JP6849311B2 - Fluorine-based resin sheet containing a phosphorescent phosphor, a laminate using this, a phosphorescent sheet, an outdoor phosphorescent label - Google Patents

Description

The present invention relates to a fluororesin sheet containing a phosphorescent phosphor, a laminate using the same, a phosphorescent sheet, and an outdoor phosphorescent label. More specifically, the present invention relates to a fluorine-based resin sheet or the like having excellent weather resistance in which a phosphorescent phosphor or the like is blended with a fluorine-based resin.

Luminescence refers to a phenomenon in which energy is absorbed by irradiation with light and emits light after the irradiation is stopped, and a substance having such a property is known as a phosphorescent phosphor or a phosphorescent substance. Zinc sulfide, calcium sulfide, zinc oxide, aluminate and the like are known as the phosphorescent phosphor, and as a method for improving the water resistance of the phosphorescent phosphor, it is mixed with phosphate or phosphorus. It is known that they are brought into contact with each other in a phosphate solution and heat-treated (see Patent Document 1 and Patent Document 2).

The phosphorescent fluorescent substance is also used for various labeling products such as a sign for protecting safety at night and a mark indicating the position of an emergency exit, and a compound obtained by adding the phosphorescent fluorescent substance to a resin is formed into a sheet. A method of molding, a method of applying a coating material containing a phosphorescent phosphor to the surface of a sheet, and the like are also provided (see Patent Documents 3 and 4).
Vinyl chloride resin and silicone resin are mainly used as the resin component for molding such a conventional sheet containing a phosphorescent phosphor (hereinafter, also referred to as “phosphorescent sheet”).

With the Great East Japan Earthquake in March 2011, the need for outdoor nighttime emergency signs, guardrail signs, etc. has increased, and phosphorescent sheets with excellent weather resistance have been demanded. In addition, JISZ9097 was established in 2014, which clearly defines the performance of the phosphorescent sheet, which was previously unclear, and maintaining the performance for a long period of time has become an urgent issue.

On the other hand, fluororesins are known to have excellent weather resistance. In particular, fluororesins protect and weather-resistant plastic plates, metal plates, and various other base materials used for interior and exterior members of buildings. It is used for the purpose of improving the properties (see Patent Document 5, Patent Document 6, and Patent Document 7).

Further, in recent years, it has been proposed to use a fluorine-based film for the surface protection layer of the back surface protective sheet of the solar cell module by taking advantage of the feature that the fluorine-based resin has excellent weather resistance (see Patent Document 8).

Japanese Patent No. 2543825 Japanese Unexamined Patent Publication No. 10-273654 JP-A-2002-19020 Japanese Patent No. 3552763 Japanese Unexamined Patent Publication No. 2006-18255 Japanese Unexamined Patent Publication No. 8-267675 Japanese Unexamined Patent Publication No. 2008-7709 Japanese Unexamined Patent Publication No. 2011-77081

When a phosphorescent sheet using a vinyl chloride resin as a resin component is used outdoors, significant deterioration such as discoloration of the vinyl chloride resin occurs. As a result, the phosphorescent phosphor contained in the phosphorescent sheet is deteriorated and decomposed, and the phosphorescent performance cannot be maintained for a long period of time. A method of providing a surface protective layer may be adopted for the purpose of preventing this, but the underlying layer is affected by long-term exposure, and the long-term retention of phosphorescent performance is insufficient for outdoor use. ..
On the other hand, a phosphorescent sheet containing a fluororesin having excellent weather resistance as a resin component has not been devised at present from the viewpoint of processing difficulty and the like.

Therefore, the present invention provides a fluorine-based resin sheet containing a resin component containing a fluorine-based resin and a phosphorescent phosphor, and particularly provides a fluorine-based resin sheet for phosphorescent labeling having excellent weather resistance for outdoor use. With the goal.

