JP2018114686A - Decorative film and manufacturing method of decorative film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative film capable of providing design of appearance close to black Japanese lacquer than conventional ones to a resin molded article.SOLUTION: The decorative film 1A can reduce an outside light reaching a coloring layer because functional layers 6A and 7A are formed on a base film 4, the coloring layer 8A is formed in an opposite side of the base film 4 side of the functional layers 6A and 7A, an adhesive layer 9 is formed in an opposite side of the functional layers 6A and 7A of the coloring layer 8A, the coloring layer 8A contains a carbon black pigment, a black dye and a resin component 22A, the black dye is also contained in the functional layers 6A and 7A, concentration of the black dye from the base film 4 side of the functional films 6A and 7A to the coloring layer 8A side changes with gradation that the base film 4 side is low and the coloring layer 8A side is high, change of color viewed by human eyes becomes natural hue and a molded article with deeper jet-black color than conventional ones can be formed.SELECTED DRAWING: Figure 1

Description

  This invention relates to the decoration film of a jet black design among the decoration films used in order to provide and decorate the exterior of a molded article. A jet black design is defined as a design with an appearance close to black jet that looks darker in appearance than a black design decorated with a general black pigment. Specifically, it refers to a black design with a small proportion of diffuse reflection, not regular reflection, of the reflection of light incident on the molded product.

  In recent years, there has been a wide range of design needs due to diversification of customer preferences in the decoration of home appliance exteriors and in-vehicle interiors, and a design pursuing a jet-black feeling imitating the design expression of black lacquer as a Japanese design expression is required. Yes.

  A general method for producing a jet black feeling is to add a carbon black pigment in the colored layer of the decorative film, and to increase the concentration of the carbon black pigment so that light incident from the surface of the molded product Is absorbed by the carbon black pigment in the colored layer.

  A conventional decorative film 1 is shown in FIG.

  The decorative film 1 which is a continuous film includes a carrier layer 2 that is not transferred to a molded product and a transfer layer 3 that is transferred to the surface of the molded product.

  The carrier layer 2 peels off the base film 4 made of PET, an acrylic film or the like that continuously supplies the decorative film 1 into the mold, and the transfer layer 3 transferred to the base film 4 and the molded product. It consists of a release layer 5.

  The transfer layer 3 includes a protective layer or hard coat layer (hereinafter referred to as HC layer) 6 for imparting strength and hardness to the surface of the molded product, a colored layer 8 expressing a jet black design, and a protective layer or HC layer. 6 and an anchor layer 7 for connecting the colored layer 8 and an adhesive layer 9 for bonding the transfer layer 3 and the injection molding resin.

  FIG. 7 shows a manufacturing process in which the decorative film 1 is transferred to the surface of the molded product by an in-mold molding method.

  In FIG. 7A, the decorative film 1 is sent to a predetermined position between the fixed mold 11 and the movable mold 12 using the foil feeding device 13. The decorative film 1 is arranged with the base film 4 facing the movable mold 12. The decorative film 1 may be preheated with a heater (not shown) and then fed into the mold so that the film can be easily molded into the mold.

  After completion of feeding the decorative film 1 to a predetermined position, in FIG. 7B, the decorative film 1 is sucked from the suction holes 14 formed in the cavity surface of the movable mold 12 to the cavity surface of the movable mold 12. Shape. At that time, the outer periphery of the decorative film 1 is fixed and positioned by a film pressing mechanism (not shown).

  In FIG. 7C, the movable mold 12 is moved and clamped.

  In FIG.7 (d), the molten resin 16 is inject | poured toward the contact bonding layer 9 of the decorating film 1 from the gate 15 of the fixed mold | type 11, and the molten resin 16 is filled in the cavity of a metal mold | die.

  When the filling of the molten resin 16 is completed in FIG. 7E, the resin 16 is cooled to a predetermined temperature, and the molded product 17 is molded.

  In FIG. 7F, the movable mold 12 is moved and the mold is opened in order to take out the molded product 17 having the transfer layer 3 transferred to the cured resin layer 16A. As a result, the carrier layer 2 of the decorative film 1 is peeled off from the molded product 17, and only the transfer layer 3 is transferred, and the protective layer or the HC layer 6 is transferred to the outermost surface of the molded product 17.

