JP2002105448A - Color phosphorescent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color phosphorescent composition having a good visibility in the daytime and a high brightness in phosphorescence and also a good weatherability. SOLUTION: The color phosphorescence composition, comprising an inorganic phosphorescence pigment, a fluorescent dye and a binder, is characterized in that the above inorganic phosphorescence pigment comprises one or more kinds of a green color phosphorescence pigment having a component of SrAl2O4: Eu, Dy and emitting green light centering the peak wavelength of 520 nm and one or more kinds of a bluish green color phosphorescent pigment having a component of Sr4Al14O25: Eu, Dy and emitting a blue light centering the peak wavelength of 490 nm and the above fluorescent dye comprises one or more kinds of a coumalin-based or perylene-based yellow fluorescent dye, a coumalin- based or perylene-based orange fluorescent dye and a coumalin-based or perylene-based red fluorescent dye.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color luminous composition which can be used for a paint used for coating a sign board and an ink used for a printed matter.

[0002]

2. Description of the Related Art Heretofore, a composition containing a luminous pigment has been used as a paint or ink for a sign board or printed matter which emits light at night. Examples of such a phosphorescent composition include, for example, JP-A-11-236524 and JP-A-11-236524.
No. 35865 proposes an ink containing a luminous pigment and a fluorescent pigment.

[0003]

However, the phosphorescent compositions proposed in the prior art have poor daytime color visibility (close to achromatic in the CIE xy chromaticity diagram).
That is, it became whitish and the color was not clearly seen). Further, the visibility can be improved by increasing the blending amount of the fluorescent pigment, but the phosphorescent luminance is reduced. As described above, it has been difficult for the conventional phosphorescent composition to simultaneously ensure good visibility during the day and high phosphorescent luminance. Furthermore, the conventional phosphorescent composition was also poor in weather resistance (the color faded with time and the original color could not be maintained).

An object of the present invention is to solve the above problems and to provide a color phosphorescent composition having good daytime visibility, high phosphorescent brightness and good weather resistance.

[0005]

Means for Solving the Problems The present inventor has conducted intensive studies in order to solve the above-mentioned problems, and when a fluorescent dye is used instead of a fluorescent pigment, the visibility and phosphorescent brightness in the daytime are good. Further, they have found that the weather resistance is large and extremely suitable, and have completed the present invention.

That is, the color phosphorescent composition of the present invention comprises:
A green phosphorescent pigment comprising an inorganic phosphorescent pigment, a fluorescent dye, and a binder, wherein the inorganic phosphorescent pigment emits green light having a peak wavelength of 520 nm as a center with components such as SrAl ₂ O ₄ : Eu, Dy, and Sr _4. Al ₁₄ O ₂₅ : One or more kinds of blue-green luminous pigments that emit blue light with a peak wavelength of 490 nm as a component such as Eu and Dy, and the fluorescent dye is a coumarin-based or perylene-based yellow fluorescent dye Coumarin-based or perylene-based orange fluorescent dye and coumarin-based or perylene-based red fluorescent dye.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The phosphorescent pigment used in the present invention is Sr
Al ₂ O ₄ : peak wavelength of 520 n with components such as Eu and Dy
a green luminous pigment that emits green light around m and Sr ₄
Al1 ₄ O _25: Eu, a peak wavelength in components such as Dy 49
A blue-green phosphorescent pigment that emits blue light with a center at 0 nm
Species or two or more species. These phosphorescent pigments have substantially the same components as bases, but have different emission colors and brightness due to differences in the mixing ratio of the main components, slight differences in the mixing of activators, differences in firing temperatures, and the like. is there. These phosphorescent pigments have high luminance and extremely excellent durability such as heat resistance and weather resistance.

Specific examples of such luminous pigments include N luminous luminova as green luminous pigments and NP-2820 as blue luminous pigments.

