JP6420560B2 - Decorative structure and manufacturing method thereof - Google Patents

Description

  The present invention relates to a decorative structure including a base material, a glitter coating film, and an ink layer, and a method for producing the decoration structure, and in particular, the glitter of the glitter material contained in the glitter coating film forms the ink layer. The present invention relates to a decorative structure that can be seen through.

  At present, synthetic resin molded products and metal substrates that are lightweight and have excellent impact resistance are widely used for various members such as mobile phones, home appliances, OA equipment, and automobiles. In addition, these synthetic resin molded articles and metal substrates are required to be provided with weather resistance and wear resistance or decorated depending on the application and the environment in which they are used. Here, paints and inks containing glittering materials are widely used because they can impart a high-class feeling to the substrate.

  Japanese Unexamined Patent Publication No. 2009-241067 (Patent Document 1) discloses a method for forming a glittering coating film in which a coating material containing a glittering material is applied to a substrate to form a glittering coating film, and then a clear coating film is formed. It is described. Japanese Patent Laid-Open No. 2012-210774 (Patent Document 2) describes an ink jet recording method. Specifically, an image is formed by ejecting a pigment ink containing a metal pigment or a pearl pigment onto a recording medium. And then applying a transparent ink.

JP 2009-2441067 A JP 2012-210774 A

  In the glittering coating film forming method described in Patent Document 1, since all the coating films are formed by painting, it may be difficult to apply decoration with high design properties to the substrate. On the other hand, in the ink jet recording method described in Patent Document 2, there is a problem that nozzle clogging is likely to occur when ejecting ink containing a glittering material, and the size of the glittering material and the design of the glittering image are problematic. There are restrictions on sex.

  Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, a decorative structure in which the brightness of the glittering material contained in the glittering coating film is seen through the ink layer, and a method for manufacturing the decorative structure Is to provide.

  As a result of intensive studies to achieve the above object, the present inventor formed a transparent ink layer by an inkjet method on a glittering coating film containing a glittering material having a specific particle size, thereby producing the glittering effect. The present inventors have found that a novel design can be expressed in which the brightness of the conductive material can be seen through the ink layer, and the present invention has been completed.

  That is, the decorative structure of the present invention is a decorative structure comprising a substrate, a glitter coating film formed on the substrate, and a transparent ink layer formed on the glitter coating film. And the said glittering coating film contains the glittering material whose average particle diameter is 3-100 micrometers, It is characterized by the above-mentioned.

  In another preferable example of the decorative structure of the present invention, the transparent ink layer has a transmittance of 15% to 90%.

  In another preferred example of the decorative structure of the present invention, a clear layer is further provided as the outermost layer.

  In addition, the method for manufacturing a decorative structure according to the present invention is a method for manufacturing the above-described decorative structure, in which a glitter paint is formed on a substrate to form a glitter coating, and an inkjet printer And a step of forming a transparent ink layer on the glitter coating film.

  In the suitable example of the manufacturing method of the decorating structure of this invention, the process of forming a clear layer as an outermost layer by coating or printing is further included.

  ADVANTAGE OF THE INVENTION According to this invention, the decoration structure which the brightness of the glittering material contained in a glittering coating film can permeate | transmit the ink layer can be provided.

It is sectional drawing of an example of the decorating structure of this invention. It is sectional drawing of the other example of the decorating structure of this invention. It is sectional drawing of the other example of the decorating structure of this invention.

  Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is a cross-sectional view of an example of the decorative structure of the present invention. The decorative structure 1 shown in FIG. 1 includes a base material 2, a glitter coating film 3 formed on the substrate 2, a transparent ink layer 4 formed on the glitter coating film 3, A glittering coating film 3 and a clear layer 5 formed on the transparent ink layer 4 are provided. In the decorative structure of the present invention, the glitter coating film refers to a coating film containing the glitter material 6. In the decorative structure of the present invention, the clear layer is not an essential element, and is formed in the outermost layer of the decorative structure for the purpose of protecting the surface of the decorative structure, particularly the ink layer. In FIG. 1, the transparent ink layer 4 is formed on a part of the surface of the glittering coating film 3 and a part of the surface of the glittering coating film 3 is exposed. The film 3 and the transparent ink layer 4 are formed on the surface. For example, when the entire surface of the glitter coating film is covered with the ink layer, the clear layer is formed only on the surface of the ink layer. Become.

