JP2012206496A - Luminous sheet and luminous tape - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a luminous sheet and luminous tape, which have increased light-emitting luminance cpmpared to a conventional such sheet, and emit light more clearly and uniformly without unevenness by reflecting with a reflecting material to create a scattered light.SOLUTION: The luminous sheet and tape comprises providing a transparent resin layer, a luminous adhesive layer containing an dhesive material and a luminous material only or both luminous material and coloring material, and a reflecting layer in this order. It is preferable that the adhesive material is an acrylic resin or silicone-based resin, and the reflecting layer comprises either a resin layer containing at least either one of white granular powders comprising barium sulfate and calcium carbonate or a metal vapor deposition layer, or a combination thereof. A substrate layer may be provided at a reflecting layer side, and an adhesion layer and a peeling layer may be provided.

Description

  The present invention is a phosphorescent sheet comprising a transparent resin layer, a phosphorescent adhesive layer containing a phosphorescent material in an adhesive material, and a reflective layer in this order, and a coating containing a conventional phosphorescent material is applied. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a luminous sheet and a luminous tape characterized in that the luminous brightness is increased as compared with a luminous sheet and the like, and the light is emitted more clearly.

  2. Description of the Related Art Conventionally, a phosphorescent sheet in which a coating film containing a phosphorescent pigment is applied or a concealing layer containing titanium oxide is provided on the back side of a sheet obtained by kneading a phosphorescent pigment in a synthetic resin is widely known. For example, Patent Document 1 discloses a phosphorescent sheet in which a coating material containing phosphorescent powder is applied to one side of a plastic film, and a concealing layer is provided on the coating layer of the coating material. However, no phosphorescent sheet has been found in which a reflective layer is provided on one side of a phosphorescent adhesive layer containing a phosphorescent pigment in the adhesive material.

  In the conventional phosphorescent sheet, a concealing layer containing titanium oxide is lined on one side of a plastic film or the like coated with a paint containing a phosphorescent pigment as described above. The purpose of lining the concealing layer was to conceal the surface of the base material or to provide the base material with anticorrosion and rust prevention properties. In many cases, an adhesive is interposed between the sheet obtained by kneading the phosphorescent pigment in the synthetic resin and the concealing layer containing titanium oxide. Furthermore, the ratio of the phosphorescent powder to the resin content in the paint of Patent Document 1 is 10 to 80, preferably 20 to 60, based on the resin 100 in terms of the solid content weight ratio. When the ratio of the phosphorescent powder is increased, the light entering / exiting path of the coating film is closed and the translucency is hindered.

JP 2003-276108 A

  In order to eliminate the drawbacks and obtain a luminous sheet and a luminous tape excellent in luminous brightness and vividness, the present inventors have intensively studied, as a result, instead of a paint containing the luminous powder, an adhesive, etc. By using a phosphorescent adhesive layer containing a phosphorescent material as a light-sensitive material and providing a reflective layer containing barium sulfate, calcium carbonate, etc. in this phosphorescent adhesive layer, the light emission path is closed and the light-transmitting property is closed when the concentration of the phosphorescent material increases. The present inventors have arrived at the present invention by finding out that the light transmission impeding factor to be hindered is improved and improving the light emission luminance, and the main problem of the present invention is that the light emission luminance is improved and unevenness compared with the conventional product. Another object of the present invention is to provide a phosphorescent sheet and a phosphorescent tape that emit light variably and emit a variety of light by overlapping a plurality of phosphorescent adhesive layers without an adhesive.

  In order to solve the above problems, the present invention includes a transparent resin layer, a phosphorescent adhesive layer containing a phosphorescent material alone or a phosphorescent material and a coloring material in an adhesive material, and a reflective layer in this order. It is set as the luminous sheet | seat characterized by becoming (Claim 1).

  In order to solve the above problems, the present invention provides a transparent resin layer, a phosphorescent adhesive layer containing a phosphorescent material alone or both a phosphorescent material and a coloring material, a reflective layer, and a base material. Layers are provided in this order to provide a luminous sheet characterized in that (claim 2).

  Moreover, in order to solve the said subject, this invention sets it as the said luminous sheet | seat characterized by providing the adhesive layer and the peeling layer in this order in the said reflective layer side or the base material layer side. (Claim 3).

  Moreover, in order to solve the said subject, it is preferable to set this invention as the said luminous sheet | seat characterized by providing a peeling layer instead of the said transparent resin layer (Claim 4).

