HK1067996B - Light-accumulating luminous road marking material and road structure - Google Patents

Description

Light-storing luminous road sign material and road structure

Technical Field

The invention relates to a light-storing and luminous road marking material and a road structure. More particularly, the present invention relates to a novel light-storing and light-emitting road marking material which has high light-storing and light-emitting properties for use as a road marking or the like, suppresses the color tone of green even when a light-storing and light-emitting pigment is used, and can be used as a white line or a yellow, orange or other color line, and a road structure using the same.

Background

A light-storing pigment which absorbs light energy of sunlight or electric lamps and emits the light energy to the outside as light after several hours is known, and it is proposed to use a good feature that recognizability can be obtained even at night or in a dark place, and to apply the pigment to a marking on a road surface. For example, Japanese patent application laid-open No. 10-82023 proposes a light storing and luminescent road marking material characterized in that a transparent or translucent light scattering layer is provided on a white or yellow substrate layer, and a transparent or translucent light storing layer containing a light storing pigment is further provided on the light scattering layer.

However, in the case of the light-storing and luminescent road marking materials known in the past, the light-storing and luminescent properties are short in duration and difficult to recognize for a long time, and there is a problem that, for example, the color tone of a mark provided on a road surface becomes green and the mark cannot be used except for a green mark because the light-storing pigment is blended and the light is emitted not only at night or in a dark place but also in the daytime. Further, when a pigment is blended to form a color tone such as white, yellow, orange, etc., there is a disadvantage that the light storage capacity is always lowered and the light-emitting property is poor.

Specifically, for example, in the case of the marking material described in the above-mentioned Japanese patent application laid-open No. Hei 10-82023, the phosphorescent property is low in practice even in the case of a repeatedly preferable formulation, and the green color formed by the phosphorescent pigment in the color tone is strong, and thus the marking material cannot be used for marking with white lines.

Further, although the conventional marking materials are disposed on the road surface, they are basically free from consideration of the anti-skid property, and prevent road surface slippage due to wetting with water or adhesion of oil, and thus are a major problem for road marking materials utilizing the light storage and emission function.

Accordingly, the present invention has been made to solve the above-mentioned conventional problems, and an object of the present invention is to provide a novel light-storing and light-emitting road marking material which is used as a road marking or the like, has required abrasion resistance, weather resistance and high light-storing and light-emitting performance, can suppress the color tone of green, is used as a white line or various color lines, and has anti-slip performance.

Disclosure of Invention

The present invention provides a method for solving the above problems, wherein 1, in a road marking material in which a light-storing and luminescent layer is formed by applying a resin paste containing a transparent resin component and a light-storing and luminescent pigment component on a road surface, a light-storing and luminescent road marking material characterized in that a transparent resin component having a viscosity of 1 pas or more at 20 ℃ is blended in a total amount of 7 to 95 wt% in the resin paste and an average particle diameter of the light-storing and luminescent pigment component contained therein is in a range of 10 to 2000 μm, and 2, a light-storing and luminescent road marking material characterized in that a light-storing and luminescent pigment component and other pigment components are contained in the resin paste is provided.

A light-storing and luminescent road marking material characterized in that the other pigment components have an average particle diameter in the range of 0.1 to 40 μm, a light-storing and luminescent road marking material characterized in that the other pigment components are at least 1 pigment selected from the group consisting of white, yellow, orange and red is provided in the range of 4, a light-storing and luminescent road marking material characterized in that the weight mixing ratio (B/A) of the light-storing and luminescent pigment component (A) to the other pigment component (B) is 3.0 or less is provided in the range of 5, a light-storing and luminescent road marking material characterized in that an oxide or a composite oxide of zirconium is mixed as a white pigment component is provided in the range of 6, and a light-storing and luminescent road marking material characterized in that the amount of the oxide or the composite oxide of zirconium mixed in the resin paste is in the range of 0.1 to 5.0 wt% of the total amount is provided in the range of 7.

The present invention also provides a light-storing and luminescent road marking material characterized in that the content of bubbles per unit volume in the resin paste is 2% or less, and a light-storing and luminescent road marking material characterized in that the resin paste is mixed and prepared in a reduced-pressure atmosphere, according to the invention of the present application, according to claim 8.

The present invention also provides 10 the light-storing and luminescent road marking material as defined above, wherein the transparent aggregate is blended with the resin paste, 11 th the light-storing and luminescent road marking material characterized in that the transparent aggregate is at least 1 of silica, fused silica and glass, and 12 th the light-storing and luminescent road marking material characterized in that the silica, fused silica and glass have a particle size in the range of 0.3 to 10mm and are blended in the range of 0.1 to 6 times the total weight of the resin paste.

The pavement marking material according to any of the above aspects, wherein the pavement marking material is applied to a road surface.

