JP2013253443A - Luminous sheet for being attached to curved surface, and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a luminous sheet for being attached to a curved surface, which can restrain warpage from being caused by a shrinkage difference, while having high emission luminance by arranging a luminous layer on a front side, and which can be easily attached to the curved surface of a cylinder and the like.SOLUTION: A luminous layer 11, which uses a thermosetting resin as a base material and into which a luminous material with a specific gravity D1 is mixed, a glass bead layer 12 into which glass beads with a specific gravity D2 are mixed, and a white reflective layer 13, into which a white pigment with a specific gravity D3 is mixed, are formed in this order by centrifugal molding. The specific gravities D1, D2 and D3 satisfy the inequality: D1>D2>D3. A luminous sheet is molded in a curved shape so that the luminous layer 11 can be positioned on a convex side.

Description

  The present invention relates to a phosphorescent sheet for curved surface mounting and a method of manufacturing the same, and more specifically, can be formed into a shape that matches a curved surface-mounted phosphorescent sheet that has a high light emission luminance and is attached to a curved surface such as a cylinder. The present invention also relates to a method for producing a phosphorescent sheet for curved surface mounting having high emission luminance.

  In underground malls, subways, buildings, etc., evacuation guidance signs for evacuation guidance in the event of a disaster are installed on the walls. Such an evacuation guide sign is desired to be installed in a place where a lot of traffic is conspicuous, so that it is required to be installed not only on a wall surface but also on a pillar surface. Generally, some pillars have a cylindrical shape, and in this case, it is necessary to be able to attach the evacuation guidance sign to a curved surface. As a thing which can be installed also on such a curved surface, there is a phosphorescent sheet that emits light even during a power failure (Patent Documents 1 to 3).

In general, the illuminance in the subway connecting passage and station building is around 100Lx, and the phosphorescent sheet installed in such a place should have an afterglow luminance of 60 mcd / m ² or more after 60 minutes in the event of a power failure due to a disaster or the like. Is desired. Thus, in order to satisfy the function of an afterglow luminance of 60 mcd / m ² or more after 60 minutes in an environment with an illuminance of 100 Lx, it is necessary to mix a large amount of phosphorescent material having a large particle diameter, for example, with a high luminance for a long time. An aluminate-based phosphorescent material capable of emitting light requires an average particle size of 100 μm or more and a kneading amount of 2000 g / m ² or more.

  However, in Patent Document 1, the particle size of the phosphorescent material used is about 40 to 80 μm, which is insufficient to satisfy the above requirement.

  Patent Documents 2 and 3 describe a phosphorescent sheet in which a layer disposed in the approximate center of a sheet made of urethane resin is a phosphorescent layer, a white reflective layer is disposed on one side, and a transparent layer is disposed on the other. . Since such a phosphorescent sheet is made of urethane resin as a base material, it can be attached to a curved surface, and it is considered that a phosphorescent sheet satisfying the above requirements can be obtained by mixing a phosphorescent material with high brightness into this phosphorescent layer. It is done.

  However, when a large amount of a large luminous material is mixed, there is a problem that the luminous layer becomes thick, the flexibility is deteriorated, and it is difficult to attach to a curved surface. Moreover, since the phosphorescent layer is an intermediate layer, there is a problem that the luminous efficiency is poor.

  This luminous efficiency problem can be solved by arranging the phosphorescent layer on the surface layer side, but the shrinkage rate after molding between the phosphorescent layer containing a large amount of phosphorescent material and the other layers containing little or no phosphorescent material. Are different from each other, there is a problem that bending occurs in the direction of a layer with little or no phosphorescent material. If the sheet is warped, there is a problem in that it may be easily peeled off or cannot be attached due to a difference in curvature from the attachment curved surface.

