JP2009209294A - Luminous bead having luminous function and retroreflective function - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a luminous bead which has luminosity, retroreflective ability and water resistance, can be combined with a water paint, used outdoors and used for forming a marking object which can be recognized even at dark place and at dark time. <P>SOLUTION: A luminous pigment is disposed around a glass bead and further coated with a water resistant and light transmissible resin to form the luminous bead provided with luminosity and retroreflective ability. Thus the luminous bead is attained, which has a luminous function and a retroreflective function and can obtain luminous paint having high visibility, can be used outdoors and can be used together with the water paint. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a phosphorescent bead having a phosphorescent function and a retroreflection function.

  2. Description of the Related Art Conventionally, a construction such as a road surface display in which a marking paint having a retroreflection function is applied by containing glass beads is known. However, in such dark places, such as at night, in tunnels, or in cloudy weather, there is no retroreflection from the markings in the dark, such as in the cloudy weather, and the marking contents are recognized. There was a problem that it was difficult.

  As a means for facilitating recognition of a sign even in a dark place, the use of a phosphorescent material is known. Patent Document 1 (Japanese Patent Application Laid-Open No. 10-088031) describes a light-storing road marking material containing a light-storing pigment mainly composed of alumina. Patent Document 2 (Japanese Patent Laid-Open No. 10-219621) describes a self-luminous road marking provided on a road marking material coating surface having a phosphorescent material. Patent Document 3 (Japanese Patent Application Laid-Open No. 10-12214) discloses a road marking sheet containing glass beads and / or a phosphorescent pigment at least near the surface of the marking sheet. Further, Patent Document 4 (Japanese Patent Laid-Open No. 11-288233) discloses a display device in which a light reflecting element and a phosphorescent element are baked together with a glaze at least near the surface of a marking sheet and integrated with a substrate. .

  The use of these phosphorescent materials for marking is an effective means for making it easy to recognize the marking contents of the marking even in a dark place, but the following problems still remain.

  One of them is that simply using a phosphorescent material in a paint is not sufficient for recognizing the contents of a sign in a dark place due to light emission from the phosphorescent material.

Another problem is that when the phosphorescent material reacts with moisture, hydrolysis occurs and the phosphorescent function is lost, so that the phosphorescent lifetime is shortened particularly when used outdoors. In addition, the use of water-based paint is desired to form a sign construction by applying, but the phosphorescent material loses its luminous properties when it reacts with water. There is a problem in that it cannot be done. In addition, when constructing a sign construction containing a phosphorescent material, the nozzle or the like may become clogged in the process of applying the paint containing the phosphorescent material using the nozzle of the phosphorescent material supply device, As a result, the workability of coating is also disadvantageous.
Japanese Patent Laid-Open No. 10-088031 JP-A-10-219621 Japanese Patent Laid-Open No. 10-12424 Japanese Patent Laid-Open No. 11-288233

  An object of the present invention is a phosphorescent bead that, when used in addition to a paint for forming a construction for marking, has a phosphorescent function and a retroreflective function, and can obtain high visibility even in a dark place. In addition, since it has water resistance, it is intended to provide a phosphorescent bead that can be used outdoors and can be applied in a water-based paint.

  The phosphorescent beads of the present invention include glass beads, a phosphorescent pigment disposed around the glass beads, and a water-resistant transparent resin that covers the glass beads and the phosphorescent pigment. The inventor of the present invention, as a result of repeated numerous studies and trials for the purpose of obtaining a water-resistant phosphorescent bead that combines a phosphorescent function and a retroreflective function, by the above configuration, It has been found that phosphorescent beads having a phosphorescent function and a retroreflective function and having sufficient water resistance can be obtained. In addition, with such a configuration, it can be found that phosphorescent beads can be produced with high productivity, and the present invention has been made.

  By using the phosphorescent beads according to the present invention, a phosphorescent sign having high visibility can be realized even in a dark place. In addition, since the phosphorescent paint according to the present invention has water resistance, it exhibits a feature that there is very little deterioration in phosphorescence even when used outdoors, and can be used together with the aqueous paint to form a sign. .