  Moreover, in order to solve the said subject, it is preferable that this invention set it as the said luminous luminous sheet | seat characterized by the said luminous luminous adhesive layer laminating | stacking a several luminous luminous adhesive layer (Claim 5). ).

  In order to solve the above-mentioned problem, the present invention is preferably the luminous sheet, wherein the adhesive material is made of an acrylic resin or a silicone resin (Claim 6). .

  In order to solve the above-mentioned problems, the present invention provides a resin layer and a metal vapor deposition material layer, wherein the reflective layer contains at least one of white powder particles composed of barium sulfate and calcium carbonate. It is preferable that the phosphorescent sheet is characterized by comprising any one of the above or a combination thereof (claim 7).

  Moreover, in order to solve the said subject, it is preferable that this invention is set as the luminous tape characterized by slitting the said luminous sheet | seat in strip | belt shape (Claim 8).

  Since the phosphorescent sheet and phosphorescent tape according to the present invention are configured as described above, the luminance is increased compared to the conventional phosphorescent sheet, and the luminous brightness is not only emitted more clearly but also reflected and scattered by the reflecting material. There is an effect that light is emitted and there is no unevenness and light is emitted uniformly. Multilayer phosphorescent sheets and multilayer phosphorescent tapes can be easily manufactured by simply laminating multiple layers of phosphorescent adhesive layers without using adhesives, and changes by changing the type of phosphorescent pigment and colorant for each layer A wide variety of color effects can be obtained. An economically advantageous effect can be expected by using a reflective layer containing barium sulfate or calcium carbonate, which is cheaper, instead of the conventional concealing layer containing expensive titanium oxide. Moreover, since the reflective layer containing barium sulfate or calcium carbonate is easily compatible with the pressure-sensitive adhesive, it is difficult to peel off and has an excellent dimensional stability. By using a transparent resin layer having a lower peel strength than the reflective layer containing barium sulfate or calcium carbonate as the release layer, the phosphorescent adhesive layer surface from which the transparent resin layer has been peeled is attached to the glass surface such as a show window from the outside. It is also possible to visually recognize black light from the inside of the glass surface.

It is explanatory drawing which shows the structure of the coloring light accumulation molding which concerns on 1st Embodiment. It is explanatory drawing which shows the structure of the coloring light storage molded object which concerns on 2nd Embodiment. It is explanatory drawing which shows the structure of the coloring light storage molded object which concerns on 3rd Embodiment. It is explanatory drawing which shows the structure of the coloring light accumulation molding which concerns on 4th Embodiment. It is explanatory drawing which shows the structure of the coloring light accumulation molding which concerns on 5th Embodiment.

  A mode for carrying out the present invention (hereinafter referred to as “embodiment”) will be described in detail below with reference to the drawings. However, the present invention is not limited to such an embodiment.

  The phosphorescent sheet 1 according to the first embodiment of the present invention includes the inventions according to claims 1, 6, and 7, and as shown in FIG. 1, the phosphorescent material alone is used for the transparent resin layer 11 and the adhesive material. Alternatively, the phosphorescent adhesive layer 12 containing both the phosphorescent material and the coloring material and the reflective layer 13 are provided in this order.

  The transparent resin layer 11 is not particularly limited as long as it is a synthetic resin film or sheet having transparency. For example, a polypropylene (PP) film, a biaxially stretched polypropylene (OPP) film, and a polyethylene (PE) Film, General-purpose polystyrene (GP-PS) film, Impact-resistant polystyrene (HI-PS) film, Biaxially stretched polystyrene (OPS) film, Polyester (PET) film, Polycarbonate (PC) film, Polyvinyl alcohol (PVA) film It can be selected from polyvinyl chloride (PVC) film, ionomer film, cellulosic plastic film, thermoplastic elastomer film and the like according to the purpose of use. Further, in addition to the single film, a multilayer film bonded by dry lamination or sand lamination through a co-extruded film or an adhesive resin layer may be used. The transparent resin layer 11 serves as a protective film and is effective for outdoor specifications.

  The adhesive material constituting the phosphorescent adhesive layer 12 is not particularly limited as long as it has translucency to transmit ultraviolet rays or the like, but depending on the type of polymer used as a raw material, a rubber adhesive, an acrylic adhesive, Silicone pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, hot-melt pressure-sensitive adhesives, and the like are included, and can be appropriately selected according to the purpose of use. As the rubber-based pressure-sensitive adhesive, natural rubber, synthetic rubber, and other elastomers are used. When the adhesive strength is weak, a tackifier may be added as necessary.