  In FIG.7 (g), the extrusion pin 18 by the side of the fixed mold | type 11 is extruded, and the molded article 17 is taken out from a metal mold | die.

  In FIG. 7 (h), the suction from the suction hole 14 of the movable mold 12 is stopped, the adsorption of the carrier layer 2 to the movable mold 12 is stopped, and the decorative film 1 used for the next molding by the foil feeding device 13 is predetermined. Send to position. Continuous operation is possible by repeating the operations shown in FIGS.

  In the case of the in-mold molding method, the base film 4 serves as a carrier for feeding the transfer layer 3 into the mold and is not transferred to the molded product 17. Therefore, the base film 4 is transferred to the molded product surface simply by taking out the molded product 17 from the mold. Since the layer 3 is transferred, a film preform and a trimming step after molding are not required. Therefore, productivity is high, and a molded product can be produced stably and efficiently at low cost (for example, see Patent Document 1).

JP 2012-96412 A

  FIG. 8 shows a molded product 17 that is transferred to a resin layer 16A in which the transfer layer 3 of the conventional decorative film 1 is cured.

  20 is a carbon black pigment particle contained in the colored layer 8, and 21 is an aggregate in which a plurality of carbon black pigment particles 20 are aggregated. Reference numeral 22 denotes a resin component contained in the colored layer 8. Reference numeral 23 denotes external light incident on the surface of the molded product, and reference numeral 24 denotes diffusely reflected light scattered inside the transfer layer 3 in which the external light 23 is transferred to the molded product 17.

  In the molded product 17 to which the conventional transfer layer 3 is transferred, the incident light from the surface of the molded product 17 is increased by increasing the amount of carbon black pigment contained in the colored layer 8. It is absorbed by the pigment to reduce the reflection of the external light 23 from the inside of the molded product 17 to the outside, thereby giving a jet black feeling.

  On the other hand, when the addition amount of the carbon black pigment in the colored layer 8 is increased in order to absorb a large amount of external light 23, the density of the carbon black pigment in the colored layer 8 increases, and the carbon black pigment particles attract each other. It becomes easy to make the aggregate 21. When the colored layer 8 is formed on the anchor layer 7 with jet black ink made of the aggregate 21, the ink viscosity is high due to poor compatibility between the carbon black pigment aggregate 21 and the resin constituting the jet black ink. It becomes easy to entrain air at the time of construction, and it becomes easy to form a minute gap (not shown) at the interface between the anchor layer 7 and the colored layer 8, and the carbon black pigment particles 20 or the carbon black pigment agglomerates inside the colored layer 8. Only the resin component 22 where the aggregate 21 does not exist locally is formed.

  In addition, when printing on the anchor layer 7 of jet black ink, the carbon black pigment is agglomerated at the interface between the anchor layer 7 and the colored layer 8 at a portion where the aggregate 21 of the carbon black pigment is present due to the difference in presence or absence of the carbon black pigment. Since the aggregate 21 has a particle size larger than that of the other carbon black pigment particles 20, fine irregularities (not shown) are formed at the interface between the anchor layer 7 and the colored layer 8 due to the influence of the aggregate 21 of the carbon black pigment. It becomes easy to be formed.

  When the external light 23 entering from the surface of the molded article 17 reaches these parts, there is no carbon black pigment inside the minute voids, irregularities or colored layer 8 between the layers, and only the resin component 22 exists, and the carbon black pigment In the portion where the particles 20 and the carbon black pigment aggregate 21 are not present, a slight difference in refractive index occurs between the portion where the carbon black pigment is present and the reflection occurs.

  At the same time, in the minute uneven portion caused by the aggregate 21 of the carbon black pigment, the external light 23 is easily scattered to all surfaces because the uneven surface is not a smooth surface when the external light 23 is reflected. The diffuse reflected light 24 is obtained. The diffuse reflected light 24 is reflected in all directions, so that the diffuse reflected light goes out of the transfer layer 3 and enters the human eye. As a result, it becomes difficult to obtain sufficient blackness due to the absorption effect of the external light 23 of the carbon black pigment in the colored layer 8. Therefore, it becomes a molded product with a jet black feeling lowered.