The present invention provides a fluorine-based resin sheet containing a resin component containing a fluorine-based resin and a phosphorescent phosphor.
In this fluorine-based resin sheet, the phosphorescent phosphor may be contained in an amount of 1 to 80 parts by mass with respect to 100 parts by mass of the resin component.
Further, in the fluorine-based resin sheet, the average particle size of the phosphorescent phosphor may be 0.1 to 5 μm.
Further, in the fluorine-based resin sheet, the resin component may be composed of 50 to 100% by mass of the fluorine-based resin and 0 to 50% by mass of the methacrylic acid ester resin. In this fluorine-based resin sheet, the resin component may be composed of 70 to 100% by mass of the fluorine-based resin and 0 to 30% by mass of the methacrylic acid ester resin.
Further, in the fluorine-based resin sheet, the fluorine-based resin may be a vinylidene fluoride-based resin.

Furthermore, the present invention also provides a laminate containing a fluorine-based resin sheet layer made of the fluorine-based resin sheet and a thermoplastic resin layer.
The present invention also provides a phosphorescent sheet using the fluororesin sheet.
Furthermore, the present invention also provides an outdoor phosphorescent label using the phosphorescent sheet.

As the composition containing the phosphorescent phosphor, there are those formed in the form of a sheet and those formed in the form of a film. Here, the "sheet" usually refers to a film having a thickness of 200 μm or more, and the “film” usually refers to a film having a thickness of less than 200 μm, but the “sheet” in the present invention is usually recognized. It is a concept including not only the "sheet" but also the "film".

According to the present invention, by blending a phosphorescent phosphor with a fluororesin, deterioration of the phosphorescent phosphor itself is suppressed due to excellent weather resistance, and the phosphorescent performance is maintained for a long period of time, especially when used outdoors. can do.
The effects described here are not necessarily limited, and may be any of the effects described in the present technology.

Hereinafter, embodiments for carrying out the present invention will be described in detail. It should be noted that the embodiments described below show an example of typical embodiments of the present invention, and the scope of the invention is not narrowly interpreted by this.

(First Embodiment)
First, the fluororesin sheet according to the first embodiment of the present invention will be described. The fluorine-based resin sheet of the present embodiment contains a resin component containing a fluorine-based resin and a phosphorescent phosphor. Further, the fluorine-based resin sheet according to the present embodiment may contain other components such as an antioxidant and a dispersant in addition to the resin component and the phosphorescent phosphor, if necessary. Hereinafter, each component of the fluororesin sheet of the present embodiment will be described.

[Fluorine resin]
The fluororesin is excellent in weather resistance and heat resistance, and is the main component of the fluororesin sheet of the present embodiment. The fluororesin is not particularly limited, and is a vinylidene fluoride (PVF) -based resin, an ethylene-tetrafluoroethylene copolymer (ETFE) -based resin, and a tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA) -based resin. Resins, vinylidene fluoride (PVDF) -based resins, ethylene-trifluoroethylene chloride (ECTFE) -based resins and the like can be used, and among them, polyvinylidene fluoride-based resins having excellent weather resistance are preferable. When a polyvinylidene fluoride-based resin is used, the structure thereof is not particularly limited as long as it is a vinyl compound having a vinylidene fluoride monomer unit, and a homopolymer of vinylidene fluoride may be used. It may be a copolymer of a polymer and another vinyl compound monomer.

Examples of the vinyl compound copolymerized with the vinylidene fluoride monomer include fluorinated vinyl compounds such as vinyl fluoride, ethylene tetrafluoroethylene, ethylene trifluoride, and propylene hexafluoride, and styrene and ethylene. , Known vinyl monomers such as butadiene and propylene.

[Methacrylic acid ester resin]
The resin component according to the present invention may contain at least a fluororesin, and if necessary, a small amount of methacrylic acid ester resin may be added to the fluororesin, particularly vinylidene fluoride resin. ..
When a vinylidene fluoride resin is used as the fluororesin in the fluororesin sheet according to the present embodiment, the vinylidene fluoride resin is inferior in adhesiveness to other materials, so the methacrylic acid ester resin is suitable. By blending in a large amount, it becomes possible to adhere to a base material or the like without using an expensive adhesive.