  In general, since the phosphorescent material is inorganic and has a large specific gravity, it is difficult to arrange the phosphorescent layer mixed with a large amount of the phosphorescent material in a single molding process in the intermediate layer of the sheet. For this reason, in Patent Documents 2 and 3, when forming a sheet by centrifugal molding, a layer that does not contain a phosphorescent material is first put into a mold to form a layer, and then a material that contains the phosphorescent material is added. Thus, a phosphorescent sheet in which the phosphorescent layer is an intermediate layer is formed such that the phosphorescent material forms a layer by specific gravity on the previous layer.

  However, this method requires two material input steps, and the work process is complicated. If this is to be done with only one material input, the phosphorescent layer becomes a surface layer due to the specific gravity and the light emission efficiency is improved, but there is a problem that warping occurs as described above.

  That is, conventionally, warping does not pose a problem even if centrifugal molding is performed with only one material input, and it has not been possible to manufacture a phosphorescent sheet with good luminous efficiency.

Japanese Patent No. 4130939 JP 2007-138619 A JP 2008-44121 A

  Therefore, the present invention is for curved surface mounting that can suppress the occurrence of warpage due to a shrinkage difference and can be easily mounted on a curved surface such as a cylinder while having a high luminous luminance by arranging the phosphorescent layer on the surface side. It is an object to provide a phosphorescent sheet.

  In addition, the present invention can suppress the occurrence of warping due to a difference in shrinkage by arranging the phosphorescent layer on the surface side, and can be easily formed into a shape matching a mounting curved surface such as a cylinder. It is an object of the present invention to provide a method of manufacturing a curved surface-mounting phosphorescent sheet.

  The other subject of this invention becomes clear by the following description.

(Claim 1)
A thermoluminescent resin as a base material, a phosphorescent layer mixed with a phosphorescent material with a specific gravity D1, a glass bead layer mixed with glass beads with a specific gravity D2, and a white reflective layer mixed with a white pigment with a specific gravity D3 The curved surface storage phosphor sheet is formed in this order by centrifugal molding, D1>D2> D3, and is formed in a curved shape so that the phosphorescent layer is on the convex side.

(Claim 2)
The said phosphorescent material is an aluminate type phosphorescent material with an average particle diameter of 100 micrometers or more, and 2000 g / m < ² > or more is mixed with respect to the said thermosetting resin, The phosphorescent material for curved-surface attachment of Claim 1 characterized by the above-mentioned. Sheet.

(Claim 3)
3. The phosphorescent sheet for curved surface attachment according to claim 1 or 2, wherein the glass beads have an average particle diameter of 60 to 100 [mu] m.

(Claim 4)
The said thermosetting resin is a transparent urethane resin, The phosphorescent sheet for curved surface attachment of Claim 1, 2, or 3 characterized by the above-mentioned.

(Claim 5)
A mixed material satisfying D1>D2> D3 obtained by mixing a phosphorescent material having a specific gravity D1, glass beads having a specific gravity D2, and a white pigment having a specific gravity D3 in a thermosetting resin is heated using a cylindrical mold. A first step of obtaining an uncured cylindrical molded product in which a phosphorescent layer, a glass bead layer, and a white reflective layer are sequentially formed from the mold surface side by centrifugal molding,
A second step of cutting the molded product into a plate shape;
A molded product cut into a plate shape is attached to a jig whose surface is formed in a curved surface and cured by performing a heat treatment for a predetermined time, and a curved phosphorescent sheet with the phosphorescent layer on the convex side is obtained. A third step to obtain;
A method for producing a phosphorescent sheet for curved surface mounting, comprising:

(Claim 6)
Centrifugal molding in the first step is a first centrifugal molding step in which the rotational speed is 50 to 300 rpm immediately after the mixed material is charged into the cylindrical mold,
1st to 3 minutes after the start of the first centrifugal molding process, a second centrifugal molding process with a rotational speed of 500 to 1500 rpm;
The method for producing a luminous sheet for curved surface attachment according to claim 5, wherein:

(Claim 7)
The said phosphorescent material is an aluminate type phosphorescent material with an average particle diameter of 100 micrometers or more, and 2000 g / m < ² > or more is mixed with respect to the said thermosetting resin, The phosphorescence for curved-surface attachment of Claim 5 or 6 characterized by the above-mentioned. Sheet manufacturing method.