  An object of this invention is to provide the decorating film which can give the design of the external appearance closer to black lacquer than before to the resin molded product.

  In the decorative film of the present invention, a functional layer is formed on a base film, a colored layer is formed on the side opposite to the base film side of the functional layer, and an adhesive layer is provided on the side opposite to the functional layer of the colored layer. Formed, the colored layer contains a carbon black pigment, a black dye, and a resin component, and the functional layer also contains a black dye, and the concentration of the black dye from the base film side to the colored layer side of the functional layer However, it is characterized in that the base film side is thin and the colored layer side is darkened.

  According to this configuration, since the functional layer containing the black dye is formed from the surface of the molded product after the transfer in a gradation in which the concentration of the black dye gradually increases in the film thickness direction, the external light reaching the colored layer Can be reduced, and a deep-black molded product can be formed. Since the appearance of the molded product is a design close to black lacquer, it is possible to provide a jet black design with high design for the appearance of the product.

Sectional drawing of the layer structure of the decorating film in Embodiment 1 of this invention Decorative film manufacturing process explanatory diagram of the same embodiment Sectional drawing of the molded article to which the transfer layer of the decorative film of the embodiment was transferred Sectional drawing of the layer structure of the decorating film in Embodiment 2 of this invention Sectional drawing of the molded article to which the transfer layer of the decorative film of the embodiment was transferred Sectional view of the layer structure of a conventional transfer-type decorative film In-mold molding process diagram Sectional view of the molded product with the transfer layer of the conventional decorative film transferred

  Embodiments of the present invention will be described below with reference to the drawings.

  In addition, the same code | symbol is attached | subjected and demonstrated about the same component as FIGS. 6-8 which shows a prior art example.

(Embodiment 1)
FIG. 1 is a cross-sectional view of the decorative film of the present invention.

  The jet black design decorative film 1A of the present invention, which is a continuous film, includes a carrier layer 2 that is not transferred to a molded product and a transfer layer 3 that is transferred to the surface of the molded product.

  The carrier layer 2 peels from the base film 4 the base film 4 made of PET, acrylic film, or the like that plays the role of continuously supplying the decorative film 1A into the mold, and the transfer layer 3 transferred to the molded product. It consists of a release layer 5.

  The thickness of the base film 4 is desirably 20 to 100 μm. When the thickness is less than 20 μm, wrinkles easily enter the film itself, and it is easy to break. When the thickness is larger than 100 μm, the roll film having the same number of windings becomes thicker than a thin film, so that the weight becomes heavier and the handling property is deteriorated. The cost of the base film 4 increases.

  The transfer layer 3 is formed between the protective layer or HC layer 6A for imparting strength and hardness to the surface of the molded product, the colored layer 8A expressing the jet black design, and the colored layer 8A and the protective layer or HC layer 6A. The anchor layer 7A that serves to connect the colored layer 8A and the protective layer or the HC layer 6A and the surface of the colored layer 8A opposite to the anchor layer 7A are bonded to the molded product. It is comprised with the adhesive layer 9 of the role. The release layer 5, the protective layer or the HC layer 6A is a functional layer.

  The colored layer 8A contains a black dye in addition to the resin component and the carbon black pigment. Specifically, it is composed of carbon black pigment particles 20A, an aggregate 21A in which a plurality of carbon black pigments are aggregated, and a resin component 22A.

  Further, in this embodiment, the protective layer or the HC layer 6A also contains a black dye. Similarly to the protective layer or the HC layer 6A and the colored layer 8A, the anchor layer 7A also contains a black dye.

  The decorative film 1 </ b> A composed of a plurality of layers is formed by 5 to 40 μm between the release layer 5 and the adhesive layer 9. These layers may be formed of a single layer or a plurality of layers.

  Fig.2 (a)-FIG.2 (d) show the manufacturing process of 1 A of decorating films.

  In FIG. 2A, a partial transfer film in which a release layer 5, a protective layer or HC layer 6A, and an anchor layer 7A are formed on a base film 4 is prepared and set in a printing machine or a coating machine.

