JP4600253B2 - Luminescent product and manufacturing method thereof - Google Patents

Description

  The present invention relates to a luminescent product such as a guide sign board, a safety sign board, and a safety guidance display board, and a method for manufacturing the same.

  Conventionally, when molding resin and rubber products containing phosphorescent pigments, the most efficient way to increase the concentration of phosphorescent pigment on one side (light emitting surface) to improve the functionality of phosphorescent pigments is to mix phosphorescent pigments with thermosetting resins. A method of forming by a centrifugal method is known (see Patent Document 1).

  However, all the phosphorescent material-containing products molded by this method had a curl phenomenon.

  This is because a layer containing a large amount of an inorganic phosphorescent material has little shrinkage after molding, but a layer having little phosphorescent material has a large shrinkage after molding, and this difference in shrinkage causes a curl phenomenon in the direction of the layer with less phosphorescent material. It is thought to occur.

  For this reason, the molded product molded by the centrifugal molding method as described above does not have a flat plate shape, and the usage to be used is limited (for a guide plate used in a plate shape, a guide sign, a road sign, etc. I can not use it).

  That is, in the case of using a flat resin and a rubber product containing a phosphorescent pigment, the phosphorescent pigment is uniformly mixed with the thermosetting resin and molded.

  However, in this case, there has been a concern that the light emission of the phosphorescent pigment inside the resin and rubber cannot be used efficiently.

  As a countermeasure, a technique is known in which a white reflective surface is provided on the back surface of the light emitting surface in order to improve the light storage performance (see Patent Document 2).

  Here, in Patent Document 2, the phosphorescent layer and the white layer are bonded with an adhesive, or the layer is formed by a coating agent containing a solvent (ketone-based or ester-based), but each layer is bonded by an adhesive. In such a case, there is a concern that it is difficult to ensure sufficient adhesive strength. In addition, when forming a layer with a coating agent, it is necessary to pay close attention to the removal of the solvent and the safety of the work (both ketone-based and ester-based solvents used for the coating agent have adverse effects on poisoning by the inhalation and the environment. This is a process that should be avoided as much as possible.

  Patent Document 3 discloses a phosphorescent sheet or film having translucent layers having different refractive indexes, such as a phosphorescent layer and a white layer, but in this case, each layer is bonded with an adhesive. There is a concern that it is difficult to ensure the strength of the bonding surface.

In addition, for the sheet-like luminescent molded product manufactured by the centrifugal molding method as described above, it is necessary to attach the white reflective surface in a separate process, but since the luminescent molded product is curled, the mounting work is not performed. There is concern that it will be very difficult.
Japanese Patent No. 3295229 JP 2002-366065 A Japanese Patent Laid-Open No. 10-37138

  The present invention has been made in view of the circumstances as described above, and suppresses the curling phenomenon of a luminescent product molded by a centrifugal molding method, and a coating agent containing an organic solvent without adhering with an adhesive. An object is to provide a light emitting product with a white layer that improves luminous performance without using it.

In order to achieve the above object, the luminescent product according to the present invention is:
A first mixture of a thermosetting resin and a first inorganic material having a specific gravity greater than that of the thermosetting resin is contained in a molded product formed by a centrifugal molding method that is heated and rotated, and contains a large amount of the first inorganic material. Two layers, a layer and a layer with a small amount of the first inorganic substance ,
After the two layers are molded, a second mixture of the thermosetting resin and a second inorganic material having a specific gravity greater than that of the thermosetting resin and having a function different from that of the first inorganic material is formed by the molding. A layer containing a large amount of the second inorganic substance in the two layers by being centrifugally molded at a rotational speed greater than the rotational speed when the first mixture is centrifugally molded by the centrifugal molding method. A second mixture layer in which a layer containing less second inorganic material and a layer not containing the second inorganic material are sequentially laminated;
It is characterized by providing.