In addition, the decorative structure of the present invention may include an undercoat coating film between the substrate and the glitter coating film. FIG. 2 is a cross-sectional view of another example of the decorative structure according to the present invention. The decorative structure 1 shown in FIG. 2 includes a base material 2, an undercoat film 7 formed on the base material 2, a glitter coating film 3 formed on the undercoat film 7, and the glitter A transparent ink layer 4 formed on the luminescent coating film 3, and the glitter coating film 3 and a clear layer 5 formed on the transparent ink layer 4. Material 6 is included.
When the glittering material contained in the glittering coating is a metallic pigment such as aluminum flakes, the pigment has a concealing property to the substrate, so that the glittering coating can be formed directly on the substrate. Although it is possible, if the glittering material is a pearl-like pigment such as pearl mica or glass, there may be a case where the concealability with respect to the substrate cannot be sufficiently obtained. In such a case, it is preferable to form an undercoat coating film between the substrate and the glitter coating film in order to ensure concealment with respect to the substrate.
In addition, when the glittering material is a very thin metallic pigment such as a vapor-deposited aluminum pigment, the pigment content tends to decrease from the viewpoint of ensuring the orientation of the pigment, and sufficient concealment with respect to the substrate is obtained. There is a risk that it may not be possible. For this reason, it is preferable to form an undercoat film between the substrate and the glitter coating film, and it is more preferable to form a black undercoat film. FIG. 3 is a cross-sectional view of another example of the decorative structure of the present invention. However, since the glittering material 6 is a very thin metallic pigment such as a vapor-deposited aluminum pigment, the decorative structure shown in FIG. 1 includes a black undercoat film 7 between the base material 2 and the glitter coating film 3.

  The decorative structure is a structure that can be decorated on a base material, such as a mobile phone, a home appliance, an exterior member of an OA device, an interior / exterior member of an automobile, a bicycle, a fishing tackle, and home use. It can be used for various materials such as small articles, ceramic building materials such as tiles and bricks, interior and exterior members of industrial machines such as chemical machinery and construction machinery, interior and exterior members of elevators, and sashes.

  The base material used for the decorative structure of the present invention is not particularly limited as long as it is a base material that requires decoration. For example, mobile phones, home appliances, OA equipment, automobiles, ceramic building materials, etc. The base material used for is mentioned. Although it does not specifically limit as a material of a base material, For example, paper, a fabric, a plastics, a metal, rubber | gum, glass, a tile, brick, cement etc. are mentioned. Moreover, a base material is used with various forms according to a use, For example, the various molded products manufactured by a shaping | molding process etc. other than a film, a sheet | seat, a board are also contained.

  Examples of the plastic include acrylonitrile-butadiene-styrene (ABS), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), polycarbonate (PC), polysulfone (PSF), and polyphenylene oxide. In addition to plastic materials such as (PPO) and polyphenylene sulfide (PPS), polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyester, polyamide, chlorinated polyethylene, and 1,2-polybutadiene thermoplastics Elastomers are also included, and a substrate can be prepared by molding these by a known molding method such as an injection molding method, an extrusion molding method, or a blow molding method.

  Examples of the metal include zinc, iron, stainless steel, steel, and those whose surfaces have been subjected to galvanization treatment or aluminum plating treatment. Specific examples of the metal substrate include hot rolled steel plate, cold rolled steel plate, and the like. Examples of the metal plate include steel plates, galvanized steel plates, and aluminum plated steel plates.

  In the decorative structure of the present invention, the glitter coating film needs to contain a glitter material having an average particle diameter of 3 to 100 μm, and is formed by coating. The average particle diameter of the glittering material is preferably 5 to 60 μm, and more preferably 10 to 40 μm. By using a glitter material having a particle size in the specific range as a glitter coating film, an excellent glitter feeling can be imparted to the ink layer. Moreover, since the particle size is too small as the particle size of the glittering material is less than 3 μm, a sufficient glitter feeling cannot be expressed. On the other hand, when the particle size of the glittering material exceeds 100 μm, the coating workability is lowered, and furthermore, it is difficult to make the glittering coating film uniform. In addition, when an ink layer formed by a printing method such as an ink jet method is used instead of the glitter coating film, it becomes easy to cause clogging of the head during ejection when the particle diameter of the glitter material is 2 μm or more. The design of the ink layer that can be made is extremely limited, and it is difficult to achieve both radiance and design. In particular, when a glittering material such as pearl mica or glass is used, it is extremely difficult to obtain high designability because there is a large difference between the particle size that can be ejected and the particle size that provides a glittering feeling. .

