Method for producing phosphorescent coating film, phosphorescent coating film, and decorative body provided with phosphorescent coating film

Abstract

To provide a method for producing a phosphorescent coating film in which phosphorescent pigments are uniformly and densely arranged without unevenness, and to provide the phosphorescent coating film.SOLUTION: A phosphorescent coating film includes: a base layer 11 made of resin; a phosphorescent pigment 12 provided on the base layer; a fill layer 13 and a top layer 14 provided so as to cover the base layer 11 and the phosphorescent pigment 12. The phosphorescent pigment 12 has an average particle diameter of 25 μm or more and 100 μm or less. The phosphorescent pigments 12 having a particle diameter of 20 μm or more are arranged in a line on the base layer 11 in a cross-sectional view. An average distance between the adjacent phosphorescent pigments 12 having a particle diameter of 20 μm or more is 99 μm or less, particularly, equal to or less than the average particle diameter of the phosphorescent pigment 12.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a method for producing a luminous coating film, a luminous coating film, and a decorative article provided with the luminous coating film. [Background technology]

[0002] Phosphorescent pigments absorb light from lighting or sunlight, becoming excited and storing the energy of that light. After the light supply is cut off, the electrons transition from the excited state to the ground state, emitting light for a certain period of time. Phosphorescent pigments are fixed in a variety of products, including signs, disaster prevention equipment, interior decoration, lighting, and toys.

[0003] Known methods for fixing phosphorescent pigments to various products generally include using phosphorescent liquid paints containing phosphorescent pigments and a vehicle for dispersing the pigments (Patent Documents 1 and 2), and phosphorescent powder paints in which phosphorescent pigment powder and resin powder are mixed (Patent Document 3). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-31894 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-66562 [Patent Document 3] Japanese Patent Application Laid-Open No. 2006-70235 Summary of the Invention [Problem to be solved by the invention]

[0005] However, when applying phosphorescent liquid paint to a substrate by spraying, the amount of paint applied varies greatly between flat areas that are easy to paint and narrow areas that are difficult to reach due to the constraints of the spray pattern, resulting in differences in film thickness. This is particularly noticeable when the substrate is a three-dimensional structure. Furthermore, even if the substrate is flat, differences in film thickness occur between areas where the spray pattern partially overlaps and areas where it does not. Furthermore, when applying phosphorescent liquid paint to a substrate using a roller or brush (hereinafter referred to as a roller, etc.), the thickness of the film varies depending on the amount of paint loaded on the roller, etc. Furthermore, at the edges of the applied roller, the roller, etc. presses and spreads the paint against the substrate, leaving more paint in some places, resulting in differences in film thickness. This occurs for both flat and three-dimensional structures. In addition to the above-mentioned phenomenon, when using a phosphorescent liquid paint, unevenness in the film thickness also appears due to dripping of the paint.

[0006] As explained above, when using a phosphorescent liquid paint, thin and thick regions frequently occur, resulting in a large difference in the amount of phosphorescent pigment fixed in each region, making it difficult to apply the phosphorescent pigment uniformly. In particular, it is difficult to fix the phosphorescent pigment uniformly and densely. Furthermore, since the phosphorescent pigment in the phosphorescent liquid paint is dispersed in the vehicle, after curing, the phosphorescent pigment is piled up in the thickness direction of the paint film, resulting in the presence of phosphorescent pigment in the paint film that contributes little to the luminous performance.

[0007] On the other hand, when a phosphorescent powder paint (dry blend type) containing phosphorescent pigments is applied to a substrate using a corona discharge paint gun (hereinafter referred to as a corona gun), which is widely used in Japan, the electrostatic Faraday cage effect causes more phosphorescent powder paint to adhere to the edges of the substrate, resulting in a difference in film thickness compared to other parts. Furthermore, when applying a phosphorescent powder paint (dry blend type) in which phosphorescent pigment is mixed in powder form to a substrate, the phosphorescent pigment adheres to the surface of the substrate in proportion to the phosphorescent pigment powder and resin powder in the phosphorescent powder paint (dry blend type), so there is a limit to how densely the phosphorescent pigment can adhere. Furthermore, except when painting on a flat surface facing upward, it is difficult to charge the phosphorescent pigment itself, so it falls off. Although it is possible to charge the phosphorescent pigment itself with a frictional charging spray gun (hereinafter referred to as a tribo gun), the coating effect is low because a corona discharge phenomenon occurs in the phosphorescent pigment itself after charging.

[0008] Patent Document 2 discloses a method in which a vehicle is applied and then phosphorescent powder particles are sprinkled on the vehicle before it hardens, resulting in a phosphorescent single layer with a thickness roughly equal to the diameter of the phosphorescent powder particles. However, it was found that simply applying a base paint and sprinkling the phosphorescent pigment on the base paint before it hardens makes it difficult to uniformly and densely fix the phosphorescent pigment. In other words, it was found that if the phosphorescent pigment is sprinkled on a base paint that has been dried until just before hardening, the phosphorescent pigment does not adhere to the base paint easily. However, if the phosphorescent pigment is sprinkled on a base paint immediately after application, the phosphorescent pigment settles in the base paint or is absorbed into the gaps in the phosphorescent pigment, resulting in a large amount of adhesion. Furthermore, the term "curing" in Patent Document 2 generally refers to the progress or completion of reactive curing to the extent that the desired coating performance is achieved. Even before curing, if the surface is dry, the phosphorescent pigment will not adhere to the base paint. For example, if a two-component reactive curing acrylic urethane resin paint is mixed with significantly less curing agent than specified, the state of the applied and dried coating is described as dry but insufficiently cured. The term "semi-cured and dry" used in this invention is a term used to distinguish the dry state specified by JIS, and is different from the original meaning of "cured."

[0009] The present invention has been made in view of the above circumstances, and has as its object to provide a method for producing a phosphorescent coating film in which phosphorescent pigments are arranged uniformly and densely without unevenness, and a phosphorescent coating film. [Means for solving the problem]

[0010] A first aspect of the method for producing a phosphorescent coating film of the present invention is characterized by comprising the steps of applying a base paint and dusting the base paint, which is at least dry to the touch but less than semi-dry, with phosphorescent pigment powder.

[0011] In the first embodiment of the method for producing a luminous coating film of the present invention, a luminous pigment powder is sprinkled on a base paint that is at least touch-dry but not semi-dry. This allows a minimal amount of luminous pigment to adhere to the surface of the base paint, and allows excess luminous pigment to fall off. This allows the luminous pigment to be uniformly and densely distributed on the surface of the coating film. In particular, the luminous pigment can be prevented from overlapping substantially in the thickness direction of the luminous coating film, meaning that the luminous pigment can be arranged in a substantially straight line across the cross section of the coating film. This allows for a reduction in the amount of luminous pigment powder used per unit area compared to conventional luminous coating films without compromising luminous performance. Furthermore, the luminous pigment powder can be recovered during the production process. Furthermore, the luminous pigment can be uniformly and densely distributed on complex three-dimensional structures, just as it is on flat surfaces.

[0012] The method for producing a luminous coating film of the present invention preferably includes a step of removing excess luminous pigment powder after the step of dusting the luminous pigment powder, in which case the luminous pigment powder can be applied to the surface of the coating film more efficiently.

[0013] The method for producing a luminous coating film of the present invention preferably includes a step of applying a clear coating or providing a clear film on the base coating to which the luminous pigment powder has been attached. In this case, the roughness of the surface can be smoothed and the feel improved. The application of the clear coating or clear film may be performed immediately after the luminous pigment has been attached or after the base coating has been sufficiently dried.

[0014] The method for producing a phosphorescent coating film of the present invention preferably further comprises a step of applying a clear coating or providing a clear film after drying the clear coating, in which case the roughness of the surface can be further smoothed.

