JP2020026192A - Vehicle exterior member, vehicle, and manufacturing method of vehicle - Google Patents

Abstract

To provide a vehicle exterior member which is superior in weather resistance and excellent in appearance decorated by melting and integrating a glaze and an inorganic pigment by forming a certain glassy layer on a metal base material molded for the vehicle exterior member, and to provide a vehicle and a manufacturing method of the vehicle.SOLUTION: A vehicle exterior member includes: a metal base material molded for the vehicle exterior member; and a glassy layer formed on the metal base material. The glassy layer includes a first glaze including a first glass frit and an inkjet ink including an inorganic pigment composed of a multiple oxide, and is formed by melting and integrating the first glass frit and the inorganic pigment.SELECTED DRAWING: None

Description

  The present invention relates to a vehicle exterior member, a vehicle, and a method for manufacturing a vehicle. More specifically, the present invention relates to a vehicle exterior member having an excellent appearance, which exhibits excellent weather resistance and is decorated by melting and integrating a glaze and an inorganic pigment, a vehicle, and a method of manufacturing the vehicle. .

  2. Description of the Related Art Conventionally, exterior members of vehicles such as automobiles are subjected to various coatings by applying a resin paint a plurality of times. Painting of exterior members for vehicles is performed for the purpose of improving weather resistance, expressing gloss and color, and the like. When a flaw occurs, the exterior member coated with these resin paints can repair the flaw by re-coating or the like.

  By the way, heretofore, a technique has been developed in which a glaze layer and an ink layer containing an inorganic pigment are formed on various substrates and fired to form an exterior having excellent weather resistance. Patent Literature 1 discloses a method for producing a printed matter in which color variation after firing is suppressed by employing a specific glaze.

JP, 2017-218356, A

  It is disclosed that the printed matter of Patent Document 1 can employ an enamel or a metal substrate as a substrate. However, the disclosure of Patent Literature 1 merely exemplifies the above-mentioned enamel or metal substrate as an example of the substrate, and is particularly applicable to the use of an exterior member of a vehicle such as an automobile or the like, There is no disclosure or suggestion regarding the state of the ink. Conventionally, the exterior of a vehicle such as an automobile may be damaged due to a collision or the like. Since resin coating is relatively inexpensive and simple, even if the exterior is damaged, it can be easily applied again. On the other hand, glass materials and the like are difficult to repair once damaged. Therefore, adoption of a glass material as a vehicle exterior member has not been studied at all.

  The present invention, unlike the above-mentioned conventional invention, shows excellent weather resistance by forming a predetermined glassy layer on a metal base material formed for an exterior member of a vehicle, and provides a glaze and an inorganic material. An object of the present invention is to provide an exterior member for a vehicle, a vehicle, and a method for manufacturing the vehicle, which have an excellent appearance, in which the pigment is melted and integrated and decorated.

  The present inventor has noted that in recent years, technology for avoiding vehicle collisions has been developed by improving driving support functions such as automatic driving technology, and that products made by firing glaze (for example, enamel products) have excellent weather resistance. And that the fired product obtained by firing the glaze exhibits an excellent color derived from each glaze. If the collision of the vehicle is avoided in the near future by improving the collision avoidance technology, the inventor of the present invention will crack and break even if the exterior member for the vehicle is fired with glaze (that is, vitreous). Therefore, it was thought that glassy material that was considered to be unusable can be applied as a vehicle exterior member. In addition, the present invention has been completed by focusing on the fact that the vitreous material can exhibit more excellent weather resistance and a high-grade appearance than a coating film coated with a conventional resin paint. That is, the vehicle exterior member, the vehicle, and the method of manufacturing the vehicle according to the present invention that solve the above-described problems mainly include the following configurations.

  (1) A metal base formed for an exterior member of a vehicle, and a glassy layer formed on the metal base, wherein the glassy layer includes a first glass frit. An exterior member for a vehicle, comprising: a glaze; and an inkjet ink containing an inorganic pigment made of a composite oxide, wherein the first glass frit and the inorganic pigment are melt-integrated layers.

  According to such a configuration, the vehicle exterior member includes the vitreous layer in which the first glass frit and the inorganic pigment are melted and integrated. Such a vehicle exterior member is excellent in various weather resistances, for example, because it is less likely to rust, fades less and is more resistant to dirt than a coating film coated with a resin paint. Further, the vitreous layer shows an excellent appearance due to the color derived from the first glaze and the inorganic pigment. Therefore, the vehicle exterior member has a high-grade appearance that is not present in conventional vehicles.