The structure of the methacrylic acid ester resin that can be blended in the resin sheet of the present embodiment is not particularly limited as long as it is a vinyl polymer based on the methacrylic acid ester monomer. Examples of the methacrylic acid ester monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate and hexyl methacrylate, and methyl methacrylate is particularly preferable. Further, the alkyl group such as propyl group, butyl group, pentyl group and hexyl group in the methacrylate ester monomer may be linear or branched. Further, this methacrylic acid ester resin is a monomer unit derived from known vinyl compounds other than methacrylic acid ester such as acrylic acid ester, styrene, ethylene, butadiene, α-methylstyrene, acrylonitrile, acrylic acid and propylene. May have.

[Mixing ratio of resin components]
The resin component in the resin sheet of the present embodiment contains the above-mentioned fluorine-based resin, or is composed of a fluorine-based resin and a methacrylic acid ester resin. When the resin component is composed of a vinylidene fluoride resin and a methacrylic acid ester resin as the actual component, the blending ratio thereof is a mass ratio of vinylidene fluoride resin: methacrylic acid ester resin = 50: 50 to 100. : 0 is desirable, more preferably vinyl fluoride resin: methacrylic acid ester resin = 60: 40 to 90:10, and even more preferably vinyl fluoride resin: methacrylic acid ester resin = 70: 30. ~ 80:20.

Here, if the blending amount of the methacrylic acid ester resin is small and the blending amount of the vinylidene fluoride resin per total mass of the resin component exceeds 95% by mass, the resin is thermally decomposed during the molding process, and the resin becomes yellow or brown. Discolors and causes deterioration of the phosphorescent phosphor.
On the other hand, if the amount of the methacrylic acid ester resin is large and the amount of vinylidene fluoride resin per total mass of the resin component is less than 70% by mass, the weather resistance is lowered, and when used outdoors for a long period of 20 years or more, Discoloration resistance may not be ensured.
The "during molding process" refers to a "compound step" in which a plurality of raw materials are mixed and melt-heated and kneaded in an extruder to form pellets, and the resin pellets are melt-heated by a film extruder. The "film-forming process" of forming a film using a die, then cooling and winding the film is shown, and the same applies to the following description.

[Phosphorescent phosphor]
A phosphorescent fluorescent substance is blended in the resin sheet of the present embodiment. The phosphorescent phosphor applicable to the present invention is not particularly limited, and known ones can be used, for example, zinc sulfide, calcium sulfide, zinc oxide, general formula M _1-X Al ₂ O _4-X . There are aluminates represented and the like. Here, M in the general formula is a mother crystal of a compound composed of at least one metal element selected from the group consisting of calcium, strontium, and barium, and X is −0.33 ≦ X ≦. In the range of 0.60, europium was added as an activator in a molar% of 0.001% or more and 10% or less with respect to the metal element represented by M, and neodym, samarium, dysprosium, holmium, erbium, thulium, etc. At least one or more elements in the group consisting of itterpium and lutetium are added in an molar% of 0.001% or more and 10% or less with respect to the metal element represented by M.
Here, the aluminate can be mixed with a phosphate or contacted in a phosphate solution to make the surface of the aluminate insoluble or sparingly soluble in water, thereby improving water resistance. it can.

The average particle size of the phosphorescent phosphor is 0.1 to 5 μm by irradiating the particle group with laser light and calculating the particle size distribution from the intensity distribution pattern of the diffracted / scattered light emitted from the particle group. , It is preferably 0.3 to 3 μm, and more preferably 0.5 to 2 μm. When the particle size of the phosphorescent phosphor is larger than 5 μm, the light irradiated to the radial edge of the granular phosphorescent phosphor may be dispersed and adversely affect the phosphorescence, and the particle size of the phosphorescent phosphor may be increased. As a result, the fluororesin sheet has to be formed thickly. On the other hand, when the particle size of the phosphorescent phosphor is smaller than 0.1 μm, it is not preferable because the target phosphorescent performance cannot be provided.