  Thus, by curling the second mixture layer on two layers having different concentrations of the first inorganic substance, the curling phenomenon that occurs when the two layers having different concentrations of the first inorganic substance are formed can be suppressed. This makes it possible to suppress deformation of the luminescent product.

  Moreover, since the 2nd mixture layer can be shape | molded simultaneously with the shaping | molding of a luminescent product, the joining force of the 2nd mixture layer with respect to a luminescent product main body can be made high. In addition, the second mixture layer is not adhered with an adhesive, and the adhesive strength can be ensured more reliably. In addition, since a coating agent containing an organic solvent is not used, it does not adversely affect safety during work.

  Here, as the thermosetting resin, it is preferable to use a urethane material.

  There is a concern that the curl phenomenon may occur even when a layer containing a large amount of the second inorganic material, a layer containing a small amount of the second inorganic material, and a layer not containing the second inorganic material are formed as the second mixture layer. Is done. However, two layers having different concentrations of the first inorganic substance are provided, and in particular, the presence of a layer containing a large amount of the first inorganic substance can suppress the occurrence of the curling phenomenon, thereby reducing the deformation of the luminescent product. Can be suppressed.

  In addition, since a layer that does not contain a phosphorescent material can be formed on the surface layer, peeling of the phosphorescent material due to wear can be prevented, and a decrease in luminance due to peeling of the phosphorescent material can be prevented. Thereby, the function and quality of a luminescent product can be improved.

The first inorganic substance is a white pigment,
The second inorganic substance is preferably a phosphorescent pigment.

  As described above, the layer containing a large amount of the first inorganic material and the layer containing a large amount of the second inorganic material are laminated so as to sandwich the layer containing the small amount of the first inorganic material. Deformation of the luminescent product can be suppressed.

In the method for manufacturing a luminescent product according to the present invention,
A layer containing a large amount of the first inorganic substance, and the first inorganic substance are obtained by a centrifugal molding method in which the first inorganic substance having a specific gravity larger than that of the thermosetting resin is mixed with the thermosetting resin and then heated and rotated. A first step of forming a molding having two layers of few layers ;
A second mixture obtained by mixing the thermosetting resin with a second inorganic substance that is formed after the first step and has a specific gravity greater than that of the thermosetting resin and having a function different from that of the first inorganic substance; It is injected into the molded product molded in one step, and the first mixture is centrifuged by the centrifugal molding method.
The two layers are rich in the second inorganic material, the layer containing little the second inorganic material, and the second inorganic material is not contained in the two layers by centrifugal molding at a rotational speed larger than the rotational speed when formed. A second step of laminating a second mixture layer in which the layers are sequentially laminated ;
It is characterized by including.

  According to this manufacturing method, the second mixture layer can be formed simultaneously with the formation of the luminescent product.

  Thereby, the joining force of the 2nd mixture layer with respect to a luminescent product main body can be made high. In addition, the second mixture layer is not adhered with an adhesive, and the adhesive strength can be ensured more reliably. In addition, since a coating agent containing an organic solvent is not used, it does not adversely affect safety during work.

  Further, by laminating the second mixture layer on two layers having different concentrations of the first inorganic substance, it becomes possible to suppress a curling phenomenon that occurs when two layers having different concentrations of the first inorganic substance are formed. The deformation of the luminescent product can be suppressed.

  Moreover, it is also preferable that the second step is performed from the time when the molded product molded in the first step starts to harden until no unreacted reactive group exists.

  Thereby, the luminescent product in which the second mixture layer is integrated with the molded product formed in the first step can be obtained, and the bonding strength of the second mixture layer to the luminescent product body can be made higher. it can.

  According to the present invention, while suppressing the curling phenomenon of the luminescent product molded by the centrifugal molding method, it is possible to improve the phosphorescent performance without adhering with an adhesive and without using a coating agent containing an organic solvent. The layer can be provided on the luminescent product.