  (2) The vitreous layer further includes a second glaze, wherein the second glaze is the same or different from the first glaze, and the second glaze is the same or different from the first glass frit. The vehicle exterior member according to (1), including a glass frit.

  According to such a configuration, the vehicle exterior member includes the vitreous layer in which the first glass frit, the inorganic pigment, and the second glass frit are melted and integrated. Such a vehicle exterior member is excellent in various weather resistances, for example, because it is less likely to rust, fades less and is more resistant to dirt than a coating film coated with a resin paint. In addition, the vitreous layer exhibits an excellent appearance due to the colors and inorganic pigments derived from the first glaze and the second glaze. Therefore, the vehicle exterior member has a high-grade appearance that is not present in conventional vehicles. Furthermore, the vitreous layer tends to retain the inorganic pigment in each of the melted glazes. Therefore, the inorganic pigment is less likely to be exposed from the surface of the vehicle exterior member, and is more difficult to elute.

  (3) A vehicle comprising the vehicle exterior member according to (1) or (2).

  According to such a configuration, the vehicle includes the vehicle exterior member. The vehicle exterior member is excellent in various weather resistances, for example, because it is less rusted, hardly fades, and resistant to dirt than a coating film coated with a resin paint. Further, the vitreous layer shows an excellent appearance due to the color derived from the first glaze and the inorganic pigment. Therefore, the vehicle provided with the vehicle exterior member has a high-grade appearance that is not present in conventional vehicles.

  (4) a preparation step of preparing a metal base material molded for an exterior member of a vehicle, and applying a first glaze including a first glass frit on the metal base material and drying the first glaze A first glaze layer forming step of forming a layer, and an ink for forming an ink layer by ink jet printing on the first glaze layer using an ink set including an ink jet ink containing an inorganic pigment composed of a complex oxide A method for manufacturing a vehicle, comprising: a layer forming step; and a firing step of firing the first glaze layer and the ink layer.

  According to such a configuration, a layer (vitreous layer) in which the inorganic pigment is dispersed in the first glass frit is provided on the metal base material formed for the exterior member of the vehicle. Such a vehicle exterior member is excellent in various weather resistances, for example, because it is less likely to rust, fades less and is more resistant to dirt than a coating film coated with a resin paint. Further, the vitreous layer shows an excellent appearance due to the color derived from the first glaze and the inorganic pigment. Therefore, a vehicle including a vehicle exterior member having a high-grade appearance that is not available in a conventional vehicle is manufactured.

  (5) After the ink layer forming step, the method further includes a second glaze layer forming step, wherein the second glaze layer forming step includes a step of forming a second glass on the ink layer that is the same as or different from the first glass frit. A step of applying a second glaze that is the same as or different from the first glaze and drying the first glaze, and drying the first glaze layer, the ink layer, and the second glaze layer. The method for manufacturing a vehicle according to (4), which is a step of firing.

  According to such a configuration, a layer (a vitreous layer) in which the inorganic pigment is dispersed between the first glass frit and the second glass frit is formed on the metal base formed for the exterior member of the vehicle. Provided. Such a vehicle exterior member is excellent in various weather resistances, for example, because it is less likely to rust, fades less and is more resistant to dirt than a coating film coated with a resin paint. In addition, the vitreous layer exhibits an excellent appearance due to the colors and inorganic pigments derived from the first glaze and the second glaze. Therefore, a vehicle including a vehicle exterior member having a high-grade appearance that is not available in a conventional vehicle is manufactured. Furthermore, the vitreous layer tends to retain the inorganic pigment in each of the melted glazes. Therefore, the inorganic pigment is less likely to be exposed from the surface of the vehicle exterior member, and is more difficult to elute.

  (6) The method of manufacturing a vehicle according to (5), further including a preliminary firing step of firing the first glaze layer and the ink layer before the second glaze layer forming step.

  According to such a configuration, the color can be finely adjusted by melting and integrating the first glaze layer and the inorganic pigment before forming the second glaze layer. In addition, before the second glaze layer is formed, the first glaze layer and the inorganic pigment are melted and integrated, so that the surface of the coating film obtained by the firing step after forming the second glaze layer is smoother. This makes it possible to form a coating film that is more resistant to dirt and has high design properties. Further, by performing the preliminary firing step, the color developability of the inorganic pigment is further improved, and a higher quality color image can be formed. The preliminary firing step is preferably performed particularly when the amount of ink applied in the ink layer forming step is large. That is, when a large amount of ink is applied, the ink layer is likely to have irregularities on the surface. In such a case, by performing the preliminary firing step, the irregularities on the surface of the ink layer are easily alleviated.