(Claim 8)
The method for producing a luminous sheet for curved surface attachment according to claim 5, 6 or 7, wherein the glass beads have an average particle diameter of 60 to 100 µm.

(Claim 9)
The said thermosetting resin is a transparent urethane resin, The manufacturing method of the luminous sheet | seat for curved-surface attachment in any one of Claims 5-8 characterized by the above-mentioned.

  According to the present invention, by arranging the phosphorescent layer on the surface side, it is possible to suppress the occurrence of warpage due to a difference in shrinkage while having high emission luminance, and it can be easily attached to a curved surface such as a cylinder. A phosphorescent sheet can be provided.

  In addition, according to the present invention, by arranging the phosphorescent layer on the surface side, it is possible to suppress the occurrence of warp due to the difference in shrinkage while having high emission luminance, and it is easy to have a shape that matches the mounting curved surface such as a cylinder. A method for producing a phosphorescent sheet for curved surface mounting that can be molded can be provided.

Sectional drawing of the luminous sheet for curved surface attachment concerning this invention Sectional drawing which shows the state which attached the phosphorescent sheet for curved surface attachment which concerns on this invention to the cylinder The figure explaining the manufacturing method of the luminous sheet for curved surface attachment which concerns on this invention The figure explaining the manufacturing method of the luminous sheet for curved surface attachment which concerns on this invention

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

  FIG. 1 is a cross-sectional view of a curved surface mounting phosphorescent sheet according to the present invention, FIG. 2 is a sectional view showing a state in which the curved surface mounting phosphorescent sheet is mounted on a cylinder, and in the figure, 1 is a curved surface mounting phosphorescent sheet (hereinafter referred to as , Simply referred to as phosphorescent sheet 1) and 100 are cylindrical pillars such as electric poles, pillars, and building pillars to which the phosphorescent sheet 1 is attached.

  The phosphorescent sheet 1 is composed of a thermosetting resin as a base material, a phosphorescent layer 11 in which a phosphorescent material with a specific gravity D1 is mixed, a glass bead layer 12 in which glass beads with a specific gravity D2 are mixed, and a white pigment with a specific gravity D3. The white reflective layer 13 is formed in this order by centrifugal molding, and the curvature of the surface of the column 100 that is a mounting curved surface is formed such that the phosphorescent layer 11 becomes a surface layer and the phosphorescent layer 11 becomes a convex side. It is formed in a curved shape according to The specific gravity has a relationship of D1> D2> D3.

  As described above, the phosphorescent sheet 1 is preliminarily formed in a curved shape in accordance with the curvature of the surface of the column 100 that is a mounting curved surface, so that a large amount of phosphorescent material having a large particle size is added to the phosphorescent layer 11 for high luminance light emission. Even if it has the luminous layer 11 that is thick and difficult to bend by mixing, it can be attached to a curved surface.

  The thermosetting resin used as the base material may be a resin having good flexibility and transparency, but it is particularly preferable to use a transparent urethane resin, and among them, a thermosetting non-yellowing urethane resin is preferable. Since the non-yellowing urethane resin is not discolored or hydrolyzed by use, a high-luminance light emitting function can be maintained over a long period of time by mixing a phosphorescent material therein.

The phosphorescent material mixed in the phosphorescent layer 11 may be, for example, strontium oxide, aluminum oxide, rare earth oxide, etc., but the aluminate-based phosphorescent material is particularly capable of emitting light with high brightness over a long period of time. Is preferred. The aluminate-based phosphorescent material is mainly composed of SrAl ₂ O ₄ : Eu, Dy (strontium aluminate: europium, dysprosium), and is a non-toxic and environmentally friendly substance.