The phosphorescent phosphor can be blended with the fluororesin within a sheet-moldable range, and the blending amount thereof is, for example, 60 parts by weight or less, preferably 50 parts by weight, based on the total mass of the resin component. Below, it is more preferably 40 parts by weight or less. Here, the larger the blending amount of the phosphorescent phosphor, the higher the afterglow brightness, but if the blending amount is too large, the viscosity of the kneaded product increases, the fluidity significantly decreases, and sheet molding becomes impossible. ..

[Other ingredients]
The fluororesin sheet according to the present invention may contain components other than the resin component and the phosphorescent phosphor, if necessary. As other components, for example, an inorganic filler can be blended. As the inorganic filler, for example, alumina, silica, zirconia and the like can be blended. By blending the inorganic filler, it is possible to provide heat resistance to the fluororesin sheet, improve the rigidity (mechanical strength), and color any color. In such a case, for the purpose of improving the dispersibility of the inorganic filler, it is preferable to blend a fatty acid ester of polyethylene glycol having excellent compatibility with a fluororesin and / or a derivative thereof.
Further, an antioxidant, a dispersant, a coupling agent, a heat stabilizer, a surfactant, an antistatic agent, an antifogging agent, an ultraviolet absorber and the like can be added to the fluororesin sheet according to the present invention. ..

The fluorine-based resin sheet according to the present embodiment is completed by kneading the resin component, a phosphorescent phosphor, and if necessary, the other components, and forming the sheet into a sheet shape.
The thickness of the fluororesin sheet is not particularly limited and can be appropriately selected depending on the usage environment of the sheet, for example, in the range of 10 to 0.02 mm, preferably 5 to 0. It is 0.05 mm, more preferably 3 to 0.1 mm.

[Manufacturing method of fluorine-based resin sheet]
Next, a method for producing the fluororesin sheet of the present embodiment will be described. When producing the fluororesin sheet of the present embodiment, first, a resin component containing a fluororesin, or a resin component composed of a fluororesin and a methacrylic acid ester resin, a phosphorescent phosphor, and, if necessary, a phosphorescent phosphor A dispersant such as a fatty acid ester of polyethylene glycol and / or a derivative thereof, and an inorganic filler such as alumina, silica and zirconia are blended in a predetermined amount and kneaded. The method of kneading each component is not particularly limited, and a melt-kneading method using a known melt-kneader such as a closed mixer or an extruder can be applied. Examples of the kneader include an FCM type kneader manufactured by Kobe Steel.

Further, for example, the vinylidene fluoride resin used for kneading and a part or all of the methacrylic acid ester resin added as necessary may be powdered or kneaded using a high kneading type twin-screw extruder. Alternatively, it can be premixed at a high temperature using a high-speed rotary mixer in advance, and then melt-kneaded by a single-screw extruder. Thereby, the dispersibility of the phosphorescent phosphor can be further improved.

Next, the obtained molding raw material (resin composition) is melt-extruded to form a sheet. The fluorine-based resin sheet of the present embodiment may be a single layer or laminated, and as a melt extrusion molding method thereof, for example, in the case of a sheet having a laminated structure, a coextrusion molding method can be applied. As a co-extrusion molding method using a T-die in which resins are bonded in a molten state to form multiple layers using a plurality of extrusion molding machines, a plurality of resin layers are molded into a sheet shape and then the respective layers are contacted. There are a multi-manifold die method in which the resins are joined and bonded, and a feed block method in which a plurality of resins are joined and bonded using a merging device and then molded into a sheet shape. In, any method may be applied.