  In the present invention, the particle size of the glittering material is a value measured based on a laser diffraction / scattering method. In the laser diffraction / scattering method, when a cumulative curve is obtained by setting the total volume of a group of particles as 100%, the particle diameter at the point where the cumulative curve is 50% is 50% (μm). In the present invention, the average particle diameter is a 50% diameter that is a cumulative median diameter (Median diameter) as a parameter for evaluating the particle diameter distribution, measured by a laser diffraction particle size distribution analyzer SALD-7000 manufactured by Shimadzu Corporation. It is the value.

  The glittering material used for the glittering coating can be appropriately selected from materials that can scatter and disperse light. For example, in addition to metallic pigments such as aluminum and pearlescent pigments such as pearl mica, stainless steel, nickel, glass, Examples thereof include mica-like iron oxide (MIO), and materials obtained by coating them. Further, the glittering material is preferably scaly because it has a high reflectance and can effectively provide a glittering feeling.

  In the decorative structure of the present invention, the content of the glittering material in the glittering coating film is preferably 0.1 to 20% by mass.

  The glitter coating film preferably contains at least one resin selected from the group consisting of acrylic resins, alkyd resins, and polyester resins. By using an acrylic resin, an alkyd resin, or a polyester resin for the glitter coating, the adhesion of the ink layer to the glitter coating can be improved. In the decorative structure of the present invention, the total content of the acrylic resin, alkyd resin and polyester resin in the glitter coating is preferably 60 to 98% by mass.

  Resins other than acrylic resin, alkyd resin, and polyester resin can be used for the glitter coating, and specific examples include urethane resin, epoxy resin, vinyl resin, polyolefin resin, silicone resin, fluorine resin, and the like. However, for example, when a large amount of a fluororesin is blended, the adhesion of the glitter coating film to the ink layer may be lowered, which is not preferable.

  Various additives such as fillers, curing accelerators, thickeners, dispersants, film-forming aids, antifoaming agents, preservatives, etc., may harm the purpose of the present invention. It can select suitably and mix | blend within the range which does not carry out.

  In the decorative structure of the present invention, the film thickness of the glitter coating film is not particularly limited, but is, for example, 5 to 100 μm.

  In the decorative structure of the present invention, the transparent ink layer is formed by printing using an ink jet printer and can express various designs. Moreover, since the transparent ink layer which comprises the decorating structure of this invention is a transparent ink layer which permeate | transmits the brightness | luminance of the glittering material contained in a glittering coating film, it is excellent in a glitter feeling. In addition, by using a glittering material for the ink layer, it is also possible to produce a glittering ink layer, but in this case, since the particle diameter of the glittering material used in the ink for an inkjet printer is too small, Sufficient glitter cannot be obtained.

  In the decorative structure of the present invention, the transmittance of the transparent ink layer is preferably 15% to 90%, and preferably 40% to 90%, from the viewpoint of imparting excellent glitter to the ink layer. More preferred. Here, the transmittance of the ink layer can be measured by the light transmittance described in JIS K7105 6.4. Examples of the method for adjusting the transmittance of the ink layer include selection of the pigment type to be used, adjustment of the pigment concentration and pigment dispersion, and adjustment of the ejection amount using image processing software during ejection. .