The fluorescent dye used in the present invention is one or more of a coumarin or perylene yellow fluorescent dye, a coumarin or perylene orange fluorescent dye and a coumarin or perylene red fluorescent dye. That is, fluorescent dyes such as general reddish rhodamine and yellowish flavin have poor weather resistance, while coumarin and perylene fluorescent dyes have chemical structures of coumarin and perylene and have weather resistance ( Especially for light) is very good.

Specific examples of coumarin-based and perylene-based fluorescent dyes include Lumogen Red R-300 as a red fluorescent dye, Lumogen Orange O-240 as an orange fluorescent dye, and Lumogen Yellow Y-Y as a yellow fluorescent dye. 083.

The color phosphorescent composition of the present invention contains a binder or a resin. The binder is used when applied to paints or inks. As the binder for the coating material, polyester varnish, acrylic salt varnish and the like can be used. These polyester varnishes and acrylic vinyl varnishes have excellent dispersibility with luminous pigments, high transparency, good adhesion to materials such as sign boards, good drying properties, and are easy to handle with one-pack type. Is preferred. As the solvent, an aromatic ketone type, a cellosolve type or the like can be used.

As the binder for the ink, polyester varnish, acrylic vinyl varnish and the like can be used. Among these, the solubility with the dye is good,
Polyester varnishes and acrylic vinyl varnishes, which are used as a binder for silk screens, are preferred because they have good coloring properties, good adhesion to materials such as printed matter, and are easy to handle in a one-pack type. As the solvent, an aromatic ketone type or a cellosolve type can be used.

The color luminous composition of the present invention contains the luminous pigment, the fluorescent dye and the binder as described above. Parts by weight, 0.00% fluorescent dye
The amount is preferably 2 to 0.5 parts by weight, more preferably 20 to 30 parts by weight of the binder, 50 to 80 parts by weight of the luminous pigment, and 0.006 to 0.1 parts by weight of the fluorescent dye. When the amount of the luminous pigment is less than 40 parts by weight, sufficient brightness cannot be obtained, and when it exceeds 90 parts by weight, it becomes difficult to uniformly disperse and mix. Also,
When the amount of the fluorescent dye is less than 0.002 parts by weight, it is difficult to develop a desired color due to poor color development at daytime,
If it exceeds 0.5 parts by weight, the phosphorescent luminance may be reduced.

The color phosphorescent composition of the present invention may contain a dispersant. By incorporating a dispersant, the phosphorescent pigment and the fluorescent dye or organic fluorescent pigment can be uniformly mixed. That is, the specific gravity of the luminous pigment differs depending on the color, and is very large at 3.5 to 4.5, while the specific gravity of the fluorescent dye is around 1, and the specific gravity difference from the luminous pigment is large. Therefore, it is difficult to uniformly disperse the paint or ink in a binder resin or a solvent. In addition, even if the dispersibility at the time of preparing the paint or ink is good, separation of the pigment or dye and the solvent occurs with the passage of time, and the phosphorescent pigment having a large specific gravity over a long period of time becomes a hard cake with a low weight part. This may make redistribution impossible. Such a problem can be solved by adding a dispersant.

As the dispersant, a fatty acid amide-based surfactant is preferable. The content of the dispersant is preferably 0.1 to 7% by mass. If the content of the dispersant is less than 0.1% by mass, there is no effect on the dispersibility, and if it exceeds 7% by mass, the viscosity increases, and a large amount of thinner must be added at the time of painting or printing. As a result, the coating film becomes thinner and the brightness decreases.

The color phosphorescent composition of the present invention may contain an ultraviolet absorber. By including an ultraviolet absorber, deterioration due to ultraviolet light can be prevented. As the ultraviolet absorber, there are benzophenone type, benzotriazole type, and the like. Among these, tinuvin P, tinuvin 326, 328, and siasorb UV-24
Is preferable because the weather resistance can be improved.

The color phosphorescent composition of the present invention can be applied to paints, inks and the like.

