JP7185823B2 - Luminescent film, manufacturing method thereof, and UV irradiation type luminescent sheet - Google Patents

Description

TECHNICAL FIELD The present invention relates to a luminescent film, a method for producing the same, and an ultraviolet irradiation type luminescent sheet.

2. Description of the Related Art Conventionally, on expressways and the like, sign devices that are arranged above lanes and display road guidance and the like have been widely used. As such a marking device, for example, there is one of the type disclosed in Patent Document 1. The marking device of the document maintains the visibility of the marking surface at night by constructing the marking surface with a retroreflective sheet and reflecting the visible light emitted from the illumination device installed on the road shoulder on the marking surface. It's like
However, in such a marking device, there are cases where drivers in the oncoming lane look directly at the irradiation device, and the irradiation device is dazzling and hinders driving. When it rains or is foggy, the light can be reflected diffusely and dazzle the driver. In addition, depending on the angle at which the driver sees the sign surface, the sign surface may appear dark or the reflected light may become too strong, resulting in poor visibility.

Therefore, as a marking device that does not use visible light, for example, the type disclosed in Patent Document 2 is known. The labeling device of the same document forms a labeling surface using a paint containing a fluorescent substance that develops fluorescence when exposed to ultraviolet rays, and irradiates the labeling surface with ultraviolet rays from an irradiation device, thereby avoiding the disadvantages caused by visible light. It is designed to improve the visibility of the sign surface at night.

Further, Patent Document 3 discloses a method for manufacturing a luminescent sheet that emits fluorescence when irradiated with ultraviolet rays. A method for manufacturing a luminescent sheet is disclosed in which a planar fluorescent display device can be easily formed by fixing the back layer in a predetermined place and irradiating the luminescent layer on the front side with ultraviolet rays.

By the way, when a sign device is installed on a highway or the like, the sign device is exposed to the elements, and the highway must be closed for cleaning. Therefore, it is desired that a sign device installed on a highway or the like can maintain good visibility without cleaning for a long period of time.
The light-emitting sheet disclosed in Patent Document 3 emits light in a planar shape. For example, by cutting the light-emitting sheet into a predetermined shape and attaching it to a display device or the like, characters and characters can be displayed when irradiated with ultraviolet rays. It can be a signage device capable of displaying graphics. However, if the thickness of the light-emitting sheet is large, dirt tends to accumulate on the stepped portion caused by the thickness of the light-emitting sheet at the location where the light-emitting sheet is attached.

On the other hand, if the thickness of the light-emitting layer is reduced in order to reduce the thickness of the light-emitting sheet, the brightness generally decreases and good visibility cannot be obtained. Further, the light-emitting layer containing the fluorescent material contains a binder resin for holding the fluorescent material, and the thickness of the light-emitting layer can also be reduced by reducing the content of the binder resin. However, if the content of the binder resin is too small, the fluorescent material tends to fall off, and the adhesion of the light-emitting layer tends to decrease.

Patent Document 4 discloses a method for directly forming a thin film of a vanadium oxide phosphor having excellent crystallinity on an organic substrate without using a binder, which has been difficult in the past.

Japanese Patent Publication No. 10-506721 Japanese Utility Model Laid-Open No. 7-4514 JP-A-7-199844 JP 2009-84531 A

As described above, the UV irradiation type luminescent sheet used for signage devices on highways and the like needs to be thin and have high brightness in order to exhibit good visibility. It has been desired that the phosphor thin film disclosed in Patent Document 4 has a higher luminance in order to apply it to an ultraviolet irradiation type light-emitting sheet for a sign device. In addition, as described above, in the conventional UV irradiation type light-emitting sheet having a light-emitting layer containing a fluorescent material, it is impossible to satisfy all the characteristics of being able to make a thin film while maintaining high brightness and having excellent adhesion. It was difficult.
The present invention has been made under such circumstances. An object of the present invention is to provide an ultraviolet irradiation type luminescent sheet having a film.

The inventors of the present invention have made intensive studies to achieve the above object, and as a result, have found that the above problems can be solved by a luminescent film containing a predetermined component and an ultraviolet irradiation type luminescent sheet having the same. The present invention has been completed based on such findings.