  The transparent ink layer usually contains a colorant, but various colors such as chromatic colors such as cyan, magenta, and yellow and achromatic colors such as white and black can be expressed by changing the type of the colorant. The colorant is not particularly limited, and known pigments and dyes can be used. Examples of the pigment include azo pigments (azo lake pigments, insoluble azo pigments, monoazo pigments, disazo pigments, condensed azo pigments, chelate azo pigments, azomethine pigments), polycyclic organic pigments (phthalocyanine pigments, anthraquinone pigments, perylene pigments, quinacridone pigments, Isoindoline pigment, benzimidazolone pigment, thioindigo pigment, dioxazine pigment, quinophthalone pigment, pyrrolopyrrole pigment), other organic pigments (nitro pigment, nitroso pigment, aniline black, fluorescent pigment, etc.), inorganic pigment (inorganic oxide pigment) , Hydroxide pigments, sulfide pigments, ferrocyanide pigments, chromate pigments, carbonate pigments, silicate pigments, phosphate pigments, carbon pigments, metal powders), metals Although complex pigments etc. are mentioned, it is not limited to these. Examples of the dye include oil-soluble dyes such as azos, anthraquinones, indigoids, phthalocyanines, carboniums, quinoneimines, methines, xanthenes, nitros, nitrosos, disperse dyes, acid dyes, reactive dyes, Cationic dyes, direct dyes and the like can be mentioned. In the decorative structure of the present invention, the content of the colorant in the transparent ink layer is preferably 0.5 to 20% by mass.

  Various additives such as a binder resin, a filler, a curing accelerator, a thickener, a dispersant, a film forming aid, an antifoaming agent, an antiseptic, and an ultraviolet absorber are added to the transparent ink layer as necessary. It can be appropriately selected and blended within a range that does not impair the object of the present invention.

  Moreover, the decorative structure of the present invention may include an opaque ink layer that does not transmit the brightness of the glittering material contained in the glittering coating film, in addition to the transparent ink layer described above. For example, an opaque ink layer can be used when expressing a part without a glittering feeling in a part of the design. The opaque ink layer is formed by printing using an ink jet printer, but its transmittance is 0% or more and less than 15% in order to prevent the transmission of the glitter material contained in the glitter coating film. It is preferable that In addition, the additive which can be mix | blended with the above-mentioned transparent ink layer can also be used for an opaque ink layer.

  The decorative structure of the present invention preferably includes a clear layer as the outermost layer for the purpose of protecting the surface of the decorative structure, particularly the ink layer. The clear layer is not particularly limited, and a transparent outermost layer usually used in the paint and ink industry can be applied. However, from the viewpoint of improving the weather resistance, the clear layer may contain an ultraviolet absorber or a light stabilizer. Preferably, from the viewpoint of improving the adhesion with the ink layer, it is preferable to include at least one resin selected from the group consisting of an acrylic resin and a urethane resin. In the decorative structure of the present invention, the total content of the acrylic resin and the urethane resin in the clear layer is preferably 10 to 90% by mass. In addition, resin other than an acrylic resin and a urethane resin can be used for the said clear layer, A polyester resin, a vinyl resin, a silicone resin, a fluororesin etc. are mentioned suitably as a specific example. Further, in the clear layer, known colorants such as pigments and dyes and matting agents can be used. In the decorative structure of the present invention, the thickness of the clear layer is not particularly limited, but is, for example, 10 to 50 μm.

  The decorative structure of the present invention preferably includes an undercoat coating film between the substrate and the glitter coating film for the purpose of ensuring the concealability to the substrate. In addition, although the undercoat film normally used in the paint industry can be applied to the undercoat film, it is necessary to have no glittering material. In the decorative structure of the present invention, the undercoat coating film preferably contains a color pigment such as titanium oxide or carbon black from the viewpoint of improving the concealability with respect to the substrate. In the decorative structure of the present invention, the content of the color pigment in the undercoat coating film is, for example, 2 to 50% by mass. In addition, a resin may be used for the undercoat coating film, and examples thereof include an acrylic resin, a urethane resin, a polyester resin, a vinyl resin, a silicone resin, and a fluorine resin. In the decorative structure of the present invention, the content of the resin in the undercoat coating film is, for example, 50 to 98% by mass. In the decorative structure of the present invention, the thickness of the undercoat coating film is not particularly limited, but is, for example, 5 to 30 μm.

  Next, the manufacturing method of the decoration structure of this invention is demonstrated in detail. The method for producing a decorative structure according to the present invention is a method for producing the above-described decorative structure, and a step of applying a glittering paint on a substrate to form a glittering coating film, and an inkjet And a step of forming a transparent ink layer on the glitter coating film by a printer.