In order to produce the color phosphorescent composition according to the present invention, for example, after a binder is put into a container,
The dispersant is introduced while stirring with a stirrer such as Despar, and the dispersant is dissolved in the binder. Next, a fluorescent dye is introduced, the color is sufficiently dissolved and colored, and the inorganic luminous pigment is dispersed with stirring to obtain a uniform state. If the viscosity is too high, it is prepared by adding a special thinner appropriately. Next, it is kneaded slowly with a ceramic three roll.

[0019]

The present invention will be described below in detail based on examples and comparative examples.

Table 1 shows the compositions of Examples 1 to 8 and Comparative Examples 1 to 8.
Table 2 shows the composition of Sample No. 8.

[0021]

[Table 1]

[0022]

[Table 2]

Each numerical value in Tables 1 and 2 indicates parts by weight.

The materials in Tables 1 and 2 are as follows.

<Phosphorescent pigment> Green phosphorescent pigment: LL G-300M (Nemoto Special Chemical Co., Ltd.) Blue-green phosphorescent pigment: P-282011 (Nichia Corporation) <Fluorescent dye> Orange fluorescent dye: Lumogen O-240 ( BSF) Red fluorescent dye: Lumogen R-300 (BSF) Yellow fluorescent dye: Lumogen Y-083 (BSF) <Fluorescent pigment> Green fluorescent pigment: FA-22 (Shinloich Co., Ltd.) Blue fluorescent pigment: FA-08 (Shinloich stock Company) Red fluorescent pigment: FA-23 (Shinloich Co., Ltd.) Yellow fluorescent pigment: FA-205 (Shinloich Co., Ltd.) Orange fluorescent pigment: FA-24 (Shinloich Co., Ltd.)

<Production method of color luminous composition> In order to prepare the above color luminous composition, first, 200 g
Weigh 30 g of the polyester-based binder, and then weigh 3 g of the dispersant into the container. After rotating the table-top disperser (Despar-Mill) for an appropriate time to sufficiently dissolve the dispersant, the fluorescent dye is weighed and added to sufficiently dissolve and develop color. Thereafter, the luminous pigment is weighed and dispersed while being sequentially stirred. After confirming that it was almost dispersed,
Stop the stirrer and then slowly knead with three ceramic rolls.

<Preparation of Test Piece> Appropriate amounts of the color phosphorescent compositions of Examples 1 to 8 and Comparative Examples 1 to 8 were applied to white paper containing no whitening dye, and applied with a 10-mil applicator to paint (coat). ) To form a uniform coating film. The wet coating film was sufficiently dried in a 50 ° C warm air oven to prepare a test piece.

<Daytime Luminance Test> Two test pieces were prepared for each of the examples and comparative examples, and one of the test pieces was exposed according to JIS Z 9107 7.3 “Weather Resistance Test” according to the rules ( Fade meter 700 hours).
The daytime luminance of the unexposed test piece and the exposed test piece was measured using a colorimetric colorimeter (a chromaticity and luminance measuring device during the day). The results are shown in Tables 3 and 4 ("daytime" and "brightness" columns). In addition, the daytime means that it is under light from the sky other than direct light from sunlight.

<Phosphorescence Luminance Test> Two test pieces were prepared for each of the examples and comparative examples, and one of the test pieces was exposed according to JIS Z 9107 7.3 “Weather Resistance Test” in accordance with the regulations (fade). Meter 700 hours).
Then, the phosphorescence luminance of the unexposed test piece and the exposed test piece was measured in accordance with JIS Z 9
170 According to the provisions of 7.11, Topcon BM-5A
(A device for measuring the luminance and chromaticity of a luminous pigment in the dark). The results are shown in Tables 3 and 4 ("After 5 minutes, 10 minutes,
20 minutes and 60 minutes later "and" Brightness "columns).

<Daytime Chromaticity Test> Two test pieces were prepared for each of the examples and comparative examples, and one of the test pieces was exposed according to JIS Z 9107 7.3 “Weather Resistance Test” ( Fade meter 700 hours).
The chromaticity of the unexposed test piece and the exposed test piece during daytime was measured. The chromaticity was measured with a colorimetric colorimeter according to JIS Z 9107 7.2. Tables 3 and 4 show the results.
(Columns for “daytime” and “coordinates”). "During the day"
Is the same as in the daytime luminance test.