  The best mode for carrying out the present invention will be exemplarily described in detail below with reference to the drawings. However, the dimensions, materials, shapes, and relative arrangements of the components described in this embodiment should be appropriately changed according to the configuration of the apparatus to which the invention is applied and various conditions. It is not intended to limit the scope to the following embodiments.

  FIG. 1 is a schematic cross-sectional view showing a luminescent product 1 according to Example 1 of the present invention.

  As shown in FIG. 1, the luminescent product 1 includes a white reflective layer (functional layer) 11 containing a very large amount of white pigment, a buffer layer 12 containing a small amount of white pigment, and a phosphorescent pigment (hereinafter referred to as a phosphorescent material). The phosphorescent material layer (functional layer) 13 contained in a large amount, the buffer layer 14 with little phosphorescent material, and the surface layer (functional layer) 15 that does not contain (mostly contain) the phosphorescent material are laminated in order. Yes.

  In the luminescent product 1, the surface of the surface layer 15 becomes the light emitting surface 16. That is, the luminescent product 1 emits light in the direction of the arrow shown in FIG. As shown in FIG. 1, in this embodiment, the luminescent product 1 is formed by laminating a white reflective layer 11, a buffer layer 12, a phosphorescent material layer 13, a buffer layer 14, and a surface layer 15. The thickness a is set to 1 to 10 mm.

  Below, the manufacturing method of the luminescent product 1 which concerns on a present Example is demonstrated.

  The manufacturing method of the luminescent product 1 according to the present example uses a heating and rotating centrifugal molding method, and a urethane material is used as a thermosetting resin. And from the 1st mixture which mixed specific gravity larger than urethane material (specific gravity 1.3 or more) with this urethane material, a layer which contains many inorganic substances using a specific gravity difference by centrifugal formation, and a layer with few inorganic substances And forming a molding including two layers. Furthermore, the inorganic material having a function different from that of the inorganic material is the same urethane material as the urethane material from the time when the molded product (a layer containing a large amount of inorganic material and a layer containing a small amount of inorganic material) starts to be completely cured. A second mixture in which is mixed is injected into the molded product, and centrifugal molding is performed.

  Here, the time until completely cured means the time until there is no unreacted reactive group. The urethane material of this example is a cast urethane material, and a main material having a reactive group (—NCO) called a prepolymer and a curing agent (amine system) react to become urethane rubber. In the urethane material constituting the first mixture, the main material and the curing agent are mixed and injected, and then cured, but the second mixture is injected while there are unreacted reactive groups. By doing so, the unreacted reactive group of the first mixture (molded product) reacts with the second mixture. Thereby, the molded object which the molded object shape | molded from the 1st mixture and the 2nd mixture were integrated will be shape | molded.

  Hereinafter, the manufacturing method of the luminescent product 1 will be specifically described.

(Process 1)
Non-yellowing polyurethane prepolymer as urethane material 30 parts by mass (hereinafter referred to simply as “parts”), amine curing agent 3 parts, inorganic white pigment (titanium white, average particle size 20 μm) 3 parts as first inorganic substance The first mixture obtained by mixing and stirring is put into a centrifugal molding machine, and centrifugal molding is performed under conditions of a temperature of 110 ° C. and a rotational speed of 1000 rpm.

(Process 2)
After centrifugal molding for 10 minutes under the conditions shown in Step 1, 100 parts of a non-yellowing polyurethane prepolymer, 10 parts of an amine-based curing agent, and a phosphorescent material (average diameter 30 μm) as a second inorganic substance
The second mixture obtained by mixing and stirring with 20 parts was put into a centrifugal molding machine, subjected to centrifugal molding for 2 minutes at a temperature of 110 ° C. and a rotational speed of 1500 rpm, and then the rotational speed was reduced to 1000 rpm. After 20 minutes, remove from the centrifugal molding machine.

