JP2008100129A - Coating film forming method and coating film - Google Patents

Abstract

Disclosed is a method for forming a coating film and a coating film that are advantageous for forming a coating film having high saturation when a light receiving angle changes while forming a coating film layer using titania.
A method of forming a coating film includes a step of forming a first coating layer 2 containing first pigment particles 21 based on titania, and a first clear layer 3 on the first coating layer 2. , Laminating the second coating layer 4 containing the second pigment particles 41 based on titania on the first clear layer 3, and the second clear layer on the second coating layer 4. Laminating the layer 5.
[Selection] Figure 1

Description

  The present invention relates to a method for forming a coating film having high design properties and a coating film.

  In Patent Document 1, a base coat layer is formed using a paint composition containing a pigment made of flaky titanium oxide and a vehicle, and a top coat is formed on the base coat layer with a clear paint containing a carboxyl group-containing polymer. A coating film forming method is disclosed.

  In Patent Document 2, a base coat layer is formed using a coating composition containing a pigment made of flaky titanium oxide having glitter and a vehicle, and a top coat with a clear coating containing a carboxyl group-containing polymer is used as the base coat layer. A method of forming a coating film formed on the substrate is disclosed.

  Patent Document 3 discloses a coating film forming method in which a colored base paint, a metallic paint containing flaky titanium oxide, and a clear paint are sequentially applied.

Patent Document 4 discloses a method of forming a coating film in which a white base paint containing flaky titania white pigment, a flaky mica, a metallic paint containing flaky titania white pigment, and a clear paint are sequentially applied.
JP 2001-131487 A Japanese Patent Laid-Open No. 11-236520 JP-A-11-10081 JP-A-11-10067

  Color is a very important factor that can have a psychological and physiological effect on humans. Usually, when coloring an object, various pigment particles are used. With pigment particles alone, it is not easy to meet the demands of various sensitivities and designs for recent colors. According to each of the above-mentioned patent documents, a titanium oxide pigment that is titania is used, but there is a limit in forming a highly saturated coating film when the light receiving angle changes.

  The present invention has been made in view of the above circumstances, and is a coating film that is advantageous for forming a coating film having high saturation when the light receiving angle changes while forming a coating film layer using titania. It is an object to provide a forming method and a coating film.

  The method for forming a coating film according to aspect 1 includes a step of forming a first coating layer containing first pigment particles based on titania and a step of laminating a first clear layer on the first coating layer. And a step of laminating a second coating layer containing titania-based second pigment particles on the first clear layer and a step of laminating the second clear layer on the second coating layer. .

  The coating film according to aspect 2 is laminated on the first coating layer containing the first pigment particles based on titania, the first clear layer laminated on the first coating layer, and the first clear layer. And a second coating layer containing second pigment particles based on titania, and a second clear layer laminated on the second coating layer.

  The first coating layer containing the first pigment particles based on titania and the second coating layer containing the second pigment particles based on titania are vertically arranged through the first clear layer. Are stacked. For this reason, the coloring by the first pigment particles and the coloring by the second pigment particles are obtained, which is advantageous for forming a coating film having high saturation when the light receiving angle changes.

  According to the present invention, it is possible to provide a method for forming a coating film and a coating film that are advantageous for forming a coating film having high saturation when the light receiving angle changes while forming a coating film layer using titania. Can do.

  According to the present invention, the first coating layer containing the first pigment particles based on titania (titanium oxide) is formed. Examples of the first pigment particles include those having translucency and / or glitter. The first coating layer preferably has first pigment particles and a first resin component that holds the first pigment particles. As a 1st resin component, the well-known resin component which forms a coating film can be employ | adopted, The thermosetting resin which has translucency (transparency) is preferable. Specific examples include acrylic resins, melamine resins, polyester resins, alkyd resins, fluororesins, epoxy resins, polyurethane resins, polyester resins, and modified resins thereof. These can be used alone or in combination. However, it is not limited to these resins.