<Phosphorescent Chromaticity Test> Two test pieces were prepared for each of the examples and comparative examples, and one of the test pieces was exposed (fade) as specified in JIS Z 9107 7.3 “Weather Resistance Test”. Meter 700 hours).
Then, the chromaticity of phosphorescence between the test piece that was not exposed and the test piece that was exposed was measured. The chromaticity was measured by measuring the values after 5, 20 and 60 minutes according to JIS Z 9170 7.11.
It was measured with Topcon BM-5A according to the rules of 107 7.2. The results are shown in Tables 3 and 4 (“After 5 minutes, 10 minutes, 2
0 minutes, 60 minutes later "and" coordinates ").

[0032]

[Table 3]

[0033]

[Table 4]

In Tables 3 and 4, "during daytime"
The unit of luminance is “cd / m ² ”, “after 5 minutes, after 10 minutes,
The unit of luminance after 20 minutes and after 60 minutes is “mcd /
m ² ”.

In the daytime chromaticity test, the chromaticity of the test piece without exposure and the chromaticity of the test piece with exposure were extracted, and their variation widths (the two in the CIE xy chromaticity diagram were connected). Table 5 and Table 6 summarize the lengths.

[0036]

[Table 5]

[0037]

[Table 6]

Further, the values in Table 5 are plotted on a CIE xy chromaticity diagram in FIG. 1 and the values in Table 6 are shown in CIE xy chromaticity diagram.
FIG. 2 shows a plot on the xy chromaticity diagram. In FIG.
Each symbol (1... 8) indicates the number of the embodiment, the symbol without “′” indicates the case without exposure, and the symbol with “′” indicates the case with exposure. Show. 2 are the same as those in FIG.

From the results of the above-mentioned phosphorescent luminance test, it was confirmed that the example had a higher luminance than the comparative example. That is, in Tables 3 and 4, the luminance without exposure, for example, 5
The luminance after one minute is 119 to 490 mcd in the embodiment.
/ M ² , 61.3 to 139 m in the comparative example.
cd / m ² .

Further, when examined in detail, Embodiment 1 and
The chromaticity is almost the same as Comparative Examples 1, 2, and 3, but the phosphorescence luminance after 5 minutes of the sample piece without exposure is 217 mcd / m ² in Example 1, whereas the comparative example is 217 mcd / m ^2. 1 is 76.
8 mcd / m ² , Comparative Example 2 was 122 mcd / m ² , Comparative Example 3 was 75.2 mcd / m ^2, and the value of the example was much larger than that of the comparative example. This is to use a fluorescent pigment to achieve the same chromaticity as a fluorescent dye,
The amount of the fluorescent pigment must be increased, and as a result,
This is probably because the amount of the phosphorescent pigment was reduced.

Further, it was confirmed that the examples had higher chromaticity weather resistance than the comparative examples. That is, as is clear from Tables 5 and 6, the variation width of the example is 0.0
232, whereas the variation in the comparative example is 0.0
84, which is three times or more the weather resistance of the example as compared with the comparative example.

As is clear from FIGS. 1 and 2,
The comparative example is an achromatic color (x = 0.11313, y = 0.318)
0), it is difficult to maintain the initial hue for a long period of time, and it is chalky.
On the other hand, in the embodiment, although the color changes in the white direction,
Since the change is small, it is understood that the original color can be maintained for a long period of time.

[0043]

According to the present invention, the color phosphorescent composition applicable to paints and inks has good daytime visibility, high phosphorescent brightness for a long time, and high weather resistance. can do.

[Brief description of the drawings]

FIG. 1 shows a CI showing a change in chromaticity of a test piece coated with the luminous pigment composition of the present invention without and with exposure.
It is an E xy chromaticity diagram.