  The phosphorescent beads according to the present invention can be used by being contained in a paint for forming a sign or the like. The paint used for forming the sign is preferably a water-based paint from the viewpoint of environmental measures at the time of application. Therefore, the phosphorescent beads according to the present invention that can be used with water-based paints are well suited to this intention.

In addition, when the phosphorescent beads according to the present invention are included in the paint, the phosphorescent beads are preferably spherical. In the operation of applying the phosphorescent beads and applying the marking object, if the nozzle of the coating device is clogged, the workability is significantly reduced. The clogging of the nozzle is often caused by the solid content in the paint, and the paint fluid containing the phosphorescent beads has a fluidity of the paint by making the phosphorescent beads contained in the paint into a well-rounded spherical one. Improved and found to help prevent nozzle clogging. In order to obtain spherical luminous beads, spherical glass beads are used, and the phosphorescent pigment arranged around the glass beads has a particle size sufficiently smaller than that of glass beads. Can be finished into phosphorescent beads. In the present invention, the term “particles are well aligned and spherical” means that the particle size distribution of the particles is small, isotropic, and the surface is smooth. The shape factor f is f = ((total surface area of particles) / (total particle volume)) × (average particle diameter)
In the case of a well-aligned sphere, this value is the smallest, where the total number of particles is n and the diameter of the aligned particles is d.
(N4π (d / 2) ² ) / (n (4π / 3) · (d / 2) ³ ) · d = 6
It becomes. When expressed quantitatively using the shape factor f, the glass beads preferably have a ratio of the standard deviation of the particle size distribution to the average particle size of 0.3 or less and the shape factor f of 10 or less. In addition, the shape factor f is more preferably 8 or less.

  By applying the phosphorescent beads according to the present invention to form an indicator, an effective indicator in which the retroreflection function and the phosphorescent property interact with each other can be obtained. This is because when a phosphorescent pigment exists around the glass beads, light is exchanged between the phosphorescent pigment and the glass beads, so that the phosphorescent pigment not only directly takes in light from the outside, but also passes through the glass beads. It is considered that light can be taken in, and when the phosphorescent pigment emits light, it can emit light via glass beads in addition to directly emitting light.

  The phosphorescent beads according to the present invention are formed by first applying a coating for marking to form a coating film, spreading the phosphorescent beads according to the present invention from above the coating film, and holding the phosphorescent beads on the coating film. It may be. In this way, the phosphorescent beads can be arranged on the surface of the coating film, and a sign with good reproduction reflection efficiency and luminous efficiency can be formed. The phosphorescent beads according to the present invention are particularly advantageous when water resistance is required.

  In addition, Patent Documents 1 and 3 above describe that the sign may be covered with a transparent or translucent rubber or resin, thereby protecting the luminous particles. However, these descriptions only describe coating the sign, and do not describe coating the phosphorescent pigment particles themselves. Simply covering the sign was never enough to protect the phosphorescent pigment against moisture. In the present invention, it is considered that the reason why the protection against moisture is very excellent is that a phosphorescent pigment is arranged around the glass beads and the glass beads arranged with the fluorescent pigment are individually coated.

  According to the present invention, a water-resistant phosphorescent bead can be obtained, and using this phosphorescent bead, it is possible to form a sign construction having a phosphorescent function and a retroreflective function and having water resistance. It was. This phosphorescent bead can be used outdoors, or it can be used as a phosphorescent paint by containing it in water-based paint. Also, when applying this phosphorescent paint, it is not necessary to evaporate a large amount of organic solvent, Can now be formed.

  Next, specific modes for carrying out the present invention will be described in detail with reference to the drawings.

  FIGS. 1A and 1B are diagrams schematically showing an embodiment of a phosphorescent bead according to the present invention. In FIG. 1A, a phosphorescent bead 10 has a configuration in which a phosphorescent pigment 14 is disposed on the surface of a glass bead 12, and this is covered with a water-resistant and translucent resin 16 for protection. In the phosphorescent beads according to the present invention, as shown in FIG. 1A, the phosphorescent pigments 14 are in contact with the surface of the glass beads 12, and these are coated with a water-resistant and translucent resin 16. As shown in FIG. 1 (b), the phosphorescent pigment 14 exists away from the surface of the glass beads 12, and these are water-resistant and translucent resin 16. It may be covered with and protected. Such a configuration allows light to enter and exit the phosphorescent beads 14, while preventing moisture from entering the interior and allowing moisture to enter and hydrolyze the phosphorescent pigment 14. This prevents the loss of the phosphorescent function.