The phosphorescent material has a higher brightness as the particle size is larger and the amount mixed is larger. Therefore, in order to satisfy the function of an afterglow brightness of 60 mcd / m ² after 60 minutes in an environment with an illuminance of 100 Lx, the thermosetting material is a base material. It is preferable to mix 2000 g / m ² or more of the resin having an average particle diameter of 100 μm or more with respect to the conductive resin. If either the average particle size or the mixing amount falls below this value, it will be insufficient to exhibit the above functions. In consideration of moldability, the upper limit is preferably set to an average particle size of 300 μm or less and a mixing amount of 3000 g / m ² or less.

  The average particle diameter of the glass beads mixed in the glass bead layer 12 is preferably 60 to 100 μm. By using a transparent glass bead, the luminous layer 11 can emit light with high brightness at night or during a power failure without impairing the light reflecting function of the lower white reflective layer 13.

  The white reflective layer 13 is disposed in the lowermost layer of the phosphorescent sheet 1, and reflects the light irradiated on the phosphorescent sheet 1 and reaching the white reflective layer 13 toward the phosphorescent layer 11. High-luminance light emission can be realized by performing efficient light irradiation and reflecting light from the luminous layer 11 that emits light toward the surface side at night or during a power failure.

  As the white pigment, a titanium-based white pigment can be generally used. In general, the average particle diameter of the white pigment is preferably 30 μm or less because of excellent uniform dispersibility.

  In the figure, for convenience of explanation, a boundary line is shown between the layers 11, 12, and 13, but the phosphorescent sheet 1 is composed of a phosphorescent material, glass beads, and white pigment in a thermosetting resin that is a base material. Is mixed and centrifuged, and these mixed materials are centrifuged to form the phosphorescent layer 11, the glass piece layer 12, and the white reflective layer 13 by the specific gravity difference. For this reason, the entire actual product is integrated with the thermosetting resin, and there is no clear boundary between the layers 11, 12, and 13.

  The white reflective layer 13 disposed on the opposite surface to the phosphorescent layer 11 among the layers 11, 12, and 13 does not include a phosphorescent material. As a result, warpage occurs due to the difference in shrinkage after molding between the phosphorescent layer 11 containing a large amount of phosphorescent material and the white reflective layer 13, and as indicated by the arrows in FIG. There exists a possibility that the diameter of the phosphorescent sheet 1 may be bent and reduced in diameter. When the diameter of the phosphorescent sheet 1 is reduced, the curvature of the mounting curved surface of the pillar 100 is different from the curvature of the inner side of the phosphorescent sheet 1, which may cause peeling even in the worst case. There is a risk that the installation itself may not be possible.

  However, since the phosphorescent sheet 1 according to the present invention interposes the glass bead layer 12 containing inorganic glass beads in the same manner as the phosphorescent material between the phosphorescent layer 11 and the white reflective layer 13, the phosphorescent sheet 1 as a whole. The ratio of the white reflective layer 13 to the glass reflective layer 13 can be reduced, and the glass bead layer 12 functions as a buffer layer for buffering the difference in shrinkage between the phosphorescent layer 11 and the white reflective layer 13, and the warp on the white reflective layer 13 side. By suppressing this, it is possible to suppress the diameter of the entire phosphorescent sheet 1 from being reduced. And since it is not necessary to reduce the thickness of the luminous layer 11 or to reduce the mixing amount of the luminous material in order to suppress the diameter reduction, there is no influence on the light emitting function of the luminous sheet 1.

  Even if the glass bead layer 12 is interposed, it is difficult to completely prevent the diameter reduction of the phosphorescent sheet 1 due to the difference in shrinkage, but the relative thickness of the glass bead layer 12 and the white reflective layer 13 is appropriately adjusted. By doing so, the degree of diameter reduction of the phosphorescent sheet 1 can be adjusted. For example, by making the thickness of the glass bead layer 12 larger than that of the white reflective layer 13, the diameter of the phosphorescent sheet 1 can be adjusted to be reduced. By adjusting the relative thicknesses of the glass bead layer 12 and the white reflective layer 13 as described above, the phosphorescent sheet 1 has a certain diameter reduction state, whereby the phosphorescent sheet 1 itself has adhesion to the column 100. You can also make it.