[How to use the fluororesin sheet]
Since the fluorine-based resin sheet according to the present invention has phosphorescent performance and high weather resistance, it can be suitably used as various signing supplies such as an outdoor night sign and a mark indicating the position of an emergency exit. Alternatively, for example, a transparent film on which a mark indicating the position of an emergency exit is indicated can be used as a base material and laminated to form various labeling products.
In addition, since it has high weather resistance, it can be used as a surface protective film to be attached to the surface of plastic, rubber, metal plate, glass, wood plate, slate, and other base materials, and protects and decorates the base material. , The design can be improved.

As described above, in the fluororesin sheet according to the present embodiment, since the phosphorescent phosphor is blended with the resin component containing the fluororesin, the weather resistance is excellent especially when used outdoors. , Deterioration of the resin component itself is suppressed, so that deterioration of the phosphorescent phosphor itself kneaded with the resin component can be suppressed, and the phosphorescent performance can be maintained for a long period of time.

[Laminate containing fluororesin sheet]
The present invention also provides a laminate containing the fluororesin sheet. The laminate according to the present invention can be obtained by laminating and laminating a fluorine-based resin sheet layer made of the fluorine-based resin sheet and a thermoplastic resin layer on which the fluorine-based resin sheet layer is laminated. Each layer will be described below.

[Fluorine-based resin sheet layer]
The fluorine-based resin sheet layer is formed from the fluorine-based resin sheet according to the present invention, and its composition and manufacturing method are the same as those of the fluorine-based resin sheet according to the first embodiment. Therefore, the description of the fluorine-based resin sheet layer is omitted.

[Thermoplastic resin layer]
The thermoplastic resin used for the thermoplastic resin layer according to the present invention is, for example, a thermoplastic polyester resin, a polyolefin resin, a polystyrene resin, a polyvinyl chloride resin, a polyarylate resin, a polycarbonate resin, or the like, and is preferably heat. It is a plastic polyester resin, a polyolefin resin, or a polystyrene resin, and particularly preferably a polyvinyl chloride resin or a polymethacrylic resin.
The method of laminating the thermoplastic resin layer on the fluororesin sheet layer is not particularly limited, and a known method can be used. For example, the thermoplastic resin layer is laminated on the fluororesin sheet layer. Method, thermal laminating method in which heat is applied to fuse, wet laminating method in which the adhesive is laminated before it dries, adhesive is coated, and then the adhesive is dried and then laminated. Examples include a dry laminating method for laminating, and a method for laminating by melt-extruding two types of resins such as coextrusion molding.

The laminate according to the present invention may contain at least the fluorine-based resin sheet layer and the thermoplastic resin layer. For example, the laminate comprises the fluorine-based resin sheet layer and the thermoplastic resin layer. It may be a double laminate. Further, it may be a multi-layered product obtained by combining a plurality of fluorine-based resin sheet layers and a plurality of thermoplastic resin layers.
Here, it is widely known that the phosphorescent phosphor is vulnerable to water. Therefore, when forming a double laminate, it is preferable to form a surface in which the fluororesin sheet layer does not come into contact with the external atmosphere. When forming the multi-layered product, it is preferable that the fluorine-based resin sheet layer is sandwiched between a pair of thermoplastic resin layers so that the fluorine-based resin sheet layer does not come into contact with the external atmosphere.

Even in the laminate according to the present invention as described above, since the phosphorescent phosphor is blended in the resin component containing the fluororesin, the resin has excellent weather resistance, especially when used outdoors. Deterioration of the component itself is suppressed, so that deterioration of the phosphorescent phosphor itself kneaded with the resin component can be suppressed, and the phosphorescent performance can be maintained for a long period of time. Further, when the fluorine-based resin sheet layer is configured so as not to come into contact with the external atmosphere, the above effect is remarkably exhibited.

Hereinafter, the present invention will be described in more detail based on Examples. It should be noted that the examples described below show an example of a typical example of the present invention, and the scope of the present invention is not narrowly interpreted by this.