  In the present invention, the phosphorescent pigment 14 possessed by the phosphorescent beads 10 is a substance that absorbs energy of irradiation light such as sunlight and electric light, and continues to emit light for a long time after the irradiation is completed by the absorbed energy.

Specific examples of such luminous pigment 14 include SrAl ₂ O ₄ : Eu, SrAl ₂ O ₄ : Eu, Dy, SrAl ₂ O ₄ : Eu, Nd, SrAl ₂ O ₄ : Eu, Pr, SrAl ₂ O ₄ : _{Eu, Sm, SrAl 2 O 4} : Eu, Tb, SrAl 2 O 4: Eu, Ho, SrAl 2 O 4: Eu, Mn, SrAl 2 O 4: Eu, Sn, SrAl 2 O 4: Eu, Bi, CaAl ₂ O ₄ : Eu, Nd, CaAl ₂ O ₄ : Eu, Sm, CaAl ₂ O ₄ : Eu, Tm, CaAl ₂ O ₄ : Eu, Nd, La, CaAl ₂ O ₄ : Eu, Nd, Ce, CaAl _{2 O 4: Eu, Nd, Pr} , CaAl 2 O 4: Eu, Nd, Sm, CaAl 2 O 4: Eu, Nd, Gd, CaAl 2 O 4: Eu, Nd, Tb, CaAl 2 O 4: Eu, Nd _{, Dy, CaAl 2 O 4:} Eu, Nd, Ho _{CaAl 2 O 4: Eu, Nd} , Er, CaAl 2 O 4: Eu, Nd, Tm, CaAl 2 O 4: Eu, Nd, Yb, CaAl 2 O 4: Eu, Nd, Lu, CaAl 2 O 4: Eu , Nd, Mn, CaAl ₂ O ₄ : Eu, Nd, Sn, CaAl ₂ O ₄ : Eu, Nd, Bi, Ca _0.9 Sr _0.1 Al ₂ O ₄ : Eu, Nd, La, Ca _0.9 Sr _0.1 Al ₂ O ₄ : Eu, Nd, Dy, Ca _0.7 Sr _0.3 Al ₂ O ₄ : Eu, Nd, Dy, Ca _0.9 Sr _0.1 Al ₂ O ₄ : Eu, Nd, Ho, Ca _0.7 Sr _0.3 Al ₂ O ₄ : Eu, Nd, Examples thereof include Ho, zinc sulfide compounds, and B ₂ O ₃ .SrO.Al ₂ O ₃ compounds. These can be used by selecting one kind, and can also be used as a mixture of two or more kinds.

  As the water-resistant and translucent resin 16 in the present invention, various water-resistant resins can be used including vinyl resins and acrylic resins. The coating thickness is desirably 9 μm or more and 14 μm or less. When the coating thickness is smaller than this range, the coating is not sufficient, and the water resistance tends to decrease. If the coating thickness is small, the chemical resistance described later also decreases. On the other hand, if the coating thickness is larger than this range, the optical properties of retroreflection tend to be affected, and the cost increases.

  In the present invention, the phosphorescent beads 10 are preferably spherical particles as described above from the viewpoint of ensuring fluidity during supply during construction. In this case, when the phosphorescent beads are present in the paint, the outer shape of the particles of the phosphorescent beads 10 only needs to be spherical. Therefore, when the phosphorescent beads are provided, the outer shape of the particles of the coated phosphorescent beads 10 is spherical. Just do it. The spherical particles in the present invention preferably have an average value of the ratio of the longest diameter to the shortest diameter of the particles in the range of 0.7 to 1.3, and this value is 0.9 to 1. Those within the range of .1 are more preferred.