[0015] In the method for producing a luminous coating film of the present invention, it is preferable that the average particle size D50 of the luminous pigment powder is 20 μm or more and 300 μm or less. In this case, the luminous pigment can be uniformly and densely applied to the surface to be coated. Through various studies, the applicant noticed that when the luminous pigment powder is sprinkled on a base paint, many of the small particles in the luminous pigment powder adhere to the base paint, and found that a desirable luminous coating film in which the luminous pigment particles are aligned in a single row can be obtained even if the average particle size D50 of the luminous pigment powder is relatively large.

[0016] In the method for producing a phosphorescent coating film of the present invention, the base coating material is preferably a reactive curing coating material. In this case, the curing conditions of the resin of the reactive curing coating material are easily controlled. Therefore, the base coating material can be maintained in a state that is more than dry to the touch but less than semi-dry for a long period of time. In the method for producing a luminous coating film of the present invention, it is preferable that the base coating and / or the clear coating contain a fluorescent pigment, which enables colored light emission in both bright and dark places.

[0017] A second aspect of the method for producing a luminous coating film of the present invention is a method for forming a luminous coating film on a translucent substrate, characterized by comprising the steps of applying a base paint to one side of the translucent material, sprinkling a luminous pigment powder on the base paint when it is at least dry to the touch but less than semi-dry, and applying a paint or providing a film on top of the base paint with the luminous pigment powder adhered thereto. After sprinkling the luminous pigment powder, it is preferable to remove any excess luminous pigment powder. The second embodiment of the method for producing a luminous coating film of the present invention also allows a minimum amount of luminous pigment to be attached to the surface of the base paint, and allows the luminous pigment to be uniformly and densely distributed on the surface of the coating. This allows for a smaller amount of luminous pigment powder to be used per unit area compared to conventional luminous coating films, without compromising luminous performance. The luminous pigment powder can also be recovered during the production process. Furthermore, the luminous pigment can be uniformly and densely distributed on complex three-dimensional structures, just as on flat surfaces. Furthermore, because the coating is applied to a translucent substrate, the use of a translucent base paint and an opaque fill paint (or opaque film) allows the luminous pigment decoration to be visible from the opposite side of the coated surface.

[0018] The luminescent coating film of the present invention comprises a base layer made of a resin and a luminescent pigment provided on said base layer, wherein the average particle size of said luminescent pigment is 25 μm or more and 100 μm or less, said luminescent pigments having a particle size of 20 μm or more are arranged in a row on said base layer in a cross-sectional view, and the average distance between adjacent luminescent pigments having a particle size of 20 μm or more is 99 μm or less. The luminous coating film of the present invention preferably has a clear layer made of a clear resin provided so as to cover the base layer and the luminous pigment or to fill in the gaps between the luminous pigments, or a clear film provided so as to cover the base layer and the luminous pigment. The luminous coating film of the present invention can reduce the amount of luminous pigment used per unit area without compromising the luminous performance compared to conventional luminous coating films. Furthermore, it exhibits uniform luminous performance even in complex three-dimensional structures.

[0019] A first aspect of the decorative body of the present invention is characterized in that the luminous coating film of the present invention is provided on a three-dimensional or flat substrate. In other words, it is a three-dimensional structure or flat body provided with the luminous coating film of the present invention. These decorative bodies can be manufactured more inexpensively than conventional luminous coatings with similar luminous properties.

[0020] A second aspect of the decorative body of the present invention is a decorative body having a luminescent coating film and a printed layer provided on a substrate, wherein the luminescent coating film has a base layer made of resin provided on the surface of the substrate, and luminescent pigments provided on the base layer, the average particle size of the luminescent pigments being 25 μm or more and 100 μm or less, the luminescent pigments having a particle size of 20 μm or more being arranged in a row on the base layer in a cross-sectional view, and the average distance between adjacent luminescent pigments having a particle size of 20 μm or more being 99 μm or less, and the printed layer being provided on the substrate or the luminescent coating film. In a second embodiment of the decorative body of the present invention, phosphorescent pigments are uniformly arranged with a predetermined gap between them on a printed layer (such as letters, marks, or designs) applied to a substrate, allowing for the creation of a new decorative effect, such as a sparkling star design. Furthermore, the decorative body can be produced more inexpensively than conventional phosphorescent coatings with similar phosphorescent properties. Such decorative bodies can be used in a variety of applications, including badges, toys, stickers, posters, and signs.

[0021] In a second embodiment of the decorative body of the present invention, the coated object is opaque, the phosphorescent coating film has a clear layer made of clear resin that is provided to cover the base layer and the phosphorescent pigments or to fill in the gaps between the phosphorescent pigments, or a clear film that is provided to cover the base layer and the phosphorescent pigments, and the printed layer is preferably provided on the surface of the coated object, the clear layer, or the clear film.

[0022] In a second embodiment of the decorative body of the present invention, the coated object is translucent, and the luminous coating film has a resin layer made of resin that is provided to cover the base layer and the luminous pigments or to fill the gaps between the luminous pigments, or a film that is provided to cover the base layer and the luminous pigments, and it is preferable that the printed layer is provided on the front surface of the coated object, the back surface of the coated object, the resin layer, or the film. [Effects of the Invention]

[0023] The method for producing a luminous coating film of the present invention allows the luminous pigment to be uniformly and densely applied to the surface to be coated. In particular, since the luminous pigment can be arranged so that it does not substantially overlap in the thickness direction of the luminous coating film, the amount of luminous pigment used per unit area can be reduced compared to conventional luminous coating films. The luminous coating film and decorative article of the present invention can provide a uniform distribution of luminous pigments even in complex three-dimensional structures, thereby enabling the luminous performance to be uniform throughout. [Brief explanation of the drawings]

[0024] [Figure 1] 1a to 1e are cross-sectional views showing embodiments of decorative articles provided with a phosphorescent coating film of the present invention. [Figure 2] FIG. 2a is a schematic diagram showing a method for measuring the distance of a phosphorescent pigment in a phosphorescent coating, and FIG. 2b is a schematic diagram showing an example of the shape of phosphorescent pigment powder. [Figure 3] 3a to 3d are cross-sectional views showing other embodiments of the decorative article of the present invention. [Figure 4] 4a to 4d are cross-sectional views showing still other embodiments of the decorative article of the present invention. [Figure 5] Schematic diagram showing the process of attaching phosphorescent pigment. [Figure 6] 6a to 6d are cross-sectional images of examples of the phosphorescent coating film of the present invention, and FIG. 6e and FIG. 6f are cross-sectional images of comparative examples. [Figure 7] Figures 7a and 7b show the particle size of each phosphorescent pigment determined from the image in Figure 6a, and Figures 7c and 7d show the particle size of each phosphorescent pigment determined from the image in Figure 6b. [Figure 8] Figures 8a and 8b show the particle size of the phosphorescent pigments determined from the image in Figure 6c, and Figures 8c and 8d show the particle size of each phosphorescent pigment determined from the image in Figure 6b. [Figure 9] 9a and 9b are photographs showing the states of Examples 10 and 11 of the phosphorescent coating film of the present invention before and after ultraviolet light irradiation, respectively. DETAILED DESCRIPTION OF THE INVENTION

[0025] First, the phosphorescent coating film of the present invention will be described. The luminous coating film 10 in Figure 1a comprises a base layer 11, luminous pigments 12 provided on the base layer 11, a fill layer 13 provided to cover the base layer 11 and the luminous pigments 12 or to fill in the gaps between the luminous pigments, and a top layer 14 provided on the fill layer 13. In Figure 1, the symbol B denotes the object to be coated, and the object B and the luminous coating film 10 together form a decorative body. Examples of the object to be coated B include a three-dimensional structure or a flat body. Examples of the three-dimensional structure include those made of metal, resin, ceramic, wood, etc. Examples of the flat body include hard flat bodies such as metal plates, resin plates, and glass plates, and soft flat bodies such as paper and resin films. Unless otherwise specified, the object to be coated B may be either translucent (or transparent) or opaque.