  Examples of the titania constituting the first pigment particles include anatase type titania and rutile type titania, but considering durability, rutile type titania is preferable. Considering the saturation due to interference light, the preferred content of the first pigment particles in the first coating layer is 1 to 30%, particularly 2 to 20%, especially 3 to 10% in pwc. It is not limited to these. pwc refers to the mass proportion of pigment particles in the solid content constituting the coating layer. Therefore, for example, when the solid content constituting the coating layer is the first pigment particle (10%) and the solid content of the resin component (90%) by mass ratio, the first pigment particle is expressed as 10% in pwc. Is done.

  The first pigment particles described above preferably include a first inner layer and a second outer layer formed of titania coated on the first inner layer. Here, as the first inner layer of the first pigment particles, at least one of mica (mica), glass flakes, silica flakes, and the like can be adopted, and those having translucency (transparency) can be adopted. The mica may be natural mica or synthetic mica. Accordingly, examples of the first pigment particles include a structure in which the surface of mica is coated with titania. A titania having translucency (transparency) can be adopted. In this case, pearly luster is exhibited by optical interference using the refractive index of titania, and various optical interferences can be developed by controlling the thickness of titania, showing the effect that the color tone changes slightly depending on the viewing angle. .

  Since the first pigment particles are embedded in the first coating layer, they are scale-like and are oriented along the surface direction of the first coating layer. As the size of the first pigment particles, the major axis L1 is, for example, 1 to 50 micrometers, particularly 5 to 20 micrometers, and the thickness t1 is, for example, 100 to 1000 nanometers, particularly 300 to 800 nanometers.

  Here, when the major axis L1 of the first pigment particles is excessive, glossiness of the coating film is likely to be generated, and when the major axis L1 is excessively small, color development is poor (interference is insufficient). If the thickness t1 of the first pigment particles is excessive, the coating film is liable to deteriorate and the underlying masking is insufficient, and if the thickness t1 is too small, pigment damage is likely to occur in the paint. However, the size of the first pigment particles is not limited to the above range.

  A first clear layer is laminated on the first coating layer. The first clear layer refers to a transparent layer having no color pigment. The first clear layer can be formed of a film-forming resin having translucency (transparency).

  A second coating layer is laminated on the first clear layer. The second coating layer contains second pigment particles based on titania. The 2nd pigment particle can illustrate what has translucency and / or luster. The second coating layer preferably has second pigment particles and a second resin component that holds the second pigment particles. As a 2nd resin component, the well-known resin component which forms a coating film can be employ | adopted, The thermosetting resin which has translucency (transparency) is preferable. Specific examples include acrylic resins, melamine resins, polyester resins, alkyd resins, fluororesins, epoxy resins, polyurethane resins, polyester resins, and modified resins thereof. These can be used alone or in combination. However, it is not limited to these resins.

  Since the second pigment particles are embedded in the coating film, it is preferable to use a scaly shape. Examples of the second pigment particle include a second inner layer and a second outer layer formed of rutile-type titania coated on the second inner layer. Examples of the second inner layer of the second pigment particles include anatase-type titania, but depending on circumstances, mica (mica), glass flakes, silica flakes, and the like may be used. When the second inner layer formed of anatase-type titania is covered and surrounded by the second outer layer formed of rutile-type titania having low photocatalytic properties, resin degradation due to the second pigment particles is suppressed. The

  The second pigment particles show a pearly luster due to light interference using the refractive index of titania, and various light interferences can be developed by controlling the thickness of titania. The color tone changes slightly depending on the viewing angle. The effect can be expected.