  According to the present invention, by forming a predetermined glassy layer on a metal substrate formed for an exterior member of a vehicle, excellent weather resistance is exhibited, and the glaze and the inorganic pigment are fused and integrated. The present invention can provide a vehicle exterior member, a vehicle, and a method for manufacturing a vehicle, which are decorated with excellent appearance.

<Vehicle exterior members>
An exterior member for a vehicle according to one embodiment of the present invention includes a metal base formed for an exterior member of a vehicle, and a vitreous layer formed on the metal base. The vitreous layer includes a first glaze including a first glass frit and an inkjet ink including an inorganic pigment composed of a composite oxide. The first glass frit and the inorganic pigment are melt-integrated. Hereinafter, each will be described.

(Metal substrate)
The metal substrate is not particularly limited. For example, the metal substrate may be a member used as a vehicle exterior member, such as a galvanized steel sheet, an aluminum steel sheet, or a stainless steel sheet.

  The metal substrate is formed for an exterior member of a vehicle before a glaze described later is applied. The molding method is not particularly limited. The molding method is press molding or the like.

(Glassy layer)
The vitreous layer includes a first glaze including a first glass frit and an inkjet ink including an inorganic pigment composed of a composite oxide. The first glass frit and the inorganic pigment are melt-integrated.

-First glaze The first glaze includes a first glass frit. The first glass frit is not particularly limited. The first glass frit mainly contains SiO ₂ . SiO ₂ is a main component of the glass frit, and is a main component forming a network structure of glass. The content of SiO ₂ is not particularly limited. For example, the content of SiO ₂ in the first glass frit is preferably 45% by mass or more, more preferably 50% by mass or more. Further, the content of SiO ₂ in the first glass frit is preferably 65% by mass or less, more preferably 59% by mass or less. By blending the first glass frit containing SiO ₂ within the above range, the vitreous layer after firing tends to exhibit excellent weather resistance, smoothness, and gloss.

The first glass frit may be made of not only SiO _{2 but also} ZnO, TiO ₂ , B ₂ O ₃ , a monovalent alkali metal oxide (Li ₂ O, Na ₂ O, K ₂ O, etc.), F ₂ or the like as appropriate. May be included.

  In addition, an auxiliary agent may be added to the first glass frit depending on the purpose of use. The auxiliary is not particularly limited. By way of example, adjuvants include lithium carbonate, sodium carbonate, potassium carbonate, lead oxide, bismuth oxide, barium carbonate, strontium carbonate, calcium carbonate, magnesium carbonate, zinc oxide, aluminum oxide, aluminum hydroxide, boric acid, oxide Zirconium, titanium oxide, natural feldspar, quartzite, borax, kaolin and the like. Auxiliaries may be used in combination.

  The content of the first glass frit is not particularly limited. As an example, the content of the first glass frit in the first glaze is preferably 50% by mass or more, more preferably 60% by mass or more. Further, to give an example, the content of the first glass frit in the first glaze is preferably 90% by mass or less, and more preferably 80% by mass or less. When the content of the first glass frit is within the above range, a uniform and thicker glaze layer can be easily formed.

  The first glaze may be blended with a pigment. The pigment is not particularly limited. As an example, the pigment is a cobalt compound, a chromium compound, an iron compound, a tin compound, a zirconium compound, a cerium compound, or the like. Pigments may be used in combination.

-Second glaze The second glaze is the same or different glaze as the first glaze and includes a second glass frit that is the same or different from the first glass frit. The second glaze is suitably included in the vitreous layer of the present embodiment.

  The second glaze includes a second glass frit. The second glaze and the second glass frit may be the same as those described above in relation to the first glaze and the first glass frit, respectively. In the vehicle exterior member of the present embodiment, the first glaze and the second glaze may be the same or different. The first glaze and the second glaze have different thermal expansion coefficients from the metal base material and the first and second glazes in order to obtain a glassy layer having a desired appearance. It is appropriately selected in consideration of the above.

  If the second glaze is applied after the application of the first glaze and the inkjet ink, as described later in connection with the method of manufacturing the vehicle, the color of the ink or the first glaze can be externally changed after firing. It is preferable that the pigment is not contained or the pigment is contained to such an extent that the color by the ink or the first glaze is hardly affected so that the color can be visually recognized. On the other hand, the second glaze may include a pigment that intentionally affects the color of the ink or the first glaze in order to express a composite color in the color of the ink or the first glaze.