[0026] The average thickness of the phosphorescent coating film 10 is 50 μm or more and 200 μm or less, preferably 150 μm or less, and particularly preferably 120 μm or less. The average thickness refers to the average value of 10 randomly measured points. Methods for measuring the film thickness include an electromagnetic film thickness meter and cross-sectional observation.

[0027] The base layer 11 is composed of a conventional film-forming resin, such as urethane resin, alkyd resin, epoxy resin, polyester resin, acrylic resin, or melamine resin. Reaction-curing resins are preferred, particularly those that undergo reaction curing in combination with isocyanates. Reaction curing makes it easier to control the drying state, and as described below, prevents uneven adhesion when sprinkled with phosphorescent pigment powder. Reaction curing in combination with isocyanates is particularly preferred, as it ensures a consistent viscosity from a dry-to-touch state to a semi-dry state, making it easier to work with. This film-forming resin may be transparent, translucent, or opaque. Fluorescent pigments or colored pigments may also be added to the film-forming resin. The average thickness of the base layer 11 is 100 μm or less, preferably 50 μm or less, particularly preferably 30 μm or less, and 10 μm or more, preferably 15 μm or more, particularly preferably 20 μm or more. The average thickness of the base layer 11 refers to the average value of 10 randomly measured points, and the measurement method can be an electromagnetic thickness meter, cross-sectional observation, or the like.

[0028] The phosphorescent pigment 12 is adhered to the base paint (base layer 11) in a state that is at least dry to the touch but less than semi-dry. The average particle size of the luminescent pigment 12 attached to the base layer is 25 μm or more and 100 μm or less. The upper limit of the average particle size of the luminescent pigment 12 is preferably 90 μm or less, more preferably 80 μm or less, particularly preferably 75 μm or less, and most preferably 70 μm or less, while the lower limit of the average particle size of the luminescent pigment is preferably 30 μm or more. If the average particle size of the luminescent pigment 12 is greater than 100 μm, it becomes difficult to densely arrange the luminescent pigments 12. On the other hand, if the average particle size of the luminescent pigment 12 is less than 25 μm, it becomes difficult to obtain sufficient luminous performance. The average particle size of the luminous pigments 12 attached to the base layer refers to the average value of the particle sizes of 10 (preferably 5) adjacent particles of luminous pigments with a particle size of 20 μm or more. The particle size of each luminous pigment is determined by the equivalent circular diameter (positive square root of "area × 4 ÷ π") of the particles (the area observed two-dimensionally on the image) observed when the cross section of the luminous coating is observed with an electron microscope. Furthermore, phosphorescent pigments (fine particles) with a particle size of less than 20 μm have less phosphorescent performance than phosphorescent pigments with an average particle size of 25 μm or more, so they can be ignored.

[0029] Furthermore, the phosphorescent pigments having a particle size of 20 μm or more calculated by the above formula are aligned in a row on the base layer 11 in the cross section of the phosphorescent coating, and the average distance between adjacent phosphorescent pigments having a particle size of 20 μm or more is 99 μm or less. The average distance between adjacent phosphorescent pigments having a particle size of 20 μm or more is preferably 50 μm or less, more preferably 40 μm or less, particularly preferably 30 μm or less, and most preferably 20 μm or less, and is substantially greater than 0. It is also preferable that the average distance between adjacent phosphorescent pigments having a particle size of 20 μm or more is shorter than the average particle size of the phosphorescent pigment. The distance between adjacent luminescent pigments with a particle size of 20 μm or more refers to the distance between adjacent luminescent pigments when viewed from above in a planar view of luminescent coating 10. For example, a gap of x2 can be seen between luminescent pigments 12b and 12c in Figure 2a, and this is the distance between luminescent pigments 12b and 12c. Furthermore, when luminescent pigments 12a and 12b are in contact when viewed from the side, or when they are separated when viewed from the side but overlap when viewed from the top, the distances "x1" and "x5" will be "0." The average distance between adjacent phosphorescent pigments refers to the average distance between any 10 (preferably 5) consecutively adjacent phosphorescent pigments with a particle size of 20 μm or more (average of 9 (preferably 4) distances). For example, Figure 2a shows six consecutively adjacent phosphorescent pigments 12a-12f and their respective distances x1-x5. "Adjacent phosphorescent pigments lined up in a row" refers to a state in which adjacent phosphorescent pigments do not substantially overlap. "Substantially no overlap" refers to a state in which the area of ​​the region where adjacent phosphorescent pigments overlap vertically (in the thickness direction) (area in a plan view, for example, R in Figure 2) is 20% or less of the area (area in a plan view) of the phosphorescent pigment below the adjacent phosphorescent pigment (phosphorescent pigment 12e in Figure 2). Note that "substantially no overlap in the thickness direction" does not completely exclude cases where two phosphorescent pigment particles overlap in the thickness direction (when the overlapping area is 80% or more). In other words, the phosphorescent coating film and decorative object of the present invention are manufactured by the phosphorescent coating film manufacturing method of the present invention described below, and excess phosphorescent pigment powder is removed using an air blower or similar. It has been found that, during this process, phosphorescent pigment powder that is blown up by the air blower or similar method slowly falls back down, resulting in overlapping in the thickness direction. Therefore, "substantially no overlap in the thickness direction" refers to a state in which, of the phosphorescent pigment particles with particle sizes of 20 μm or more visible in a planar view of the phosphorescent coating, the proportion of two phosphorescent pigment particles that overlap in the thickness direction is 30% or less, preferably 20% or less, more preferably 15% or less, and most preferably 10% or less. Furthermore, phosphorescent pigment powder is an extremely hard particle, and as will be described later, it is crushed to a uniform particle size using a method such as ball milling, but it can take on a variety of shapes. For example, as shown in Figure 2b, it has been found that depending on the cross section (X-ray cross section in Figure 2, viewed from the direction of the arrow), one phosphorescent pigment powder appears to have been split into two pieces, representing two phosphorescent pigments. Therefore, the phosphorescent pigment particles do not actually overlap in the thickness direction, and due to the shape of the phosphorescent pigment, the cross section of the phosphorescent coating film may contain up to three, and in particular up to two, phosphorescent pigment particles that are overlapping in the thickness direction out of ten phosphorescent pigment particles with a particle size of 20 μm or more that are lined up in a row in the base layer. It should be noted that, due to the manufacturing method, it is extremely rare for three or more phosphorescent pigment particles to overlap in the thickness direction.

[0030] The phosphorescent pigment 12 is not particularly limited, but any known phosphorescent pigment can be used. For example, an aluminate of an alkaline earth metal doped with an activator (e.g., calcium aluminate compound, strontium aluminate compound, barium aluminate compound) or zinc sulfide (ZnS) bound to copper or chlorine can be used. In particular, SrAl2O4 and Sr4Al 14 O 25 Preferred examples include strontium aluminate compounds such as those doped with a lanthanoid rare earth element (europium (Eu) and / or dysprosium (Dy)) as an activator. Such phosphorescent pigments can be obtained by preparing spherical γ-Al2O3, SrCO3, Eu2O3, Dy2O3, and H3BO3 powders as raw material powders, weighing them out so that the Al / (Sr + Eu + Dy) molar ratio is between 1.90 and 1.99 (preferably between 1.97 and 1.99) and the H3BO3 content is between 0.5% and 2.5% by weight (preferably between 2.0% and 2.5% by weight), mixing the powders, placing the resulting mixture in a crucible, and heating it at 1350-1450°C for 2-4 hours in a reducing atmosphere. The resulting mass is then pulverized by ball milling or other means, and the resulting pulverized material is screened to a uniform particle size (preferably between about 60 μm and 100 μm) to produce a form suitable for use in paints and other applications. However, as mentioned above, phosphorescent pigments are hard, so their shape varies. The phosphorescent pigment is not limited to the phosphorescent pigment manufactured by the above manufacturing process, but may be a commercially available strontium aluminate phosphorescent pigment or a phosphorescent phosphor manufactured by other manufacturing processes.