  In FIG.2 (b), the colored layer 8A by jet black ink is formed on the peeling layer 5 with a printing machine or a coating machine. The printing and coating method can be formed by gravure coater, comma coater, roll coat, gravure printing, screen printing, ink jet printing and the like. Other than these printing and coating methods, it is not necessary to be limited to the above as long as the same effect can be obtained.

  The jet black ink used for the colored layer 8A forms a smooth surface when printed or applied to the anchor layer 7A, a resin component, a carbon black pigment, a solvent, a dispersant as an auxiliary agent for improving the dispersibility of the pigment. It contains a leveling agent that facilitates the cleaning, and contains a black dye.

  In FIG. 2C, the solvent component in the colored layer 8A gradually permeates the anchor layer 7A. At this time, a black dye having a size smaller than that of the carbon black pigment is dissolved in the solvent of the colored layer 8A, and the black dye also penetrates into the anchor layer 7A together with the solvent, so that the anchor layer 7A becomes a black dye. Colored with. The size of the black dye is smaller than the gap between the black dyes in the anchor layer 7A, the protective layer, or the resin layer constituting the HC layer 6A. Further, the voids in the anchor layer 7A and the protective layer or the resin layer of the HC layer 6A are smaller than the size of the carbon black pigment. Therefore, only the black dye penetrates together with the solvent. The gaps existing in the anchor layer 7A, the protective layer, or the resin layer in the HC layer 6A are gaps formed when the resin molecules overlap with each other and have a very small size, and are infinitely present in the resin layer.

  In FIG. 2 (d), the solvent of the colored layer 8A and the black dye pass through the anchor layer 7A, the solvent of the colored layer 8A and the black dye penetrate into the protective layer or HC layer 6A, and the protective layer or HC layer 6A. Is also colored with a black dye. Thereafter, the solvent component is volatilized by a heat drying step, and the black dye in the protective layer or the HC layer 6A, the anchor layer 7A, and the colored layer 8A is fixed. The fixed black dye spreads innumerable gaps in the anchor layer 7A, the protective layer, or the resin layer in the HC layer 6A through the solvent, and at that time, a part of the black dye remains in the gap and is directly dried by heating. It is fixed later and is uniformly dispersed and fixed in the surface direction in the film. Further, since the black dye gradually permeates with the solvent from the colored layer 8A to the protective layer or the HC layer 6A in the thickness direction in the film, a smooth shading is formed in the thickness direction. Thereby, the density gradient of the black dye is formed from the anchor layer 7A to the protective layer or the HC layer 6A. The concentration of the black dye in the form in which the concentration of the black dye in the anchor layer 7A near the colored layer 8A is high and the concentration of the black dye on the protective layer close to the release layer 5 or the HC layer 6A is reduced can be achieved. A natural gradation of black dye is formed from the protective layer or HC layer 6A to the thickness direction of the colored layer 8A.

  When it is desired to allow the solvent and black dye in the colored layer 8A to permeate in a shorter time, nanoparticles are contained in the anchor layer 7A, the protective layer, or the HC layer 6A in order to more effectively form minute voids. May be. By including the nanoparticles, the nanoparticles are overlapped in the anchor layer 7A or the protective layer or the HC layer 6A to form a path, and more gaps can be formed in the resin layer than when the nanoparticles are not included. Become. Therefore, the solvent of the colored layer 8A and the black dye can easily permeate in a short time through a greater number of gaps formed in the resin layer through the path formed by the overlap of the nanoparticles formed in the resin layer.

  The size of the nanoparticles contained in the anchor layer 7A, the protective layer, or the HC layer 6A must be smaller than the average particle size of the carbon black pigment used in the colored layer 8A. The nanoparticles are not particularly limited as long as gaps can be formed even with inorganic fine particles such as silica and talc and organic fine particles such as urethane beads and acrylic beads, but the resin that forms the anchor layer 7A, the protective layer, or the HC layer 6A. It is preferable to use a material having a refractive index close to that of the material. The reason is that the difference in refractive index between the particles and the resin in the anchor layer 7A, the protective layer or the HC layer 6A is small, so that when light enters the protective layer or the HC layer 6A or the anchor layer 7A, This is because light reflection hardly occurs. Nanoparticles may be porous, fibrous or solid particles having a more porous void than nanoparticles, and are not particularly limited as long as the purpose of forming a gap in the layer can be achieved.