FIG. 2 is a CIE xy chromaticity diagram showing a change in chromaticity of a test piece coated with a phosphorescent pigment composition using a fluorescent pigment without and with exposure.

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[Procedure amendment]

[Submission date] April 27, 2001 (2001.4.2
7)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0025

[Correction method] Change

[Correction contents]

<Phosphorescent pigment> Green phosphorescent pigment: LL G-300M (Nemoto Specialty Chemical Co., Ltd.) Blue-green phosphorescent pigment: P-282011 (Nichia Corporation) <Fluorescent dye> Orange fluorescent dye: Lumogen O-240 ( BASF) Red fluorescent dye: Lumogen R-300 (BASF) Yellow fluorescent dye: Lumogen Y-083 (BASF) <Fluorescent pigment> Green fluorescent pigment: FA-22 (Shinloich Co., Ltd.) Blue fluorescent pigment: FA-08 (Shinloich stock Company) Red fluorescent pigment: FA-23 (Shinloich Co., Ltd.) Yellow fluorescent pigment: FA-205 (Shinloich Co., Ltd.) Orange fluorescent pigment: FA-24 (Shinloich Co., Ltd.)

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0029

[Correction method] Change

[Correction contents]

<Phosphorescence Luminance Test> Two test pieces were prepared for each of the examples and comparative examples, and one of the test pieces was exposed according to JIS Z 9107 7.3 “Weather Resistance Test” in accordance with the regulations (fade). Meter 700 hours).
Then, the phosphorescence luminance of the unexposed test piece and the exposed test piece was measured in accordance with JIS Z 9
107 According to the provisions of 7.11, Topcon BM-5A
(A device for measuring the luminance and chromaticity of a luminous pigment in the dark). The results are shown in Tables 3 and 4 ("After 5 minutes, 10 minutes,
20 minutes and 60 minutes later "and" Brightness "columns).

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction contents]

<Phosphorescent Chromaticity Test> Two test pieces were prepared for each of the examples and comparative examples, and one of the test pieces was exposed (fade) as specified in JIS Z 9107 7.3 “Weather Resistance Test”. Meter 700 hours).
Then, the chromaticity of phosphorescence between the test piece that was not exposed and the test piece that was exposed was measured. The chromaticity was measured by measuring the values after 5, 20 and 60 minutes in accordance with JISZ 9107 7.11, 2 according to JIS Z 9107 7.11.
It was measured with Topcon BM-5A according to the rules of 107 7.2. The results are shown in Tables 3 and 4 (“After 5 minutes, 10 minutes, 2
0 minutes, 60 minutes later "and" coordinates ").

Claims (4)

[Claims] An inorganic phosphorescent pigment, a fluorescent dye, and a binder, wherein the inorganic phosphorescent pigment is SrAl ₂ O ₄ : E.
a green phosphorescent pigment that emits green light with a peak wavelength of 520 nm as a center by components such as u and Dy, and Sr ₄ Al
₁₄ O ₂₅ : peak wavelength of 490 n with components such as Eu and Dy
one or more blue-green phosphorescent pigments that emit blue light around m, wherein the fluorescent dye is a coumarin-based or perylene-based yellow fluorescent dye, a coumarin-based or perylene-based orange fluorescent dye, and a coumarin-based or perylene-based fluorescent dye. A color phosphorescent composition comprising one or more of a series of red fluorescent dyes. 2. The binder is 10 to 40 parts by weight, the phosphorescent pigment is 40 to 90 parts by weight, and the fluorescent dye is 0.002 to 0.002 parts by weight.
2. The color luminous composition according to claim 1, wherein the amount is 0.5 part by weight. 3. The color luminous composition according to claim 1, wherein the binder is a polyester varnish or an acrylic vinyl varnish. 4. A fatty acid amide-based dispersant having a dispersant content of 0.1%.
4. The color phosphorescent composition according to claim 2, comprising 1 to 7 parts by weight.