[0031] The fill layer 13 is made of a conventional film-forming resin, such as urethane resin, alkyd resin, epoxy resin, polyester resin, acrylic resin, or melamine resin, and may be in liquid or powder form. This film-forming resin is translucent, preferably transparent. In this specification, the fill layer 13 refers to a layer formed by applying a clear coating immediately after applying a phosphorescent pigment. The film thickness of the fill layer 13 is 100 μm or less, preferably 50 μm or less, particularly preferably 30 μm or less, and 10 μm or more, preferably 15 μm or more, particularly preferably 20 μm or more. The film thickness of the fill layer 13 is the average value of 10 randomly measured points, and can be measured using an electromagnetic film thickness meter or by observing a cross-sectional view. Note that this film thickness includes the portion of the phosphorescent pigment that protrudes from the clear paint film applied as the fill layer 13.

[0032] The top layer 14 is composed of a conventional film-forming resin, such as a urethane resin, alkyd resin, epoxy resin, polyester resin, acrylic resin, or melamine resin, and may be in liquid or powder form. This film-forming resin is translucent, preferably transparent. In this specification, the top layer 14 refers to a layer formed by applying a clear coating to a dried surface. While not particularly limited, it is preferable to use the same film-forming resin for the fill layer 13 and the top layer 14. The film thickness of the top layer 14 is 100 μm or less, preferably 50 μm or less, particularly preferably 30 μm or less, and 15 μm or more, preferably 20 μm or more, particularly preferably 25 μm or more. The film thickness of the top layer 14 is the average value of 10 randomly measured points, and can be measured using an electromagnetic film thickness meter or by observing a cross-sectional view. Note that this film thickness includes the phosphorescent pigment protruding from the clear paint coating applied as the fill layer 13 and the top layer 14.

[0033] In this way, the phosphorescent coating film 10 has the phosphorescent pigment uniformly and densely arranged, which allows the entire structure to exhibit stable and uniform phosphorescent performance. In particular, a three-dimensional structure provided with this phosphorescent coating film 10 is prone to uneven thickness in the base layer 11, but because the phosphorescent pigment is uniformly and densely fixed in both the thin and thick portions of the base layer 11, the three-dimensional structure can exhibit uniform phosphorescent performance.

[0034] The phosphorescent coating of the present invention is not limited to the phosphorescent coating 10 of FIG. 1. For example, fluorescent pigments may be mixed into the base layer 11, fill layer 13, and / or top layer 14 of the phosphorescent coating 10 of FIG. 1a to color it. This allows it to be colored in bright places and colored and luminescent in dark places. In particular, by mixing fluorescent pigments into all layers, differences in color development due to differences in film thickness are mitigated, and even complex three-dimensional structures can be colored uniformly in bright places. Furthermore, color pigments may be mixed into the base layer 11, fill layer 13, and / or top layer 14, either alone or together. The phosphorescent coating film 10A in FIG. 1b has a primer layer P underneath a base layer 11. Depending on the material of the surface to be coated, the primer layer P can be provided, or the base layer 11 can be provided directly. Examples of primer layers P include conventionally known film-forming resins such as urethane resins, alkyd resins, epoxy resins, polyester resins, acrylic resins, and melamine resins. The primer layer P is preferably colored, and is particularly preferably white. The phosphorescent coating film 10B in Figure 1c and the phosphorescent coating film 10C in Figure 1d are obtained by omitting the fill layer 13 or the top layer 14 from the phosphorescent coating film 10 in Figure 1a, respectively. Depending on the desired degree of roughness on the surface of the final product to be coated and the coating quality, the states shown in Figures 1(c) and (d) may also be acceptable. The phosphorescent coating film 10D in Figure 1e has a clear film 15 instead of the fill layer 13 or top layer 14. The clear film 15 is a resin film that contains at least a portion that is translucent, but it may be partially opaque. For example, a transparent film may have a pattern or character printed on it, with the portion being opaque. Examples of film materials include polyolefin films such as polyethylene and polypropylene films, and polyvinyl chloride. By covering the base layer 11 and phosphorescent pigment 12 with the clear film 15, as in this phosphorescent coating film 10D, the uniformly and densely arranged phosphorescent pigment does not fall off due to external forces. In particular, using a heat-shrinkable film as the clear film 15 allows application to three-dimensional structures, ensuring consistent phosphorescent performance in the three-dimensional structure. As a variation of the phosphorescent coating film 10D, a primer layer may be provided between the substrate B and the base layer 11, and a fill layer 13 or top layer 14 may be provided below the clear film 15.

[0035] Next, an embodiment of a decorative body in which a phosphorescent coating film and a printed layer are provided on an object to be coated will be described. Decorative body 1A in FIG. 3a to decorative body 1D in FIG. 3d are formed by providing a print layer and a phosphorescent coating film on opaque coated object B. The decorative body 1A in Fig. 3a comprises an opaque substrate B, a luminous coating film 10, and a printed layer Z, with the printed layer Z being provided on the surface (one side) of the substrate B. Alternatively, the printed layer Z is provided between the substrate B and the luminous coating film 10. The luminous coating film 10 is substantially the same as the luminous coating film 10 in Fig. 1a, except that the base layer 11 is translucent or transparent. The printing layer Z is used to provide the coated object B with decorations such as letters, marks, or designs. The inventors noticed that when a printed layer 30 is provided under a base layer 11 with a row of phosphorescent pigments 12, the decoration of the printed layer 30, such as letters, marks, and designs, can be seen from above. They also discovered that the decoration of the printed layer 30 can be made to stand out even in the dark by the light emitted from the phosphorescent pigment. This makes it possible to impart a decoration not previously possible to the coated object B.

[0036] The decorative body 1B in Fig. 3b has a printed layer Z provided on the top layer 14 of the luminous coating film 10. In this case, the base layer 11 may be opaque or translucent. The printed layer Z may also be provided between the fill layer 13 and the top layer 14. The decorative body 1C in Fig. 3c comprises an opaque substrate B, a luminous coating film 10D, and a printed layer Z, with the printed layer Z being provided on the surface of the substrate B. The luminous coating film 10D is substantially the same as the luminous coating film 10D in Fig. 1e, except that the base layer 11 is translucent or transparent. The decorative body 1D in Fig. 3d comprises a transparent substrate B, a phosphorescent coating film 10D, and a printed layer Z, with the printed layer Z being provided on the surface of a clear film 15. In this case, the base layer 11 may be either translucent or opaque. These decorative bodies 1A to 1D are made by laminating a printed layer Z and a phosphorescent coating film, so that the phosphorescent pigment is evenly distributed around the printed layer (pattern such as letters, marks, or designs), allowing for a new decoration that gives the pattern of the printed layer a design resembling the twinkling of stars. Although decorative bodies 1A to 1D are provided with luminous coating film 10 and luminous coating film 10D, luminous coating film 10A in FIG. 1b, luminous coating film 10B in FIG. 1c, or luminous coating film 10C in FIG. 1d may also be used. In these cases, printed layer Z may be provided on at least one of the surface of substrate B, on clear layer 13, on top layer 14, or on clear film 15. For each layer, at least the layers outside printed layer Z and pigment 12 must be translucent.