  The thermal expansion coefficients of the first glaze and the second glaze may be the same or different. Further, the thermal expansion coefficients of the first glaze and the second glaze may be the same as or different from the thermal expansion coefficients of the metal base material. The coefficient of thermal expansion of the first glaze and the second glaze (and the metal substrate) can be appropriately adjusted so as to have a desired appearance after firing (for example, to cause milk penetration).

-Ink The inkjet ink (hereinafter, also simply referred to as ink) contains an inorganic pigment composed of a composite oxide. The inorganic pigment is a coloring material used in the ink, and is made of a metal, a metal oxide or a metal salt. The inorganic pigment used in the present embodiment is a composite oxide-based inorganic pigment composed of a composite oxide. The type of the composite oxide is not particularly limited. It is preferable that the inorganic pigment of the present embodiment contains a yellow component, a red component, a blue component, and a black component, among others. The ink set is a combination of inks composed of these color components.

  The yellow component preferably contains a praseodymium pigment. Since the praseodymium-based pigment is contained as a yellow component, an ink set using such an ink containing a yellow component can express a vivid yellow color, and hardly undergo discoloration or decoloration due to firing. More specifically, Pr-Zr-Si is illustrated as a yellow component.

  In addition, an antimony-based pigment, a vanadium-based pigment, or the like may be appropriately blended with the yellow component. Examples of the antimony pigment include lead antimony yellow, antimony titanium chrome yellow, antimony titanium yellow, and the like. Examples of the vanadium pigment include tin-vanadium yellow and zirconium vanadium yellow.

  The mixing ratio of the yellow component is not particularly limited. For example, the yellow component is preferably contained in the ink in an amount of 20% by mass or more, more preferably 30% by mass or more. Further, the yellow component is preferably contained at 50% by mass or less, more preferably at 45% by mass or less. When the yellow component is contained within the above range, the ink set can express a more vivid yellow color, and discoloration and decoloration due to firing are less likely to occur.

  The red component preferably contains at least one selected from tin-chromium pigments, gold pigments, and cadmium pigments. By including at least one selected from a tin-chromium pigment, a gold pigment, and a cadmium pigment as a red component, an ink set using an ink containing such a red component is capable of expressing a vivid red color, Discoloration and decoloring due to firing are unlikely to occur. More specifically, examples of the red component include Sn-Cr-Ca-Si, Sn-Cr, Sn-Cr-Ca, a glass-containing gold pigment, colloidal gold particles, and Cd-S-Se.

  The mixing ratio of the red component is not particularly limited. As an example, the red component is preferably contained in the ink in an amount of 20% by mass or more, more preferably 30% by mass or more. The red component is preferably contained at 50% by mass or less, more preferably at 45% by mass or less. When the red component is included within the above range, the ink set can express a more vivid red color, and discoloration and decoloration due to firing are less likely to occur.

  The blue component preferably contains a cobalt-based pigment. By containing a cobalt-based pigment as a blue component, an ink set using such an ink containing a blue component can express a vivid blue color, and hardly undergo discoloration or decoloration due to firing. More specifically, the blue component is exemplified by Co-Al-Cr and Co-Al.

  The mixing ratio of the blue component is not particularly limited. For example, the blue component is preferably contained in the ink in an amount of 20% by mass or more, more preferably 30% by mass or more. Further, the blue component is preferably contained at 50% by mass or less, more preferably at 45% by mass or less. When the blue component is included in the above range, the ink set can express a more vivid blue color, and discoloration and decoloration due to firing are less likely to occur.

  The black component preferably contains a cobalt ferrite pigment. By containing a cobalt ferrite pigment as a black component, an ink set using such an ink containing a black component can express a vivid black color, and is unlikely to be discolored or decolored by firing. More specifically, examples of the black component include Co-Mn-Fe-Cr-Ni, Co-Fe-Cr-Ni, and Fe-Cr-Ni-Mn.

  The black component may be appropriately blended with a manganese ferrite pigment or the like. Examples of the manganese ferrite pigment include manganese ferrite black and manganese ferrite copper black.

  The mixing ratio of the black component is not particularly limited. To give an example, the black component is preferably contained in the ink in an amount of 20% by mass or more, more preferably 30% by mass or more. Further, the black component is preferably contained at 50% by mass or less, more preferably at 45% by mass or less. When the black component is included within the above range, the ink set can express a more vivid black color, and discoloration and decoloration due to firing are less likely to occur.

