JP6202883B2 - Lusterless paint for coating on metal vapor deposited films - Google Patents

Description

  The present invention relates to a phosphorescent (light-emitting) paint and a manufactured body manufactured thereby.

  In general, a technique is known in which a phosphorescent paint containing a color pigment and a phosphorescent material is applied to form a product that emits a bright color in a bright place and a bright phosphorescence in a dark place.

  Vivid colors in the light place are important as enhancing the design of the product during daytime hours. On the other hand, vivid phosphorescence in a dark place is important as it enhances the design of the manufactured product in the time zone after sunset and has an energy saving effect by saving electricity.

  For example, if an emblem is manufactured by applying a phosphorescent paint to the surface of an automobile emblem base material, the emblem can exhibit its original design by sunlight during daylight hours. On the other hand, even in the time zone after sunset, the design of the emblem can be exhibited by the product itself emitting bright phosphorescence without illuminating with an electric light.

  Conventionally, it has been generally known as an idea that a phosphorescent paint is applied not only on a plastic surface but also on a metal vapor deposition film.

  Patent Documents 1 and 2 include, for example, inventions that have one of the features that a luminous layer is disposed on a metal vapor deposition film.

Japanese Patent Laid-Open No. 10-29268

Japanese Patent No. 4751240

  However, the conventional technique has a problem that the composition of the phosphorescent paint that does not easily peel off from the metal deposition film has been clarified (hereinafter, “Problem 1”). Further, in the conventional technique, when the formed product is exposed to hot water for a long time, the adhesion of the paint to the metal vapor deposition film surface is low, so the hot water penetrates into the metal vapor deposition film surface, and the metal vapor deposition film Has a problem that it corrodes inside the phosphorescent layer (hereinafter, “Problem 2”).

  Therefore, the present invention provides a phosphorescent paint that has a high adhesion enough to prevent the penetration of hot water into the metal vapor deposition film surface and can form a phosphorescent layer having a composition that is difficult to peel off from the metal vapor deposition film. It is what.

  In order to solve the problems 1 and 2, the phosphorescent material contains a resin having a certain component among the aluminum chelate curable acrylic resins.

  Mainly according to the present invention having such a configuration, the phosphorescent coating material that can form a phosphorescent layer having a high adhesion enough to prevent the penetration of hot water into the metal vapor deposition film surface and having a composition that is difficult to peel off from the metal vapor deposition film It became possible to provide. As a result, the original advantages of the phosphorescent paint can be maintained, and the design can be improved and labor and costs can be reduced.

The figure which shows the result of the warm water resistance experiment which changed with resin Figure showing the results of experiments conducted with different resins The figure which shows the figure which shows the experimental result which carried out by changing the addition amount of phosphorescent material The figure which shows the figure which shows the experimental result implemented by changing the addition amount of a color pigment. Diagram showing an example of the coating process The figure which shows an example of sectional drawing of a manufacturing body Diagram showing an example of the coating process The figure which shows an example of sectional drawing of a manufacturing body Diagram showing an example of the coating process The figure which shows an example of sectional drawing of a manufacturing body Diagram showing an example of the coating process The figure which shows an example of sectional drawing of a manufacturing body Diagram showing an example of the coating process The figure which shows an example of sectional drawing of a manufacturing body Diagram showing the range that can be applied with the same phosphorescent paint

<Summary of invention>
The present invention is a phosphorescent paint for coating on a metal vapor-deposited film containing an aluminum chelate curable acrylic resin and strontium aluminate as a phosphorescent material, and a product obtained by applying the phosphorescent paint.
Below, the coating component of a luminous paint and the application | coating method for forming a manufacturing body are demonstrated.

<Paint ingredients>
(Main resin)
As the main resin of the paint component, for example, two resins, an acrylic resin and an aluminum chelate curable acrylic resin, can be considered. The aluminum chelate curable acrylic resin is a resin obtained by blending an aluminum chelate with an acrylic resin having a carboxyl group in the molecule. The aluminum chelate curable acrylic resin has a characteristic that a three-dimensional structure is formed by a chelate bond, so that a chemically and physically strong coating film can be obtained.

