JP3546320B2 - Luminescent flooring - Google Patents

Description

[0001]
[Industrial applications]
The present invention relates to a luminescent flooring produced from a luminescent composite sheet. The luminous flooring material of the present invention emits light even when it becomes true darkness after external stimulus such as sunlight or electric light stops, and has high luminous brightness and long afterglow time. Therefore, the flooring material of the present invention manufactured exclusively by using the property has a function of guiding emergency evacuees at night.
[0002]
[Description of the Prior Art]
A phenomenon in which luminescence is emitted at a considerably high yield by an external stimulus such as light, heat, or radiation is called fluorescence, and a substance having such properties is called a phosphor. The phenomenon of continuing to emit light even after the action of the external stimulus has ceased is called phosphorescence, and a substance having such properties is sometimes called a phosphor to distinguish it. In addition, there is a case where a fluorescent substance includes both fluorescent light and phosphorescent light, but in general, it is often a fluorescent substance that includes both light emission. A phosphor having a long decay time, that is, a long afterglow time, may be referred to as a phosphorescent phosphor.
[0003]
Because some substances simultaneously emit fluorescence and phosphorescence, it is extremely difficult to distinguish between fluorescence and phosphorescence during stimulation. In some cases, the luminescence after the stimulation is stopped is distinguished from the afterglow. In any case, there is no contention that the term luminescence can be used as a superordinate term including the terms fluorescence, phosphorescence and afterglow. Therefore, in the present invention, light emission is used as a general concept including fluorescence, phosphorescence, and afterglow, unless otherwise required. Therefore, the luminescent pigment is used as a term including a phosphor, a fluorescent pigment, a phosphor, a phosphorescent pigment, a luminous body, a luminous pigment, and the like.
[0004]
Conventionally, as a fluorescent composite sheet, a medical fluorescent intensifying screen and a fluorescent material in which a phosphor layer of 100 to 300 μm and a transparent protective layer of 5 to 20 μm are laminated on the surface of a support made of cardboard or a plastic material. A fluorescent plate or the like is used which is applied to an appropriate support and used to examine the presence or absence of radiation and the intensity thereof.
[0005]
By the way, when resin-based composite sheets having various structures are used as flooring materials, the flooring materials must have excellent basic properties such as walking, abrasion resistance, water resistance, and chemical resistance. Furthermore, at the time of a disaster such as a fire or an earthquake, if the floor of a building emits light even if the electric system fails and goes dark, it is effective for evacuation guidance. In this way, it can be said that providing a floor material with a light emitting function is a requirement that is not inferior to the above-described basic characteristics.
[0006]
However, since the conventional fluorescent composite sheet is used for a very special purpose, it is impossible to produce flooring even if the conventional technology is applied. Evacuation guidance can be displayed by applying fluorescent paint directly on the floor or pasting fluorescent tape, but hospitals and schools where a large number of people walk and frequently move furniture, equipment, etc. In the case of buildings and the like, there is a drawback that the surface wears quickly and the evacuation guidance function is impaired.
[0007]
[Problems to be solved by the invention]
Therefore, the problem to be solved by the invention is that, after external stimuli such as sunlight or electric lights are stopped, a flooring made of a luminescent composite sheet that emits light even in the darkness cannot be manufactured. It is.
[0008]
Still another problem to be solved by the invention will be clarified sequentially below.
[0009]
[Means for Solving the Problems]
The present inventors, in formulating means for solving the problem, in the composite sheet, walking, abrasion resistance, water resistance, a method of imparting basic properties as a floor material such as chemical resistance, In addition, a method of providing a function of emitting light even in the case of a true darkness after the external stimulus such as sunlight or an electric light is stopped was examined.
[0010]
The present invention, which is a means for solving the problem achieved as a result, basically includes a backing material, a base synthetic resin layer, a colored synthetic resin layer, a luminescent pigment-containing synthetic resin layer, and a transparent protective layer laminated. It is a flooring made of an integrated luminescent composite sheet.