<First step>
In the method for producing a decorative structure according to the present invention, first, a glitter paint is formed on a substrate by applying a glitter paint. Here, the substrate and the glitter coating are as described above. Further, the glitter paint can be prepared by mixing a glitter material having an average particle diameter of 3 to 100 μm and various additives appropriately selected as necessary, but various forms can be used depending on the type of the solvent. Any of water-based paints, organic solvent-based paints, powder paints, and ultraviolet curable paints may be used.

  The solvent used for the glitter paint is not particularly limited, and a solvent usually used in the paint industry can be used. In the case of water-based paints, it is water. In the case of organic solvent-based paints, alcohols such as methanol, ethanol and isopropanol, carbitols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether, acetone Organic solvents such as ketones such as methyl ethyl ketone, cyclohexanone and isophorone, aliphatic esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as toluene and xylene, and alicyclic hydrocarbons such as cyclohexanone, For UV curable paints, stearyl acrylate, acryloylmorpholine, tridecyl acrylate, lauryl acrylate, N, N-dimethylacrylamide, decyl acrylate, phenoxyethyl acrylate, isodecyl Acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, isooctyl acrylate, octyl acrylate, dicyclopentenyloxyethyl acrylate, cyclohexyl acrylate, N-vinylcaprolactam, 2-ethylhexyl-diglycol acrylate, EO ( Ethylene oxide) modified 2-ethylhexyl acrylate, neopentyl glycol acrylate benzoate, N-vinyl-2-pyrrolidone, N-vinylimidazole, tetrahydrofurfuryl acrylate, methoxydipropylene glycol acrylate, (2-methyl-2-ethyl- 1,3-dioxolan-4-yl) methyl acrylate, cyclic trimethylolpropane formal acrylate Monofunctional monomers such as ethoxy-diethylene glycol acrylate, 2- (2′-vinyloxyethoxy) ethyl acrylate, 1,10-decanediol diacrylate, 2-methyl-1,8-octanediol diacrylate, 2-butyl-2 -Ethyl-1,3-propanediol diacrylate, 1,9-nonanediol diacrylate, 1,8-octanediol diacrylate, 1,7-heptanediol diacrylate, polytetramethylene glycol diacrylate, 3-methyl- 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, hydroxypivalate neopentyl glycol diacrylate, tripropylene glycol diacrylate, 1, Bifunctional monomers such as 4-butanediol diacrylate and dipropylene glycol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated glycerin triacrylate Polyfunctional monomers such as tetramethylol methane triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, EO-modified diglycerin tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and Acrylate oligomer, urethane acrylic Polymerizable monomers and oligomers such as over preparative oligomers and the like. In addition, these media may be used individually by 1 type, and may be used in combination of 2 or more types. In the glitter paint, the content of the solvent can be arbitrarily determined depending on the form of the paint to be used, the type of the solvent, and the like, but it is preferably 35 to 95% by mass in the glitter paint.

  Further, the glittering paint is applied by a usual industrial coating method such as roller coating, curtain flow coater coating, air spray coating, shower air cut coating, electrostatic coating, dipping coating, vacuum coating and the like.

  In addition, in the manufacturing method of the decorating structure of this invention, before forming a glittering coating film, you may apply | coat a primer coating on a base material and may form a primer coating film. In this case, the glitter coating film is formed by applying a glitter paint on the undercoat coating film. Here, the undercoat coating film is as described above. The undercoat used for forming the undercoat can be prepared by appropriately selecting and mixing various additives as described above, but can take various forms depending on the type of solvent. It is. In addition, what was mentioned in description of a glittering paint can be utilized for the solvent which can be used for undercoat, and the coating method of undercoat.