  Acrylic pressure-sensitive adhesives are made of acrylic acid ester copolymers. Usually, this polymer is copolymerized with a functional group-containing monomer such as acrylic acid or hydroxyethyl acrylate that can be cross-linked with a cross-linking agent. It is used by adding a cross-linking agent such as three-dimensional. In addition, since the acrylic polymer has high polarity, it is difficult to adhere to a low-polar adherend such as polyolefin, and it is preferable to modify the acrylic polymer by adding a tackifier. There are solvent type and emulsion type.

  Silicone pressure-sensitive adhesives are widely used in a temperature range because they are excellent in cold resistance, heat resistance, chemical resistance and weather resistance. However, silicone resin is used as a tackifier because silicone itself is poor in tackiness. It is possible to obtain the necessary adhesiveness by changing the composition ratio of silicone rubber and silicone resin. In order to improve heat resistance, it is preferable to use a crosslinking agent such as benzoyl peroxide. A urethane-based adhesive is made of a urethane resin and has excellent removability and low odor, skin irritation, and moisture permeability, but is relatively weak in tackiness and tackiness. The pressure-sensitive adhesive material constituting the phosphorescent pressure-sensitive adhesive layer of the present invention is preferably an acrylic pressure-sensitive adhesive or a silicone pressure-sensitive adhesive because it is excellent in translucency and pressure-sensitive adhesiveness.

  The method for forming the phosphorescent adhesive layer containing the phosphorescent material alone or both the phosphorescent material and the coloring material in the adhesive material is not particularly limited. For example, the polymer or phosphorescent pigment as a raw material of the adhesive material Phosphorescent adhesive obtained by stirring and mixing phosphorescent materials such as other colorants, organic solvents, crosslinking agents, and tackifiers, antioxidants, softeners, dispersants, thickeners, etc., if necessary The solution is applied on a transparent plastic film and then dried to obtain a phosphorescent adhesive layer. In the case of an emulsion-type pressure-sensitive adhesive, it may be used in combination with water or an organic solvent instead of the organic solvent. For example, photopolymerizable prepolymers such as polyester acrylate, polyurethane acrylate, and epoxy acrylate, photopolymerizable compounds such as acrylates, etc. are added within the range that does not impair the required properties. May be. An ionizing radiation curable resin that is cross-linked by electron beam irradiation may be used.

  Examples of the coloring material may include solvent-soluble pigments, organic pigments, and dyes. The coloring material can be used within the range of the addition amount that maintains translucency such as an inorganic pigment made of fine particles in addition to the transparent coloring material, and the fluorescent coloring material is particularly preferable since it is clear and improves visibility. Moreover, the kind of phosphorescent material is not specifically limited, A commercially available phosphorescent material can be used, However, It is preferable to use the phosphorescent material which exhibits as high luminance light emission as possible, and has water resistance.

  The blending ratio of the phosphorescent material to the adhesive material of the phosphorescent sheet of the present invention is 50 to 300, preferably 90 to 200, based on the adhesive material 100 in terms of solid mass ratio. The blending ratio of the color pigment is 0.5 to 5.0, preferably 2.0 to 3.0 with respect to the adhesive material 100 with an organic fluorescent dye or an inorganic dye such as cobalt. This is because if the blending ratio of the color pigment is less than 0.5, the coloring effect is not exhibited, and if it exceeds 5.0, the light emission luminance may decrease. The emission luminance has a strong correlation with the basis weight of the phosphorescent material, and the luminance is increased when the proportion of the phosphorescent material is increased with respect to the adhesive material. When the ratio of the phosphorescent material exceeds a certain limit, the light entering / exiting path is closed, the translucency is hindered, and the light emission luminance tends to decrease. This phenomenon is particularly noticeable in a conventional type phosphorescent sheet in which phosphorescent paint is applied or kneaded into an adhesive material. In the phosphorescent sheet of the present invention, the increase in emission luminance is remarkably increased as compared with the conventional phosphorescent sheet. This phenomenon is considered below.