Further, the present invention provides 14 th of the above road marking materials, wherein after the resin paste is applied to the road surface, the transparent aggregate is spread before the resin paste is cured and embedded in the light storing and light emitting layer with at least a part of the outer shape thereof exposed, 15 th of the road marking materials characterized in that the transparent aggregate is embedded in 50 vol% or more of the aggregate, 16 th of the road marking materials characterized in that the transparent aggregate protrudes in the range of 0.05 to 5mm from the cured surface portion of the resin paste, 17 th of the road marking materials characterized in that the applied thickness of the resin paste is 1 to 5mm, 18 th of the road marking materials characterized in that the transparent aggregate is at least 1 of silica, fused silica and glass, the particle size is 0.3 to 10mm, and the amount of the light storing and light emitting aggregate is 1 to 30Kg/m²A light-storing and light-emitting road marking material scattered in the above ratio.

The 19 th provides a road marking material comprising the transparent aggregate of any of the 12 th to 14 th inventions described above blended in a resin paste, wherein the surface of the light-storing luminescent layer is ground or the cured surface portion of the resin paste is removed by water jet treatment after applying the resin paste on the road surface and curing the resin paste, and the 20 th provides a light-storing luminescent road marking material removed in the range of 0.1 to 2mm from the cured surface portion of the resin paste.

The light-storing and light-emitting road structure characterized in that any of the above-mentioned road marking materials is disposed on the road surface is provided 21, the light-storing and light-emitting road structure characterized in that a white base coat is previously disposed on the road surface on which the road marking material is disposed is provided 22, the light-storing and light-emitting road structure characterized in that the road marking material is disposed on the road surface through a primer layer is provided 23, and the light-storing and light-emitting road structure characterized in that the road marking material is disposed on the road surface or on the white base coat through a primer layer is provided.

Drawings

Fig. 1 is a sectional view for explaining water spray treatment and the like.

Fig. 2 is a sectional view illustrating embedding of the transparent aggregate.

Detailed Description

The invention of the present application is an invention having the above-described features, and embodiments of the invention will be described below.

The present invention is characterized in that, in the case of a road marking material having high light-storing and light-emitting properties and suppressed in the color tone of green, which is used as a white line or other color line for marking a road, a light-storing and light-emitting layer is basically formed by applying a resin paste containing both a transparent resin component and a light-storing and light-emitting pigment component on the road surface.

The transparent resin component in this case may be any of various resin components as long as it is transparent and can be cured after being applied to a road surface, and a resin paste can be formed. Of course, a resin component having durability as a road marking, that is, weather resistance or light resistance, water resistance, and appropriate strength or hardness may be used. Examples of the resin include various resins such as a methacrylic resin component, an acrylic resin component, an unsaturated polyester resin component, an epoxy resin component, and a silicone resin component.

The "transparency" in the transparent resin component means a resin having high light transmittance, and may be white or other color tone as long as it is a resin having high light transmittance. In general, a resin having a light transmittance of 70% or more, preferably 85% or more, of ultraviolet ray is preferably used for such light transmittance.

The transparent resin component is a resin forming a resin paste, and thus can be in a liquid, viscous, or paste form. Therefore, it can be a resin component in which a polymer and a monomer are mixed, for example. Namely, any of the following states.

(1) The resin (polymer) itself

(2) Mixed state of polymer and monomer

(3) Mixed state of polymer and oligomer

(4) Mixed state of oligomer and monomer

(5) Mixed state of polymer, oligomer and monomer

The transparent resin component, which is a basic component of the resin paste, is a resin component that secures adhesion of a light-storing luminescent layer for marking or the like to a road surface, or functions as a dispersion binder of a light-storing luminescent pigment or the like, and secures light transmittance, water resistance, abrasion resistance, or the like after curing. In the present invention, the amount of the transparent resin component is 7 to 95 wt% based on the total weight of the resin paste. More preferably 15 to 60% by weight. When the amount exceeds 95% by weight, the pigment component or the light-storing luminescent pigment component is not sufficiently blended, and thus high light-storing luminescent properties cannot be obtained. In view of the surface hardness, wear resistance, and the like of the marking material on a road surface on which a bicycle travels, it is preferably 60 wt% or less in practice. On the other hand, when the amount of the transparent resin is too small than 7% by weight, it is difficult to obtain sufficient adhesive strength and water resistance as a light-storing and light-emitting layer when the resin is applied to a road surface as a mark or the like, and the amount varies depending on the kind of the transparent resin component, but when the resin paste is applied directly to a road surface, for example, a concrete surface or an asphalt surface, the amount of the transparent resin is generally 20% by weight or more, and when the resin paste is applied through an undercoat layer, it is preferably 15% by weight or more. More practically, the road marking material has good adhesion strength to a road base surface and surface hardness, is abrasion-resistant and water-resistant, and has high light-storing and light-emitting properties, and is more preferably within a range of 20 to 40 wt% in order to have desired high density when directly applied.