[0037] Decorative body 2A in Fig. 4a to decorative body 2D in Fig. 4d are formed by providing a printed layer and a phosphorescent coating film on a translucent substrate B. Examples of translucent substrate B include three-dimensional structures or flat bodies (for example, hard flat bodies such as acrylic plates or glass plates, or soft flat bodies such as clear films) made of a translucent (or transparent) material (for example, resin or glass). The decorative body 2A in Figure 4a comprises a transparent substrate B, a luminous coating film 10E, and a printed layer Z, with the printed layer Z provided on the back surface (opposite the luminous coating film 10E) of the substrate B. In this decorative body 2A, the decoration of the printed layer Z and the luminous coating film 10E can be seen from the back surface of the substrate B (the bottom side in Figure 4). The luminous coating film 10E comprises a base layer 11E applied to the surface of the substrate B, a luminous pigment 12E applied on the base layer 11E, a fill layer 13E applied to cover the base layer 11E and the luminous pigment 12E or to fill the gaps between the luminous pigments, and a top layer 14E applied on the fill layer 13E. The base layer 11E between the print layer Z and the luminous pigment 12E is translucent. Meanwhile, the fill layer 13E or the top layer 14E may be translucent or opaque. This can be selected depending on whether the decoration of the decorative body 2A is to be visible from the front or back side of the substrate B. In other words, if the decoration is to be visible from the back side of the substrate B, the fill layer 13E and the top layer 14E are opaque, and if the decoration is to be visible from the front side of the substrate B, the fill layer 13E and the top layer 14E are translucent. Otherwise, base layer 11E, fill layer 13E, and top layer 14E are substantially the same as base layer 11, fill layer 13, and top layer 14, respectively, of phosphorescent coating 10 of FIG.

[0038] The decorative body 2B in Fig. 4b has a printed layer Z provided on the surface of the transparent substrate B (i.e., between the substrate B and the phosphorescent coating film 10). Otherwise, it is substantially the same as the decorative body 2A in Fig. 4a. In the decorative body 2C of Figure 4c, a printed layer Z is provided on a top layer 14E of a luminous coating film 10E. In this case, the fill layer 13E between the printed layer Z and the luminous pigment 12E and the top layer 14E are translucent, and the base layer 11E can be selected appropriately depending on which side the decoration is to be shown on. The decorative body 2D in Figure 4d uses a film 15F as the phosphorescent coating 10F. In other words, film 15F is used in place of the fill layer 13E and top layer 14E of the phosphorescent coating 10E in Figure 4a. Here, the printed layer Z is provided on the back surface of the substrate B, but it may also be provided on the front surface of the substrate B or on top of the film 15F. Note that, with regard to each layer, the layer between the printed layer Z and the phosphorescent pigment 12E is translucent, but the other layers can be selected appropriately depending on the side on which the decoration is to be displayed. Alternatively, the phosphorescent coating may be formed by providing a primer P (not shown) between the substrate and the base layer, or by omitting either the fill layer or the top layer, or both (not shown). In either case, each layer can be made translucent or opaque depending on the direction in which the decoration is to be displayed.

[0039] Next, the method for producing the phosphorescent coating film of the present invention will be described. The method for manufacturing a phosphorescent coating film includes the steps of applying a base paint (S1), dusting with phosphorescent pigment powder (S2), removing excess phosphorescent pigment powder (S3), and applying a clear paint (S4). If a primer layer P is to be provided, the method includes the step of applying a primer paint to the coating surface before step S1.

[0040] In the step (S1) of applying a base paint, the base paint is applied to a surface to be coated. The base coating material is preferably one that can maintain a state of at least dry to the touch but less than semi-dry at room temperature for 5 minutes or more, preferably 10 minutes or more, and particularly preferably 20 minutes or more after application to the surface to be coated. When a primer layer is provided, the base coating material is preferably translucent. The base paint is not particularly limited, but examples thereof include reactive curing paints that form a coating film by curing reaction between monomers or polymers, and volatile drying paints that form a coating film by volatilizing and drying the solvent. However, reactive curing paints are preferred because they are easy to control from a dry to touch state to a state less than semi-dry. Reaction-curing paints include room-temperature reaction-curing paints, which undergo a slow curing reaction at room temperature, and bake-reaction-curing paints, which undergo a curing reaction upon heating. Both can be adjusted to achieve a state of more than touch-dry but less than semi-dry by adjusting the components. However, room-temperature-curing paints are preferred because they require simple equipment. Examples of room-temperature reaction-curing paints include paints that cure by polymerization with oxygen in the atmosphere, and two-component paints in which the curing agent reacts with the resin and cures by polymerization. Two-component paints are preferred because they allow the time required for the state of more than touch-dry but less than semi-dry to be adjusted by adjusting the glass transition point of the base resin and the type of solvent. In particular, reaction-curing paints that use isocyanate as a curing agent for reaction curing are preferred because they can maintain a consistent viscosity from a state of more than touch-dry but less than semi-dry.

[0041] The process (S2) of sprinkling phosphorescent pigment powder involves drying and curing the applied base paint until it is at least dry to the touch but less than semi-dry, and then adhering the phosphorescent pigment powder to the base paint in that state. The process of drying and curing the applied base paint can be natural drying and curing or heat drying and curing, as long as the base paint is dried to a state that is more than dry to the touch but less than semi-dry. The drying and curing time can also be selected appropriately depending on the base paint. The phosphorescent pigment powder has an average particle size D50 of 300 μm or less and contains particles with an average particle size D50 of at least 100 μm or less. The particles also include secondary particles. The upper limit of the average particle size D50 of the phosphorescent pigment powder is preferably 200 μm or less, more preferably 150 μm or less, particularly preferably 100 μm or less, and most preferably 90 μm or less. Meanwhile, the lower limit of the average particle size D50 of the phosphorescent pigment powder is 20 μm or more, preferably 30 μm or more, more preferably 40 μm or more, and most preferably 50 μm or more. The average particle size D50 of the phosphorescent pigment powder refers to the volume-based median diameter determined by laser diffraction particle size distribution measurement. The average particle size D50 of the phosphorescent pigment powder can be measured, for example, using a Shimadzu SALD-2300 (WingSALD II) laser diffraction particle size distribution analyzer (wet measurement, fresh water as the solvent). Through various investigations, the present applicant has found that when a phosphorescent pigment powder is sprinkled onto a base paint, many of the smaller particles in the phosphorescent pigment powder adhere to the base paint. In other words, phosphorescent pigment powders are generally known to have a relatively large variation in particle size. Therefore, when such phosphorescent pigment powder is sprinkled onto the base layer 11, the particles adhere to the base layer 11 continuously. As shown in Figure 5, after the initial particles adhere, there is less space for larger particles to adhere. Therefore, the average particle size of the phosphorescent pigment adhering to the phosphorescent coating film is smaller than the average particle size D50 of the phosphorescent pigment powder. Thus, the present applicant has found that a desirable phosphorescent coating film can be obtained even when the average particle size D50 of the phosphorescent pigment powder is relatively large. Touch-dry is an evaluation standard specified in JIS K 5600-1-1 (1999) "4.3.5," and refers to the state when the fingertip is not soiled when lightly touched to the center of the coating surface. Semi-hardened dryness is an evaluation specified in "4.3.5" of JIS K 5600-1-1 (1999), and refers to the state when the center of the painted surface is gently rubbed with a fingertip and no scratches are left on the painted surface. When the phosphorescent pigment is applied before the paint is dry to the touch, the phosphorescent pigment that has been applied to the base paint settles or the base paint is absorbed into the gaps between the phosphorescent pigments, and then re-adheres to the absorbed base paint, making it easier for the phosphorescent pigments to overlap in the thickness direction.

[0042] The method for applying the phosphorescent pigment powder is not particularly limited, but examples include spraying the powder onto the object or surface to be applied, sprinkling the powder from above, or passing the powder through a space filled with the powder. By dusting the base paint with phosphorescent pigment powder in this way, which is dry to the touch but not yet semi-dry, the phosphorescent pigment can be applied more densely and uniformly than in paints that already contain phosphorescent pigment. In particular, the phosphorescent pigment can be fixed to the coating surface without overlapping in the thickness direction. In other words, a high-quality phosphorescent coating film can be formed with a small amount of phosphorescent pigment attached. Furthermore, by sprinkling phosphorescent pigment powder onto the base paint rather than paint containing phosphorescent pigment, the constraints of the paint manufacturing process (dispersion process, etc.) due to the high hardness characteristics and distorted shape of the phosphorescent pigment powder are eliminated, as well as wear and damage to sliding parts along the paint transport route.