Inorganic pigments according to the present embodiment, preferably has an average particle diameter (D ₅₀ average particle size) is 200nm or more, and more preferably 250nm or more. Further, the inorganic pigment preferably has an average particle size of 380 nm or less. When the average particle size is within the above range, color variation is less likely to occur. The average particle diameter can be measured by a dynamic light scattering method using a Zetasizer Nano series manufactured by Malvern Instruments Limited.

  The ink set of the present embodiment preferably contains a dispersant and a solvent in order to uniformly disperse the inorganic pigment. The concentration of the inorganic pigment is preferably at least 20% by mass, more preferably at least 30% by mass, based on the ink. Further, the concentration of the inorganic pigment is preferably 50% by mass or less, more preferably 45% by mass or less based on the ink. When the concentration of the inorganic pigment is within the above range, the ink has an appropriate concentration and excellent storage stability.

  The dispersant is not particularly limited. As an example, the dispersant is an anionic compound, a cationic compound, a nonionic compound, an amphoteric compound, a polymer compound, or the like. Among these, from the viewpoint of obtaining excellent dispersibility, the dispersant is preferably a polymer type, and more preferably a dispersant having an acidic adsorbing group or a basic adsorbing group at the terminal.

  The solvent is not particularly limited as long as the solvent can uniformly disperse the inorganic pigment. Among them, an organic solvent is preferable as the solvent because the ink is hard to dry and the ejection stability of the ink is excellent.

  As the organic solvent, fatty acid esters and glycol ethers are preferable. Fatty acid esters include methyl caprylate, methyl caprate, methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, bovine fatty acid methyl, soy fatty acid methyl, rice sugar fatty acid methyl, rapeseed fatty acid methyl N-butyl palmitate, n-butyl stearate, n-butyl soybean fatty acid, n-butyl rapeseed fatty acid, i-butyl rice sugar fatty acid, i-butyl rapeseed fatty acid, octyl palmitate, octyl oleate, octyl rapeseed fatty acid, Examples include the vegetable fatty acid octyl, isopropyl myristate, isopropyl palmitate and the like. Examples of glycol ethers include diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.

  The surface tension of the ink is preferably 20 mN / m or more, and more preferably 22 mN / m or more. The surface tension of the ink is preferably 30 mN / m or less, more preferably 27 mN / m or less. When the surface tension of the ink is within the above range, the ink is less likely to overflow from the surface of the recording head, and the continuous ejection property is excellent. In addition, the ink shows excellent coloring properties and has an excellent appearance after firing.

  The ink of the ink set of the present embodiment may include a surface tension adjuster, a viscosity adjuster, a specific resistance adjuster, a heat stabilizer, an antioxidant, a reduction inhibitor, a preservative, a pH adjuster, and a defoaming agent, if necessary. Additives such as agents, wetting agents and the like may be added.

  The method for preparing the ink of the ink set is not particularly limited. As an example, the ink can be prepared by mixing the above raw materials, dispersing the mixture using a dispersing machine such as a roll mill, a ball mill, a colloid mill, a jet mill, a bead mill, a sand mill, and then performing filtration.

  Returning to the description of the entire vitreous layer, the vitreous layer is a layer in which the above-described first glass frit and the inorganic pigment are fused and integrated. Preferably, the vitreous layer of the present embodiment is a layer in which the first glass frit, the inorganic pigment, and the second glass frit are melted and integrated. Melting and integration of the first glass frit, the inorganic pigment, and the suitably blended second glass frit are performed by a firing step described later.

  In the vitreous layer, the inorganic pigment is dispersed in the molten first glass frit. Preferably, the vitreous layer of the present embodiment includes a second glaze, and the inorganic pigment is dispersed in the molten first glass frit and the second glass frit. The surface of the vitreous layer that is in contact with the metal substrate has a component derived from the glaze provided on the metal substrate (for example, in the case of a manufacturing method described later, the first glass frit or the like contained in the first glaze). Component) is present. On the other hand, when the vitreous layer contains the second glaze, the surface opposite to the surface in contact with the metal base is made of a component derived from the other glaze (for example, in the case of a manufacturing method described later, the second glaze is A large amount of the second glass frit and the like included therein. The vehicle exterior member of the present embodiment can express various external appearances by the color derived from the first glaze (and the color by the inorganic pigment in the ink). In particular, when two or more glazes (for example, a first glaze and a second glaze) are included, each of these glazes is fired to obtain a color derived from each glaze (and an inorganic pigment in the ink). Colors) can be combined to express a wide variety of appearances. Such an appearance is a high-grade appearance not found in a conventional resin-coated vehicle.