The transparent resin component preferably has a viscosity of 1 pas (20 ℃ C.) or more, more preferably 3 pas (20 ℃ C.) or more. By using such a transparent resin component having a relatively high viscosity, a light-storing and light-emitting pigment component having a relatively large particle diameter, which is expected to have a higher light-storing and light-emitting property, can be uniformly dispersed, and a good light-storing and light-emitting property can be achieved as a road marking material after curing.

The viscosity of the transparent resin component can be adjusted by controlling the ratio of the polymer to the monomer in a mixed state, for example, depending on the kind of the resin.

For example, in the case of an MMA resin component, the relationship between the viscosity and the MMA polymer content as a slurry (product of Mitsubishi Yang corporation, etc.) in a state of being mixed with an MMA polymer and an MMA monomer can be adjusted as shown in Table 1.

TABLE 1

Viscosity Pa.s (20 ℃ C.)	MMA Polymer content (% by weight)
		1.52.03.35.510.014.0	252729313335

If the viscosity is too high, the operation is difficult in practice for mixing and uniformly dispersing the light-storing and light-emitting pigment or the like in the resin paste. Therefore, as a general standard, the upper limit of the viscosity may be about 100 pas (20 ℃ C.).

The light-storing light-emitting pigment component is mixed into the transparent resin component to form a resin paste, but the resin paste may contain the following components.

Other pigment ingredients

Transparent aggregate

In addition to these, a curing catalyst, a curing aid, a viscosity modifier, an ultraviolet ray aging inhibitor, an antibacterial agent, and the like may be added as appropriate as long as the object and effect of the present invention are not impaired.

As the light-storing and light-emitting pigment to be mixed with the transparent resin component, various pigments which have been conventionally known and are mainly commercially available can be used, and examples thereof include strontium aluminate-based pigments and zinc sulfide. As these light-storing luminescent pigments, pigments having an average particle diameter of 10 μm or more can be used, but the present invention is more preferably 20 to 2000. mu.m, still more preferably 30 to 300. mu.m. Most preferably, pigments having a larger particle size of 100 μm or more are used.

Conventionally, it has been difficult to use such a large-particle-diameter light-storing luminescent pigment because it has been difficult to uniformly disperse the light-storing luminescent pigment.

In the present invention, a transparent resin component having a relatively high viscosity of 1 pas (20 ℃) or higher is used to uniformly disperse the pigment component into the resin paste, thereby obtaining a road marking material having a uniform dispersion.

By using a light-storing and light-emitting pigment component having a relatively large particle diameter, the light-storing and light-emitting pigment component can absorb a larger amount of energy and can emit light continuously for a long time.

The amount of the light-storing pigment component is preferably 5% by weight or more based on the total weight of the resin paste. When the amount is less than 5% by weight, it is difficult to obtain a sufficient light-storing and light-emitting function as required.

In the present invention, as a standard of a general light accumulation and emission function, it is considered that the D65 common light source 200Lx is used to irradiate 3mcd/m from a saturated state to a lower limit value at which a person can recognize the contour of an object²The time for which the luminance continues to emit light is preferably 8 hours or more, and from this viewpoint, the mixing ratio of the light-storing pigment component to the transparent resin component is also selected in consideration of the combination with other compounding components.

Further, the light-storing and luminescent road marking material of the present invention may be appropriately mixed with other pigment components together with the light-storing and luminescent pigment component. In this case, the weight ratio of the light-storing and luminescent pigment component (A) to the other pigment components is preferably 3.0 or less as B/A. When the B/A ratio exceeds 3.0, the other pigment components are mostly inorganic particles, and absorb light from the outside which masks the light storage and emission pigment component, thereby inhibiting the storage and subsequent emission.

As the other pigment component, pigments of various hues are available, but as the road marking material for a sign or the like, for example, white pigments, yellow pigments, orange and red pigments are representatively exemplified. Examples of the white pigment include zirconia-based pigments, titania-based pigments, and alumina hydroxide-based pigments. Among them, a white pigment composed of an oxide or composite oxide such as zirconia or zircon (zirconium silicate) is more preferable in terms of a light storage and emission effect because the light shielding property is smaller than that of other pigments.

Examples of the yellow pigment include chrome yellow, cadmium yellow, and nickel titanium yellow, and examples of the orange and red pigments include iron oxide red, cadmium red, and molybdenum red. Of course, various pigments such as blue, green, and black may be considered. These pigment components may be used as a single type of pigment, or as a combination of several types of pigments.

When the above-mentioned zirconium oxide or composite oxide is blended as a white pigment, the content is preferably in the range of 0.1 to 5.0 wt% based on the total amount of the resin paste.

The average particle diameter of these other pigment components is preferably in the range of about 0.1 to 40 μm. This is because the large particle diameter exceeding 40 μm makes it easy to mask the light-storing and luminescent pigment component by mixing.

In addition to these, it is needless to say that an organic pigment may be appropriately blended together with the above-mentioned inorganic pigment. In the present invention, transparent aggregate such as silica, glass, and crystal may be mixed.