[0043] The process (S3) of removing excess phosphorescent pigment powder is a process of removing any phosphorescent pigment that is not adhering to the base paint that is at least touch dry but not semi-dry. For example, this can be done by blowing air or vibrating the object. When using air blowing, the phosphorescent pigment is removed with a relatively weak breeze. This may blow away the phosphorescent pigment or deform the base layer.

[0044] The step (S4) of applying a clear coating is a step of applying a clear coating so as to cover the phosphorescent pigment adhered to the base coating or to fill in the gaps between the phosphorescent pigment. A preferred method of applying the clear coating is air spraying. The clear coating is a translucent coating. This can smooth out any roughness on the surface of the phosphorescent coating film. The clear coating may be applied immediately after the phosphorescent pigment is applied, or after the phosphorescent pigment has been applied and the base coating has dried. However, applying the clear coating immediately after the phosphorescent pigment is applied (without a drying step) is preferred, as it shortens the process. Furthermore, after the clear coating is applied and dried, another clear coating may be applied. The clear coating material is not particularly limited and does not have to be a reactive curing type. The coating form is also not limited, and may be a powder coating material, a solvent-based liquid coating material, a water-based liquid coating material, or a solventless liquid coating material. As the resin for forming the coating film of the clear coating, conventionally known resins such as urethane resin, alkyd resin, epoxy resin, polyester resin, acrylic resin, melamine resin, etc. can be used.

[0045] The luminous coating film formed by this manufacturing method has luminous pigments densely, uniformly, and substantially without overlapping. For example, in the cross section of the luminous coating film, the gaps between adjacent luminous pigments in a line can be made very small. In other words, a high-quality luminous coating film can be formed with a small amount of luminous pigment attached. In particular, since substantial overlapping of the luminous pigments can be prevented, a luminous coating film can be formed uniformly even on complex three-dimensional structures.

[0046] In this method of manufacturing a phosphorescent coating, a step (S4) of applying a clear coating is carried out after a step (S3) of removing excess phosphorescent pigment powder. However, instead of the step (S4) of applying a clear coating, a step (S4-1) of providing a clear film to cover the phosphorescent pigment adhered to the base coating may be carried out. The clear film is essentially the same as the clear film 15 in Figure 1d, as long as at least a portion of it is translucent. Examples of film materials include polyolefin films such as polyethylene film and polypropylene film, and transparent resin films such as polyvinyl chloride. When a printing layer is provided, the printing is carried out depending on the location where the printing layer is to be provided.

[0047] Finally, the method for producing a luminous coating film of the present invention, which forms a luminous coating film on a translucent substrate, will be described. This manufacturing method includes the steps of applying a base paint to one surface of a translucent object (S1A), dusting with a phosphorescent pigment powder (S2A), removing excess phosphorescent pigment powder (S3A), and applying the paint (S4A). If a primer layer P is to be provided, a primer paint may be applied to the surface to be coated before step S1A. The step (S1A) of applying a base paint to one surface of a translucent object to be coated is substantially the same as the above-described step (S1), in which the base paint is applied to the surface to be coated (one surface). The step (S2A) of sprinkling the phosphorescent pigment powder and the step (S3A) of removing excess phosphorescent pigment powder are substantially the same as the above-described steps (S2) and (S3), respectively. The paint application step (S4A) is a step in which the paint is applied so as to cover the phosphorescent pigment attached to the base paint or to fill in the gaps between the phosphorescent pigment. Depending on the type of phosphorescent coating film to be produced, either translucent (or transparent) or opaque paint is applied. For example, in the case of decorative body 1A in Figure 4a, an opaque fill layer or top layer is applied using opaque paint. Other than that, the process is essentially the same as the aforementioned step (S4). Although the step of applying paint (S4A) is performed after the step of removing excess phosphorescent pigment powder (S3A), a step of providing a film (S4A-1) may be performed instead. The film is substantially the same as film 15F of decorative body 2D in Figure 4d, and can be either translucent (or transparent) or opaque depending on the direction from which the decoration is to be viewed. The luminous coating film formed by this manufacturing method also has the luminous pigment adhered densely, uniformly, and with substantially no overlapping, meaning that a high-quality luminous coating film can be formed with a small amount of adhered luminous pigment. [Example]

[0048] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0049] "Measurement of the amount of attached luminescent pigment" Aluminum foil was wrapped around a 5 cm x 10 cm tin plate, and a primer coating (Shinto Paint Co., Ltd., Shinto Multi Primer SP, 20% white paste mixed) was applied with an air spray to a thickness of 10-15 μm. Five minutes later, a base coating (Shinto Paint Co., Ltd., Urethane Clear HP, a coating based on acrylic resin and cured by reaction with isocyanate) was applied with an air spray to a thickness of 20-30 μm (this was designated "before spraying 1"). The base coating was allowed to dry to the touch but not completely dry, and then a phosphorescent pigment powder (LTI Corporation, α-vega 60 μm, 200 mesh classification) was sprayed on top. The excess phosphorescent pigment powder was then removed with an air blower to form a phosphorescent coating film (this was designated "after spraying 2"). Three such phosphorescent coating films were prepared, and the aluminum foil was removed from the tin plate and cut into 2 cm squares, which were then weighed (Examples 1-3). The weight of each phosphorescent coating was measured before and after spraying the phosphorescent pigment powder, and the weight of the attached phosphorescent pigment powder was calculated. The results are shown in Table 1.

[0050] [Table 1]

[0051] The average coating weight of the phosphorescent coating film in Examples 1 to 3 was 62.5 g / m 2 In the present invention, the phosphorescent pigment powder that has not been applied to the object to be coated can be recovered, so the average applied amount does not deviate significantly from the actual amount used. This is the case with 200 g / m of phosphorescent tape (LTI Corporation, α-FLASH series). 2 In comparison, the figure is 670 g / m when calculated with a 30% coating efficiency of the phosphorescent paint. 2 It was found that the amount of phosphorescent pigment powder used per unit area can be significantly reduced by the present invention.

[0052] [Example 4] A primer paint (Shinto Paint Co., Ltd., Shinto Multi Primer SP, mixed with 20% white paste) was applied to a 5 cm x 10 cm tin plate (coated surface) using an air spray to a film thickness of 10-15 μm. Five minutes later, a base paint (Shinto Paint Co., Ltd., Urethane Clear HP) was applied using an air spray to a film thickness of 20-30 μm. The base paint was allowed to dry to the touch but not completely dry, and then a phosphorescent pigment powder (LTI Corporation, α-vega 60 μm, 200 mesh classification) was sprayed on top. Any excess phosphorescent pigment powder was removed with an air blower to form a phosphorescent coating. This is Example 4.

[0053] [Example 5] A primer paint (Shinto Paint Co., Ltd., Shinto Multi Primer SP, mixed with 20% white paste) was applied to a 5 cm x 10 cm tin plate (coated surface) using an air spray to a film thickness of 10-15 μm. Five minutes later, a base paint (Urethane Clear HP, Shinto Paint Co., Ltd.) was applied using an air spray to a film thickness of 20-30 μm. The base paint was allowed to dry to the touch but not completely dry, and then a phosphorescent pigment powder (α-vega 60 μm, 200 mesh classification, LTI Corporation) was sprayed on top, and excess phosphorescent pigment powder was removed using an air blower. Next, a fill clear paint (Urethane Clear HP, Shinto Paint Co., Ltd.) was applied using an air spray to a film thickness of 10-20 μm to form a phosphorescent coating. This is Example 5.