  The vitreous layer of the present embodiment is held in a state where the inorganic pigment is dispersed in the glaze, and is hardly exposed on the surface of the vitreous layer. In particular, when the vitreous layer contains the first glaze and the second glaze, the inorganic pigment is easily held in a state dispersed in these glazes, and is hardly exposed by the surface of the vitreous layer. Therefore, the inorganic pigment hardly elutes with time. Further, since the inorganic pigment is held in a dispersed state in the glassy layer, a deep design can be formed.

  In addition, the surface of the vitreous layer exhibits excellent smoothness because the inorganic pigment is hardly exposed and the glaze is formed by thermal melting of the glaze by firing.

  The vehicle to which the vehicle exterior member of the present embodiment is applied is not particularly limited. By way of example, vehicles include all vehicles that transport or drive people or objects, such as cars, motorcycles, bicycles, rail vehicles, ships, aircraft, and the like. The vehicle exterior member of the present embodiment is particularly suitable when the vehicle is an automobile. That is, as described above, in the technical field of automobiles, in recent years, the development of driving assistance functions such as automatic driving technology has been rapidly developed, and thereby collisions of automobiles are being avoided. Therefore, when the vehicle exterior member of the present embodiment is applied as an exterior member of an automobile, the resulting automobile is more likely to avoid a collision by appropriately operating a driving support function or the like. As a result, the automobile may use a glassy exterior member that has not been used until now (that is, the vehicle exterior member of the present embodiment). In addition, by using the vehicle exterior member of the present embodiment, the vehicle can exhibit a new high-grade glassy appearance instead of the conventional appearance using a resin paint. Furthermore, automobiles are more excellent in weather resistance than when a conventional resin paint is applied.

  As described above, according to the present embodiment, the vehicle exterior member includes the vitreous layer in which the first glass frit and the inorganic pigment are melted and integrated. Such a vehicle exterior member is resistant to rust, fading, and dirt. Therefore, the vehicle exterior member has various weather resistances better than, for example, a coating film coated with a resin paint. Further, the vehicle including the vehicle exterior member of the present embodiment also has the same excellent weather resistance. The vitreous layer also has an excellent appearance due to the colors and inorganic pigments derived from the first glaze and the second glaze preferably included. Therefore, by using the vehicle exterior member, it is possible to obtain a vehicle having a high-grade appearance that is not available in a conventional vehicle. A vehicle provided with a vehicle exterior member also has the same effect.

  In addition, in the said embodiment, the case where the vitreous layer was directly formed on the metal base material was illustrated. Instead of this, in the vehicle exterior member, the glassy layer may be indirectly formed on the metal base after various processes are performed on the surface of the metal base.

<Vehicle manufacturing method>
The method for manufacturing a vehicle according to one embodiment of the present invention includes a preparing step of preparing a metal base formed for a vehicle exterior member, and a step of forming a first glaze including a first glass frit on the metal base. A first glaze layer forming step of applying and drying to form a first glaze layer, and ink jetting using an ink set including an ink jet ink containing an inorganic pigment composed of a composite oxide on the first glaze layer. The method includes an ink layer forming step of forming an ink layer by printing, and a firing step of firing the first glaze layer and the ink layer. Hereinafter, each step will be described.

(Preparation process)
The preparation step is a step of preparing a metal base material formed for a vehicle exterior member. The metal base material and the method of molding the metal base material for the vehicle exterior member are the same as those described above in relation to the embodiment of the vehicle exterior member. The first glaze layer forming step is performed on the metal base material prepared in the preparing step.

(First glaze layer forming step)
The first glaze layer forming step is a step of forming a first glaze layer by applying a first glaze including a first glass frit to a metal substrate and drying the first glaze. The first glaze is similar to that described above in connection with the embodiment of the vehicle exterior member.

  The method of applying the first glaze is not particularly limited. As an example, the first glaze is prepared by preparing a slurry to which a solvent for suspension (water, an organic solvent and the like, including additives as necessary) is added, and brushing the slurry on a metal substrate. , Spraying or the like. For the purpose of improving the melting property of the glaze during firing, the glaze may be applied after a process such as pulverization or dispersion in a slurry state. Further, the first glaze may be applied by an inkjet recording method.