[Example 1]
In Example 1, as shown in Table 1 below, 100% by mass of vinylidene fluoride resin as a resin component and 10 parts by mass of a phosphorescent phosphor were blended with a tumbler. Then, it was kneaded by a twin-screw extruder having a diameter of 45 mm to obtain a compound (resin composition). Next, a fluororesin sheet having a thickness of 300 μm was obtained by using a sheet film-forming machine in which a coat hanger die having a slit of 1.5 mm and a width of 400 mm was attached to a single-screw extruder having a diameter of 40 mm.
As the vinylidene fluoride resin, Kinner K720 manufactured by Arkema Co., Ltd. was used. As the phosphorescent phosphor, N Luminous G-300M manufactured by Nemoto & Co., Ltd. was used.

[Example 2]
In Example 2, as shown in Table 1, a fluororesin sheet having a thickness of 300 μm was obtained by using the same production method as in Example 1 except that the phosphorescent phosphor was blended in an amount of 20% by mass. It was.

[Example 3]
In Example 3, as shown in Table 1, a fluorine-based resin sheet having a thickness of 300 μm was obtained by using the same production method as in Example 1 except that the phosphorescent phosphor was blended in an amount of 45% by mass. It was.

[Example 4]
In Example 4, as shown in Table 1, 30 parts by mass of a phosphorescent phosphor is blended with 100 parts by mass of a resin component composed of 90% by mass of vinylidene fluoride resin and 10% by mass of methacrylic acid ester resin. Then, using the same production method as in Example 1, a fluororesin sheet having a thickness of 300 μm was obtained.
As the methacrylic acid ester resin, Hypet HBS000 manufactured by Mitsubishi Rayon Co., Ltd. was used.

[Example 5]
In Example 5, as shown in Table 1, the same method as in Example 4 was used except that the vinylidene fluoride resin was changed to 75% by mass and the methacrylic acid ester resin was changed to 25% by mass. A fluororesin sheet having a thickness of 300 μm was obtained.

[Example 6]
In Example 6, as shown in Table 1, the same method as in Example 4 was used except that the vinylidene fluoride resin was changed to 50% by mass and the methacrylic acid ester resin was changed to 50% by mass in the resin components. A fluororesin sheet having a thickness of 300 μm was obtained.

[Example 7]
In Example 7, as shown in Table 1, the same method as in Example 4 was used except that the vinylidene fluoride resin was changed to 40% by mass and the methacrylic acid ester resin was changed to 60% by mass in the resin components. A fluororesin sheet having a thickness of 300 μm was obtained.

[Example 8]
In Example 8, as shown in Table 1, the same method as in Example 4 was used except that the vinylidene fluoride resin was changed to 20% by mass and the methacrylic acid ester resin was changed to 80% by mass in the resin components. A fluororesin sheet having a thickness of 300 μm was obtained.

[Comparative Example 1]
As Comparative Example 1, as shown in Table 2 below, 30 parts by mass of a phosphorescent phosphor was blended with a tumbler with 100% by mass of a polyethylene terephthalate resin as a resin component. Then, it was kneaded by a twin-screw extruder having a diameter of 45 mm to obtain a compound (resin composition). Next, a phosphorescent sheet having a thickness of 300 μm was obtained by using a sheet film-forming machine in which a coat hanger die having a slit of 1.5 mm and a width of 400 mm was attached to a single-screw extruder having a diameter of 40 mm.
As the polyethylene terephthalate resin, MA-2101 manufactured by Unitika Ltd. was used. Further, as the phosphorescent phosphor, N luminous G-300M manufactured by Nemoto & Co., Ltd. was used.

[Comparative Example 2]
As Comparative Example 2, a phosphorescent sheet having a thickness of 300 μm was obtained by using the same method as in Comparative Example 1 except that a polyvinyl chloride resin was used as a resin component.
As the polyvinyl chloride resin, TE-650 manufactured by Taiyo PVC Co., Ltd. was used.