That is, the present invention relates to the following.
[1] Vanadium oxide particles (A) represented by the composition formula MVO ₃ (M is one or more atoms selected from the group consisting of K, Rb, and Cs),
A composition formula MVO formed from one or more organic acid metal salts (b1) selected from the group consisting of organic acid potassium salts, organic acid rubidium salts, and organic acid cesium salts, and organic acid vanadium salts (b2) ₃ (M is the same as above) vanadium oxide crystal (B) and
one or more additives (C) selected from the group consisting of one or more organic acid metal salts (c1) selected from the group consisting of organic acid zirconium salts and organic acid titanium salts and silane coupling agents (c2); A luminescent film containing
[2] The light-emitting film according to [1] above, wherein the organic acid metal salt (b1) is a fatty acid metal salt.
[3] The light-emitting film according to [1] or [2] above, wherein the organic acid vanadium salt (b2) is a fatty acid vanadium salt.
[4] The light-emitting film according to any one of [1] to [3] above, wherein the organic acid metal salt (c1) is a fatty acid metal salt.
[5] The luminescent film according to any one of [1] to [4] above, wherein the component (A) has an average secondary particle size of 1 to 50 μm.
[6] The luminescent film according to any one of [1] to [5] above, wherein the component (A) is CsVO ₃ particles.
[7] The above [1] to [6], wherein the component (c2) is one or more silane coupling agents having a group selected from the group consisting of an epoxy group, a vinyl group, and a (meth)acryloyl group. The light emitting film according to any one of items 1 and 2.
[8] The luminescent film according to any one of [1] to [7] above, wherein the component (C) contains both the component (c1) and the component (c2).
[9] The above [1] to [8], wherein the content of the component (C) in the light emitting film is 0.01 to 50 parts by mass with respect to 100 parts by mass of the solid content of the component (A). The light emitting film according to any one of items 1 and 2.
[10] The luminescent film according to any one of [1] to [9] above, which has a thickness of 0.1 to 50 μm.
[11] A method for producing a light-emitting film, comprising the following steps (I) and (II).
Step (I): Vanadium oxide particles (A) represented by the composition formula MVO ₃ (M is one or more atoms selected from the group consisting of K, Rb, and Cs), organic acid potassium salt, organic acid One or more organic acid metal salts (b1) selected from the group consisting of rubidium salts and organic acid cesium salts, organic acid vanadium salts (b2), and the group consisting of organic acid zirconium salts and organic acid titanium salts A step of applying a coating liquid containing one or more additives (C) selected from the group consisting of one or more organic acid metal salts (c1) and silane coupling agents (c2) to form a coating film. (II): The luminescent film according to any one of the above [1] to [10], wherein the coating film is maintained at a temperature of 10° C. to 450° C. and then irradiated with ultraviolet rays having a wavelength of 400 nm or less [12]. An ultraviolet irradiation type luminescent sheet having.
[13] The UV irradiation type luminescent sheet according to [12] above, which has an antifouling layer, the luminescent film, and a reflective layer in this order.
[14] The UV irradiation type luminescent sheet according to [13] above, wherein the reflective layer is an adhesive reflective layer.
[15] The UV irradiation type luminescent sheet according to [13] above, further comprising an adhesive layer on the surface of the luminescent sheet on the reflective layer side.

According to the present invention, a luminescent film that develops fluorescence when irradiated with ultraviolet rays, can maintain high brightness even when thinned, and has excellent adhesion, a method for producing the same, and an ultraviolet irradiation type luminescent sheet having the luminescent film. can be provided. Since the light-emitting film and the ultraviolet irradiation-type light-emitting sheet are thin and have high brightness, when applied to a sign device installed on a highway, for example, dirt does not easily accumulate on the steps caused by the thickness of the sheet, and cleaning is possible. It becomes possible to maintain good visibility without performing for a long period of time.

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows an example of a structure of the ultraviolet irradiation type light emitting sheet of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows an example of a structure of the ultraviolet irradiation type light emitting sheet of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows an example of a structure of the ultraviolet irradiation type light emitting sheet of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows an example of a structure of the ultraviolet irradiation type light emitting sheet of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows an example of a structure of the ultraviolet irradiation type light emitting sheet of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows an example of a structure of the ultraviolet irradiation type light emitting sheet of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows an example of a structure of the ultraviolet irradiation type light emitting sheet of this invention. FIG. 6 is an explanatory view showing an example of a method for manufacturing the ultraviolet irradiation type luminescent sheet having the configuration shown in FIG. 5; BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram (partially enlarged view) which shows an example of the ultraviolet irradiation type|mold label|marker which overlaps and sticks the ultraviolet irradiation type|mold light emitting sheet of this invention. FIG. 2 is a schematic plan view showing an example of a label portion of an ultraviolet irradiation type labeling device formed by laminating the ultraviolet irradiation type luminescent sheets of the present invention.