The transparent aggregate is effective not only for imparting physical properties such as strength and abrasion resistance required for improvement to a cured product as a road marking material, but also for effectively increasing the light storage and light emission effects of the light storage and emission pigment due to its transparency by utilizing the light transmission through the inside of the particles and the light diffuse reflection function at the particle surface interface. In addition, it is important to add a transparent aggregate, and as described later, the addition of a resin paste to a road surface and the roughening by rough grinding or water-jet treatment after curing the paste contribute to further improving the light-storing and light-emitting function and imparting the anti-skid property to the road marking material.

Silica or glass is most preferable as such a transparent aggregate, and silica or glass may be used alone or in combination. The transparent aggregate has a particle diameter of 0.3 to 10mm, preferably 0.1 to 6 times the total weight of the resin paste.

When the particle size is less than 0.3mm or the compounding amount is less than 0.1 times by weight, the addition effect is not so remarkable. On the other hand, if the particle size exceeds 10mm or if the amount is more than 6 times by weight, the strength of the molded article is undesirably deteriorated.

In addition to these transparent aggregates, inorganic fillers may be added. The particle size of such filler is less than 0.1mm, and is, for example, fused silica powder, quartz (silica) powder, calcium carbonate, aluminum hydroxide, plastic powder, glass powder, or the like.

The light-storing and luminescent road marking material of the present invention is prepared by mixing a light-storing and luminescent pigment component with the above-mentioned transparent resin component, or by adding 1 or more components among other pigment components or transparent aggregate to the above-mentioned transparent resin component to prepare a resin paste.

Here, the mixing method is adopted to adjust to an extremely important condition. In particular, it is important to use a light-storing and light-emitting pigment having a relatively large particle diameter and to use a transparent resin component having high viscosity as a matrix for uniformly dispersing the pigment.

It should be emphasized that, according to the invention of the present application, the above preparation provides a method for making the bubble content per unit volume of the resin paste 2% or less.

In general, stirring is performed during mixing, and the stirring conditions are such that the bubble content is 2% or less, and the selection of the stirring apparatus, the number of revolutions during stirring, the atmosphere during stirring, and the like are controlled.

The pigment component having a smaller particle diameter or a smaller specific gravity than the light-storing light-emitting pigment component generates bubbles when mixed with stirring, and the light-storing light-emitting pigment component is easily masked when the mixed product is formed or when the mixed product floats on the surface portion due to the remaining bubbles. When the content of bubbles per unit volume of the mixed preparation exceeds 2%, the problem of masking cannot be ignored.

In order to control the bubble content, it is effective to prepare the mixture by mixing under an atmosphere reduced in pressure of 50kPa or more from normal pressure. By mixing under a reduced-pressure atmosphere, the remaining of bubbles can be effectively suppressed. When the degree of decompression is small, this effect is insufficient.

The bubble content can be measured, for example, by a method of measuring the volume reduction rate at a reduced pressure of 100kPa from normal pressure after filling the container.

In addition, in order to improve the light storage/emission performance, it is also effective to suppress the mixing of foreign matter at the time of the hybrid modulation. In particular, it is preferable to suppress the mixing of foreign matters such as metal from the stirring device.

Therefore, it is effective to contrive a method of making the hardness of the inner surface of the mixing container or the surface of the stirring blade constituting the mixing device larger than the hardness of the pigment or the transparent aggregate. As a convenient method, a method of coating the inner surface of the mixing vessel or the stirring blade with a transparent or white coating material is also effective. Thus, even if a slight amount of foreign matter is mixed, the light storage and emission performance is not substantially or completely affected.

Examples of the transparent or white coating material include a flame sprayed film of alumina, a bonded ceramic plate, glass, silicone rubber, silicone resin, fluororesin, MMA resin, and the like.

The resin paste mixed and prepared as described above is applied to the road surface by a suitable method and then cured. Thus, a road marking material having a predetermined shape and forming a light-storing and light-emitting layer and a road structure in which the marking material is disposed are integrated with each other are realized.

The invention of the present application proposes several important solutions in connection with the site work of laying and curing on the road surface.

First, as described above, in the 1 st step, a transparent aggregate is mixed into a resin paste, the resin paste is applied to a road surface and cured, and then the surface layer portion of the cured body is roughly ground or subjected to water jet treatment.

As described above, since the surface portion is concentrated by floating of other pigment components having small particle diameters other than the light-storing pigment with the application of the resin paste, light transmission or light emission for light storage may be masked, and when this problem cannot be ignored, it is effective to remove the masking layer (portion) by rough grinding or water jet treatment of the surface of the cured body.

That is, for example, as shown in fig. 1, a cross section is shown in which a transparent aggregate is blended in a resin paste in advance, and after the resin paste is laid on a road surface 1 and cured, the surface portion of a light-storing luminescent layer 2 containing the transparent aggregate 3 is subjected to rough grinding (a) or water jet treatment (B), and only the cured portion of the surface of the resin paste is partially removed.