[0011]
The luminescent flooring material of the present invention emits light by utilizing a reflected light from the white synthetic resin layer by laminating a white synthetic resin layer between the base synthetic resin layer and the luminescent pigment-containing synthetic resin layer. The effect can be further enhanced.
[0012]
The configuration of the present invention will be described in detail. The base synthetic resin layer, which is one of the constituent elements of the present invention, is a synthetic resin layer containing a coloring material, a fiber, a filler, and the like. Although the synthetic resin used for the base synthetic resin layer is not particularly limited, for example, polyvinyl chloride, polyethylene, polypropylene, acrylic resin, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride- Examples thereof include an ethylene copolymer, a vinyl chloride-vinylidene chloride copolymer, and a mixture of polyvinyl chloride and acrylonitrile-butadiene rubber.
[0013]
An inorganic filler is blended into the base synthetic resin layer in order to impart dimensional stability as a floor material. The inorganic filler preferably has a relatively small particle size, for example, a range of 60 to 200 mesh. The inorganic filler may be a conventionally used one, and examples thereof include calcium carbonate, talc, clay and silica sand. The amount of the inorganic filler is in the range of 100 to 400 parts by weight based on 100 parts by weight of the synthetic resin component. When the amount is less than 100 parts by weight, the dimensional stability of the flooring material is poor, and when it is more than 400 parts by weight, the abrasion resistance is poor.
[0014]
In addition, ordinary plastic additives such as a stabilizer, a foaming agent, a foaming aid, a coloring agent, an antistatic agent, and a flame retardant are added to the base synthetic resin layer, if necessary. Usually, the thickness of the base synthetic resin layer is in the range of 1.0 to 5.0 mm, preferably 1.5 to 3.0 mm.
[0015]
The synthetic resin, which is the main material for producing the base synthetic resin layer, is not limited to pure raw materials, and may use various recycled products. Alternatively, depending on conditions, the base synthetic resin layer may not be colored white. In such a case, if the luminescent pigment-containing synthetic resin layer is directly laminated on the base synthetic resin layer, the efficiency of reflecting light emitted from the luminescent pigment-containing synthetic resin layer is low, and therefore, the luminous luminance of the luminescent pigment-containing synthetic resin layer is low. Is disadvantageously reduced.
[0016]
The colored synthetic resin layer, which is one of the constituent elements of the flooring material of the present invention, is a layer having a function of reflecting light emitted from the luminescent pigment-containing synthetic resin layer on the surface. Therefore, the colored synthetic resin layer of the flooring of the present invention is colored white. Therefore, the pigment used is arbitrarily selected from titanium oxide, zinc white, barium sulfate and the like. Usually, the thickness of the colored synthetic resin layer is preferably in the range of 0.1 to 0.3 mm.
[0017]
By the way, when the flooring material of the present invention is used in large facilities used by a large number of people such as hospitals, hotels, underground shopping malls, etc., it is most strongly required that the afterglow luminance is as high as possible and the afterglow time is as long as possible. And excellent in light resistance, weather resistance and the like. However, all of the sulfide-based phosphors have a persistence time of 45 minutes to 500 minutes when measured by a predetermined measurement method.
[0018]
Furthermore, sulfide-based phosphors have poor light resistance and weather resistance, and are deteriorated by ultraviolet light and moisture and do not emit light. Therefore, they may not be used outdoors at all ("Light-storing materials" by Yoshihiko Murayama, Industrial Materials, Vol.44 No. 5, pp. 54-57; 1996).
[0019]
For the reasons described above, the present inventors have a long afterglow time blended into the flooring to provide an evacuation guidance function, high afterglow luminance, light resistance, and a good phosphorescent pigment with good weather resistance, The aluminate phosphor described in Japanese Patent Application Laid-Open No. 7-11250 filed by Nemoto Special Chemical Co., Ltd. was selected. One _{X K · Y L · Z P} [ where, M is selected calcium, barium, strontium, magnesium, and mixtures thereof: MAl ₂ O _4; this aluminate phosphor of the general formula X is an activator consisting of europium; Y and Z are activators selected from the group consisting of lanthanum series elements and manganese, tin and bismuth; K is 0.1% by mole to M. 001 to 10, L represents 0 to 10 in mol% based on M, and P represents 0 to 10 in mol% based on M. ] Is represented.