[Light emitting film]
The light-emitting film of the present invention comprises vanadium oxide particles (A) represented by the composition formula MVO ₃ (M is one or more atoms selected from the group consisting of K, Rb, and Cs), an organic acid potassium salt, An organic acid metal salt (b1) selected from the group consisting of organic acid rubidium salts and organic acid cesium salts, and an organic acid vanadium salt ( _b2 ). is the same as), and one or more organic acid metal salts (c1) selected from the group consisting of organic acid zirconium salts and organic acid titanium salts, and a silane coupling agent ( It is characterized by containing one or more additives (C) selected from the group consisting of c2). The luminescent film of the present invention may further contain other components described later.
Since the light-emitting film of the present invention has the above structure, it can be made thinner while maintaining high luminance, and is excellent in adhesion. Each component contained in the light-emitting film of the present invention will be described below.

<Vanadium oxide particles (A)>
The luminescent film of the present _invention comprises vanadium oxide particles (A) (hereinafter simply referred to as "vanadium oxide particles (A)” or “component (A)”). The component (A) has the property of developing fluorescence when irradiated with ultraviolet rays.
Patent Document 4 discloses a vanadium oxide phosphor thin film formed using components corresponding to components (b1) and (b2) to be described later. In addition to the vanadium oxide crystals (B) formed from the components ) and (b2), by using the above component (A) in combination, it is possible to obtain a light-emitting film capable of exhibiting higher luminance even when the film is made thin. .
The vanadium oxide constituting component (A) is represented by the composition formula _MVO3 , where M is one or more atoms selected from the group consisting of K, Rb, and Cs. That is, component (A) is one or more particles selected from KVO ₃ , RbVO ₃ , and CsVO ₃ . Among these, the component (A) is preferably CsVO ₃ particles from the viewpoint of expressing high brightness.
The shape of the particles of component (A) is not particularly limited, and examples thereof include spherical, plate-like, needle-like, and the like. The particles of component (A) are preferable from the viewpoint of the luminous performance of the luminescent film, which is obtained in the state of secondary particles in which the primary particles are aggregated.

The vanadium oxide particles as component (A) preferably have an average secondary particle size of 1 μm or more, more preferably 5 μm or more, and even more preferably 5 μm or more, from the viewpoint of obtaining a light-emitting film that can exhibit high brightness even with a thin film. is 10 μm or more. By setting the average secondary particle size of the particles of the component (A) to 1 μm or more, it is possible to obtain a light-emitting film with higher brightness. The average secondary particle size of the particles of component (A) is preferably 50 µm or less, more preferably 40 µm or less, and still more preferably 30 µm or less.
The average secondary particle size of component (A) can be measured with a laser diffraction particle size distribution analyzer.

The method for producing vanadium oxide particles as component (A) is not particularly limited, and conventionally known methods can be used. For example, the CVD method, hydrothermal synthesis, solvothermal synthesis, thermal decomposition method, and production method by irradiating an ultraviolet laser onto a metal-containing organic compound that is a raw material of vanadium oxide particles can be used.

<Vanadium oxide crystal (B)>
The light-emitting film of the present invention comprises one or more organic acid metal salts (b1) selected from the group consisting of organic acid potassium salts, organic acid rubidium salts, and organic acid cesium salts, and organic acid vanadium salts (b2). Formed vanadium oxide crystals (B) represented by the composition formula MVO ₃ (M is the same as above) (hereinafter simply referred to as “vanadium oxide crystals (B)” or “(B) component”) there is).
Here, "one or more organic acid metal salts (b1) selected from the group consisting of organic acid potassium salts, organic acid rubidium salts, and organic acid cesium salts (hereinafter sometimes referred to as "(b1) component") and _a vanadium oxide crystal ( B)” is specifically a vanadium oxide represented by the composition formula MVO ₃ , which is obtained by irradiating a coating film obtained by coating a solution containing components (b1) and (b2) with ultraviolet rays. refers to crystals. The details of the method for forming vanadium oxide crystals will be described in the method for producing a light-emitting film, which will be described later.
The vanadium oxide crystals (B), like the component (A), have the property of emitting fluorescence when irradiated with ultraviolet light. also exhibit high luminance.