When the resin paste is applied, the pigment component having a large covering property, i.e., a light-shielding property, and a small particle diameter is likely to be accumulated in the surface layer portion. The mask layer 4 formed by the aggregation of such pigment components blocks the transmission of light, and therefore, the light storage and emission performance is lowered. Rough grinding or water jet treatment is effective for improving the light storage emission performance by removing such a masking layer 4.

In either case of water jet treatment or rough grinding, it is preferable to remove the cured surface layer portion of the resin paste in a thickness range of 0.1 to 2mm in order to remove the masking layer 4.

As the rough grinding means, various means such as rotary grinding using a diamond disk can be used.

The uneven surface formed by the above surface portion treatment, particularly the water jet treatment, effectively imparts an anti-slip function to the light-storing and light-emitting road marking material of the present invention.

In addition, not only when a transparent aggregate is blended in the resin paste in advance, but also in the present invention, after the resin paste is applied to the road surface, the transparent aggregate is spread and embedded in the light-storing and light-emitting layer with at least a part of the outer shape thereof exposed, and improvement of the light-storing and light-emitting performance and the anti-slip function are similarly achieved. That is, for example, as shown in a partial cross-sectional view of fig. 2 showing that a transparent aggregate is embedded, after a resin paste is applied to a road surface 1, the scattered transparent aggregate 3 is embedded in a cured light-storing and light-emitting layer 2, and at least a part of the outer shape of the aggregate is exposed to the outside from the surface of the light-storing and light-emitting layer 2.

The transparent aggregate in this case is a natural stone, and has a shape much larger than that of the phosphorescent pigment blended in the resin paste, and also has a strength and hardness, and has a so-called aggregate property such as silica, fused silica, or glass.

In fact, from the viewpoints of physical properties such as strength of adhesive integration in the light-storing and light-emitting layer 2, peeling resistance, and the effect of increasing light-storing emission (as compared with the case where the transparent aggregate is not spread), it is preferable that the silica, the fused silica, and the glass are embedded in the light-storing and light-emitting layer 2 in an amount of 50% by volume or more of the outer shape of the transparent aggregate, or are exposed at a height of 0.1mm to 5mm from the surface of the light-storing and light-emitting layer 2. In addition, considering the range of particle size of 0.3 to 10mm, more preferably 2.0 to 3.0mm range of transparent aggregate.

The amount of the dispersion is 1 to 30kg/m²Preferably 3 to 10kg/m²The range of (1).

The thickness of the light-storing and light-emitting layer 2 is not particularly limited, and may be in the range of 1 to 5 mm.

In actual construction, after the resin paste is applied to the road surface 1, the transparent aggregate 3 is spread in a state where the resin paste has fluidity or is semi-cured, and is partially embedded in the resin paste by its own weight or is further pressed from above by a roller or the like as necessary. Then, the resin paste is cured, and the transparent aggregate 3 is embedded integrally with the light-storing and light-emitting layer 2.

Due to the texture structure having the above characteristics, the light storage emission effect of the marker material of the present invention is significantly increased as compared with the case where the transparent aggregate is not used. This is estimated to be largely due to the increased surface area for light that absorbs sunlight or fluorescent light energy due to the presence of transparent aggregate.

Further, due to the presence of the transparent aggregate exposed to the outside, unevenness is formed on the surface portion after the marking material is applied, thereby improving the anti-slip property of the surface portion. Such anti-skid performance is extremely important from the viewpoint of preventing a pedestrian from slipping or a traffic accident caused by a crosswalk or a pedestrian road surface, which is made of a marking material.

The size, amount of scattering, ratio of exposure, or height of the transparent aggregate according to the present invention is important in order to improve the grip performance.

In addition, in the present invention, in order to make the light accumulation and emission effect more remarkable, it is also effective to provide a white undercoat layer in advance at a desired position before applying the above resin paste. The white undercoat layer may be made of various materials, mainly those known in the past.

Of course, in the present invention, not only the white base coat layer but also a primer layer may be provided in advance in order to improve the adhesive strength depending on the state or properties of the road surface portion such as concrete or asphalt, the kind or properties of the transparent resin, and the road marking material of the present invention may be disposed on the primer layer to be integrated therewith.

As the primer layer in this case, it is considered that the main purpose is to seal (block) the road surface portion, or to improve the adhesion. For example, it is also effective to use a known material such as a urethane resin-based, epoxy-based, or asphalt-based material, which has been conventionally used for repairing or sealing a road surface, or a transparent resin component constituting the light-storing and luminescent road marking material of the present invention, or a resin mainly containing the transparent resin component, as the primer layer. In the latter case, the adhesiveness between the layers can be improved by the identity with the resin component of the upper light-storing and light-emitting road marking material.

The present invention as described above provides a light-storing and light-emitting road marking material which has high light-storing and light-emitting properties for use as a road marking or the like, can suppress the color tone of green even when a light-storing and light-emitting pigment is used, and can be used as a white line or a yellow, orange or other color line.