  In addition, if the protective layer or the HC layer 6A also serves as the anchor layer 7A as needed, there is no problem even if the anchor layer 7A is eliminated.

  In addition, as for the protective layer or the HC layer 6A and the anchor layer 7A, there is no problem even if each layer is formed of two or more layers as necessary.

  Further, an antifouling layer (hydrophilic layer, water repellent layer), an antireflection layer or the like may be formed as another functional layer on the protective film or the base film side of the HC layer 6A.

  Details of each layer in the manufacturing process of FIGS. 2A to 2D were as follows.

  A base film 4 having an average film thickness of 50 μm was used. The release layer 5 was a melamine resin material and the average film thickness was 1 μm after drying. The protective layer or the HC layer 6A was an after-curing type ultraviolet curable acrylic resin-based material, and the average film thickness was 5 μm after drying. The anchor layer 7A was a two-component curing type acrylic urethane resin-based material, and the average film thickness was 2 μm after drying. The colored layer 8A was formed by screen printing twice. The colored layer 8A was formed so that the average film thickness after drying was about 12 μm in total for the two times. The jet black ink forming the colored layer 8A is a two-component curing type urethane-based resin, and 25% by mass of carbon black pigment and aggregate thereof are added as a proportion in the jet black ink, and 2% by mass of black dye is added. A jet black ink was created and used. The carbon black pigment having an average particle diameter of 15 nm was used.

  The resin for forming the colored layer 8A may be formed using an ultraviolet curable resin capable of increasing the hardness other than the two-component curable resin, a thermosetting resin, or a thermoplastic resin. In addition to urethane-based resins, it is possible to use general materials such as acrylic-based and polyvinyl chloride-based resins. Similarly, the layers other than the colored layer 8A are not particularly limited as long as the same effects can be obtained in the type of ink, coating material, and resin system of the main material. Finally, the adhesive layer 9 was formed using a commercially available adhesive so that the average film thickness after drying was 2 μm.

  FIG. 3 is a cross-sectional view of a molded product 17A to which the transfer layer 3 of the decorative film 1A is transferred. Here, the functional layers of the protective layer or the HC layer 6A, the anchor layer 7A, and the colored layer 8A are shown partially enlarged as in FIG.

  For molding, a decorative film 1A is set in a general in-mold molding die, ABS resin is injected into the die toward the adhesive layer 9 and cooled to form a resin layer 16A. A molded product 17A was obtained. The resin for injection molding may be appropriately selected according to the use such as PC, PMMA, PP, etc. instead of the ABS resin, and the adhesive for forming the adhesive layer 9 is also appropriately selected according to the injection molding resin. It ’s fine.

The content concentration per unit volume of the color dye containing the black dye also in the colored layer 8A, the protective layer or the HC layer 6A and the anchor layer 7A of the transfer layer 3 transferred to the resin layer 16A is:
Protective layer or HC layer 6A <anchor layer 7A <colored layer 8A
The density gradient of the black dye is formed in a gradation from the surface of the protective layer or HC layer 6A to the colored layer 8A.

  When the external light 23 incident from the outermost surface of the molded product 17A passes through the protective layer or the HC layer 6A, a part of the external light 23 is absorbed by a part of the black dye in the protective layer or the HC layer 6A. . A part of the external light 23 that has reached the next anchor layer 7A is absorbed by the black dye in the anchor layer 7A. The external light 23 finally reaching the colored layer 8A is mostly absorbed by the carbon black pigment particles 20A and aggregates 21A thereof, but is also absorbed by the black dye contained in the colored layer 8A.

  Thus, since the external light 23 incident from the surface of the molded product 17A is gently absorbed from the protective layer or the HC layer 6A to the colored layer 8A, the ratio of the external light 23 reaching the colored layer 8A is small. Become.

  The average particle size of the carbon black pigment particles 20A used in the colored layer 8A is preferably 5 nm or more and 30 nm or less. By using a carbon black pigment having an average particle diameter in this range as a pigment of jet black ink forming the colored layer 8A, the average size of the aggregate when the carbon black pigment aggregate is formed is also reduced.

