPa, it is suitable for sticking to a three-dimensional curved surface portion.

(2) Elongation rate
The elongation was determined by the following equation (1) using the tensile strength obtained in the tensile test. In the following formula (1), La is the length of the test piece before the tensile test is performed, and Lb is the length of the test piece when the test piece breaks in the tensile test. When the elongation is 150% or more, it is possible to sufficiently follow the shape of the substrate having the cubic curved surface portion.
Elongation rate (%) = {(Lb−La) / La} × 100 (1)

(3) Appearance before molding The degree of jet-blackness (depth of blackness) and brightness (surface gloss) were visually checked, and the difference in appearance from a coated article using a black paint was evaluated according to the following criteria.
：: There is no difference in jet black degree and brightness.
Δ: There is no difference in brightness, but the jet black degree is inferior.
X: Inferior blackness degree and brightness feeling.

(4) Appearance after molding The separator was peeled off from the jet-black film, and was applied to a base material by vacuum / pressure molding (TOM molding at an elongation of 100%. Thereafter, the jet black degree (blackness depth) and brightness ( The gloss of the surface was visually checked, and the difference in appearance from the jet-black film before molding was evaluated according to the following criteria: As a base material, an ABS resin smartphone cover was used.
：: No change in jet black degree and brightness.
Δ: Although the color of the substrate could not be confirmed, the degree of jet black and the sense of brightness were reduced.
X: The jet black degree and the brightness were reduced, and the color of the substrate was confirmed.

(5) Formability to curved surface shape Separate the separator from the jet-black decorative film cut to 700 mm x 700 mm, and apply vacuum / pressure molding (TOM molding) at a molding temperature of 120 ° C to a substrate having a three-dimensional curved surface. It was determined based on the following criteria based on whether or not it adhered and extended 100% or more to follow the shape of the three-dimensional curved surface portion. A smartphone cover made of ABS resin was used as the base material.
〇: The film follows the end of the substrate, and there is no tearing or peeling of the film.
Δ: The film follows the end of the base material, but is broken.
×: The film did not follow the edge of the substrate and was peeled off.

As can be seen from Tables 1 and 2, the jet-black decorative films of Examples 1 and 4 to 7 had favorable results in all of tensile strength, elongation, appearance before and after molding, and moldability. In Examples 2 and 3, the thickness of the surface film layer was thinner than in Example 1 and the gloss after molding was slightly reduced. In Example 8, the primary average particles of the black pigment were smaller than in Example 1. Although the dispersibility is low due to the large diameter, the appearance before and after molding is slightly reduced, but the jet-black decorative film that has the same appearance as the jet-black painted product and is suitable for pasting to a three-dimensional curved surface part Obtained. On the other hand, the jet-black decorative film of Comparative Example 1 had an inferior appearance before and after molding because the total light transmittance of the surface film layer was as low as 70%. Comparative Example 2 had a low jet black degree because the content of the black pigment was low. In Comparative Example 3, since the black pigment content was large, it was considered that the black pigment was agglomerated and the jet black degree was low. In Comparative Examples 4 and 5, since the ratio of the thickness of the surface film layer to the thickness of the base film layer was less than 0.3, the moldability was insufficient. In Comparative Example 6, since the base film layer was thin, a sufficient jet-black tint could not be maintained after molding. In Comparative Example 7, the moldability was insufficient because the base film layer was thick.

Reference Signs List 10 jet-black decorative film 11 separator 12 adhesive layer 13 base film layer 14 surface film layer

Claims (7)

An adhesive layer, a base film layer, and a surface film layer are sequentially laminated,
The base film layer contains a vinyl chloride resin, a plasticizer, and a black pigment,
The content of the black pigment is 0.5 parts by weight or more and 10 parts by weight or less based on 100 parts by weight of the vinyl chloride resin,
The thickness of the base film layer is 100 μm or more and 300 μm or less,
The surface film layer contains a vinyl chloride resin or an acrylic resin,
The total light transmittance of the surface film layer is 80% or more,
A jet-black decorative film, wherein a ratio of a thickness of the surface film layer to a thickness of the base film layer is 0.3 or more and 1.0 or less. The jet-black decorative film according to claim 1, wherein the acrylic resin is polymethyl methacrylate. The jet-black decorative film according to claim 1, wherein the black pigment is carbon black. The jet-black decorative film according to any one of claims 1 to 3, wherein the jet-black decorative film has a tensile strength at 80C of 1 to 30 MPa. The jet-black decorative film according to any of claims 1 to 4, wherein the jet-black decorative film has an elongation at 80 ° C of 150% or more. A decorative molded article comprising a substrate having a three-dimensional curved surface portion and a decorative film covering the three-dimensional curved surface portion,
The decorative film is the jet-black decorative film according to any one of claims 1 to 5, and is attached to the three-dimensional curved surface portion via the adhesive layer. Decorative molded products. A step of forming an adhesive layer,
A step of obtaining a black resin composition by further mixing a vinyl chloride resin with a master batch containing a black pigment, a vinyl chloride resin, and a plasticizer,
Laminating the black resin composition on the adhesive layer, forming a base film layer,
Laminating a resin composition containing a vinyl chloride resin or an acrylic resin on the base film layer, and forming a surface film layer,
The content of the black pigment with respect to the entire master batch is 20 to 25% by weight,
The content of the black pigment in the black resin composition is 0.5 parts by weight or more and 10 parts by weight or less based on 100 parts by weight of the vinyl chloride resin,
The thickness of the base film layer is 100 μm or more and 300 μm or less,
The total light transmittance of the surface film layer is 80% or more,
The method of manufacturing a jet-black decorative film, wherein a ratio of a thickness of the surface film layer to a thickness of the base film layer is 0.3 or more and 1.0 or less.

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