  FIG. 1 is a diagram showing the results of a hot water experiment conducted under the condition that the product is brought into contact with hot water having a water temperature of 40 degrees Celsius for 24 hours. The experimental condition is that a polycarbonate of about 3 mm is used as a base material, and a UV undercoating film for metal deposition is formed thereon by spraying, and a metal deposition film of about 50 nm to 100 nm is further formed thereon. The method is to apply a phosphorescent paint on the finished product. In order from the left, the resin name, resin type, and hot water resistance experimental results are described. In the warm water resistance column, “◯” indicates that there is no particular problem, “Δ” indicates that the metal vapor-deposited film is slightly corroded, or that the metal vapor-deposited film is slightly discolored in white, and “×” indicates that the metal is It means that the deposited film is clearly corroded or the deposited metal film is clearly turned white.

  As shown in FIG. 1, in the case of an acrylic resin, when the water temperature is kept in contact with hot water having a temperature of 40 ° C. for 24 hours, the metal vapor deposition film is corroded, and the metal vapor deposition film turns white. On the other hand, with an aluminum chelate curable acrylic resin, a chemically and physically strong coating film is obtained even when the water temperature is kept at 40 ° C. for 24 hours. Since permeation can be avoided, the metal vapor deposition film does not corrode and the metal vapor deposition film does not turn white. Therefore, as the main resin, it is desirable to select an aluminum chelate curable acrylic resin that is a resin that can withstand warm water for a long time, not an acrylic resin.

Moreover, about Tg of main resin, when it is too high, a luminous layer becomes easy to peel from a metal vapor deposition film. On the other hand, as for the acid value of the main resin, when the acid value is too high, the phosphorescent layer easily peels off from the plastic surface, and when the acid value is too low, the phosphorescent layer easily peels off from the metal vapor deposition film.
Thus, the adhesion between the plastic surface and the metal vapor deposition film is greatly influenced by the Tg and acid value of the main resin. Note that “Tg” is a temperature when an amorphous solid is heated, and the solid that does not have fluidity like a crystal at low temperatures rapidly decreases in rigidity and viscosity and increases in fluidity.

  FIG. 2 shows the relationship between the Tg and acid value of each resin and the high adhesion to the metal vapor deposition film and the plastic surface. In the adhesion test, the peeled surfaces were compared by attaching and peeling the adhesive surface of the cellophane tape to the phosphorescent layer of the finished product according to Japanese Industrial Standard “K5600-5-6”. In order from the left, the resin name, Tg, acid value, adhesion to the metal deposition film, and adhesion to the plastic surface are described. And in the column of adhesion to the metal vapor deposition film, “◯” means that the phosphorescent layer is not peeled off from the metal vapor deposited film, and “×” means that the phosphorescent layer is peeled off from the metal vapor deposited film at the peeling surface 100%. Means. In the column of adhesion to the plastic surface, “◯” means that the phosphorescent layer is not peeled off from the plastic surface, and “Δ” means that the phosphorescent layer is peeled off from the plastic surface to the extent that the peeling surface does not reach 100%. .

  As shown in FIG. 2, when the Tg of the main resin is 94 degrees Celsius, the phosphorescent layer is peeled off from the metal vapor deposition film at the peeling surface 100%. On the other hand, when the Tg of the main resin is 60 degrees Celsius, the phosphorescent layer does not peel from the metal vapor deposition film. Therefore, the Tg of the main resin is preferably about 60 degrees Celsius or less, specifically 65 degrees or less, and more preferably 60 degrees Celsius or less.

When the acid value of the main resin is 1, the phosphorescent layer is peeled off from the metal vapor-deposited film with a peeling surface of 100%. On the other hand, when the acid value of the main resin is 2, the phosphorescent layer is not peeled off from the metal vapor deposition film.
Furthermore, when the acid value of the main resin is 60, the phosphorescent layer is peeled off from the plastic surface to the extent that the peeled surface does not reach 100%. On the other hand, when the acid value of the main resin is 43, the phosphorescent layer is not peeled off from the plastic surface.
Therefore, the acid value of the main resin is preferably 2 or more and 43 or less, specifically 2 or more and 50 or less, and more preferably 2 or more and 43 or less.