The vanadium oxide crystal (B) is formed from the (b1) component and the (b2) component, and is represented by the composition formula MVO ₃ (where M is the same as above). M may be the same atom as M in the component (A), or may be different. From the viewpoint of obtaining high luminance, the (B) component is preferably _CsVO3 .

(Organic acid metal salt (b1))
The organic acid metal salt (b1) is one or more selected from the group consisting of an organic acid potassium salt, an organic acid rubidium salt, and an organic acid cesium salt, and the brightness of the formed vanadium oxide crystal (B) is is preferably an organic acid cesium salt. In the following description, "organic acid metal salt" refers to a salt compound formed from an organic acid and a metal.
The organic acid constituting component (b1) is not particularly limited, but examples include fatty acids, and weakly acidic compounds having a carboxy group, a hydroxy group, or an enol group, which are soluble in organic solvents. From the same viewpoint as above, the organic acid metal salt (b1) is preferably a fatty acid metal salt, more preferably a fatty acid cesium salt.

Examples of the fatty acid include saturated fatty acids and unsaturated fatty acids having 6 to 30 carbon atoms, with saturated fatty acids being preferred. The number of carbon atoms in the fatty acid is preferably 6-20, more preferably 6-18, even more preferably 6-12, still more preferably 8-10.
Examples of saturated fatty acids having 6 to 30 carbon atoms include hexanoic acid, heptanoic acid, octylic acid, nonanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid, and docosane. acids, tetracosanoic acid, hexacosanoic acid, octacosanoic acid, triacontanoic acid, and the like. The term "octylic acid" as used herein is a concept that includes 2-ethylhexanoic acid, n-octanoic acid, and isooctanoic acid.
Examples of unsaturated fatty acids having 6 to 30 carbon atoms include oleic acid, linoleic acid, and linolenic acid.
Examples of fatty acids other than the above include rosin acid, linseed oil fatty acid, soybean oil fatty acid, and tall oil acid.

Examples of the compounds having a carboxyl group include carboxyl group-containing compounds other than the fatty acids, such as citric acid, oxalic acid, bile acid, sugar acid, 12-hydroxystearic acid, hydroxycinnamic acid, and folic acid. amino acids such as alanine and arginine; aromatic acids such as benzoic acid and phthalic acid; and naphthenic acid.
Examples of compounds having a hydroxy group or an enol group include ascorbic acid, α acid, imidic acid, erythorbic acid, croconic acid, kojic acid, squaric acid, sulfinic acid, teichoic acid, dehydroacetic acid, delta acid, uric acid, hydroxamic acid, humic acid, fulvic acid, phosphonic acid and the like.
The organic acids constituting the component (b1) may be used alone or in combination of two or more. Among them, the fatty acid as the organic acid constituting the component (b1) has 6 to 30 carbon atoms (preferably 6 to 20, more preferably 6 to 18, still more preferably 6 to 12, still more preferably 8 to 10). Saturated fatty acids are preferred, one or more selected from the group consisting of octylic acid, nonanoic acid and decanoic acid are more preferred, and octylic acid is even more preferred.
A preferred compound as component (b1) is one or more selected from the group consisting of cesium octylate, cesium nonanoate, cesium decanoate, and cesium naphthenate, and a particularly preferred compound is cesium octylate.
(b1) component can also be used individually by 1 type or in combination of 2 or more types.

(Organic acid vanadium salt (b2))
The organic acid vanadium salt (b2) is a salt compound formed from an organic acid and vanadium. Although there are no particular restrictions on the organic acid that constitutes the component (b2), the same organic acids as those exemplified for the component (b1) can be mentioned.
The organic acids constituting the component (b2) may be used alone or in combination of two or more.

Among them, the organic acid vanadium salt (b2) is preferably a fatty acid vanadium salt and has 6 to 30 carbon atoms (preferably 6 to 20, more preferably 6 to 18, still more preferably 6 to 12, still more preferably 8 10) is more preferably a vanadium salt of a saturated fatty acid. A preferred compound as component (b2) is one or more vanadium salts selected from the group consisting of octylic acid, nonanoic acid, decanoic acid and naphthenic acid, with vanadium octylate being more preferred.
Moreover, (b2) component can also be used individually by 1 type or in combination of 2 or more types.