  The ratio of the carbon black pigment particles 20A and the aggregates 21A thereof in the jet black ink forming the colored layer 8A is preferably 10% by mass to 40% by mass, and may be in the range of 15% by mass to 30% by mass. More preferred.

  The ratio of the black dye in the jet black ink forming the colored layer 8A is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.1% by mass or more and 5% by mass or less.

  By setting the addition concentration of the carbon black pigment within the above range, the density of the carbon black pigment in the colored layer 8A does not become too high, and the proportion of the carbon black pigment particles that attract each other to form an aggregate can be reduced. As a result, the compatibility between the carbon black pigment in the jet black ink and the resin is improved, and the viscosity of the jet black ink can be lowered. Moreover, since the level of the jet black ink is improved when the jet black ink is printed or applied on the anchor layer 7A and the viscosity does not become too high, the viscosity of the jet black ink is lowered. Air entrainment is also reduced, making it difficult to form minute voids (not shown) at the interface between the anchor layer 7A and the colored layer 8A, and carbon black pigment particles 20A or aggregates of carbon black pigment are formed inside the colored layer 8A. The number of resin components 22A only where 21A does not exist locally is also reduced. Further, since the size of the aggregate 21A of the carbon black pigment in the jet black ink is also reduced, the anchor layer is present even in a portion where the aggregate 21A is present due to the difference in the presence or absence of the carbon black pigment when the jet black ink is printed on the anchor layer 7A. It is difficult to form minute uneven portions (not shown) at the interface between 7A and the colored layer 8A.

  Further, since the colored layer 8A contains a black dye that is homogeneously dispersed in the resin component 22A, unlike the colored layer 8 of the conventional decorative film, there is locally a carbon black pigment or an aggregate thereof. Since the external light 23 that has entered from the molded product can be absorbed even at a place where the light is not applied, the scattering of the external light 23 is reduced and the generation of diffuse reflected light 24 is reduced. As a result, since the diffused reflected light 24 emitted to the outside of the molded product 17A is reduced, whitishness is suppressed by the appearance of the molded product 17A, and the molded product is closer to black lacquer with a jet black feeling.

  Further, since the gradation of the black dye is smoothly changed from the protective layer or the HC layer 6A and becomes thicker in the thickness direction, the color changes even when viewed from the surface of the molded product 17A with human eyes. Natural color. If necessary, a black resin material may be produced by using a black resin material for the resin layer 16 </ b> A or including a black dye in the adhesive layer 9.

  In this way, a jet black design expression close to high-quality black jet lacquer is possible, and a jet black design with small diffuse reflection on the surface of the molded product can be realized. This technology can be widely applied to, for example, the design of audio equipment such as television and audio by mobile molding, thermal transfer, roll transfer, exterior moldings for mobile devices, exterior casings for white goods, or interior parts for automobiles.

(Embodiment 2)
FIG. 4 shows a decorative film 1B of the second embodiment. FIG. 5 shows a molded product 17B in-mold molded using the decorative film 1B. The same components used in FIGS. 1 to 3 and FIGS. 6 to 8 are denoted by the same reference numerals and description thereof is omitted.

  In the decorative film 1B, the second colored layer 8B is added between the colored layer 8A and the adhesive layer 9 as compared with the decorative film 1A.

  The second colored layer 8B is configured as follows.

  20B is carbon black pigment particles contained in the second colored layer 8B, 21B is an aggregate of the carbon black pigment particles, and 22B is a resin component. A carbon black pigment having an average particle size larger than that of the colored layer 8A of Embodiment 1 is used for the second colored layer 8B. The average particle size of the carbon black pigment particles 20B used in the second colored layer 8B is preferably 50 nm to 500 nm, and more preferably 75 nm to 300 nm. By using a carbon black pigment having an average particle diameter in this range as a pigment of jet black ink forming the colored layer 8A, the average size of the aggregate when the carbon black pigment aggregate is formed is also reduced. The proportion of carbon black pigment particles 20B and aggregates 21B in the jet black ink forming the second colored layer 8B is preferably 30% by mass to 55% by mass, and in the range of 35% by mass to 50% by mass. If it is more preferable. Further, the ratio of the black dye in the jet black ink forming the second colored layer 8B is preferably 0.01% by mass or more and 10% by mass or less as in the first embodiment, and may be 0.1% by mass or more and 5% by mass or less. More preferred.