  In the conventional type phosphorescent sheet, in the vicinity of the upper limit concentration of phosphorescent powder, the phosphorescent powder in the dry paint or resin is fixed in close contact or in close contact with the vehicle or resin, so that the light entering / exiting path is closed and translucency is improved. It becomes an obstructive factor, and only the phosphorescent pigment on the surface of the phosphorescent sheet emits light, and the inner phosphorescent pigment does not emit light, or even if it emits light, it is blocked by the phosphorescent pigment on the surface and is not emitted to the outside, so the emission luminance is high Does not improve. On the other hand, the phosphorescent sheet of the present application is dispersed in a state where the phosphorescent pigment particles in the phosphorescent adhesive layer composed of the adhesive having deformation fluidity are separated from each other via the adhesive. Light entering and exiting the adhesive filled in the gaps between the particles is formed, light rays such as ultraviolet rays are transmitted through the entrance and exit light path, and light emitted by the ultraviolet rays hitting the phosphorescent pigment scattered inside the phosphorescent adhesive layer Is reflected on the reflection layer, and is emitted to the outside again through the input / output light path, so that it is presumed that the emission luminance increases.

  Here, the phosphorescent material used in the embodiment of the present invention is stimulated by some energy, emits the sucked energy as visible light or light having a wavelength close to that, such as ultraviolet light and infrared light, and continues even after the stimulation is stopped. A phosphorescent substance or a fluorescent substance having the property of exhibiting this phenomenon, including a phosphorescent pigment and a fluorescent pigment. As the former phosphorescent substance, for example, a substance obtained by adding a small amount of copper as an activator to a crystal of zinc sulfide and cadmium sulfide (cadmium sulfide has a safety problem and is not currently used) depends on its composition. Light emitting red, zinc sulfide added with a small amount of copper as activator, green light emitting, aluminate added with europium (Eu) as activator, or rare earth as coactivator Those added with elements or transition metals emit green or blue light.

  In addition, the fluorescent substance with respect to the phosphorescent substance is an optical effect that occurs when a certain substance is irradiated with light and emits light of other wavelengths, that is, visible light when ultraviolet light hits a liquid or solid. Fluorescent substances such as calcium, barium, magnesium, cadmium (cadmium is a safety issue and is not currently used), sulfides, silicates, phosphates, tungstic acid A substance that emits fluorescence, mainly composed of salt. In addition, there are organic and inorganic fluorescent materials, and some inorganic materials have so-called phosphorescent properties that emit fluorescence even after ultraviolet irradiation is stopped. Are also included in the present invention.

In recent years, for (Sr, M ₁ ) O— (Mg, M ₂ ) O— (Si, Ge) O ₂ based fluorescent matrix (M ₁ = Ca, Sr, Ba, M ₂ = Be, Zn, Cd) Ln (Sc, Y, La, Ce, Pr, Nd, Sm, Cd, Tb, Dy, Ho, Er, Tm, Yb, Lu, In, Bi, Sn ) And containing a halogen element (a kind of element selected from F, Cl, Br, and I), an Eu-activated silicate phosphorescent phosphor emitting blue to green light is disclosed. (See Japanese Patent Nos. 3257742 and 3257947). This phosphorescent phosphor is also included in the present invention.

  The reflective layer 13 is not limited as long as it has a reflective function, but for example, a synthetic resin film or sheet in which a reflective material is dispersed and mixed is preferable. The material of this reflector is not particularly limited, but for example, barium sulfate, calcium carbonate, magnesium carbonate, titanium oxide, mica, talc, kaolin, clay, celite, perlite, barita, silica, silica sand, dolomite, Any one or two of white powder and granule made of limestone, gypsum, hollow balloon, aluminum, aluminum hydroxide, metal, various shells, glass, zirconium oxide, antimony trioxide, molybdenum dioxide and pearl What combined the above is preferable. In the first embodiment, the reflective layer containing barium sulfate or calcium carbonate is particularly preferable because it is easy to become familiar with the pressure-sensitive adhesive, and is difficult to peel off and is excellent in heat dimensional stability. You may print or apply | coat to the base material 14, or apply | coat or apply | coat the ink or coating material which these reflectors disperse-mixed, or you may form in the film or sheet | seat which disperse-mixed the said powder or the granular material in the synthetic resin. By providing such a reflection layer, not only the luminance is improved and the coloring becomes clear, but also the light is reflected by the reflecting material to become scattered light, and the light is evenly emitted without unevenness. Further, it may be combined with a metal vapor-deposited layer in which a metal such as aluminum, chromium, zinc, gold, silver, platinum or nickel is vapor-deposited on a thermoplastic resin film or a resin layer in which the white powder particles are dispersed and mixed. .