  Here, as the phosphorescent material, for example, strontium oxide, aluminum oxide, rare earth oxide and the like can be suitably applied.

(Process 3)
After taking out from the centrifugal molding machine in step 2, the sheet-like luminescent product 1 is obtained by performing heat treatment at a temperature of 80 ° C. for 12 hours.

  As described above, by performing centrifugal molding under the conditions shown in Step 1, a molded article having two layers of the white reflective layer 11 containing a large amount of white pigment and the buffer layer 12 containing little white pigment is formed. The

  Here, the centrifugal molding is performed under the condition of Step 1 with the rotation speed set at 1000 rpm, but the rotation speed may be 200 to 2000 rpm.

  In addition to the white reflective layer 11 and the buffer layer 12, by performing centrifugal molding under the conditions of step 2, the phosphorescent material layer 13 containing a very large amount of phosphorescent material, the buffer layer 14 having a small amount of phosphorescent material, and the phosphorescent material The surface layer 15 that does not contain is molded. Thus, in step 2, by performing molding at a rotational speed greater than that in the case of step 1, a layer (surface layer 15) that does not contain a phosphorescent material can be formed. In addition, the luminous material layer 13 containing very much luminous material, the buffer layer 14 with few luminous materials, and the surface layer 15 which does not contain a luminous material comprise the 2nd mixture layer based on this invention.

  In Step 2, the number of rotations increased by 2 to 50% (the number of rotations of 220 to 3000 rpm) from the number of rotations in Step 1, and after the molding for 1 to 3 minutes, the previous number of rotations (200 to 2000 rpm) The number of revolutions) may be returned to the mold, and it may be molded for 10 to 30 minutes, and then removed from the centrifugal molding machine.

  Moreover, 2-70% is preferable and, as for the ratio of the inorganic substance (white pigment, luminous material) with respect to urethane material (non-yellowing polyurethane prepolymer), it is more preferable in it being 10-50%.

  In FIG. 1, for convenience of explanation, the layers are separated by a broken line, but actually, the boundaries of the layers are not clear but are mixed.

  In the present embodiment, as described above, the luminescent product 1 is formed by the centrifugal molding method.

  Here, when a layer containing a large amount of phosphorescent material and a layer having a small amount of phosphorescent material are molded by centrifugal molding, the shrinkage after molding differs between a layer containing a large amount of phosphorescent material and a layer having a small amount of phosphorescent material. Become.

  Strontium oxide, aluminum oxide, rare earth oxide, etc. used as a phosphorescent material hardly shrink when the heat treatment temperature is around 100 ° C. Therefore, such a layer containing a large amount of phosphorescent material hardly contracts. On the other hand, shrinkage occurs in a layer with less phosphorescent material.

For this reason, in a molded product composed of only a layer containing a large amount of phosphorescent material and a layer having a small amount of phosphorescent material, a curl phenomenon occurs in the direction of the layer having a small amount of phosphorescent material due to this difference in shrinkage.

  In this example, by manufacturing the luminescent product 1 by the above-described manufacturing method, as shown in FIG. 1, in addition to the layer containing a large amount of phosphorescent material and the layer containing little phosphorescent material, the white reflective layer 11 is laminated. ing. Here, the titanium oxide used for the white reflective layer 11 does not shrink due to the metal oxide, similarly to the phosphorescent material. Therefore, the curling phenomenon of the molded product can be suppressed, and deformation of the luminescent product 1 can be suppressed.

Further, in the luminescent product 1, the white reflective layer 11 is formed on the back side of the light emitting surface 16, so that it is possible to improve the light storage performance, and the luminance of 5 mcd / m ² or more after 240 minutes from the light emission. Can be secured. Here, the luminance of 5 mcd / m ² is a luminance that allows a bright and clear object to be confirmed.