<Second step>
In the method for producing a decorative structure according to the present invention, a transparent ink layer is then formed on the glitter coating film by an ink jet printer. Here, as described above, the transparent ink layer is a transparent ink layer that transmits the brightness of the glittering material contained in the glittering coating film. The ink used for forming the ink layer can be prepared by appropriately selecting and mixing the various additives as described above, but can take various forms depending on the type of solvent. Any of ink, organic solvent-based ink, and ultraviolet curable ink may be used. The solvent used for the ink is not particularly limited, and a solvent usually used in the ink industry can be used. In the case of water-based ink, it is water, and in the case of organic solvent-based ink, alcohols such as methanol, ethanol and isopropanol, carbitols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether, acetone Organic solvents such as ketones such as methyl ethyl ketone, cyclohexanone and isophorone, aliphatic esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as toluene and xylene, and alicyclic hydrocarbons such as cyclohexanone, In the case of UV curable ink, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dipropylene glycol mono (meth) acrylate, (meth ) Acrylamide, N-vinylpyrrolidone, isobornyl acrylate, phenoxy acrylate, ethyl carbitol acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate, dipentaerythritol hexa (meth) ) Polymerizable monomers such as reactive monomers such as acrylates and silicone-based acrylates or mixtures thereof. In addition, these media may be used individually by 1 type, and may be used in combination of 2 or more types. In the ink, the content of the solvent can be arbitrarily determined depending on the form of the ink to be used, the type of the solvent, and the like, but is preferably 50 to 95% by mass in the ink.

  In the method for producing a decorative structure according to the present invention, an ink layer is formed by an ink jet printer, so that a complicated design can be easily formed. The ink jet printer needs to be appropriately selected depending on the type of ink, and examples thereof include a method of ejecting ink by an ink on demand method, and examples thereof include a piezo method and a thermal method.

  In addition, in the method for producing a decorative structure of the present invention, an opaque ink layer that does not transmit the brightness of the glittering material contained in the glittering coating film is separately applied to the glittering coating by an inkjet printer, in addition to the transparent ink layer described above. It may be formed on a film. As a result, it is possible to express a part having no glitter feeling in a part of the design. The ink used for forming the opaque ink layer can also use the same solvent as the ink used for forming the transparent ink layer, and can take various forms depending on the type of solvent. It is.

<Third step>
In the method for producing a decorative structure according to the present invention, the clear layer may be formed as the outermost layer by painting or printing. Although the clear layer is as described above, any of a coating method and a printing method can be used for forming the clear layer. In addition, since the clear layer is the outermost layer, for example, when the entire surface of the glitter coating film is covered with the ink layer, the clear layer is formed only on the surface of the ink layer, and is one of the glitter coating films. When the portion is exposed, the clear layer is formed on the surface of the ink layer and the surface of the exposed glittering coating film.

  The raw material used for forming the clear layer is prepared according to a normal method depending on the coating method or the printing method, and varies depending on the type of solvent used as described in the description of the glitter paint and ink layer ink. It is possible to take various forms. Examples of the coating method include roller coating, curtain flow coater coating, air spray coating, shower air cut coating, brush coating, electrostatic coating, dipping coating, vacuum coating, and the like. Printing methods include screen printing. , Direct printing, inkjet method, and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

<Preparation of test plate>
Lubricant paints 1 to 4 were prepared by adding an appropriate amount of thinner to the blended formulation comprising the raw materials shown in Table 1 and mixing with a stirrer so that the viscosity was 16 seconds / Ford Cup # 4. Next, a white or black coating material (Dainippon Paint Co., Ltd., trade name: Acrose # 6000) was applied to a 150 mm × 150 mm × 0.75 mm tin plate and dried. The tin plate coated with the white coating material was used as the white coated plate, and the tin plate coated with the black coating material was used as the black coated plate. Super Bright Silver 2000 (manufactured by Dainippon Paint Co., Ltd.) containing the glitter paints 1-4 prepared on the white, black, and unpainted tin plates and vapor-deposited aluminum (brilliant pigment) having an average particle size of 12 μm. After spraying according to the formulation shown in Tables 3 to 5, it was baked and dried at 140 ° C. for 30 minutes to prepare a test plate having a glittering coating film.

<Preparation of ink>
The raw materials according to the formulation shown in Table 2 were mixed with glass beads for dispersion, and the resulting mixture was kneaded for 4 hours in a bead mill. After kneading, filtration was performed to remove the glass beads, and inks (C-1, M-1, Y-1, K-1, K-2, K-3) were prepared.

<Examples 1-11, 15-31, 35-38, 42-52, 56-66, 70-86>
Test patterns of ink duty (%) shown in Tables 3 to 5 with the inks C-1, M-1, Y-1, K-1, K-2, or K-3 using a piezo ink jet printer Was printed on the surface of the glitter coating film. The ink duty can be changed by using Adobe Systems Photoshop, thereby adjusting the ink discharge amount. The distance between the print head and the substrate was 3 mm. After printing, using an LED lamp with a wavelength of 395 nm, the ink was directly irradiated with ultraviolet light under irradiation conditions of 400 mJ / cm ² , and this was cured, and Examples 1 to 11, 15 to 31, 35 to 38, 42 to 52, Coated materials of 56 to 66 and 70 to 86 were produced.