  In the phosphorescent beads 10, the retroreflectivity is high if the amount of the phosphorescent pigments 14 arranged around the glass beads 12 is small, but the phosphorescent property is small. On the other hand, if the amount of the phosphorescent pigments 14 is large, the retroreflectivity decreases. , Phosphorescence increases. For this reason, it is preferable that the quantity of the luminous pigment 14 arrange | positioned around the glass bead 12 is the range of 0.1 to 10% of a glass bead by weight ratio from these balance, Moreover, 0.5 to 5% More preferably, it is the range. The amount of the resin covering the glass beads 12 and the phosphorescent pigment 14 may be an amount sufficient to ensure water resistance by the coating.

  The phosphorescent bead 10 is a method of attaching a phosphorescent pigment to the surface of the glass bead and coating and curing it with a liquid resin, or a method of coating and curing the glass beads with a liquid resin containing the phosphorescent pigment, It can manufacture by the method of.

  From the viewpoint of obtaining higher retroreflective properties, the glass beads 12 are preferably substantially spherical and have a particle diameter of 0.01 to 2 mm, more preferably approximately spherical and have a particle diameter of 0.1 to 1 mm. These glass beads have a refractive index of about 1.5 to 2.5, and incident light is retroreflected by the light refraction. As described above, the glass beads 12 are made spherical, the phosphorescent pigments 14 are arranged around the glass beads 12, and the phosphorescent beads 10 covered with the resin 16 are made spherical, whereby the fluidity of the paint containing the glass beads 12 is obtained. Can be increased. For example, when these particles are supplied from a hopper nozzle to a road surface to which a paint is applied, there is no clogging of the nozzle, and stable particle supply becomes possible, thereby enabling a stable application operation.

  In the preparation of a coating material containing the phosphorescent beads 10 and used for forming a sign, etc., a coloring pigment such as titanium dioxide or chrome lead, or an extender pigment such as calcium carbonate or talc can be used as a coating additive. As a dispersion medium for dispersing these, water can be mainly used, and if necessary, a solvent such as an aromatic, ketone, ester, or alcohol solvent can be used to form a paint. In road marking paints, a paint type is used in a room temperature type or a heating type. In addition to this, a melt type that is not a paint type using a solvent is used to form a road surface display construction, and can be applied to any of these cases.

When constructing these signs, as shown in FIG. 2, if the phosphorescent beads 10 are present near the surface of the coating film 24 on the base 22 of the sign 20, the paint for the phosphorescent function and the retroreflective function. This is preferable because the influence of the above can be reduced. For this reason, as a method of applying the phosphorescent beads 10 to the display object, in addition to the method of adding the phosphorescent beads 10 to the paint and mixing and applying the same, the phosphorescent beads 10 are present near the surface of the indicator. In addition, as described above, a method of spraying and fixing the phosphorescent beads 10 on the undried coating film 22 can be used.
(Example 1)

  In accordance with the Japan Highway Public Corporation “Lane Mark Test Construction Procedure”, a sample was prepared by forming 0.42 kg of phosphorescent beads on 0.4 L of paint on a sample plate per square meter of coating surface. As the phosphorescent function, the luminance change and the retroreflective function with the elapsed time after the end of irradiation were measured. The phosphorescent beads used here are phosphorescent pigment GSS300FF (average particle size 4 μm, particle size distribution width 0.5-8 μm) manufactured by Nemoto Special Chemical Co., Ltd. These are resin-coated particles that are arranged around and coated with an acrylic silicone resin (Momentive Performance Materials Japan GK (silicon acryl varnish TSR171 manufactured by GE Toshiba Silicone)) with a thickness of 10 μm.

  FIG. 3 is a diagram schematically showing a cross section of the manufactured sample. As shown in FIG. 3, the sample 30 is obtained by dispersing and fixing phosphorescent beads 32 on a paint 36 applied on a sample board 34. As the paint 36, two kinds of epoxy paint and latex paint which is a water-based paint were used.

The measurement of the luminous function was performed based on JIS Z 9100 regarding safety sign boards. For the measurement of luminance, BM-5A manufactured by Topcon Corporation was used, the measurement angle was 2 degrees, and the measurement distance was 1.1 m. A D ₆₅ fluorescent lamp for color comparison / color inspection (manufactured by Toshiba Lighting & Technology Corp.) was used as the light source for irradiation. The work was irradiated with this irradiation light for 20 minutes, and the luminance was measured after 5 minutes, 10 minutes, 20 minutes, and 60 minutes after the irradiation was stopped. The measurement location was approximately the center of the sample surface. The range is about 27 mm.