  In addition, according to the manufacturing method of the present embodiment, the white reflective layer 11 that improves the luminance of the luminescent product 1 can be simultaneously formed when the luminescent product 1 is formed. Thereby, the joining force of the white reflective layer 11 with respect to the luminescent product 1 main body can be made high.

  Further, in the luminescent product 1, the white reflective layer is formed at the same time as the luminescent product 1 by the above-described manufacturing method, and is not bonded by an adhesive, so that the adhesive strength is more reliably secured. can do. Moreover, since the luminescent product 1 does not use a coating agent containing an organic solvent, it does not adversely affect safety during work.

  Further, in the luminescent product 1 according to this example, a layer not containing a phosphorescent material is formed on the surface layer 15.

  When the phosphorescent material is present on the surface layer, the phosphorescent material is peeled off due to wear, and the portion from which the phosphorescent material is peeled becomes an uneven surface, which may cause fogging and may significantly reduce the luminance.

  Since the surface layer 15 of the present embodiment does not contain a phosphorescent material, the luminescent product 1 can be suitably applied even in places where wear resistance is required such as on the road surface.

  In this embodiment, the buffer layers 12 and 14 are formed, so that the effect of improving the strength of the luminescent product 1 and improving the rubber elastic function can be obtained.

  FIG. 2 is a schematic cross-sectional view showing a luminescent product 2 according to Example 2 of the present invention.

  As shown in FIG. 2, the luminescent product 2 includes, in order, a phosphorescent material layer 21 containing an extremely large amount of phosphorescent material, a buffer layer 22 containing a small amount of phosphorescent material, and a white reflective layer 23 containing an extremely large amount of white pigment. It is configured by being laminated.

  In the luminescent product 2, the surface of the phosphorescent material layer 21 is the light emitting surface 24. That is, the luminescent product 2 emits light in the direction of the arrow shown in FIG.

  In Example 1 described above, the centrifugal molding method was used, and after forming the white reflective layer 11 and the buffer layer 12 with less white pigment, the phosphorescent material layer 13 and the buffer layer 14 with less phosphorescent material were formed. In contrast, in this example, the same centrifugal molding method as in Example 1 is used, but after forming a phosphorescent material layer and a buffer layer with few phosphorescent materials, a white reflective layer is formed.

  Hereinafter, the manufacturing method of the luminescent product 2 according to the present embodiment will be described.

(Process 1)
The first mixture obtained by mixing and stirring 100 parts of non-yellowing polyurethane prepolymer as urethane material, 10 parts of amine curing agent and 20 parts of phosphorescent material as the first inorganic substance is put into a centrifugal molding machine. Then, centrifugal molding is performed under conditions of a temperature of 110 ° C. and a rotational speed of 1000 rpm.

(Process 2)
After centrifugal molding for 5 minutes under the conditions shown in Step 1, 30 parts of a non-yellowing polyurethane prepolymer, 3 parts of an amine curing agent, and 3 parts of an inorganic white pigment (titanium white) as a second inorganic substance The second mixture obtained by mixing and stirring is put into a centrifugal molding machine, subjected to centrifugal molding for 30 minutes at a temperature of 110 ° C. and a rotational speed of 1000 rpm, and then taken out from the centrifugal molding machine.

(Process 3)
After taking out from the centrifugal molding machine in step 2, a sheet-like luminescent product 2 is obtained by performing heat treatment at a temperature of 80 ° C. for 12 hours.

  As described above, by performing centrifugal molding under the conditions shown in step 1, a molded product having two layers of the phosphorescent material layer 21 containing a very large amount of phosphorescent material and the buffer layer 22 having a small amount of phosphorescent material is formed. The

  Further, by performing centrifugal molding under the conditions of step 2, in addition to the phosphorescent material layer 21 and the buffer layer 22, the white reflective layer 23 containing a large amount of white pigment is molded. Here, the white reflective layer 23 constitutes a second mixture layer according to the present invention.