  Next, the phosphorescent sheet 1 according to the second embodiment of the present invention includes the inventions of claims 2, 6 and 7, and as shown in FIG. 2, the phosphorescent sheet according to the first embodiment of the present invention. Except for providing the base material layer 14 on the reflective layer side of the light-sensitive sheet 1, it is the same as the phosphorescent sheet 1 according to the first embodiment. The base material layer 14 includes a transparent base material and an opaque base material, and is not particularly limited. For example, a thermoplastic resin such as polypropylene, polyethylene, or polyethylene terephthalate, or a metal plate such as aluminum or stainless steel, Other known tape base materials are widely included, such as woven fabric, nonwoven fabric, paper, and synthetic resin processed fabric in which soft vinyl chloride sol is coated on both sides of a synthetic fiber fabric.

  Next, the phosphorescent sheet 1 according to the third embodiment of the present invention includes the inventions of claims 3, 6 and 7, and as shown in FIG. 3, the reflective layer 13 side or the base material layer 14 side. Is the same as the luminous sheet 1 according to the first embodiment except that the adhesive layer 15 and the release layer 16 are provided in this order. Since the adhesive layer 15 is the same as the adhesive material constituting the phosphorescent adhesive layer 12 in the first embodiment of the present invention, description thereof is omitted. The release layer 16 can be a commercially available release paper in which a release agent such as silicone is coated on the paper. For example, a polyolefin film such as polyethylene or polypropylene or a plastic film with a release agent applied thereto can be used. Can be used.

  The luminous sheet according to the fourth embodiment of the present invention includes the inventions of claims 4, 6 and 7, except that a release layer is provided in place of the transparent resin layer as shown in FIG. This is the same as the luminous sheet 1 according to the first embodiment. The release layer is the same as that used in the third embodiment. This release layer also includes a release resin provided on one side of the transparent resin layer according to the first embodiment. A phosphorescent sheet and a phosphorescent tape in which the surface provided with the release agent is bonded to the phosphorescent adhesive layer side are also included in the present invention.

  Next, the phosphorescent sheet 1 according to the fifth embodiment of the present invention includes the inventions of claims 5, 6, and 7, and as shown in FIG. 4, the phosphorescent adhesive layer 12 includes a plurality of phosphorescent adhesives. Except for laminating the layer 12 to form the multilayer phosphorescent adhesive layer 12a, it is the same as the phosphorescent sheet 1 according to the first embodiment. In the multi-layer phosphorescent adhesive layer 12a, each layer may be composed of the same composition, or may be composed of different composition.

  Next, a phosphorescent tape according to a sixth embodiment of the present invention includes the invention according to claim 8 and is formed by slitting the phosphorescent sheet into a strip shape. The production method of the phosphorescent tape according to the present embodiment is not particularly limited, but, for example, the wide phosphorescent sheet 1 is wound around a hollow paper tube, and the paper tube and the paper tube are cut at a suitable interval with a cutter. Obtained by cutting.

  Although the thickness of each layer which comprises the luminous sheet | seat of this invention is not specifically limited, The transparent resin layer 11 is 1-200 micrometers, Preferably it is 20-90 micrometers. This is because if the thickness is less than 1 μm, it is not sufficient to protect the phosphorescent layer and the bonding process becomes difficult, and if it exceeds 200 μm, the translucency may be hindered.

  The phosphorescent adhesive layer 12 is 50 to 2000 μm, preferably 100 to 1000 μm. If the thickness is less than 50 μm, the target luminance may not be obtained, and if it exceeds 2000 μm, the cost increases. Therefore, it is preferable to select an optimum thickness in consideration of the manufacturing cost.

  The reflective layer 13 is 10-300 micrometers, Preferably, it is 30-200 micrometers. If the thickness is less than 10 μm, the reflection function may not be sufficiently exhibited, and it is preferable to select the thickness within a range in which the concealing property such as the hue of the base material layer is maintained.

  The base material layer 14 is generally 20 to 3000 μm, preferably 50 to 2000 μm. The pressure-sensitive adhesive layer 15 is 10 to 200 μm, preferably 20 to 150 μm. The release layer 16 has a thickness of 5 to 100 μm, preferably 10 to 80 μm. Each of these layers is not particularly limited as long as it basically has a thickness suitable for workability and purpose of use.