  Since each layer 11, 12, 13 of the phosphorescent sheet 1 is centrifugally molded using the specific gravity difference of the phosphorescent material, glass beads and white pigment, the relative thickness of the glass bead layer 12 and the white reflective layer 13 is determined. Can be adjusted by appropriately adjusting the mixing amount of the glass beads and the white pigment.

  The total thickness of the phosphorescent sheet 1 can be about 1 to 10 mm.

  As shown in FIG. 2, the phosphorescent sheet 1 is fixed to the mounting curved surface of the pillar 100 using an adhesive, an adhesive, or the like. Arbitrary characters and figures for evacuation guidance display can be formed on the surface of the phosphorescent layer 11. In addition, the evacuation guide sign may be configured by forming the outer shape of the phosphorescent sheet 1 itself into an arbitrary character or figure shape and attaching it to the surface of the pillar 100 in combination. Since the surface side of the phosphorescent sheet 1 is the phosphorescent layer 11, it is possible to emit light with high brightness in the direction of the arrow in FIG.

  Next, an example of the manufacturing method of the phosphorescent sheet 1 will be described with reference to FIGS.

(First step)
In FIG. 3, reference numeral 200 denotes a centrifugal molding machine having a cylindrical mold 202 that is rotated by a drive source 201.

  100 parts by mass of non-yellowing polyurethane prepolymer as thermosetting resin (hereinafter simply referred to as “parts”), 10 parts of amine-based curing agent, 150 parts of phosphorescent material (aluminate-based phosphorescent material; specific gravity 3.6) And 10 parts of glass beads (specific gravity 2.5 to 2.6), 0.5 parts of titanium-based white pigment (specific gravity 1.1), and 0.01 part of a reaction accelerator are mixed and uniformly mixed at 50 to 80 ° C. The stirred mixed material is put into a cylindrical mold 202 heated to 60 to 150 ° C. and rotated to perform centrifugal molding.

  The rotational speed is a low-speed rotation of 50 to 300 rpm immediately after the mixed material is charged, and this is continued for 1 to 3 minutes so that the mixed material has a uniform thickness in the cylindrical mold 202 (first centrifugal molding step). After 1 to 3 minutes, when the mixed material has a uniform thickness, the rotational speed is set to 500 to 1500 rpm (second centrifugal molding step).

  Since the specific gravity of each of the phosphorescent material, glass beads, and white pigment in the mixed material is a relationship of phosphorescent material> glass beads> white pigment, from the mold surface 202a side in descending order of specific gravity by the second centrifugal molding step, The phosphorescent material, the glass beads, and the white pigment are formed in this order, and the phosphorescent layer 11, the glass bead layer 12, and the white reflective layer 13 are formed, respectively.

  After the second centrifugal molding step is continued for 15 to 20 minutes, the cylindrical molded product is taken out from the cylindrical mold 202.

(Second step)
Subsequently, the obtained cylindrical molded product is cut into a width and cut into a plate shape according to a desired product shape.

  The molded product taken out from the cylindrical mold 202 is in an uncured state, and is a semi-cured molded product having an unreacted reactive group (—NCO). For this reason, even if a molded product is placed on a flat plate, it can be easily cut without warping.

(Third step)
Next, the molded product cut into the product shape is mounted on a jig 300 as shown in FIG.

  The jig 300 has a convexly curved jig body 302 having a curved surface having a curvature (diameter) that matches the curvature (diameter) of the mounting curved surface of the column 100 (see FIG. 2) on the base 301. . After the molded product cut into the product shape is mounted on the jig body 302 so that the phosphorescent layer 11 is on the upper surface, heat treatment is performed at 80 ° C. for 12 hours to completely remove unreacted reactive groups. React to cure the molded product. Thereby, the phosphorescent layer 11 side becomes a convex side, and the curved phosphorescent sheet 1 matching the mounting curved surface of the column 100 is obtained.