The following examples are given to explain the present invention in more detail. Of course, the present invention is not limited by the following examples.

Further, in the following examples, evaluation of luminescence property by light accumulation was carried out by irradiating 200Lx (lux) with a D65 common light source to a saturation state according to JIS light accumulation safety marking plate Z9100-1987, and then obtaining a luminance of 3mcd/m²The time of (d) was used as an evaluation criterion.

Examples

< example 1>

As MMA resin syrup in which MMA polymer and MMA monomer are mixed, various syrups having different MMA polymer content and viscosity are prepared, and a light-storing luminescent pigment component or the like is mixed into the syrup so as to have the following mixing ratio (by weight).

MMA resin syrup 35.5

Resin curing agent 0.5

Strontium aluminate series light-storing luminous pigment 52.0

(manufactured by Ishikaki Kaisha, average particle size 100 μm)

Aluminum hydroxide 12.0

(average particle diameter 8 μm)

The mixing was carried out under a reduced pressure atmosphere of 0.1 atm. In this case, the content of bubbles per unit volume of the mixed preparation is 1% or less.

The prepared mixed preparation was applied to the surface of a concrete sample having the same composition as the road surface and cured.

The adhesive strength to the surface of the molded solidified body sample at a viscosity of 1.0 to 10.0 pas (20 ℃ C.) is 150N/cm²(concrete substrate destruction), and good abrasion resistance, 0.02g (according to JIS A1452).

Furthermore, the measured luminance of the molded cured product was 3mcd/m²The luminescence property of the luminescence sample was evaluated. The results are shown in Table 2.

TABLE 2

MMA resin syrup viscosity Pa.s (20 ℃ C.)	To 3mcd/mTime of (hours)
		0.51.01.52.06.010.0	389101313

As can be seen from Table 2, when the viscosity of the resin slurry was less than 1.0 pas (20 ℃ C.), it reached 3mcd/m²The time of (2) is hardly more than 8 hours. On the other hand, when the temperature is 1.0 pas (20 ℃ C.) or more, the time is more than 8 hours and up to 14 hours or more.

< example 2>

In example 1, a molded cured product was prepared in the same manner as in example 1 using an MMA resin slurry having a viscosity of 6.0 pas (20 ℃) and using strontium aluminate-based phosphorescent pigments having different average particle diameters. In any case, the adhesive strength to the sample surface is 100 to 160N/cm²(concrete base material destruction) and abrasion resistance of 0.01 to 0.02g (according to JIS A1452).

The measurement of various cured formed bodies reaches 3mcd/m²Time of (d). The results are shown in Table 3.

TABLE 3

Average particle diameter (μm)	To 3mcd/mTime of (hours)
		5103050100150300	38911141822

It is confirmed from Table 3 that the light-accumulating luminous performance is extremely remarkably improved by using the light-accumulating luminous pigment component having a large particle diameter. On the other hand, when the particle diameter is smaller than 10 μm, the particle diameter is 3mcd/m²Does not exceed 8 hours.

< example 3>

In example 1, an MMA resin slurry having a viscosity of 6.0 pas (20 ℃) was used, and the mixture was stirred and mixed while changing the atmosphere during the mixing or changing the mixing apparatus.

The measurement was carried out at 3mcd/m in each case²The results are shown in Table 4. The degree of reduced pressure (kPa) in Table 4 indicates the degree of reduced pressure from normal pressure.

The mixing device A, B, C is shown below.

A: the inner surface of the mixing container and the stirring blades are made of stainless steel

B: in A, only the surface of the stirring blade is coated with silicon rubber

C: in A, the inner surface of the mixing container and the surface of the stirring blade are both coated with silicone rubber.

TABLE 4

Degree of decompression (kPa)	Mixing device	To 3mcd/mTime of (hours)
			9080605030506080	AAAAABBC	13131387101518

As is clear from Table 4, it was confirmed that the reduction of pressure by 5kPa or more was effective and that the silicone rubber coated on the inner surface of the mixing device and the surface of the stirring blade imparted good performance.

< example 4>

An MMA resin slurry (viscosity: 6.0 pas (20 ℃ C.)) obtained by mixing an MMA polymer and an MMA monomer was prepared, and a light-storing luminescent pigment component and the like were mixed in the slurry so as to have the following mixing ratio (by weight).

MMA resin syrup 35.5

Resin curing agent 0.5

Strontium aluminate series light-storing luminous pigment 54.0

(manufactured by Ishikaki Kaisha, average particle size 150 μm)

Other pigments 10.0

(average particle diameter 30 μm)

Molded cured bodies obtained when various pigments were used were produced in the same manner as in example 1, and the measured value was 3mcd/m²Time of (d). The results are shown in Table 5.