  Although the manufacturing method of the luminous sheet of the present invention is not particularly limited, for example, it is obtained by stirring and mixing a compounding agent such as a luminous pigment, an adhesive resin, a crosslinking agent, an organic solvent, etc. in a container. The phosphorescent adhesive solution is applied onto a transparent film that becomes a transparent resin layer, and is heat-dried to obtain a phosphorescent adhesive sheet. The phosphorescent adhesive layer side of this phosphorescent adhesive sheet is bonded to a sheet serving as a reflective layer and a base material layer, thereby storing the light. A sheet is obtained. In order to attach the sheet serving as the reflective layer and the base material layer to the phosphorescent adhesive layer, the adherend is pressed and bonded with two pressure rolls. When heat-crosslinking is performed like a silicone-based adhesive resin depending on the type of the cross-linking agent, it is cooled after being heated to 100 to 180 ° C.

  The phosphorescent adhesive solution can be applied onto a long film by a known coating technique using a coater. The coater used in the present invention is not particularly limited, and various known coaters can be used. Examples include knife coaters, reverse roll coaters, direct roll coaters, gravure coaters, die coaters, bar coaters, lip coaters, and rotary screens. The knife coater is most widely used together with the roll coater and is simple in design and low in cost. On the other hand, there is a drawback that a streak-like scratch is generated, but a thick coating can be obtained by one pull. Since the roll coater can accurately control the roll gap, it is used for obtaining a coating film having an accurate thickness. In order to obtain the multi-layered luminous adhesive layer according to the invention of claim 5, the coating is repeated a plurality of times. It is also possible to obtain a multi-layered phosphorescent adhesive layer in one step by providing supply heads for the phosphorescent adhesive solution at a plurality of locations. Furthermore, if a phosphorescent adhesive layer containing different phosphorescent materials and color pigments is provided for each layer, a phosphorescent sheet exhibiting more various color effects can be obtained.

  In order to attach the sheet to be the reflective layer and base material layer to the phosphorescent adhesive layer, various laminators are used, and the adherend surface is transferred along a heated rotating roll while the adherend surface is near the melting point of the resin with an infrared heater or the like. After being heated, the sheet is passed between two pressure-bonding rolls and wound after being cooled. Those that cannot be fused are bonded using an adhesive.

  In the case of a rubber-based adhesive or a hot-melt adhesive, it can be produced by a calendar coating method or an extruder method. For example, in the calendar coating method, a composition containing a phosphorescent material in an adhesive material such as natural rubber, petroleum resin, calcium carbonate, or process oil is kneaded with a Banbury mixer or kneader, and then manufactured with a three-calendar or reverse L-calender. It is formed into a film and laminated with a film or sheet to be a transparent resin layer, a reflective layer, a base material layer, etc. by topping or using a laminator.

  By the extruder method, the composition is kneaded by an extruder to produce a phosphorescent adhesive material, and this phosphorescent adhesive material is formed into a film by a calendar method or a T-die method, and a transparent resin layer, a reflective layer, a base material layer, The desired phosphorescent sheet is obtained by laminating the film or sheet. According to Japanese Patent Laid-Open No. 11-216764, there is disclosed a method for producing a rubber adhesive in an extruder having a main screw and a planetary screw that rotates and revolves around the main screw.

  The phosphorescent sheet and the phosphorescent tape according to the present invention will be described more specifically with reference to examples and comparative examples below, but the present invention is not limited thereto by any means.

Example 1
As a phosphorescent pigment, 50 parts by weight of Chrysanthemum manufactured by Ryokan Co., Ltd., 50 parts by weight of acrylic resin (SK Dyne 1717 manufactured by Soken Chemical Co., Ltd.) as an adhesive resin, 2 parts by mass of a crosslinking agent (L45 manufactured by Soken Chemical Co., Ltd.), organic A transparent polyethylene terephthalate (hereinafter referred to as “PET”) film (manufactured by Toray Industries, Inc.) is a phosphorescent adhesive solution obtained by stirring and mixing 30 parts by mass of methyl ethyl ketone (MEK) as a solvent in a container with a mixer. (Lummirror (registered trademark) T60 # 50) and dried by heating to obtain a phosphorescent adhesive sheet having a thickness of 100 μm. Next, the step of applying and drying the phosphorescent adhesive solution to the phosphorescent adhesive sheet was repeated to laminate a total of seven phosphorescent adhesive layers 12 to obtain a multilayer phosphorescent adhesive layer 12a having a total thickness of 700 μm. . A multilayer phosphorescent adhesive layer 12a according to the fifth embodiment is formed by laminating a 100 μm-thick barium sulfate-containing sheet (UX201-188 manufactured by Teijin DuPont) as the reflective layer 13 on the multilayer phosphorescent adhesive layer 12a side. A phosphorescent sheet 1 was obtained. The obtained phosphorescent sheet 1 was irradiated with an ordinary light source fluorescent lamp D65 at an excitation illuminance of 200 lux for 20 minutes, and the afterglow brightness after 20 minutes in the dark was 214 mcd / m ² and emitted uniformly. Further, when this phosphorescent sheet was left in water at room temperature for 1 month, no abnormality was observed in its appearance, and the afterglow luminance under the same conditions was 212 mcd / m ² . There was no deterioration in phosphorescent performance.