  The drying method is not particularly limited. As an example, the first glaze can be dried by air drying or forced drying. The thickness of the obtained first glaze layer is not particularly limited. As an example, the thickness of the first glaze layer is preferably 3 μm or more, more preferably 50 μm or more. Also, the thickness of the first glaze layer is preferably 150 μm or less, more preferably 100 μm or less. When the thickness of the first glaze layer is within the above range, the inorganic pigment in the ink layer melts into the first glaze layer, and the inorganic pigment can be covered by the glass derived from the first glaze, and It is easy to obtain a vehicle exterior member excellent in quality. An ink layer forming step is performed on the metal substrate on which the first glaze layer has been formed.

(Ink layer forming step)
The ink layer forming step is a step of forming an ink layer on the first glaze layer by ink-jet printing using an ink set including an ink-jet ink containing an inorganic pigment composed of a composite oxide.

  The method of performing ink-jet printing (ink-jet recording method) is not particularly limited. For example, the ink jet recording method includes a charge modulation method, a micro dot method, a charge ejection control method, a continuous method such as an ink mist method, a piezo method, a pulse jet method, a bubble jet (registered trademark) method, and an electrostatic suction method. And on-demand methods. In addition, the ink jet recording method may be adopted as either a line type in which the recording head is fixed and ejected to the recording medium or a serial type in which the recording head is moved relatively to the recording medium.

In the inkjet printing method of the present embodiment, the ink is preferably applied to the metal base material (the first glaze layer after drying) so as to be 0.01 g / m ² or more, and 0.1 g / m ^2. It is more preferable to be provided so as to be as described above. Further, the ink is preferably applied to be 60 g / m ² or less, and more preferably 50 g / m ² or less. The ink is applied so as to have the above application amount, so that a desired image is easily expressed and the ink does not easily overflow. The metal substrate on which the ink layer has been formed may be subjected to a firing step described later, or may be subjected to a second glaze layer forming step before the firing step. In the vehicle manufacturing method of the present embodiment, it is preferable that the second glaze layer forming step is performed.

(Second glaze layer forming step)
The second glaze layer forming step is a step preferably performed after the ink layer forming step. The second glaze layer forming step includes a second glass frit that is the same as or different from the first glass frit on the ink layer, and A second glaze, which is the same as or different from the glaze, and is dried to form a second glaze layer. The second glaze is similar to that described above in connection with the embodiment of the vehicle exterior member.

  The method of applying and drying the second glaze is the same as the method of applying and drying the first glaze described above. The second glaze may be applied by an inkjet recording method.

  The thickness of the obtained second glaze layer is not particularly limited. As an example, the thickness of the second glaze layer is preferably 3 μm or more, more preferably 50 μm or more. The thickness of the second glaze layer is preferably 150 μm or less, more preferably 100 μm or less. When the thickness of the second glaze layer is within the above range, the inorganic pigment in the ink layer melts into the second glaze layer, and the inorganic pigment can be covered with the glass derived from the second glaze, and It is easy to obtain a vehicle exterior member excellent in quality. The baking step is performed on the metal substrate on which the second glaze layer has been formed.

(Firing process)
The firing step is a step of firing the first glaze layer and the ink layer. The firing step is a step of firing the first glaze layer, the ink layer, and the second glaze layer when the above-described second glaze layer forming step is performed. The firing temperature is not particularly limited. As an example, the firing temperature is 730 ° C to 790 ° C. The firing time can be appropriately selected depending on the type of the metal substrate, the type of the firing furnace, and the like. For example, when the metal substrate is a steel plate, the firing time is about 3 to 5 minutes.

  By performing the firing step, the first glaze in the first glaze layer and the second glaze in the suitably formed second glaze layer are melted, and the vitreous layer holding the inorganic pigment therein is formed. It is formed. When the second glaze layer is formed, the first glaze layer and the second glaze layer are melted and mixed with each other by the firing step. As a result, the surface of the metal base (the area in contact with the metal base) is mainly covered with glassy material derived from the first glaze, and the area near the outer surface of the metal base is mainly covered with the second glaze. It is covered with glass of origin. Whether or not the inorganic pigment is covered with glass can be evaluated, for example, by measuring the reflectance using a gloss meter (IG-410, manufactured by Horiba, Ltd.).

  By performing the firing step, the vehicle exterior member is manufactured. The obtained vehicle exterior member is appropriately combined with another vehicle member separately prepared by another known process. Thereby, the vehicle is manufactured.