TABLE 5

Other pigments	To 3mcd/mTime of (hours)
		Titanium oxide aluminum hydroxide titanium hydride (50):aluminumhydroxide (50):zirconzircon zircon (50): aluminum hydroxide (50)	815101817

Table 5 shows that zircon, which is a white pigment, has a small masking property and therefore has a good light-storing and light-emitting property.

< example 5>

In the implementation ofIn example 4, aluminum hydroxide was used as another pigment, and the mixing ratio of the light-storing luminescent pigment (A) and the aluminum hydroxide pigment (B) was changed to 3mcd/m²The time of (2) was evaluated. The results are shown in Table 6.

TABLE 6

Weight ratio (B/A)	To 3mcd/mTime of (hours)
		0.1500.1851.052.253.54	15151496

As is clear from Table 6, when the weight ratio B/A exceeds 3, the light-storing and light-emitting properties rapidly decrease.

< example 6>

In example 4, aluminum hydroxide was used as another pigment, and the content of each component was measured to be 3mcd/m²Time of (d). The results are shown in Table 7.

TABLE 7

MMA resin slurry	Light-storing luminescent pigment	Aluminum hydroxide	To 3mcd/mTime of (hours)
				15.222.535.558.686.496.0	54.043.054.035.010.03.5	30.020.010.05.43.00	1415151083

< example 7>

In example 4, the other pigment was aluminum hydroxide, the amount of the strontium aluminate type phosphorescent pigment blended was 24.0, and silica powder having an average particle diameter of 1mm was blended as a transparent aggregate at a ratio of 30.0.

Although the amount of the phosphorescent pigment is greatly reduced, the luminance is 3mcd/m²The time of (2) is about 8 hours, and the effect is better.

The weight ratio of the transparent component (C) to the aggregate (D) was 0.845, and after changing the weight ratio to 3.0, the luminance reached 3mcd/m²The time of (2) was 9 hours.

< example 8>

In example 4 when aluminum hydroxide was used as another pigment, a molded cured body was prepared using a silicone resin (KE 1310S, manufactured by shin-Etsu chemical Co., Ltd.) instead of the MMA resin slurry. The viscosity of the silicone resin was about 50 pas (20 ℃).

The cured body has a luminance of 3mcd/m²The time of (2) was 14 hours. It was confirmed that good light accumulation was obtainedAnd (4) luminous performance.

< example 9>

In example 7, after applying a resin paste having a weight ratio D/C of 3, the surface of a cured body having a thickness of 3mm was treated with water spray, and a portion having a thickness of about 0.5mm was removed from the cured surface portion to roughen the surface.

The rough surface body slip resistance value BPN (ASTM E303) was 65 on the wet side and 70 on the dry side, and it was confirmed that the slip resistance was good and reached 3mcd/m²The time of (2) is extended from 9 hours to 10 hours before the treatment.

< example 10>

In example 4, the other resin paste containing aluminum hydroxide as a pigment was applied to a thickness of 4mm and then cured at a rate of 5kg/m²Glass powder with a particle size of 1 to 5mm is scattered at a ratio of about 55% by volume and cured in a state protruding from a range of 0.1 to 1.4 mm.

The cured product had a slip resistance value BPN (ASTM E303) of 66 on the wet side and 69 on the dry side, and it was confirmed that the slip resistance was good and reached 3mcd/m²Extended to 17 hours.

< example 11>

Using the resin paste obtained in example 1 at 6.0 pas (20 ℃), a white road coating material was applied in advance as an undercoat layer (2 mm in thickness) to the asphalt surface of the sample, and the resin paste was applied and cured on the undercoat layer.

When measured, the concentration reached 3mcd/m²And initial luminance after 15 minutes. The results are shown in Table 8. As seen from Table 8, the light storage and emission properties were significantly improved due to the presence of the white undercoat layer.

TABLE 8

Color of the base coat	To 3mcd/mTime of (hours)	Initial luminance (3 mcd/m))
			Silver asphalt surface	181613	482355205

< comparative example >

The light storage and emission properties were measured by molding as disclosed in Japanese patent application laid-open No. Hei 10-82023, which has been known in the past. As an optimum result, 3mcd/m is achieved²The time of (2) was 5 hours and 15 minutes. The emission color is a color with a strong light-storing pigment color (green).

< example 12>

Using the resin paste of 6.0 pas (20 ℃ C.) in example 1, a paste was prepared in a weight ratio of 28.5, and the paste was applied to an actual concrete pavement sample to a thickness of 2 mm.

The adhesion strength was evaluated after one week and 2 weeks of application by a warm water resistance (60 ℃ warm water) immersion test for cases where a sealer was previously applied as a primer layer and cases where no sealer was previously applied.

The results are shown in Table 9.

Sufficient adhesive strength is obtained even when the sealer is not applied, and the adhesive strength is further improved by applying the sealer.