[0020]
Phosphors included in the above general formula include europium-activated strontium aluminate (SrAl ₂ O ₄ : Eu), europium-activated-dysprosium co-activated strontium aluminate (SrAl ₂ O ₄ : Eu, Dy), europium-activated neodymium co-activator strontium aluminate _{(SrAl 2 O 4: Eu,} Nd), europium-activated - praseodymium co-activated strontium aluminate _{(SrAl 2 O 4: Eu,} Pr), europium-activated - samarium co-activated strontium aluminate (SrAl ₂ O ₄ : Eu, Sm), europium activated-tin co-activated strontium aluminate (SrAl ₂ O ₄ : Eu, Sn), europium activated-neodymium co-activated calcium aluminate (CaAl ₂ O ₄ : Eu, Nd), europium Activation - samarium co-activated calcium aluminate _{(CaAl 2 O 4: Eu,} Sm), europium-activated - thulium co-activated calcium aluminate _{(CaAl 2 O 4: Eu,} Tm), europium-activated - neodymium - lanthanum co-activated calcium aluminate _{(CaAl 2 O 4: Eu,} Nd, La), europium-activated - neodymium - gadolinium co-activated calcium aluminate _{(CaAl 2 O 4: Eu,} Nd, Gd), europium-activated - neodymium - erbium co-activated calcium aluminate (CaAl ₂ O ₄ : Eu, Nd, Er) and the like.
[0021]
These aluminate phosphorescent phosphors have the afterglow time and emission luminance of 10 times or more as measured by the same method as the sulfide phosphor. As these aluminate phosphorescent phosphors, those manufactured and sold by Nemoto Special Chemical Co., Ltd. under the registered trademark of "N-night light" can be easily obtained.
[0022]
What is important when producing the luminescent flooring material of the present invention using the aluminate luminous phosphor described above is that the thickness and the afterglow luminance of the resin layer containing the aluminate luminous phosphor are important. Relationship. Up to a layer thickness of 0.5 mm, the afterglow luminance is almost proportional to the thickness. However, the aluminate phosphorescent phosphor has a relatively good translucency, and a thickness of 0.1 mm transmits about 50% of light. Therefore, by making the base of the resin layer containing the aluminate luminous phosphor white, the reflection effect can be used. Therefore, the thickness of the resin layer containing the aluminate luminous phosphor is 0.1%. The range is preferably 3 to 3 mm.
[0023]
In order to arrange and disperse the above-described aluminate phosphorescent phosphor three-dimensionally in the transparent synthetic resin layer so that the luminous bodies are not concealed, the resin used for the luminescent pigment-containing synthetic resin layer, for example, polychlorinated resin It is appropriately selected in the range of 5 to 300% based on vinyl. That is, when a floor material is manufactured from the luminescent composite sheet of the present invention, it is preferably set in the range of 5 to 50% in consideration of various physical properties such as abrasion resistance and walking property required for the floor material. If it exceeds 50%, the durability as a floor material is inferior, while if it is less than 5%, the luminance is inferior. In the case of manufacturing a product in which light emission luminance is more important than strength from the light emitting composite sheet of the present invention, the filling can be performed up to about 300%.
[0024]
In order to produce the above-mentioned base synthetic resin layer, colored synthetic resin layer, and luminescent pigment-containing synthetic resin layer, a plasticizer such as DOP, a filler such as DOP is added to an arbitrary resin such as polyvinyl chloride (degree of polymerization: 1000). After mixing calcium carbonate, a stabilizer, a pigment, or a luminescent pigment, kneading them with an intensive mixer, kneading them sufficiently with a mixing roll, and forming a sheet of a predetermined thickness with a roll calender . The three sheets thus formed are adhered by a calendar method to form a composite sheet.