  Since the second pigment particles are embedded in the second coating film layer, the second pigment particles have a scaly shape and are oriented along the surface direction of the second coating film layer. For the second pigment particles, the major axis L2 is, for example, 5 to 20 micrometers, in particular 8 to 15 micrometers, and the thickness t2 is, for example, 50 to 400 nanometers, in particular 100 to 350 nanometers. Here, if the major axis L2 of the second pigment particles is excessive, the coating film tends to induce gloss deterioration, and if the major axis L2 is too small, color development (insufficient interference) tends to occur. When the thickness t2 of the second pigment particles is excessive, the gloss of the coating film is likely to deteriorate, and when the thickness t2 is excessively small, the pigment is easily damaged in the paint. However, the size of the second pigment particles is not limited to the above range.

  Note that L1 = L2, L1≈L2, L1 <L2, and L1> L2. Alternatively, t1 = t2, t1≈t2, t1 <t2, and t1> t2.

  Considering the saturation due to interference light, the preferred content of the second pigment particles in the second coating layer is 1 to 30%, particularly 2 to 20%, especially 3 to 10% in pwc. It is not limited to these.

  A second clear layer is laminated on the second coating layer. The second clear layer refers to a transparent layer having no color pigment. The second clear layer has translucency (transparency). The second clear layer covers and protects the second coating layer.

  The form which apply | coats a 1st coating-film layer, a 1st clear layer, a 2nd coating-film layer, and a 2nd clear layer is illustrated. The lamination form of each layer is not particularly limited, and examples thereof include, but are not limited to, a spray method, a dipping method, and a roll coat method. In this case, a liquid composition dissolved or dispersed in an organic solvent or an aqueous solvent can be applied to the substrate. As the organic solvent, those usually used in the paint field can be adopted. Examples include hydrocarbons such as toluene and xylene, ketones such as acetone, methyl ketone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, and alcohols. Is done. A preferable addition amount of the solvent is 20 to 200% by mass with respect to the coating film-forming resin, but is not limited thereto. The coating film according to the present invention can be widely used for vehicle bodies, vehicle-mounted components, building materials, office supplies, and the like.

(Example 1)
Examples of the present invention will be specifically described below.

  First, as shown in FIG. 1, an iron-based substrate 1 (steel plate) in which a primer layer 11 is laminated on an electrodeposition coating layer 10 is used. Next, the first coating layer 2 containing the first pigment particles 21 based on titania and the resin component 23 as the base material is laminated on the primer layer 11 of the base material. The resin component 23 of the first coating layer 2 is an acrylic melamine resin. The first pigment particles 21 have translucency (transparency) and glitter.

  According to the present embodiment, the first pigment particles 21 are embedded in the first coating layer 2 and thus have a scaly shape. As shown in FIG. 2, the first pigment particle 21 has a multilayer structure, and includes a first inner layer 21a and a first outer layer 21c formed of titania (rutile type) covered with the first inner layer 21a. Yes. Here, the first inner layer 21a of the first pigment particles 21 is formed of mica (mica) which is a layered silicate compound. Therefore, the first pigment particles 21 have a structure in which the surface of mica is coated with titania. Mica and titania are transparent. In this case, according to the first pigment particles 21, by using the refractive index of titania, optical interference of reflected light is generated, and pearly luster is obtained by the optical interference. In this case, by controlling the thickness of titania covered with translucent mica, color development due to various light interferences can be expected, and the effect of slightly changing the color tone depending on the viewing angle can be obtained. As the size of the first pigment particles 21, the major axis L1 is 5 to 20 micrometers, and the thickness t1 is 300 to 800 nanometers.

  Next, a first clear layer 3 based on an acrylic polyester resin is laminated on the first coating layer 2.