TABLE 9

Sealing material	Strength (N/cm) after 1 week of bonding)	Strength (N/cm) after 2 weeks of adhesion)
			Is free of	142	134
Polyurethane sealing material	359	340
			MMA resin sealing material	265	260

(MMA resin sealant and resin paste are the same resin component)

< example 13>

The same test as in example 12 was conducted on the asphalt pavement. In this case, the coating of the sealer as the primer layer is not performed.

As a result, the adhesion after one week was strongThe degree is 332N/cm²And the bonding strength after 2 weeks was 330N/cm²。

Possibility of industrial utilization

As described in detail above, according to the present invention, there is provided a novel light-storing and light-emitting road marking material which has required abrasion resistance, weather resistance, high light-storing and light-emitting properties, can suppress the color tone of green, can be used as white lines or various color lines, and has anti-slip properties, and which is used as a road marking or the like.

Claims (25)

1. A light-storing and luminescent road marking material comprising a light-storing and luminescent layer formed by applying a resin paste containing a transparent resin component and a light-storing and luminescent pigment component on the road surface, wherein the transparent resin component having a viscosity of 1 pas or more at 20 ℃ is blended in the resin paste in an amount of 7 to 95 wt% in total, and the light-storing and luminescent pigment component having an average particle diameter of 10 to 2000 mu m is contained.

2. The light-storing and luminescent road marking material according to claim 1, wherein the resin paste contains a light-storing and luminescent pigment component and other pigment components.

3. The light-accumulating and luminescent road marking material according to claim 2, wherein the other pigment component has an average particle diameter in the range of 0.1 to 40 μm.

4. A light-accumulating luminescent road marking material as claimed in claim 2 or 3, characterized in that the further pigment component is at least 1 pigment out of white, yellow, orange and red.

5. The light-storing and luminescent road marking material according to claim 2, wherein the weight mixing ratio (B/A) of the light-storing and luminescent pigment component (A) to the other pigment component (B) is 3.0 or less.

6. The light-accumulating and luminescent road marking material according to claim 4, characterized by containing an oxide or composite oxide of zirconium as a white pigment component.

7. The light-storing and luminescent road marking material according to claim 6, wherein the amount of the zirconium oxide or the composite oxide blended in the resin paste is in the range of 0.1 to 5.0% by weight of the total amount.

8. The light-storing and luminescent road marking material according to claim 1, wherein the content of bubbles per unit volume in the resin paste is 2% or less.

9. The light-storing and luminescent road marking material according to claim 1 or 8, wherein the resin paste is a mixture prepared under a reduced pressure atmosphere.

10. The light-storing and luminescent road marking material according to claim 1, wherein a transparent aggregate is blended in the resin paste.

11. The light-storing and luminescent road marking material according to claim 10, wherein the transparent aggregate is at least 1 selected from the group consisting of silica, fused silica and glass.

12. The light-storing and luminescent road marking material according to claim 11, wherein the silica, the fused silica and the glass have a particle size of 0.3 to 10mm and are blended in a range of 0.1 to 6 times the total weight of the resin paste.

13. A light-storing and luminescent pavement marking material according to claim 1 or 12, which is applied to a pavement surface.

14. The light-storing and luminescent road marking material according to claim 1, wherein after the resin paste is applied to the road surface, the transparent aggregate is spread before the resin paste is cured, and the light-storing and luminescent layer is embedded in a state where at least a part of the outer shape of the aggregate is exposed.

15. The light-storing and luminescent road marking material according to claim 14, wherein 50% by volume or more of each transparent aggregate is embedded.

16. The light-storing and luminescent road marking material according to claim 14, wherein the transparent aggregate protrudes in a range of 0.05 to 5mm from a cured surface portion of the resin paste.

17. The light-accumulating and luminescent road marking material according to claim 14, wherein the resin paste is applied to a thickness in the range of 1 to 5 mm.

18. The light-storing luminescent road marking material according to claim 14, characterized in that the transparent aggregate is at least 1 selected from the group consisting of silica, fused silica and glass,the particle size is in the range of 0.3 to 10mm, and is 1 to 30kg/m²The mixture is spread according to the proportion of (1).

19. The light-storing and luminescent road marking material according to claim 14, wherein after applying a resin paste on the road surface and curing the resin paste, the surface of the light-storing and luminescent layer is roughly ground, or the cured surface portion of the resin paste is removed by water jet treatment.

20. The light-storing and luminescent road marking material according to claim 19, characterized in that it is removed in the range of 0.1 to 2mm from the cured surface portion of the resin paste.

21. A light-storing and luminescent road structure characterized in that the road marking material according to any one of claims 1 to 20 is disposed on a road surface.

22. The pavement structure of claim 21, wherein a white base coat is previously provided on the surface of the pavement on which the pavement marking material is provided.

23. The pavement structure of claim 21, wherein the pavement marking material is disposed on the surface of the pavement via a primer layer.

24. The road construction of claim 21 or 22, characterized in that the road surface is pre-roughened.

25. The pavement structure of claim 22, wherein the pavement marking material is disposed over the white basecoat layer by way of a primer layer.