  From the above, the main resin is an aluminum chelate curable acrylic resin, desirably having a Tg of 60 degrees Celsius or less and an acid value of 2 or more and 50 or less, and further having a Tg of 65 degrees Celsius or less and an acid value of 2 More than 43 is desirable.

(Selection of phosphorescent material)
As a phosphorescent material used for blending with the above resin, strontium aluminate is desirable. The strontium aluminate is not limited to a specific one. For example, the chemical composition may be the main component Sr4Al14O25 and the activator Eu, Dy, or the chemical composition may be the main component SrAl2O4 and the activator Eu. , Dy may be used.

  With the former phosphorescent material, the phosphorescent layer formed by applying it emits blue or blue-green light. On the other hand, in the case of the latter phosphorescent material, the phosphorescent layer formed by applying it emits yellow or yellow-green light. It is only necessary to select a phosphorescent material based on these characteristics.For example, as a phosphorescent paint for automobile parts, select a phosphorescent material that can form a phosphorescent layer that emits blue light that has permeated the image as an environmentally friendly color. Just do it.

(About average particle size of phosphorescent material)
As for the average particle diameter of the phosphorescent paint, it is desirable that the uniformity of the coating film is maintained and that the spray gun is not clogged in consideration of work efficiency.

  When the average particle diameter of the phosphorescent pigment exceeds 50 μm, the spray gun is clogged and the particle feeling is conspicuous, so that the uniform appearance is not obtained.

  On the other hand, when the average particle diameter of the phosphorescent pigment is less than 15 μm, aggregates are generated in the coating film, which impairs the design.

  On the other hand, if the average particle diameter of the phosphorescent pigment is in the range of 15 μm to 50 μm, the uniformity of the coating film is maintained, and the spray gun is not clogged in the paintability.

  Therefore, the average particle diameter of the phosphorescent pigment is desirably in the range of 15 μm to 50 μm.

(About the amount of phosphorescent material added)
Regarding the amount of phosphorescent material added, it is desirable that the uniformity of the coating film is maintained, the phosphorescence state is good, and the spray gun is not clogged.

  FIG. 3 illustrates the relationship between the amount of phosphorescent material added, coating film uniformity, phosphorescence state, and spray gun clogging. In order from the top, the addition amount of the phosphorescent material, the uniformity of the coating film, the phosphorescence state, and the clogging of the spray gun are described. And in the column of the uniformity of the coating film, “◯” means that it is uniform and good, “Δ” means that the uniformity is slightly inferior, and “×” means that there is no uniformity. . In the column of phosphorescence state, “◯” means uniform phosphorescence, “Δ” means that there is some phosphorescence unevenness, and “x” means that phosphorescence unevenness is obvious. In the spray gun clogging column, “○” means that the spray gun is not clogged, “△” means that the spray gun is clogged slightly, and “×” means that the spray gun is clogged significantly. Yes.

  As shown in FIG. 3, when the weight% of the total amount of the phosphorescent material is 40%, the spray gun is not clogged but phosphorescence unevenness occurs. And as the value of weight% in the whole phosphorescent material is further lowered, the phosphorescence unevenness becomes severe and the phosphorescence state becomes even worse. Furthermore, if the weight% of the total amount of the phosphorescent material is less than 30%, the phosphorescence state is not deteriorated and the uniformity of the coating film is also impaired.

  On the other hand, when the weight% of the total amount of the phosphorescent material is 60%, the spray gun is slightly clogged although the phosphorescence state is good. As the weight percentage of the phosphorescent material is further increased, the spray gun becomes clogged. Furthermore, when the weight% in the total amount of the phosphorescent material is 70% or more, not only the work efficiency is deteriorated but also the uniformity of the coating film is impaired.

  On the other hand, if the weight percentage of the total amount of the phosphorescent material is 50%, the uniformity of the coating film is maintained, the phosphorescence state is good, and the spray gun is not clogged.

  From the above, regarding the amount of the phosphorescent material added, it is desirable that the weight percentage of the total phosphorescent material is about 50%, specifically 45% or more and 55% or less, and more preferably 50%. desirable.

(About colored pigments)
In order to develop a pigment having a good coloring state in a bright place and a phosphorescent state in a dark place, the coloring pigment concentration is sufficient for both the colored state in a bright place and the phosphorescent state in a dark place. It is desirable.