The results are shown in Table 1.

  FIG. 4 shows the elapsed time change of the emission luminance after the irradiation. From Table 1 or FIG. 4, it was confirmed that light emission was observed even after 60 minutes had passed since irradiation, and the phosphorescent property was exhibited.

  In addition, retroreflectivity was measured for the sample used for the above phosphorescence measurement. For the measurement, a retroreflective function measuring instrument (MX-7) was used, and the measurement was performed at approximately five locations in the center of the sample plate. Table 2 shows the average value of the measured values at these five locations as retroreflective brightness. In Table 2, as a reference sample, a glass bead having no phosphorescent pigment on the surface is used, and the same weight as the above sample is dispersed and prepared in a paint, and the retroreflective luminance is measured under the same conditions. The results were compared with the results of retroreflectance measurement of the samples.

Table 2 shows the measurement results. The retroreflective brightness of the sample dispersed and fixed with phosphorescent beads having a phosphorescent pigment around it is about ¼ of the retroreflective brightness of the sample fixed by spraying glass beads as it is. It was confirmed to show.

  Next, each of the above samples was immersed in water, and the change in the phosphorescent function with the passage of the immersion time was examined. FIG. 5 shows the result.

As can be seen from FIG. 5, no change in the phosphorescent function was observed even after 4 months of immersion in water. At the same time, the retroreflective property was also measured, but the retroreflective property was not observed at all even after 4 months, and had high water resistance. confirmed.
(Example 2)
The chemical resistance test of the phosphorescent beads according to the present invention was performed. As in the case of Example 1, the phosphorescent beads composition was obtained by comparing the phosphorescent pigment GSS300FF (average particle size 4 μm, particle size distribution width 0.5-8 μm) manufactured by Nemoto Special Chemical Co., Ltd. with respect to glass beads. Resin-coated particles with a thickness of 10 μm coated with acrylic silicone resin (Momentive Performance Materials Japan GK (silicon acryl varnish TSR171) manufactured by Momentive Performance Materials Japan LLC) It is.
As the chemical solution for the test, 10 ml of each of 1) 95% ethyl alcohol, 2) 2% caustic soda, 3) 0.4% hydrochloric acid, and 4) pure water (reference) were prepared. Immerse 4g of this phosphorescent bead in chemical solution and keep it soaked for 2 days, then remove it and examine its appearance, brightness after irradiation and its change over time, and retroreflection brightness. It was. As a result, in any case, no significant change was observed compared to before immersion, and it was found that these chemicals have chemical resistance.

  According to the present invention, phosphorescent beads having water resistance, phosphorescence and retroreflective properties can be obtained, and can be used for forming a sign that can be used outdoors and can be recognized even in a dark place or in a dark place. Such phosphorescent beads are useful as materials for road markings, and can also be used for architectural markings and other decorative markings. Therefore, their industrial applicability is considered to be great.

It is typical sectional drawing which showed one Embodiment of the phosphorescent bead which concerns on this invention. It is the figure which showed an example of the label | marker using the phosphorescent bead which concerns on this invention. In the Example of this invention, it is typical sectional drawing of the sample used for the measurement of these changes by the measurement of luminous property and retroreflectiveness, and immersion in water. It is the figure which showed the change by the elapsed time of the light-emitting luminance after irradiating light with respect to each sample of an Example. It is the figure which showed the change of the light brightness by the immersion time after immersing each sample of an Example in water.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 ... Phosphorescent beads, 12 ... Glass beads, 14 ... Phosphorescent pigment, 16 ... Water-resistant translucent resin, 20 ... Marking object, 22 ... Base, 24 ... Coating, 30 ... Sample, 32 ... phosphorescent beads, 34 ... sample board, 36 ... paint.

Claims (1)

Glass beads,
A phosphorescent pigment disposed around the glass beads;
A phosphorescent bead comprising the water-resistant transparent resin that coats the glass bead and the phosphorescent pigment.

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