  As described above, according to the present embodiment, the layer in which the inorganic pigment is dispersed in the molten first glass frit (vitreous layer) is provided on the metal base material formed for the vehicle exterior member. Such a vehicle exterior member is excellent in various weather resistances, for example, because it is less likely to rust, fades less and is more resistant to dirt than a coating film coated with a resin paint. Further, the vitreous layer shows an excellent appearance due to the color derived from the first glaze and the inorganic pigment. Therefore, a vehicle including a vehicle exterior member having a high-grade appearance that is not available in a conventional vehicle is manufactured. In the case where the second glaze layer forming step is performed, a layer (a vitreous layer) in which the inorganic pigment is dispersed between the first glass frit and the second glass frit is formed for a vehicle exterior member. Provided on a metal substrate. Such a vehicle exterior member is more resistant to rust, less fading, and more resistant to dirt than a coating film coated with a resin paint, for example, and thus has various weather resistances. In addition, the vitreous layer exhibits an excellent appearance due to the colors and inorganic pigments derived from the first glaze and the second glaze. Therefore, a vehicle including a vehicle exterior member having a high-grade appearance that is not available in a conventional vehicle is manufactured. Furthermore, the vitreous layer tends to retain the inorganic pigment in each of the melted glazes. Therefore, the inorganic pigment is less likely to be exposed from the surface of the vehicle exterior member, and is more difficult to elute.

  The vehicle of the present embodiment is preferably a vehicle equipped with a driving support function such as an automatic driving technique. The driving assistance function (driving assistance device) includes, for example, an imaging unit that captures another vehicle running around the vehicle or an article that may be an obstacle, and whether the vehicle or the article collides based on an image captured by the imaging unit. It comprises a prediction means for predicting whether or not, and an information providing means for providing information of the prediction. These means are programmed and integrated into the vehicle electronically. This makes it easier for the vehicle to avoid a collision or the like, so that the vehicle exterior member is less likely to be damaged.

  In the present embodiment, the case where the firing step is performed after the ink layer forming step, preferably after the second glaze layer forming step has been exemplified. Alternatively, in the vehicle manufacturing method according to the present embodiment, when the second glaze layer forming step is performed, the first glaze layer and the ink layer are preliminarily fired before the second glaze layer forming step. A firing step may be employed. The conditions for the preliminary firing step are not particularly limited. The conditions of the preliminary firing step may be the conditions described above in relation to the firing step.

  By performing the preliminary firing step, the first glaze layer and the inorganic pigment are melted and integrated before forming the second glaze layer, and the obtained color can be finely adjusted. In addition, before the second glaze layer is formed, the first glaze layer and the inorganic pigment are melted and integrated, so that the surface of the coating film obtained by the firing step after forming the second glaze layer is smoother. This makes it possible to form a coating film that is more resistant to dirt and has high design properties. Further, by performing the preliminary firing step, the color developability of the inorganic pigment is further improved, and a higher quality color image can be formed. The preliminary firing step is preferably performed particularly when the amount of ink applied in the ink layer forming step is large. That is, when a large amount of ink is applied, the ink layer is likely to have irregularities on the surface. In such a case, by performing the preliminary firing step, the irregularities on the surface of the ink layer are easily alleviated.

Claims (6)

A metal base formed for an exterior member of a vehicle, and having a vitreous layer formed on the metal base,
The vitreous layer,
A first glaze including a first glass frit, and an inkjet ink including an inorganic pigment composed of a composite oxide,
An exterior member for a vehicle, wherein the first glass frit and the inorganic pigment are a layer integrated by fusion. The vitreous layer further includes a second glaze;
The second glaze is
The same or different from the first glaze,
The vehicle exterior member according to claim 1, further comprising a second glass frit that is the same as or different from the first glass frit.   A vehicle comprising the vehicle exterior member according to claim 1. A preparation step of preparing a metal base material molded for an exterior member of a vehicle,
A first glaze layer forming step of applying a first glaze including a first glass frit on the metal base material and drying to form a first glaze layer;
An ink layer forming step of forming an ink layer by ink-jet printing on the first glaze layer using an ink set including an ink-jet ink containing an inorganic pigment composed of a complex oxide;
A baking step of baking the first glaze layer and the ink layer. After the ink layer forming step, the method further includes a second glaze layer forming step,
The second glaze layer forming step includes:
A second glass frit that is the same as or different from the first glass frit on the ink layer, and a second glaze that is the same as or different from the first glaze is applied and dried;
The vehicle manufacturing method according to claim 4, wherein the firing step is a step of firing the first glaze layer, the ink layer, and the second glaze layer.   The vehicle manufacturing method according to claim 5, further comprising a preliminary firing step of firing the first glaze layer and the ink layer before the second glaze layer forming step.