  FIG. 4 shows the relationship between the amount of the color pigment added, the colored state and the phosphorescent state. In order from the top, the addition amount of the color pigment, the coloring state, and the phosphorescence state are described. In the column of the colored state, “◯” indicates that the color is sufficiently colored, “Δ” indicates that the color of the phosphor material is slightly noticeable, and “X” indicates that the color of the phosphor material is clearly noticeable. I mean. In the column of phosphorescence state, “◯” indicates that the phosphorescence is bright, “△” indicates that the phosphorescence state is slightly inferior but is sufficiently shining, and “×” indicates that phosphorescence is clearly inhibited by coloring. I mean. In this experiment, similar results can be obtained even when the color pigment is changed to a color dye.

  As shown in FIG. 4, when the amount of the color pigment added to the entire phosphorescent paint becomes 1% by weight, the phosphorescent state is not inhibited, but the color of the phosphorescent material becomes conspicuous in a bright place and sufficient coloring is obtained. I can't.

  On the other hand, when the additional amount of the color pigment relative to the entire phosphorescent paint is 10% by weight, the phosphorescent state is hindered although the colored state in the bright place is sufficient.

  On the other hand, if the amount of the colored pigment added to the entire phosphorescent paint is 3% by weight, a bright phosphorescence can be obtained although the color of the phosphorescent pigment is slightly noticeable. On the other hand, if it is 5% by weight, sufficient coloring can be obtained although the phosphorescence state is slightly inferior.

  From the above, the additional amount of the color pigment with respect to the entire phosphorescent paint is in the range of about 3 wt% to 5 wt%, specifically, 2.5 wt% or more and 5.5 wt% or less. Desirably, it is desirable that it is 3 wt% or more and 5 wt% or less.

(Ingenuity on coloring)
Various types of color pigments can be considered.
For example, if it is particularly desired to make the phosphorescent state stand out, a highly transparent coloring pigment or coloring dye may be used, or a cold colored coloring pigment or coloring dye that does not inhibit the phosphorescent state may be used. . On the other hand, if it is desired to characterize the product that the colors in the bright place and the dark place are different, a warm color coloring pigment or coloring dye may be used as long as the phosphorescent state is not inhibited. Furthermore, if it is desired to produce a product having a pastel color, a fluorescent pigment or a fluorescent dye may be used.

<Application method>
The phosphorescent material is generally a hard substance. Therefore, it is desirable that the spray gun be subjected to a treatment for preventing the needle from being worn. Specifically, it is desirable to use a nitriding spray gun to prevent needle wear.

  As for the diameter of the spray gun, it is desirable that the spray gun can be applied without clogging and the atomization is sufficient. When the diameter of the spray gun is less than 1.0 mmφ, the spray gun is clogged. On the other hand, when the diameter of the spray gun exceeds 1.3 mmφ, atomization is insufficient. On the other hand, when the diameter of the spray gun is 1.0 mmφ or more and 1.3 mmφ or less, the spray gun is not clogged and the atomization is sufficient. Therefore, it is desirable that the diameter of the spray gun be 1.0 mmφ or more and 1.3 mmφ or less.

  In order to prevent precipitation of the phosphorescent material, it is desirable to apply with constant stirring.

  In order to prevent blistering and shifting, it is desirable to leave it at room temperature for a period of 5 minutes or more from the formation of the phosphorescent coating film to the drying of the coating film surface.

(Production process)
The phosphorescent paint obtained by the invention mainly having the above-described structure has high adhesion not only on the metal vapor-deposited film but also on the plastic surface and the silicone polymer film. Therefore, various processes can be considered in the manufacturing method of the manufactured body. For example, the following manufacturing process can be assumed.

(Product made of plastic surface and phosphorescent layer)
As shown in FIG. 5, when a plastic surface is formed (0501), a product can be manufactured by applying a phosphorescent paint to the surface to form a phosphorescent layer (0502).

  FIG. 6 is a cross-sectional view of a manufactured body manufactured by the process of FIG. There is a “2” phosphorescent layer on the “1” plastic surface.