[Comparative Example 3]
As Comparative Example 3, a phosphorescent sheet having a thickness of 300 μm was obtained by using the same method as in Comparative Example 1 except that a polycarbonate resin was used as the resin component.
As the polycarbonate resin, Panlite L1250 manufactured by Teijin Chemicals Ltd. was used.

[Comparative Example 4]
As Comparative Example 4, a phosphorescent sheet having a thickness of 300 μm was obtained by using the same method as in Comparative Example 1 except that a methacrylic acid ester resin was used as a resin component.
As the methacrylic acid ester resin, Hypet HBS000 manufactured by Mitsubishi Rayon Co., Ltd. was used.

Next, the afterglow brightness and weather resistance of the phosphorescent sheets of each Example and each Comparative Example were evaluated by the following methods.

<Afterglow brightness>
A circular test piece having a diameter of 20 mm is cut out from each phosphorescent sheet, and a D65 light source is used on the surface layer side of the test piece (in the case of a single-layer sheet, either side) so that the illuminance is 200 looks. Light was applied perpendicularly to the sample for 20 minutes. Immediately after the irradiation, the test piece was moved into a dark box, and the afterglow brightness of the test piece was measured every predetermined time.
An OL-500A manufactured by Konica Minolta Co., Ltd. was used as the illuminometer, and a BM-100 manufactured by Topcon Co., Ltd. was used as the luminance meter. Three test pieces were used and the average value was adopted.

The measurement results are summarized in Table 3 below.

<Weather resistance>
A 40 mm × 100 mm test piece was cut out from each phosphorescent sheet, and this test piece was set in a weather meter manufactured by Iwasaki Electric Co., Ltd., and an accelerated test was conducted in accordance with the JIS K7350-2 method. After a lapse of a predetermined time, it was taken out (implemented for up to 4000 hours), and the afterglow brightness was measured by the above-mentioned method.

Table 4 below summarizes the afterglow brightness of the test pieces taken out after exposure to the weather meter after 20 minutes.

As shown in Table 4, the phosphorescent sheet (fluorine-based resin sheet) according to the present invention retains almost all the afterglow brightness even after the weather resistance test (after exposure to the weather meter), and is weather resistant as compared with Comparative Examples 1 to 4. It was confirmed that the sex was remarkably excellent.

The fluororesin sheet containing a phosphorescent phosphor according to the present invention has extremely excellent weather resistance, and is a phosphorescent sheet for outdoor phosphorescent signs, that is, various labeling supplies such as outdoor night signs and marks indicating the position of emergency exits. Is suitable as.

Claims (5)

Contains a resin component containing a fluorinated resin and a phosphorescent phosphor,
The fluorine-based resin is a fluorine-based resin sheet which is a vinylidene fluoride-based resin (however, a fluorine-based resin sheet containing a fluorescent whitening compound having maximum absorption in the near-ultraviolet region of 400 to 450 nm, and a vinylidene fluoride resin. 100 parts by mass of _Sr 4 _Al 14 _O 25: and a fluorine-based resin sheet layer made of E u, except fluorine-based resin sheet comprising a Dy40 parts by mass),
With a thermoplastic resin layer,
Laminates containing . The laminate according to claim 1, wherein the phosphorescent phosphor is contained in an amount of 1 to 80 parts by mass with respect to 100 parts by mass of the resin component. The laminate according to claim 1 or 2, wherein the phosphorescent phosphor has a particle size of 0.1 to 5 μm. The laminate according to any one of claims 1 to 3, wherein the resin component comprises 50 to 100% by mass of a fluororesin and 0 to 50% by mass of a methacrylic acid ester resin. The laminate according to any one of claims 1 to 3, wherein the resin component comprises 70 to 100% by mass of a fluororesin and 0 to 30% by mass of a methacrylic acid ester resin.