(Example 2)
In Example 1, instead of the transparent PET film (Lumirror (registered trademark) T60 # 50 manufactured by Toray Industries, Inc.) serving as the transparent resin layer 11, the transparent PET film (Lumirror (registered trademark) T60 manufactured by Toray Industries, Inc.) serving as the release layer 16 is used. Except using the film which formed the thin film of the silicone type release agent for # 50), the luminous sheet 1 which consists of the multilayer luminous storage adhesive layer 12a which concerns on 4th and 5th embodiment was obtained like Example 1. The obtained phosphorescent sheet 1 was irradiated for 20 minutes at an excitation illuminance of 200 lux with the ordinary light source fluorescent lamp D65, and the afterglow luminance after 20 minutes in the dark was 210 mcd / m ² , and emitted uniformly. Further, when this phosphorescent sheet was left in water at room temperature for 1 month, no abnormality was observed in its appearance, and the afterglow luminance under the same conditions was 208 mcd / m ² . There was no deterioration in phosphorescent performance.

(Example 3)
In Example 1, 67 parts by mass of Chrysbright manufactured by Ryojo Co., Ltd. as the phosphorescent pigment, 33 parts by mass of silicone resin (SD4580 manufactured by Toray Dow Corning) as the adhesive resin, and a crosslinking agent (SRX212 manufactured by Toray Dow Corning) 5 parts of the phosphorescent adhesive layer are laminated on the phosphorescent adhesive sheet obtained by using 1 part by mass of methyl ethyl ketone (MEK) as an organic solvent and 30 parts by mass of the organic solvent, and the multilayer phosphorescent adhesive layer 12a having a total thickness of 500 μm in total. The multilayer phosphorescent adhesive layer 12a according to the fourth embodiment is obtained in the same manner as in Example 1 except that a 188 μm-thick calcium carbonate-containing sheet is attached as the reflective layer 13 to the multilayer phosphorescent adhesive layer 12a. A phosphorescent sheet 1 was obtained. The afterglow brightness | luminance which measured the obtained luminous sheet 1 on the same conditions as Example 1 was 220 mcd / m < ² >, and emitted light uniformly. Furthermore, when this luminous sheet was left in water for 1 month under the same conditions as in Example 1, no abnormality was observed in the appearance, and the afterglow luminance was 217 mcd / m ² . There was no deterioration in phosphorescent performance.

Example 4
A laminated composite of polyethylene core material with a total thickness of 3 mm and aluminum (Alpolic (registered trademark) manufactured by Mitsubishi Plastics) to be the base material layer 14 is pasted on the luminous sheet 1 obtained in Example 1 and Example 2. In addition, the luminous sheet 1 according to the second embodiment was obtained. When the afterglow brightness | luminance after irradiating the obtained luminous sheet | seat 1 for 20 minutes by excitation illuminance 200 lux with the regular light source fluorescent lamp D65 was measured, it is the same as the afterglow brightness | luminance of the luminous sheet | seat 1 of Example 1 and Example 2. It was confirmed that there was. The afterglow brightness after standing in water at room temperature for 1 month was the same. There was no deterioration in phosphorescent performance.

(Example 5)
An acrylic adhesive (manufactured by Soken Chemical Co., Ltd.) is applied to a 25 μm PET film (Toray Film Processing Co., Ltd., Therapy (registered trademark) WZ) that becomes the release layer 16 on the phosphorescent sheet 1 obtained in Example 1 and Example 2. The applied release material was bonded to obtain luminous sheet 1 according to the third embodiment. When the afterglow brightness | luminance after irradiating the obtained luminous sheet | seat 1 for 20 minutes by excitation illuminance 200 lux with the regular light source fluorescent lamp D65 was measured, it is the same as the afterglow brightness | luminance of the luminous sheet | seat 1 of Example 1 and Example 2. It was confirmed that there was. The afterglow brightness after standing in water at room temperature for 1 month was the same. There was no deterioration in phosphorescent performance.