<Examples 12-14, 32-34, 39-41, 53-55, 67-69, 87-89>
After setting an ink set composed of four types of inks of C-1, M-1, Y-1, and K-1 using a piezo ink jet printer, the total discharge amount is shown in Tables 3 to 5 A test pattern was printed on the surface of the glittering coating film by simultaneously ejecting ink of each color so that the duty (%) was obtained. The ink duty can be changed by using Adobe Systems Photoshop, thereby adjusting the ink discharge amount. The distance between the print head and the substrate was 3 mm. After printing, using an LED lamp with a wavelength of 395 nm, the ink was directly irradiated with ultraviolet light under irradiation conditions of 400 mJ / cm ² , and this was cured, and Examples 12-14, 32-34, 39-41, 53-55, Coated materials 67-69 and 87-89 were produced.

<Comparative Examples 1-5>
Using a piezo inkjet printer, a test pattern of 100% ink duty was printed on the surface of the glitter coating film with the ink K-1. The distance between the print head and the substrate was 3 mm. After printing, using an LED lamp with a wavelength of 395 nm, the ink was directly irradiated with ultraviolet light under irradiation conditions of 400 mJ / cm ² , and this was cured to produce coated materials of Comparative Examples 1-5.

<Comparative Examples 6-9>
A glittering ink containing a photoaluminum pigment having an average particle diameter of 1.001 μm described in Examples of JP 2012-35595 A was prepared, and PX-G930 (manufactured by Seiko Epson Corporation) was used as an inkjet printer. A test pattern of 100% ink duty was printed on each white coated plate to prepare a test plate having a glitter ink layer. Next, a test pattern of the ink duty (%) shown in Table 5 was printed on the surface of the glittering ink layer with the ink C-1, M-1, Y-1, or K-1. The distance between the print head and the substrate was 3 mm. After printing, using an LED lamp with a wavelength of 395 nm, the ink was directly irradiated with ultraviolet light under irradiation conditions of 400 mJ / cm ² , and the ink was cured to prepare coated materials of Comparative Examples 6-9.

<Comparative Examples 10-12>
A glittering ink containing a photoaluminum pigment having an average particle diameter of 1.001 μm described in Examples of JP 2012-35595 A was prepared, and PX-G930 (manufactured by Seiko Epson Corporation) was used as an inkjet printer. A test pattern of 100% ink duty was printed on each white coated plate to prepare a test plate having a glitter ink layer. Next, after setting an ink set composed of four types of inks C-1, M-1, Y-1, and K-1, each color is set so that the total discharge amount becomes the ink duty (%) shown in Table 5. A test pattern was printed on the surface of the glitter ink layer by simultaneously discharging the inks. The distance between the print head and the substrate was 3 mm. After printing, using an LED lamp with a wavelength of 395 nm, the ink was directly irradiated with ultraviolet light under irradiation conditions of 400 mJ / cm ² , and this was cured to prepare the coated materials of Comparative Examples 10-12.

<Preparation of clear layer>
According to the formulation shown in Table 6, a main agent and a curing agent were prepared, a curing agent was added to the main agent, and a thinner was further added to adjust the viscosity to 22 seconds / Ford Cup # 4 to obtain a clear paint. Next, the clear paint is applied so as to cover the entire surface of the coated material on which the ink is printed by a gravity air cup gun (paint nozzle diameter: 1.3 mm, air pressure: 4 MPa, discharge amount: 120 cc / min). Painted by hand blow 3 times. Here, the gravity type air cup gun was separated from the base material by 20 to 25 cm, and the moving speed of the gun was 30 to 50 cm / s. Next, the coated material coated with the clear paint was heated to 60 ° C. and cured to produce decorative structures of Examples 35-41.