  Next, the second coating layer 4 is laminated on the first clear layer 3. The 2nd coating layer 4 contains the 2nd pigment particle 41 which uses titania as a base material, and the resin component 43 holding this. The resin component 43 which comprises the 2nd coating layer 4 has translucency (transparency), The material is an acrylic melamine resin. The second pigment particles 41 have translucency (transparency) and glitter. As schematically shown in FIG. 3, the second pigment particle 41 has a multilayer structure, a second inner layer 41 a based on anatase-type titania, and a rutile type coated with the second inner layer 41 a. And a second outer layer 41c formed of titania. Such second pigment particles 41 have high strength, are difficult to break when external force is applied, and have high durability. Here, even if the concavo-convex portion is formed on the surface of the second inner layer 41a, the concavo-convex portion is smoothed by the second outer layer 41c, so that the reflectivity is improved and the interference color can be improved.

  According to the second pigment particles 41, a pearly luster is obtained by light interference using the refractive index of titania, and by developing the titania thickness, various color developments due to light interference can be expected, depending on the viewing angle. An effect that the color tone slightly changes can be obtained. The rutile type constituting the second outer layer 41c has a lower photocatalytic property than the anatase type constituting the second inner layer 41a, and thus can contribute to the extension of the life of the resin.

  Since the second pigment particles 41 are embedded in the second coating film layer 4, the second pigment particles 41 have a scaly shape and are oriented along the surface direction of the second coating film layer 4. As the size of the second pigment particles 41, the major axis L2 is 8 to 15 micrometers and the thickness t2 is 100 to 350 nanometers. When the second pigment particles 41 having a high aspect ratio are provided in the upper layer, irregular reflection is suppressed and a dense feeling can be expressed (if the aspect ratio is low, it is glaring).

  According to the present embodiment, as shown in FIG. 1, the second coating layer 4 containing the second pigment particles 41 is relatively above the second coating layer 2 containing the first pigment particles 21. (Incident light side). That is, the first coating layer 2 containing the first pigment particles 21 is disposed on the lower side (the side far from the incident light side) than the second coating layer 4 containing the second pigment particles 41. ing. This is because the first pigment particles 21 are higher in light reflectivity than the second pigment particles 41, and the light reflectivity is ensured.

  On the 2nd coating layer 4, the 2nd clear layer 5 which uses acrylic polyester resin as a base material is laminated | stacked. According to the present embodiment, in FIG. 1, the thickness K2 of the first coating layer 2 is 10 to 20 micrometers. The thickness K3 of the first clear layer 3 is 25 to 40 micrometers. The thickness K4 of the second coating layer 4 is 10 to 20 micrometers. The thickness K5 of the second clear layer 5 is 25 to 40 micrometers. However, the thickness is not limited to these.

  In this embodiment, the electrodeposition coating layer 10 is applied to the substrate 1 (steel plate) by cationic electrodeposition coating. Further, the primer layer 11 is applied with an intermediate coating. An aqueous base paint is spray-coated on the substrate 1 (steel plate) on which these coating films have been heat-cured, and preheated at 80 ° C. for 3 minutes to form the first coating layer 2. Further, a clear paint was applied and heated at 140 ° C. for 30 minutes to cure the first clear layer 3. Further, a water-based base coating is applied to form the second coating layer 4, and the clear coating is applied again to form the second clear layer 5.

  In this embodiment, the light A1 incident on the coating film is reflected by the surface of the second pigment particles 41 contained in the second coating film layer 4 on the upper side relatively toward the outside of the coating film, The light is reflected from the surface of the first pigment particles 21 contained in the first coating layer 2 on the lower side and travels outward from the coating. The presence of the first clear layer 3 affects the optical path difference of light, and consequently the saturation.

  As described above, according to the present embodiment, the first coating layer 2 containing the first pigment particles 21, using different types of titania-based first pigment particles 21 and titania-based second pigment particles 41, and The second coating layer 4 containing the second pigment particles 41 is laminated via the first clear layer 3 in the vertical direction. For this reason, the coloring effect by the 1st coating layer 2 containing the 1st pigment particle 21 and the coloring effect by the 2nd coating layer 4 containing the 2nd pigment particle 41 are combined, and it colors in a wide range. This is advantageous. Therefore, it is advantageous to achieve both a strong saturation and a moderate saturation change.