  The other layers are formed in the same configuration as in the first embodiment. In the second colored layer 8B, the colored layer 8A is formed on the anchor layer 7A, and then the second colored layer 8B is formed on the colored layer 8A. The second colored layer 8B can be formed by using the same printing and coating method as the colored layer 8A.

  The decorative film 1B uses a base film 4 having an average film thickness of 50 μm, like the decorative film 1A, the release layer 5 is a melamine resin-based material, the average film thickness is 1 μm after drying, and a protective layer Alternatively, the HC layer 6A is an after-curing type ultraviolet curable acrylic resin-based material and the average film thickness is 5 μm after drying, and the anchor layer 7A is a two-component curable urethane urethane-based material and has an average film thickness. After drying, it was formed at 2 μm, and the colored layer 8A was formed by one screen printing, and the average film thickness after drying was 3 μm. The jet black ink forming the colored layer 8A uses a two-component curing type urethane-based resin, and the carbon black pigment particles 20A and aggregates 21A thereof are added in an amount of 25% by mass as a ratio in the jet black ink, and the black dye is 2% by mass. Created and used a jet black ink with a% addition. For the colored layer 8A, a carbon black pigment having an average particle diameter of 15 nm was used.

  The second colored layer 8B was formed so that the average film thickness after drying by screen printing was 3 μm. The second colored layer 8B uses a two-component curing type urethane resin, and as a proportion in the jet black ink, the carbon black pigment particles 20B and aggregates 21B thereof are added at 45% by mass, and the black dye is added at 2% by mass. Created and used the jet black ink. As the second colored layer 8B, a carbon black pigment having an average particle diameter of 200 nm was used.

  The resin for forming the colored layer 8A and the second colored layer 8B is formed by using an ultraviolet curable resin capable of increasing the hardness other than the two-component curable resin, or a thermosetting resin, as in the first embodiment. Or a thermoplastic resin. In addition to urethane-based resins, it is possible to use general materials such as acrylic-based and vinyl chloride-based resins. Similarly, the layers other than the colored layer 8A are not particularly limited as long as the same effects can be obtained in the type of ink, coating material, and resin system of the main material. Finally, the adhesive layer 9 was formed using a commercially available adhesive so that the average film thickness after drying was 2 μm.

  The molded product 17B using the decorative film 1B can also be formed in-mold by forming a resin layer 16A by injection molding using an ABS resin using a general molding die. Similarly to the first embodiment, the resin for injection molding may be appropriately selected according to the use, such as PC, PMMA, PP, etc., instead of the ABS resin, and the adhesive for forming the adhesive layer 9 is also injection molded for the resin. What is necessary is just to select suitably according to resin.

  As shown in FIG. 5, when the external light 23 incident from the outermost surface of the molded product 17B passes through the protective layer or HC layer 6A, a part of the external light 23 is a black dye in the protective layer or HC layer 6A. Is absorbed into a part of. Part of the external light 23 that has reached the next anchor layer 7A is also absorbed by the black dye in the anchor layer 7A. The external light 23 that finally reaches the colored layer 8A is mostly absorbed by the carbon black pigment particles 20A and aggregates 21A thereof, and is also absorbed by the black dye contained in the colored layer 8A. Since most of the external light 23 that has passed through the colored layer 8A is absorbed before passing through the colored layer 8A, the amount of external light 23 that has reached the second colored layer 8B is small, and the carbon black particles having a large average particle diameter And the amount can be sufficiently absorbed by the aggregate.

  Since the carbon black pigment used for the second colored layer 8B is larger than the average particle diameter of the carbon black pigment used for the colored layer 8A, the carbon black pigment is used rather than the jet black ink used for the colored layer 8A. And the compatibility of the resin and the viscosity of the jet black ink tend to increase, and the leveling property of the jet black ink when printing or coating the jet black ink forming the second colored layer 8B on the colored layer 8A deteriorates. In addition, air entrainment at the time of printing and coating increases due to high viscosity, and it becomes easy to form a minute gap not shown at the interface between the colored layer 8A and the second colored layer 8B, and the inside of the second colored layer 8B. The carbon black pigment particles 20B or the carbon black pigment aggregates 21B are not located locally in the resin layer 22A alone and there are more places than the colored layer 8A. It becomes trend.