  According to this manufacturing method, the phosphorescent sheet 1 that can be attached to a curved surface can be easily obtained even if a large amount of phosphorescent material having a large particle size is mixed in the phosphorescent layer 11 for high luminance light emission.

  In addition, the mixed material only needs to be put into the cylindrical mold 202 once, and the luminous layer 11 is made a surface layer by utilizing the difference in specific gravity of the material, but high luminance emission is possible, but there is a difference in shrinkage. It is possible to obtain a phosphorescent sheet 1 that can be attached to a curved surface, in which an undesired reduction in diameter due to the warping caused is suppressed.

1: Curved phosphorescent sheet 11: Phosphorescent layer 12: Glass bead layer 13: White reflective layer 100: Column 200: Centrifugal molding machine 201: Drive source 202: Cylindrical mold 202a: Mold surface 300: Jig 301: Base Table 302: Jig body

Claims (9)

  A thermoluminescent resin as a base material, a phosphorescent layer mixed with a phosphorescent material with a specific gravity D1, a glass bead layer mixed with glass beads with a specific gravity D2, and a white reflective layer mixed with a white pigment with a specific gravity D3 The curved surface storage phosphor sheet is formed in this order by centrifugal molding, D1> D2> D3, and is formed in a curved shape so that the phosphorescent layer is on the convex side. The said phosphorescent material is an aluminate type phosphorescent material with an average particle diameter of 100 micrometers or more, and 2000 g / m < ² > or more is mixed with respect to the said thermosetting resin, The phosphorescent material for curved-surface attachment of Claim 1 characterized by the above-mentioned. Sheet.   3. The phosphorescent sheet for curved surface attachment according to claim 1 or 2, wherein the glass beads have an average particle diameter of 60 to 100 [mu] m.   The said thermosetting resin is a transparent urethane resin, The phosphorescent sheet for curved surface attachment of Claim 1, 2, or 3 characterized by the above-mentioned. A mixed material satisfying D1>D2> D3 obtained by mixing a phosphorescent material having a specific gravity D1, glass beads having a specific gravity D2, and a white pigment having a specific gravity D3 in a thermosetting resin is heated using a cylindrical mold. A first step of obtaining an uncured cylindrical molded product in which a phosphorescent layer, a glass bead layer, and a white reflective layer are sequentially formed from the mold surface side by centrifugal molding,
A second step of cutting the molded product into a plate shape;
A molded product cut into a plate shape is attached to a jig whose surface is formed in a curved surface and cured by performing a heat treatment for a predetermined time, and a curved phosphorescent sheet with the phosphorescent layer on the convex side is obtained. A third step to obtain;
A method for producing a phosphorescent sheet for curved surface mounting, comprising: Centrifugal molding in the first step is a first centrifugal molding step in which the rotational speed is 50 to 300 rpm immediately after the mixed material is charged into the cylindrical mold,
1st to 3 minutes after the start of the first centrifugal molding process, a second centrifugal molding process with a rotational speed of 500 to 1500 rpm;
The method for producing a luminous sheet for curved surface attachment according to claim 5, wherein: The said phosphorescent material is an aluminate type phosphorescent material with an average particle diameter of 100 micrometers or more, and 2000 g / m < ² > or more is mixed with respect to the said thermosetting resin, The phosphorescence for curved-surface attachment of Claim 5 or 6 characterized by the above-mentioned. Sheet manufacturing method.   The method for producing a luminous sheet for curved surface attachment according to claim 5, 6 or 7, wherein the glass beads have an average particle diameter of 60 to 100 µm.   The said thermosetting resin is a transparent urethane resin, The manufacturing method of the luminous sheet | seat for curved-surface attachment in any one of Claims 5-8 characterized by the above-mentioned.

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