[0054] [Example 6] A primer paint (Shinto Paint Co., Ltd., Shinto Multi Primer SP, mixed with 20% white paste) was applied to a 5 cm x 10 cm tin plate (coated surface) using an air spray to a film thickness of 10 to 15 μm. Five minutes later, a base paint (Urethane Clear HP, Shinto Paint Co., Ltd.) was applied using an air spray to a film thickness of 20 to 30 μm. The base paint was allowed to dry to the touch but not completely dry, and then a phosphorescent pigment powder (α-vega 60 μm, 200 mesh classification, LTI Corporation) was sprayed on top. Excess phosphorescent pigment powder was removed with an air blower. Next, a fill clear paint (Urethane Clear HP, Shinto Paint Co., Ltd.) was applied using an air spray to a film thickness of 10 to 20 μm. After drying at 100°C for 20 minutes, a top clear paint (Urethane Clear HP, Shinto Paint Co., Ltd.) was applied using an air spray to a film thickness of 30 μm to form a phosphorescent coating. This is Example 6.

[0055] [Example 7] A primer paint (Shinto Multi Primer SP, 20% white paste mixed, manufactured by Shinto Paint Co., Ltd.) was applied to a 5 cm x 10 cm tin plate (the surface to be coated) using an air spray to a thickness of 10-15 μm. After 5 minutes, a base paint (Urethane Clear HP, manufactured by Shinto Paint Co., Ltd.) was applied using an air spray to a thickness of 20-30 μm. The base paint was allowed to dry to the touch but not completely dry. A phosphorescent pigment powder (α-Vega 100 μm, 200 mesh classification, manufactured by LTI Corporation) was then sprayed on top, and excess phosphorescent pigment powder was removed using an air blower. Next, a fill clear paint (Urethane Clear HP, manufactured by Shinto Paint Co., Ltd.) was applied using an air spray to a thickness of 10-20 μm, and excess phosphorescent pigment powder was removed using an air blower. After drying at 100°C for 20 minutes, a top clear paint (Urethane Clear HP manufactured by Shinto Paint Co., Ltd.) was applied with an air spray to a film thickness of 30µm to form a phosphorescent coating film. This is Example 7.

[0056] [Comparative Example 1] A primer paint (Shinto Paint Co., Ltd., Shinto Multi Primer SP, mixed with 20% white paste) was applied to a 5cm x 10cm tin plate (coating surface) with an air spray to a film thickness of 10-15μm, and after 5 minutes, a base paint (Shinto Paint Co., Ltd., Urethane Clear HP) was applied with an air spray to a film thickness of 20-30μm. A phosphorescent pigment powder (LTI Corporation, α-vega 60μm, 200 mesh classification) was sprayed on top of the base paint, which was not yet dry to the touch, and excess phosphorescent pigment powder was removed with an air blower to form a phosphorescent coating film. This is Comparative Example 1.

[0057] Comparative Example 2 A primer paint (Shinto Paint, Shinto Multi Primer SP, mixed with 20% white paste) was applied to a tinplate (surface to be coated) with an air spray to a film thickness of 10 to 15 μm, and dried at 80°C for 10 minutes. Then, a phosphorescent paint (Shinto Paint Co., Ltd., Road Color Hotaru) was applied to the primer with an applicator to a film thickness of 60 μm, forming a phosphorescent coating film. This is Comparative Example 2.

[0058] A colored epoxy resin was applied over the phosphorescent coatings of Examples 4 to 7 and then cut. The cross sections were photographed using a laser microscope (Keyence Corporation, VK-X150). These images are shown in Figures 6a to 6d. Images of the cross sections of the phosphorescent coatings of Comparative Examples 1 and 2, photographed using a laser microscope (Keyence Corporation, VK-X150), are shown in Figures 6e and 6f. In the images of Figures 6a to 6e, the upper layer is a layer of epoxy resin used to photograph the cross section. This is because wrapping the surface in epoxy resin and polishing it makes it possible to easily photograph the cross section. In Figure 6a, the phosphorescent coating of Example 4 shows that the phosphorescent pigment protrudes from the upper layer. In Figure 6b, the phosphorescent coating of Example 5 shows that the fill layer covers most of the phosphorescent pigment. In Figure 6c, the phosphorescent coating of Example 6 shows that the clear layer completely covers the phosphorescent pigment. In all of the cross-sectional images (Figures 6a to 6c), the phosphorescent pigment is essentially lined up in a row, with the gap between adjacent phosphorescent pigments being less than 30 μm (i.e., the average distance is also less than 30 μm). Furthermore, Figure 6d shows a phosphorescent coating made with phosphorescent pigment powder with a large average particle size D50. The two phosphorescent pigments on the far right are stacked one above the other, but overall they are essentially lined up in a row. On the other hand, in the phosphorescent coating film of Comparative Example 1 (Figure 6e), the phosphorescent pigments overlap in the thickness direction of the coating film, with some overlapping by three or more particles. It can also be seen that in the phosphorescent coating film of Comparative Example 1, the settled phosphorescent pigment is embedded in the primer layer, and the epoxy resin in the upper layer has penetrated into the base layer. From these findings, it can be seen that even when excess phosphorescent pigment powder is removed with an air blower, the phosphorescent pigment settles within the base paint. It is also believed that the base paint is absorbed through the gaps between adjacent phosphorescent pigments, creating a porous surface. Furthermore, in the phosphorescent coating film of Comparative Example 2 in Figure 6f, it can be seen that the phosphorescent pigment dispersed in the vehicle is piled up. As such, it was confirmed that the luminous pigment in the luminous coating film of the present invention (Figs. 6a to 6d) is more uniformly and densely distributed than in the luminous coating films of Comparative Examples 1 and 2, and is arranged substantially in a line on the base layer 11. It was also confirmed that the luminous coating film of the present invention allows for a reduction in the amount of luminous pigment used per unit area compared to conventional luminous coating films.

[0059] [Particle size of phosphorescent pigment] Using Microsoft Excel VBA, the particle size of each phosphorescent pigment was determined from the images in Figures 6a to 6d. The process is as follows: The first step is to surround the outer periphery of the phosphorescent pigment to be measured using a freeform shape. The second step is to obtain the coordinates of all vertices. The third step is to calculate all distances (points) between adjacent vertices (vectors) (calculating the cross product). The fourth step is to calculate the area by multiplying the sum of the cross products by the square of the distance unit (μ / 1 point). The fifth step is to calculate the diameter by taking the positive square root of "area x 4 ÷ π". Figure 7a shows the outlines of each phosphorescent pigment in the image of Figure 6a, and Figure 7b shows the calculated diameter of the phosphorescent pigment. Figures 7c, 8a, and 8c show the outlines of each phosphorescent pigment in the images of Figures 6b, 6c, and 6d, respectively, and Figures 7d, 8b, and 8d show the calculated diameter of the phosphorescent pigment. In Figure 7b, phosphorescent pigments b3 and b4 have a particle size of 20 μm or less and are therefore not considered. In Figure 8b, phosphorescent pigment f3 has a particle size of 20 μm or less and is therefore not considered. In Figure 8b, phosphorescent pigments b9 and b10 overlap. However, this represents less than three of the ten phosphorescent pigments with a particle size of 20 μm or more that are aligned in a row in a planar view. It is assumed that phosphorescent pigments f9 and f10 represent a single piece of phosphorescent pigment that has been cut off. These results confirmed that the phosphorescent pigment has an average particle size of 25 μm or more and 100 μm or less, that the phosphorescent pigments with a particle size of 20 μm or more are substantially aligned in a row on the base layer, and that the average distance between adjacent phosphorescent pigments with a particle size of 20 μm or more is 99 μm or less (especially, equal to or less than the average particle size of the phosphorescent pigment). Furthermore, it was confirmed that the average particle size of the phosphorescent pigment was smaller than the average particle size D50 of the phosphorescent pigment powder used. This is presumably due to the fact that it is produced using the phosphorescent coating film manufacturing method of the present invention, as mentioned above. Furthermore, as mentioned above, phosphorescent pigment powder is a very hard particle, and it is difficult to shape it, so it takes on a variety of shapes, and it is presumed that differences also arise due to differences in measurement methods.