[0025]
The luminescent flooring material of the present invention manufactured by the above-described method has a backing material laminated on the lower surface of the base synthetic resin layer. The backing material used in the present invention is arbitrarily selected from woven fabrics such as plain woven fabric and knitted fabric, paper, felt, asbestos paper, and nonwoven fabric as desired.
[0026]
A transparent protective layer is laminated on the surface of the luminescent pigment-containing synthetic resin layer. The transparent protective layer is formed, for example, by mixing 100 parts by weight of polyvinyl chloride, 40 parts by weight of a plasticizer DOP, 3 parts by weight of a stabilizer, and 5 parts by weight of epoxidized soybean to form, for example, a 0.1 mm-thick film to form a luminescent pigment. What is necessary is just to adhere to the surface of the containing synthetic resin layer. The thickness of the transparent protective layer is usually sufficient in the range of 0.1 to 0.3 mm.
[0027]
Hereinafter, the present invention will be specifically described with reference to examples.
Embodiment 1
[Production of base synthetic resin layer]
Component ratio (parts by weight)
Agricultural Bicycle Recycled Product 65
DOP14
Calcium carbonate 122
Stabilizer (Ba-Zn based) 3
Used floor material crushed material 23
[0028]
[Production of white synthetic resin layer]
Component ratio (parts by weight)
Vinyl chloride resin (degree of polymerization 1100) 100
DOP33
Epoxidized soybean oil 2
Calcium carbonate 10
Stabilizer 3
Pigment (titanium white) 5
[0029]
[Production of luminescent pigment-containing synthetic resin layer]
Component ratio (parts by weight)
Vinyl chloride resin (degree of polymerization 1100) 100
DOP33
Epoxidized soybean oil 2
Stabilizer 3
Nemoto Special Chemical Co., Ltd. “N-Night” (Note 1) 58
(Note 1) One of "N-Nightlight" manufactured by Nemoto Special Chemical Co., Ltd. It is composed of raw materials consisting of 0.94 mol of strontium carbonate, 1.0 mol of alumina, 0.005 mol of europium and 0.025 mol of dysprosium. manufactured europium activated - dysprosium co-activated strontium aluminate _{(SrAl 2 O 4: Eu,} Dy) was used.
[0030]
[Production of transparent protective layer]
Component ratio (parts by weight)
Vinyl chloride resin (degree of polymerization 1100) 100
DOP30
Epoxidized soybean oil 2
Stabilizer 3
[0031]
The composition for the base synthetic resin layer was kneaded with an intensive mixer, rolled into a sheet having a thickness of 1.7 mm by extrusion, and bonded to a nonwoven fabric as a backing material to which an adhesive was applied. The temperature of the extruder cylinder in this step was 160 to 190 ° C., and the lamination pressure was 5 to 10 kg / cm ² .
[0032]
Next, the composition for a white synthetic resin layer was rolled to a thickness of 0.2 mm with a calender roll, and laminated on the upper surface of the base synthetic resin layer in the same manner as described above. The temperature of the calender roll in this step was 170 to 180 ° C., and the lamination pressure was 5 to 10 kg / cm ² .
[0033]
Subsequently, the composition for a luminescent pigment-containing synthetic resin layer was rolled to a thickness of 0.4 mm in the same manner as the method for rolling the composition for a white synthetic resin layer, and laminated on the white synthetic resin layer in the same manner as above. . The temperature of the calender roll in this step was 165 to 175 ° C., and the lamination pressure was 5 to 10 kg / cm ² .
[0034]
Finally, the composition for a transparent protective layer was rolled to a thickness of 0.1 mm and laminated on the surface of the luminescent pigment-containing synthetic resin layer. The temperature of the calender roll in this step was 170 to 180 ° C., and the lamination pressure was 5 to 10 kg / cm ² .