  That is, according to this example, there is provided a coating film forming method and a coating film that are advantageous for forming a coating film having high saturation when the light receiving angle changes while forming a coating film layer using titania. Can be provided.

(Test Example 1)
Based on Example 1, a coating film according to Test Example 1 (see FIG. 1) is formed. The first pigment particles 21 embedded in the first coating layer 2 are scaly, and the first inner layer 21a formed of scaly titania-coated mica and the titania coated with the first inner layer 21a ( And a first outer layer 21c formed of a rutile type. As the size of the first pigment particles 21, the major axis L1 is 15 micrometers on average and the thickness t1 is 350 nanometers on average. The resin component 23 of the first coating layer 2 is an acrylic melamine resin. As a composition of the liquid coating composition for forming the first coating layer 2, the first pigment particle 21 is 5% by pwc, and the resin component (solid content) is 25% by mass.

  The second pigment particles 41 embedded in the second coating layer 4 are scaly, and a scaly second inner layer 41a formed of anatase-type titania and a rutile coated with the second inner layer 41a. What consists of the 2nd outer layer 41c formed with the type | mold titania is used. As the size of the second pigment particles 41, the long diameter L2 is 12 micrometers on average and the thickness t2 is 270 nanometers on average. The resin component 23 of the first coating layer 2 is an acrylic melamine resin. As a composition of the liquid coating composition forming the second coating layer 4, the first pigment particle 21 is 5% by pwc, and the resin component (solid content) is 25% by mass.

  In Test Example 1, the thickness K2 of the first coating layer 2 functioning as a color intermediate coating layer was 13 micrometers, the thickness K3 of the first clear layer 3 (material: acrylic polyester) was 30 micrometers, The thickness K4 of the two coating layer 4 is 13 micrometers, and the thickness K5 of the second clear layer 5 (material: acrylic melamine) is 30 micrometers. Each layer is painted by means of spray painting.

(Reference Example 1)
FIG. 4 schematically shows a cross section of the coating film of Reference Example 1. In this case, as shown in FIG. 4, a color intermediate coating layer 2B (thickness: 30 micrometers), a coating layer 4B (thickness: 13 micrometers), and a clear layer 5B (thickness: 30 micrometers) are formed on the test piece. Are stacked in this order. In the color intermediate coating layer 2B, the pigment particles are titania white pigment and organic red pigment, and the resin component is polyester urethane. The coating film layer 4B is formed of pigment particles having both the first pigment particles 21 and the second pigment particles 41, and a resin component (material: acrylic melamine) that holds the pigment particles. As a composition of the coating composition for forming the coating layer 4B, the first pigment particle 21 is 5% by pwc, the second pigment particle 41 is 5%, and the resin component (solid content) is 25% by mass. To do. As the 1st pigment particle 21 and the 2nd pigment particle 41, the same thing as Test Example 1 is used.

(Reference Example 2)
FIG. 5 schematically shows a cross section of the coating film of Reference Example 2. In this case, as shown in FIG. 5, a color intermediate coating layer 2C (thickness: 30 micrometers), a coating layer 4C (thickness: 13 micrometers), a clear layer 5C (material: acrylic polyester, thickness) on the test piece. : 30 micrometers) are stacked in this order. In the color intermediate coating layer 2C, the material of the pigment particles is titania white pigment and organic red pigment, and the material of the resin component is polyester urethane resin. As a composition of the coating composition for forming the coating layer 4C, the second pigment particle 41 is 10% by pwc, and the resin component (solid content) is 25% by mass. As the second pigment particles 41 of the coating layer 4C, those similar to those in Test Example 1 are used.