[0060] [Example 8] A base paint (Urethane Clear HP White, manufactured by Shinto Paint Co., Ltd.) was applied to a 73 mm diameter metal disk using an air spray to a film thickness of 20 to 30 μm. The base paint was dried to a state that was more than dry to the touch but less than semi-dry, and then a phosphorescent pigment powder (α-vega 60 μm, 200 mesh classification, manufactured by LTI Corporation) was sprayed on top, and excess phosphorescent pigment powder was removed with an air blower. Next, the tin plate was covered with a clear film and caulked to form a phosphorescent coating. This is Example 8.

[0061] [Example 9] A primer paint (Shinto Paint Co., Ltd., Shinto Multi Primer SP, mixed with 20% white paste) was applied to a 5 cm x 10 cm tin plate (coated surface) using an air spray to a film thickness of 10-15 μm. After 5 minutes, a base paint (Shinto Paint Co., Ltd., Urethane Clear HP) was applied using an air spray to a film thickness of 20-30 μm. The base paint was allowed to dry to the touch but not completely dry, and then a phosphorescent pigment powder (LTI Corporation, α-vega 60 μm, 200 mesh classification) was sprayed on top. Excess phosphorescent pigment powder was then removed with an air blower. The tin plate was then covered with a heat-shrinkable film (PVC material, XADMIN brand), and the heat-shrinkable film was heated with a hair dryer to form a phosphorescent coating. This is Example 9.

[0062] The phosphorescent coating films of Example 4 (without clear layer), Example 6 (with clear layer), Example 8 (clear film), Example 9 (heat-shrinkable film), and Comparative Example 2 (phosphorescent paint) were prepared, and these coating films were lightly rubbed up and down against the epoxy resin coating film once (up and down 1 cm) to check whether the epoxy resin coating film was scratched. The results are shown in Table 2. Here, those with no noticeable scratches were marked with an ◯, and those with noticeable scratches were marked with an X.

[0063] [Table 2]

[0064] The phosphorescent coating films of Example 1 and Comparative Example 2 damaged other coating films. On the other hand, the phosphorescent coating films of Examples 4, 8, and 9 did not damage other coating films. This shows that if a clear layer or clear film is not provided, there is a risk of scratches due to contact with other products.

[0065] [Example 10] A base paint (Urethane Clear HP manufactured by Shinto Paint Co., Ltd.) was then applied to an A4-sized paper with a printed pattern using an air spray to a film thickness of 20 to 30 μm (this is referred to as "before spraying 1"). The base paint was dried to a state that was more than dry to the touch but less than semi-dry, and then a phosphorescent pigment powder (α-vega 60 μm, 200 mesh classification, manufactured by LTI Corporation) was sprayed on top, and excess phosphorescent pigment powder was removed with an air blower to produce paper (flat body) with a phosphorescent coating. This is referred to as Example 10.

[0066] [Example 11] A base paint (Urethane Clear HP White, manufactured by Shinto Paint Co., Ltd.) was applied to a 73 mm diameter metal disk using an air spray to a film thickness of 20 to 30 μm (this is referred to as "Before Spraying 1"). The base paint was dried to a state that was more than dry to the touch but less than semi-dry, and then a phosphorescent pigment powder (α-vega 60 μm, 200 mesh classification, manufactured by LTI Corporation) was sprayed on top, and excess phosphorescent pigment powder was removed with an air blower. A partially printed clear film was then crimped to produce a can badge. This is referred to as Example 11. Photographs of the paper of Example 10 and the badge of Example 11 when they were illuminated with a 200 Lux D65 light source are shown in Figures 9a and 9b. Despite the presence of a luminous coating, the design of the printed layer was visible in both the paper of Example 10 and the badge of Example 11. In particular, when illuminated, it was found that a sparkling design could be imparted to the pattern of the printed layer, creating a decoration not previously possible. It is also expected that the same effect can be obtained by applying a clear film instead of the clear paint (fill clear paint) on the paper of Example 10, or by applying fill clear and / or top clear after spraying the phosphorescent pigment on the can badge of Example 11. [Explanation of symbols]

[0067] B Object to be coated P primer layer Z printing layer 1A, 1B, 1C, 1D, 2A, 2B, 2C, 2D decoration 10, 10A, 10B, 10C, 10D, 10E, 10F Luminous coating 11, 11E base layer 12, 12E Phosphorescent pigment 13, 13E Fill layer 14, 14E top layer 15 Clear film 15F film

Claims

1. Applying a base paint; and sprinkling a phosphorescent pigment powder on the base paint in a state that is at least dry to the touch but less than semi-dry. Manufacturing method for phosphorescent coating.

2. After the step of sprinkling the phosphorescent pigment powder, a step of removing excess phosphorescent pigment powder is included. A method for producing the phosphorescent coating film according to claim 1.

3. A step of applying a clear coating or providing a clear film on the base coating to which the phosphorescent pigment powder has been attached is included. A method for producing the phosphorescent coating film according to claim 2.

4. After drying the clear coating, a step of applying a clear coating or providing a clear film is further included. A method for producing the phosphorescent coating film according to claim 3.

5. The average particle size D50 of the phosphorescent pigment powder is 20 μm or more and 300 μm or less. The method for producing the phosphorescent coating film according to any one of claims 1 to 4.

6. The base paint is a reaction-curing paint. The method for producing the phosphorescent coating film according to any one of claims 1 to 4.

7. The base paint and / or the clear paint contain a fluorescent pigment. A method for producing the phosphorescent coating film according to claim 3.

8. A method for producing a phosphorescent coating film by forming a phosphorescent coating film on a translucent substrate, applying a base paint to one surface of the translucent material; A step of sprinkling a phosphorescent pigment powder on the base paint in a state that is at least dry to the touch but less than semi-dry; A step of applying a paint or providing a film on the base paint to which the phosphorescent pigment powder has been attached, Manufacturing method for phosphorescent coating.

9. a base layer made of resin; a phosphorescent pigment provided on the base layer, The average particle size of the phosphorescent pigment is 25 μm or more and 100 μm or less, The phosphorescent coating film, wherein the phosphorescent pigments having a particle size of 20 μm or more are arranged in a row on the base layer in a cross-sectional view, and the average distance between adjacent phosphorescent pigments having a particle size of 20 μm or more is 99 μm or less.

10. A clear layer made of a clear resin provided so as to cover the base layer and the phosphorescent pigment or to fill the gaps between the phosphorescent pigments, or a clear film provided so as to cover the base layer and the phosphorescent pigment, The luminescent coating film according to claim 9.

11. A decorative body, comprising a three-dimensional or planar substrate to be coated and the phosphorescent coating film according to claim 9 or 10 provided thereon.

12. A decorative body having a phosphorescent coating film and a printing layer on a coated object, the phosphorescent coating film has a base layer made of a resin provided on the surface of the substrate, and phosphorescent pigments provided on the base layer, the phosphorescent pigments having an average particle size of 25 μm or more and 100 μm or less, the phosphorescent pigments having a particle size of 20 μm or more are arranged in a row on the base layer in a cross-sectional view, and the average distance between adjacent phosphorescent pigments having a particle size of 20 μm or more is 99 μm or less, The printing layer is provided on the substrate or the phosphorescent coating film. Decorative body.

13. The substrate is opaque, the phosphorescent coating film has a clear layer made of a clear resin provided so as to cover the base layer and the phosphorescent pigment or to fill gaps between the phosphorescent pigments, or a clear film provided so as to cover the base layer and the phosphorescent pigment; The printing layer is provided on the surface of the substrate, the clear layer, or the clear film; The decorative article according to claim 12.

14. The substrate is translucent, the phosphorescent coating film has a resin layer made of a resin provided so as to cover the base layer and the phosphorescent pigment or to fill gaps between the phosphorescent pigments, or a film provided so as to cover the base layer and the phosphorescent pigment, The printing layer is provided on the surface of the substrate, the back surface of the substrate, the resin layer, or the film. The decorative article according to claim 12.

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