[0035]
According to the method described above, a backing material having a thickness of 0.1 mm, a base synthetic resin layer having a thickness of 1.7 mm, a white synthetic resin layer having a thickness of 0.2 mm, a luminescent pigment-containing synthetic resin layer having a thickness of 0.4 mm, And a flooring material having a total thickness of 2.5 mm with a transparent protective layer having a thickness of 0.1 mm was produced. The peel strength of each layer of the flooring material is about 2.5 kg / 5 cm or more between the backing material and the base synthetic resin layer, and about 5.0 kg / 5 cm or more between the base synthetic resin layer and the white resin layer. The distance between the luminescent pigment-containing synthetic resin layers was about 5.0 kg / 5 cm or more, and the distance between the luminescent pigment-containing synthetic resin layers and the transparent protective layer was about 4.0 kg / 5 cm or more.
[0036]
Embodiment 2
"N-Nightlight" manufactured by Nemoto Special Chemical Co., Ltd. used in Example 1 was produced with a raw material mixture of 0.92 mol of strontium carbonate, 1.0 mol of alumina, 0.005 mol of europium, and 0.035 mol of dysprosium. A luminescent flooring material was manufactured in the same procedure as in Example 1 except that the europium-activated and dysprosium-co-activated strontium aluminate (SrAl ₂ O ₄ : Eu, Dy) was used.
[0037]
Embodiment 3
"N-Nightlight" manufactured by Nemoto Special Chemical Co., Ltd. used in Example 1 was replaced with calcium carbonate 0. Luminescent flooring in the same procedure as in Example 1 except that alumina, europium as an activator, and europium activated-neodymium co-activated calcium aluminate (CaAl ₂ O ₄ : Eu, Nd) produced from neodymium as an activator are used. Was manufactured.
[0038]
[Comparative example]
A luminescent composite flooring material was manufactured in the same procedure as in Example 1 except that “N-Nightlight” manufactured by Nemoto Special Chemical Co., Ltd. used in Example 1 was replaced with a zinc sulfide / copper (ZnS: Cu) pigment.
[0039]
[Example of construction test]
After laying a luminescent flooring produced in Examples 1, 2, and 3 tiled cut into tested building floor 90cm square was irradiated 5 min light 1000 lux conventional light source D _65, 10 results average afterglow luminance of the three samples in minutes and after 60 minutes was measured to be respectively 30mcd / ^{m 2,} and 6mcd / ^{m 2,.} The time required for the afterglow luminance to attenuate to 0.3 mcd / m ² was 2,000 minutes or more.
[0040]
On the other hand, when the result of the same test using the comparative example was compared with that of the example, the performance was 1/30 to 1/40 of the example.
[0041]
【The invention's effect】
As described above, the luminescent flooring material of the present invention has various physical properties as a flooring material, and has a high residual property even after the external stimulus such as sunlight or an electric light is stopped and the light is completely darkened. It emits light at a high luminance for a long time, so it has excellent effects for emergency evacuation guidance in the event of a disaster such as an earthquake or fire.

Claims (1)

Backing material, base synthetic resin layer, colored synthetic resin layer, luminescent pigment-containing synthetic resin layer, and a transparent protective layer is laminated and integrated luminescent flooring,
  The thickness of the base synthetic resin layer is 1.0 to 5.0 mm, the thickness of the colored synthetic resin layer is 0.1 to 0.3 mm, the thickness of the luminescent pigment-containing synthetic resin layer is 0.1 to 3 mm, And the thickness of the transparent protective layer is in the range of 0.1 to 0.3 mm,
  The luminescent pigment has a general formula: MAl ₂ O ₄ : X _K ・ Y _L ・ Z _P [Where M is a metal selected from the group consisting of calcium, barium, strontium, magnesium, and mixtures thereof] _; x is an activator consisting of europium; Y and Z are activators selected from the group consisting of lanthanum series elements and manganese, tin and bismuth; K is 0.001 to 10 mol% to M , L represents 0 to 10 in mol% to M, and P represents 0 to 10 in mol% to M. A phosphorescent phosphorescent aluminate represented by the formula:
  The luminescent floor material, wherein the colored synthetic resin layer is white.