(Comparative Example 1)
FIG. 6 schematically shows a cross section of the coating film of Comparative Example 1. In this case, as shown in FIG. 6, a color intermediate coating layer 2D (thickness: 30 micrometers), a coating layer 4D (thickness: 13 micrometers), a clear layer 5D (material: polyester urethane, thickness) on the test piece. : 30 micrometers) are stacked in this order. In the coating layer 4D, the first pigment particles 21 in which the first inner layer 21a formed of mica is coated with the first outer layer 21c of titania are used, and the material of the resin component is acrylic melamine. As a composition of the coating composition for forming the coating layer D, the first pigment particle 21 is 5% by pwc, and the resin component (solid content) is 25% by mass.

(Evaluation)
As shown in FIG. 7, the tester enters light ( _D65 lamp) into the coating film according to Test Example 1 with the incident angle fixed at 60 degrees, and changes the light receiving angle θA for the specularly reflected light. Then, the saturation at the light receiving angle was measured by a three-dimensional variable angle spectral colorimetry system (Murakami Color Research Laboratory, GCM-4). The coating films according to Reference Examples 1 and 2 and the coating film according to Comparative Example 1 were similarly tested.

  In this case, in order to ensure weather resistance, the pigment concentration in the coating film was set to 10% in pwc. The colors of the first coating layer 2, the color intermediate layer B, and the color intermediate layer C that function as the color intermediate layer were set in a range of Δab <10 with respect to the interference color of the titania pigment.

  FIG. 8 shows the test results. In FIG. 8, the characteristic line X1 represents the coating film of Test Example 1, the characteristic line X2 represents the coating film of Reference Example 1, the characteristic line X3 represents the coating film of Reference Example 2, and the characteristic line X4 represents Comparative Example 1. The coating film is shown. The characteristic lines X1 to X4 are compared.

  In Comparative Example 1, as shown by the characteristic line X4, the saturation is relatively high when the light reception angle is 20 degrees or less, and the saturation gradually decreases as the light reception angle increases, and from the region where the light reception angle exceeds about 50 degrees. The saturation is increasing.

  In Test Example 1, as shown by the characteristic line X1, the saturation is higher and better than Comparative Example 1 when the light receiving angle is 20 degrees or less, and even when the light receiving angle is within the range of 20 degrees to 45 degrees, it is more than that of Comparative Example 1. Is also highly saturated.

  In Reference Example 1, as indicated by the characteristic line X2, the saturation is high when the light reception angle is 20 degrees or less, and the saturation is higher than that of Comparative Example 1 even within the range of the light reception angle of 20 degrees to 45 degrees.

  In Reference Example 2, as indicated by the characteristic line X3, although the saturation is low when the light reception angle is 20 degrees or less, the saturation is higher than that of Comparative Example 1 even in the range of the light reception angle of 20 degrees to 45 degrees. Here, considering both the saturation in a small area where the light reception angle is 20 degrees or less and the saturation in the area where the light reception angle is increased from 20 degrees to 45 degrees, it can be said that Test Example 1 is the best overall. .

(Other)
The present invention is not limited to the embodiments described above and shown in the drawings, and can be modified as appropriate without departing from the scope of the invention. The following technical idea can also be grasped from the above description.

  (Additional Item 1) Formation of a coating film including a step of forming a coating layer containing first pigment particles and second pigment particles based on titania, and a step of laminating a clear layer on the coating layer In the method, the first pigment particles include a first inner layer formed of any one of mica, glass flakes, and silica flakes, and a first outer layer formed of titania coated on the first inner layer. The method of forming a coating film, wherein the second pigment particles include a second inner layer formed of anatase-type titania and a second outer layer formed of rutile-type titania coated on the second inner layer. Color development by the first pigment particles and color development by the second pigment particles are comprehensively obtained, which is advantageous for forming a coating film having high saturation when the light receiving angle changes.