(Comparative Example 1)
As a phosphorescent pigment, 55 parts by weight of Chrysanthemum manufactured by Ryojo Co., Ltd. and 45 parts by mass of translucent urethane resin (Vainsol U-250, manufactured by Yushi Kogyo Co., Ltd.) are heated and mixed in a kneader to press-mold and thicken. A phosphorescent molded sheet having a thickness of 300 μm was obtained. A 188 μm-thick titanium oxide-containing sheet (Lumirror (registered trademark) E20 manufactured by Toray Industries, Inc.) was bonded to the phosphorescent molded sheet with an adhesive to obtain a phosphorescent sheet of Comparative Example 1. The afterglow brightness | luminance which measured the phosphorescence sheet | seat of the obtained comparative example 1 on the same conditions as the said Example was 56 mcd / m < ² >, and the light emission degree was uneven and nonuniform. Furthermore, when this phosphorescent sheet was left in water for 1 month under the same conditions as in the examples, peeling of the sheet was observed and the afterglow luminance was 48 mcd / m ² .

The ratio (parts by mass) of the phosphorescent pigment to the adhesive material of the phosphorescent sheet according to Examples 1 and 2 and Comparative Example 1 is 96 for the adhesive material (adhesive resin and crosslinking agent) 100, respectively. The afterglow luminances (mcd / m ² ) measured under the same conditions were 214, 220, and 56, respectively. From the above results, the phosphorescent sheet of the present application is strong as a result of the light entering and exiting light path being formed even when the phosphorescent pigment has a high concentration of 90 to 200 mass ratio with respect to the adhesive material (adhesive resin and crosslinking agent) 100. It was demonstrated that afterglow brightness was obtained. On the other hand, the phosphorescent sheet of Comparative Example 1 in which the phosphorescent pigment is kneaded into the resin of the conventional method corresponds to an intermediate level between the phosphorescent pigment concentration of Example 1 and Example 2, but the afterglow luminance is implemented. It was confirmed that it was only a quarter of the example.

  Moreover, the luminous pigment density | concentration of the luminous sheet | seat of Example 1, 2 is about 49 wt% and about 66 wt%, respectively. Under the condition of irradiation for 20 minutes at an excitation illuminance of 200 lux with the ordinary light source fluorescent lamp D65, the thickness and concentration of the phosphorescent adhesive layer can be selected within a pigment concentration range of 67 wt% or less. On the other hand, at a high pigment concentration exceeding 67 wt%, the afterglow brightness was further improved when the irradiation time was extended to 2 hours. In other words, the light storage capacity does not become full after irradiation for 20 minutes. This is presumed to be because the incoming / outgoing light path is hindered when the pigment concentration increases.

  The phosphorescent sheet of the present invention not only emits light more clearly than the conventional phosphorescent sheet by providing a phosphorescent adhesive layer containing a phosphorescent material and a reflective layer in the adhesive material. Provided is a phosphorescent sheet that is reflected by a reflecting material to become scattered light and emits light uniformly and without unevenness. Moreover, it is extremely useful economically because of cost reduction.

  1: phosphorescent sheet, 11: transparent resin layer, 12: phosphorescent adhesive layer, 12a: multilayer phosphorescent adhesive layer, 13: reflective layer, 14: base material layer, 15: adhesive layer, 16: release layer

Claims (8)

A phosphorescent sheet comprising a transparent resin layer, a phosphorescent adhesive layer containing a phosphorescent material alone or both a phosphorescent material and a coloring material, and a reflective layer in this order. A phosphorescent property comprising a transparent resin layer, a phosphorescent adhesive layer containing a phosphorescent material alone or both a phosphorescent material and a coloring material, a reflective layer, and a base material layer in this order. Sheet. The phosphorescent sheet according to claim 1, wherein an adhesive layer and a release layer are provided in this order on the reflective layer side or the base material layer side. The luminous sheet according to claim 1, wherein a release layer is provided instead of the transparent resin layer. The phosphorescent sheet according to any one of claims 1 to 4, wherein the phosphorescent adhesive layer is formed by laminating a plurality of phosphorescent adhesive layers. The phosphorescent sheet according to any one of claims 1 to 5, wherein the adhesive material comprises an acrylic resin or a silicone resin. The reflective layer is composed of a resin layer containing at least one of white powder particles composed of barium sulfate and calcium carbonate, a metal vapor deposition material layer, or a combination thereof. The luminous sheet according to any one of claims 1 to 6. A phosphorescent tape obtained by slitting the phosphorescent sheet according to any one of claims 1 to 7 into a strip shape.

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