  However, in the configuration of the second embodiment, since most of the external light 23 is absorbed by the colored layer 8A, the uneven portions or voids, or pigments formed in the minute regions in the second colored layer 8B Even when there is a density unevenness occurrence site in the second colored layer 8B that exists locally, the second colored layer 8B has an amount that can sufficiently absorb the remaining external light 23 and reaches the second colored layer 8B. Light 23 is reduced. This makes it possible to use a carbon black pigment having a large average particle diameter, thereby reducing the classification work of the carbon black pigment and reducing the production cost of the carbon rack pigment. As a result, the cost of jet black ink can be reduced. Further, since the concealing property against the see-through is increased by increasing the average particle diameter of the carbon black pigment, the total thickness of the colored layer composed of the colored layer 8A and the second colored layer 8B is set to that of the first embodiment. It can be made thinner than the colored layer 8A. As a result, it is possible to obtain an effect of reducing foil burrs that tend to remain on the end face of the molded product due to the thick transfer layer, which is a problem during in-mold molding.

  As a result, it is possible to obtain a jet-black feeling similar to that of the configuration of the first embodiment even in the configuration of the second embodiment while reducing the thickness of the two-layer colored layer, and diffuse reflection that goes out of the molded product 17B. Light 24 is reduced and the whiteness of the appearance of the molded product 17B is suppressed, and a molded product closer to black lacquer with a jet black feeling can be obtained.

  INDUSTRIAL APPLICABILITY The present invention can be widely applied to the design of audio equipment such as television and audio by mobile molding, thermal transfer, roll transfer, exterior moldings for mobile devices, exterior casings for white goods, or interior parts for automobiles.

1A, 1B Decorative film 2 Carrier layer 3 Transfer layer 4 Base film 5 Release layer 6, 6A Protective layer or hard coat layer 7, 7A Anchor layer 8A Colored layer 8B Second colored layer 9 Adhesive layer 16A Cured resin layer 17A, 17B Molded product 20A, 20B Carbon black pigment particle 21A, 21B Aggregate 22A, 22B Resin component 23 External light 24 Diffuse reflected light

Claims (8)

A functional layer is formed on the base film, a colored layer is formed on the side opposite to the base film side of the functional layer, an adhesive layer is formed on the side of the colored layer opposite to the functional layer, and the colored layer is made of carbon. Containing a black pigment, a black dye and a resin component, and the functional layer also contains a black dye,
The concentration of the black dye from the base film side of the functional layer to the colored layer side has changed to a gradation that the base film side is thin and the colored layer side is dark,
Decorative film.   In the carbon black pigment contained in the colored layer, a part of the carbon black pigment exists in an aggregated state in the colored layer, and the black dye and the resin component are disposed outside the aggregate. The decorative film according to claim 1, wherein the decorative film is provided. The functional layer is a protective layer or a hard coat layer,
The decorative film according to claim 1 or 2.   A gap exists in the functional layer, and the gap is larger than the size of the black dye and smaller than the size of the carbon black pigment particles contained in the colored layer. 3. The decorative film according to any one of 3.   The decorative film according to any one of claims 1 to 3, wherein a gap larger than the size of the black dye is present in the functional layer, and the black dye is present in the gap.   The colored layer is formed of a plurality of layers, and the size of the carbon black pigment particles contained in the colored layer close to the functional layer is larger than the size of the carbon black pigment particles contained in the colored layer far from the functional layer. The decorative film according to claim 1, wherein the decorative film is also small.   The molded product in which the transfer layer which consists of lamination | stacking of the said colored layer and the said functional layer of the decorating film of Claim 1 is transcribe | transferred and decorated by the resin layer. A colored layer containing a carbon black pigment, a black dye, and a solvent is formed on the side opposite to the base film of the functional layer formed on the base film,
The solvent of the colored layer and the black dye are permeated through the gaps in the functional layer so that the concentration of the black dye is thin from the base film side to the colored layer side of the functional layer, and the base film side is thinly colored. Create a gradient density gradient that darkens the layer side,
A method for producing a decorative film.