<Transmissivity>
The transmittance of the ink layer was measured according to the method described in JIS K7105 6.4. A transparent acrylic plate having a thickness of 2 mm was used as the substrate, and a 100% ink duty test pattern and a 50% ink duty test pattern were printed using a piezo inkjet printer. Here, the transmittance and haze (cloudiness) of each color of C, M, Y, and K and the test pattern (ink layer) in the case of simultaneous ejection of C, M, Y, and K were measured. The ink duty can be changed by using Adobe Systems Photoshop, thereby adjusting the ink discharge amount. The results are shown in Table 7.

<Mirror gloss>
Using a BYK Gardner micro-trigloss gloss meter, gloss values of 20 °, 60 ° and 85 ° were measured. The results are shown in Tables 3-5.

<Appearance evaluation> (Evaluation of visual brightness)
Appearance evaluation was conducted by 10 employees of Dainippon Paint Co., Ltd. Specifically, according to the following evaluation criteria, the decorative structures of the examples and comparative examples that were produced were separated from outdoor places and windows that were exposed to sunlight, and were each seen indoors with a fluorescent light on, giving a feeling of radiance. A score was assigned according to the degree obtained, and a total score of 10 people was obtained. The results are shown in Tables 3-5.
(Evaluation criteria)
・ Strong radiance can be confirmed… 2 points ・ Lust can be confirmed ・ ・ ・ 1 point ・ Lust can not be confirmed ・ ・ ・ 0 points

  As can be seen from Tables 3 to 5, from the Examples, a decorative structure having a high design property that allows the glitter of the glitter coating film to be seen through the ink layer was obtained. When the ink duty was 20% or 50%, all the evaluators were able to confirm a strong glitter. In addition, the brilliancy tends to be confirmed more strongly outdoors in sunlight than indoors. Especially for paint films using glass or pearl mica, when the paint film is observed in sunlight, The glittering material that passed through the layer appeared to shine brilliantly and was very excellent in aesthetics.

Details regarding the materials listed in the table are given below.
* 1 ACRYDEC A-322 (acrylic resin, manufactured by DIC)
* 2 Super Becamine L-117-60 (melamine resin, manufactured by DIC)
* 3 HR9901 (resin-coated type aluminum pigment (bright material), average particle size 22 μm, manufactured by Asahi Kasei Chemicals)
* 4 MS750 (aluminum pigment (brilliant material), average particle size 6 μm, manufactured by Toyo Aluminum)
* 5 GT1030RSJ3 (Glass flake pigment (brilliant material), average particle size 25 μm, manufactured by Nippon Sheet Glass Co., Ltd.)
* 6 Merck T60-10WNT (pearl mica pigment (brilliant material), average particle size 20 μm, manufactured by Merck & Co., Inc.)
* 7 Disper BYK-168 (by Big Chemie Japan)
* 8 ACRYDIC WAU-137 (acrylic polyol, manufactured by DIC)
* 9 Disparon LC-915 (Surface conditioner, manufactured by Enomoto Kasei Co., Ltd.)
* 10 CHISORB 292 (Light stabilizer, manufactured by Double Honda Chemical Co., Ltd.)

DESCRIPTION OF SYMBOLS 1 Decorative structure 2 Base material 3 Glossy coating film 4 Transparent ink layer 5 Clear layer 6 Glossy material 7 Undercoat coating film

Claims (5)

A decorative structure comprising a substrate, a glitter coating film formed on the substrate, and a transparent ink layer formed on the glitter coating film by an ink jet printer, the glitter coating film have an average particle diameter include photoluminescent material 3 to 100 m, Ri transmittance of 15% to 90% der of the transparent ink layer is measured by the method described in JIS K7105 6.4, wherein the transparent ink layer A decorative structure characterized by not including a flip-flop pigment-containing layer in the upper layer .   The decorative structure according to claim 1, wherein the transparent ink layer has a transmittance of 40% to 90%.   The decorative structure according to claim 1, further comprising a clear layer as an outermost layer.   It is a manufacturing method of the decorating structure of any one of Claims 1-3, Comprising: The process of apply | coating a glitter paint on a base material, and forming the glitter coating film, The said glitter by an inkjet printer And a step of forming a transparent ink layer on the adhesive coating film.   Furthermore, the process of forming a clear layer as an outermost layer by coating or printing is included, The manufacturing method of the decorating structure of Claim 4 characterized by the above-mentioned.