  In FIG. 2, for convenience of explanation, the layers are separated by a broken line, but actually, the boundaries of the layers are not clear but are mixed.

  In this example, as described above, as in Example 1, the luminescent product 2 was formed by centrifugal molding, thereby forming a layer containing a large amount of phosphorescent material and a layer containing few phosphorescent materials as shown in FIG. In addition, since the white reflective layer 23 is laminated in order, the curling phenomenon of the molded product can be suppressed as in Example 1, and the deformation of the luminescent product 2 can be suppressed.

Further, in the luminescent product 2, by forming the white reflective layer 23 on the back side of the light emitting surface 24, it becomes possible to improve the light storage performance, and the luminance of 5 mcd / m ² or more after 240 minutes from emitting light. Can be secured.

  In addition, according to the manufacturing method of the present embodiment, the white reflective layer 23 that improves the luminance of the luminescent product 2 can be simultaneously formed when the luminescent product 2 is formed. Thereby, the joining force of the white reflective layer 23 with respect to the luminescent product 2 main body can be made high.

  As described above, in the luminescent product 2, the white reflective layer is formed at the same time as the luminescent product 2 by the above-described manufacturing method, and is not bonded by an adhesive, so that the adhesive strength is more reliably obtained. Can be secured. Moreover, since the luminescent product 2 does not use a coating agent containing an organic solvent, it does not adversely affect safety during work.

FIG. 1 is a schematic sectional view showing a luminescent product according to Example 1 of the present invention. FIG. 2 is a schematic cross-sectional view showing a luminescent product according to Example 2 of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 2 Luminous product 11 White reflection layer 12 Buffer layer with few white pigments 13 Phosphorescent material layer 14 Buffer layer with few phosphorescent materials 15 Surface layer 16 Light emitting surface 21 Luminous material layer 22 Buffer layer with few phosphorescent materials 23 White reflective layer 24 Light emission surface

Claims (4)

A first mixture of a thermosetting resin and a first inorganic material having a specific gravity greater than that of the thermosetting resin is contained in a molded product formed by a centrifugal molding method that is heated and rotated, and contains a large amount of the first inorganic material. Two layers, a layer and a layer with a small amount of the first inorganic substance ,
After the two layers are molded, a second mixture of the thermosetting resin and a second inorganic material having a specific gravity greater than that of the thermosetting resin and having a function different from that of the first inorganic material is formed by the molding. A layer containing a large amount of the second inorganic substance in the two layers by being centrifugally molded at a rotational speed greater than the rotational speed when the first mixture is centrifugally molded by the centrifugal molding method. A second mixture layer in which a layer containing less second inorganic material and a layer not containing the second inorganic material are sequentially laminated;
A luminescent product characterized by comprising: The first inorganic substance is a white pigment,
The luminescent product according to claim 1 , wherein the second inorganic substance is a phosphorescent pigment. A layer containing a large amount of the first inorganic substance, and the first inorganic substance are obtained by a centrifugal molding method in which the first inorganic substance having a specific gravity larger than that of the thermosetting resin is mixed with the thermosetting resin and then heated and rotated. A first step of forming a molding having two layers of few layers ;
A second mixture obtained by mixing the thermosetting resin with a second inorganic substance that is formed after the first step and has a specific gravity greater than that of the thermosetting resin and having a function different from that of the first inorganic substance; The two layers are injected into the molded product formed in one step and subjected to centrifugal molding at a rotational speed larger than the rotational speed when the first mixture is centrifugally molded by the centrifugal molding method . A second step of laminating a layer containing a large amount of two inorganic materials, a layer containing a small amount of the second inorganic material, and a second mixture layer obtained by sequentially laminating a layer not containing the second inorganic material ;
The manufacturing method of the luminescent product characterized by including. The second step, according to claim 3, wherein said molded product is molded in a first step, wherein the carried out that between the time began to cure until the reaction unreacted groups no longer exist Manufacturing method of luminescent products.

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