(Additional Item 2) In a coating film including a coating layer containing first pigment particles and second pigment particles based on titania, and a clear layer laminated on the coating layer, the first pigment particles and One of the second pigment particles includes a first inner layer formed of any one of mica, glass flakes, and silica flakes, and a first outer layer formed of titania coated on the first inner layer. ,
The other of the first pigment particles and the second pigment particles includes a first inner layer formed of anatase-type titania, and a second outer layer formed of rutile-type titania coated on the first inner layer. Coating film. Color development by the first pigment particles and color development by the second pigment particles are comprehensively obtained, which is advantageous for forming a coating film having high saturation when the light receiving angle changes.

  (Additional Item 3) In a method of forming a coating film comprising a step of forming a coating layer containing titania-based pigment particles and a step of laminating a clear layer on the coating layer, at least the pigment particles Part of the method is to form an inner layer formed of anatase-type titania and a coating film formed of rutile-type titania coated on the inner layer.

  (Additional Item 4) In a coating film including a titania-based pigment particle-containing coating layer and a clear layer laminated on the coating layer, at least a part of the pigment particles is anatase-type titania. And a coating film formed of rutile-type titania coated on the inner layer.

  The present invention can be used for a coating film forming method and a coating film. This coating film can be widely used for the bodies of vehicles such as automobiles and motorcycles, vehicle-mounted components, building materials, office supplies, and the like.

It is a conceptual diagram which concerns on an Example and shows a coating film typically in a cross section. It is a conceptual diagram which concerns on an Example and shows typically the 1st pigment particle currently embed | buried under the 1st coating-film layer of a coating film in a cross section. It is a conceptual diagram which concerns on an Example and shows typically the 2nd pigment particle embed | buried under the 2nd coating-film layer of a coating film by making a cross section. It is a conceptual diagram which concerns on the reference example 1, and shows a coating film typically in a cross section. It is a conceptual diagram which concerns on the reference example 2, and shows a coating film typically in a cross section. It is a conceptual diagram which concerns on the comparative example 1 and shows a coating film typically in a cross section. It is a conceptual diagram which shows the colorimetry method typically. It is a graph which shows the test result of a colorimetry method.

Explanation of symbols

  2 is a first coating layer, 21 is a first pigment particle, 21a is a first inner layer, 21c is a first outer layer, 3 is a first clear layer, 4 is a second coating layer, 41 is a second pigment particle, 41a Is the second inner layer, 41c is the second outer layer, and 5 is the second clear layer.

Claims (8)

  A step of forming a first coating layer containing first pigment particles based on titania, a step of laminating a first clear layer on the first coating layer, and a second step based on titania. A method for forming a coating film, comprising: laminating a second coating layer containing pigment particles on the first clear layer; and laminating a second clear layer on the second clear layer.   2. The first pigment particle according to claim 1, wherein the first pigment particles include a first inner layer formed of any one of mica, glass flakes, and silica flakes, and a first outer layer formed of titania coated on the first inner layer. A method for forming a coating film comprising:   3. The method for forming a coating film according to claim 1, wherein the second pigment particles include a second inner layer and a second outer layer formed of rutile-type titania coated on the second inner layer.   4. The method for forming a coating film according to claim 3, wherein the second inner layer of the second pigment particles is formed of anatase type titania.   A first coating layer containing first pigment particles based on titania, a first clear layer laminated on the first coating layer, and a titania base material laminated on the first clear layer The coating film which comprises the 2nd coating film layer containing the 2nd pigment particle to perform, and the 2nd clear layer laminated | stacked on the said 2nd coating film layer.   6. The first pigment particle according to claim 5, wherein the first pigment particles are a first inner layer formed of any one of mica, glass flakes, and silica flakes, and a first outer layer formed of titania coated on the first inner layer. Coating film equipped with.   7. The method for forming a coating film according to claim 5, wherein the second pigment particles include a second inner layer and a second outer layer formed of rutile-type titania coated on the second inner layer.   8. The method for forming a coating film according to claim 7, wherein the second inner layer of the second pigment particles is formed of anatase type titania.

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