  There are various ways to use this manufactured body. When a light source such as an electric light is present, the product is mounted so that the phosphorescent layer is on the light source side. The light may be emitted by passing through the phosphorescent layer and the plastic and reaching the outside air, and on the other hand, while the light source is not emitting light, the phosphorescent layer emits the phosphorescent light.

(Manufactured body consisting of plastic surface, metal vapor deposition film, phosphorescent layer)
As shown in FIG. 7, when a metal vapor deposition film is formed on the formed plastic surface (0701) (0702), a phosphorescent coating is applied to the surface to form a phosphorescent layer (0703). It can also be manufactured.

  FIG. 8 is a cross-sectional view of the manufactured body manufactured by the process of FIG. A metal deposition film “3” is present on the plastic surface “1”, and a phosphorescent layer “2” is present thereon.

(Manufactured body consisting of plastic surface, undercoating film, metal vapor deposition film, phosphorescent layer)
As shown in FIG. 9, when an under coating film was formed on the formed plastic surface (0901) (0902) and a metal vapor deposition film was further formed thereon (0903), a phosphorescent paint was applied to the surface. Thus, a product can be manufactured by forming a phosphorescent layer (0904).

  FIG. 10 is a cross-sectional view of a manufactured body manufactured by the process of FIG. There is a “4” undercoat on the “1” plastic surface, a “3” metal deposit on it, and a “2” phosphorescent layer on it.

(Product made of plastic surface, metal deposition film, silicone polymer film, phosphorescent layer)
As shown in FIG. 11, when a metal vapor deposition film is formed on the formed plastic surface (1101) (1102) and a silicone polymer film is further formed thereon (1103), a phosphorescent paint is applied to the surface. Then, a product can be manufactured by forming a phosphorescent layer (1104).

  12 is a cross-sectional view of a manufactured body manufactured by the process of FIG. There is a metal vapor deposition film of “3” on the plastic surface of “1”, a silicone polymer film of “5” thereon, and a phosphorescent layer of “2” thereon.

(Product made of plastic surface, undercoating film, metal deposition film, silicone polymer film, phosphorescent layer)
As shown in FIG. 13, an undercoat film is formed on the formed plastic surface (1301) (1302), a metal vapor deposition film is formed thereon (1303), and a silicone polymer film is further formed thereon. In the case of (1304), a phosphor can be applied to the surface to form a phosphorescent layer (1305) to produce a product.

  14 is a cross-sectional view of a manufactured body manufactured by the process of FIG. There is a metal deposition film of “3” on an undercoating film of “4” formed on a plastic substrate of “1”, a silicone polymer film of “5” is present thereon, and further There is a “2” phosphorescent layer on top.

  Further, as shown in FIG. 15, in the case where one or two or more of a plastic surface (1501), a silicone polymer film (1503), and a metal vapor deposition film (1502) are mixed, 1 is added to the surface. A product can also be manufactured by applying one phosphorescent paint at a time and forming a phosphorescent layer on the whole.

  It should be noted that the present invention is not limited only to the method described above, and it is needless to say that various modifications can be made without departing from the gist of the present invention.

1. ・ Plastic surface 2. ・ Phosphorescent layer 3. ・ Metal vapor deposition film 4. ・ Under coating film 5. ・ Silicone polymer film

Claims (5)

  A phosphorescent paint for coating on a metal vapor-deposited film comprising an aluminum chelate curable acrylic resin having a Tg of 65 degrees Celsius or less and an acid value of 2 to 50 and strontium aluminate as a phosphorescent material.   2. The phosphorescent paint for coating on a metal vapor deposition film according to claim 1, wherein an average particle diameter of the phosphorescent material made of strontium aluminate is in a range of 15 μm to 50 μm.   The phosphorescent paint for coating on a metal vapor-deposited film according to claim 1 or 2, wherein the weight percentage of the phosphorescent material made of strontium aluminate is 45% to 55%.   The phosphorescent paint for coating on a metal vapor deposition film according to any one of claims 1 to 3, further comprising a pigment added in a range of 2.5 wt% to 5.5 wt% with respect to the whole.   A plastic surface, a metal vapor-deposited film formed directly or indirectly on the plastic surface, and a phosphorescent paint according to any one of claims 1 to 4 formed on the metal vapor-deposited film. A product made of a phosphorescent layer.

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