<Additive (C)>
Further, the light-emitting film of the present invention is one selected from the group consisting of one or more organic acid metal salts (c1) selected from the group consisting of organic acid zirconium salts and organic acid titanium salts and the silane coupling agent (c2). It is characterized by containing at least one additive (C) (hereinafter sometimes simply referred to as "additive (C)" or "component (C)").
By including the component (C) in the light-emitting film of the present invention, the components (A) and (B), which are fluorescent materials, are prevented from falling off from the film, and the content of the components (A) and (B) Even with a luminescent film having a high ratio, the adhesiveness to an adherend when used as an ultraviolet irradiation type luminescent sheet is improved. Additives may lower the brightness of the light-emitting film, but in the present invention, by using the specific component (C), adhesion can be imparted without lowering the brightness of the light-emitting film.

(One or more organic acid metal salts (c1) selected from the group consisting of organic acid zirconium salts and organic acid titanium salts)
The organic acid metal salt (c1) (hereinafter sometimes simply referred to as "component (c1)") is one or more selected from the group consisting of zirconium salts of organic acids and titanium salts of organic acids, and has excellent adhesion and color tone. from the point of view, organic acid zirconium salts are preferred.
Examples of the organic acid constituting component (c1) include those exemplified for component (b1) above, and fatty acids are preferred. That is, the organic acid metal salt (c1) is preferably a fatty acid metal salt.
The organic acids constituting component (c1) may be used alone or in combination of two or more. Among them, the fatty acid as the organic acid constituting the component (c1) has 6 to 30 carbon atoms (preferably 6 to 20, more preferably 6 to 18, still more preferably 6 to 12, still more preferably 8 to 10). Saturated fatty acids are preferred, one or more selected from octylic acid, nonanoic acid and decanoic acid are more preferred, and octylic acid is even more preferred.
A preferred compound as component (c1) is one or more selected from the group consisting of zirconium octoate, zirconium nonanoate, zirconium decanoate, and zirconium naphthenate, and a particularly preferred compound is zirconium octoate.
(c1) component can also be used individually by 1 type or in combination of 2 or more types.

(Silane coupling agent (c2))
As the silane coupling agent (c2) (hereinafter sometimes simply referred to as "component (c2)"), conventionally known silane coupling agents can be used without any particular limitation. For example, a silane coupling agent having an epoxy group, a silane coupling agent having a vinyl group, a silane coupling agent having a (meth)acryloyl group, a silane coupling agent having an amino group, and a silane coupling agent having a mercapto group. etc.
Silane coupling agents having an epoxy group include, for example, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like.
Silane coupling agents having a vinyl group include vinyltrimethoxysilane and vinyltriethoxysilane.
Silane coupling agents having a (meth)acryloyl group include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. , 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropyltriethoxysilane and the like.
Silane coupling agents having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(amino ethyl)-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)- 2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride and the like.
Silane coupling agents having a mercapto group include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.
In addition, as silane coupling agents other than the above, p-styryltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, bis(triethoxysilylpropyl)tetrasulfide, and 3- isocyanatopropyltriethoxysilane and the like.

Among the above, from the viewpoint of obtaining adhesion, the component (c2) is preferably one or more silane coupling agents having a group selected from the group consisting of an epoxy group, a vinyl group, a (meth)acryloyl group, and an amino group. From the viewpoint of adhesion and color tone of the light-emitting film, one or more silane coupling agents having a group selected from the group consisting of an epoxy group, a vinyl group, and a (meth)acryloyl group are more preferable, and 3-glycidoxypropyl. At least one selected from the group consisting of trimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane is more preferred.
(c2) component can also be used individually by 1 type or in combination of 2 or more types.

The component (C) may be at least one selected from the group consisting of components (c1) and (c2). It preferably contains a component, and more preferably contains both the (c1) component and the (c2) component. A particularly preferred combination of component (c1) and component (c2) is that component (c1) is a zirconium salt of an organic acid and component (c2) is selected from the group consisting of an epoxy group, a vinyl group, and a (meth)acryloyl group. is a combination of one or more silane coupling agents having a group that is

<Other ingredients>
In addition to the above components (A), (B), and (C), the light-emitting film of the present invention may include other general fluorescent materials for fine adjustment of luminance and chromaticity within a range that does not impair the object of the present invention. It can also contain bodies, pigments, and the like. In addition, a dispersant, a viscosity modifier, a leveling agent, etc. may be included as appropriate.

<Content of each component in the luminescent film>
The preferable content of each component in the light-emitting film of the present invention is as follows.
The content of the component (A) in the light-emitting film of the present invention is preferably 30 to 95% by mass, more preferably 35 to 90% by mass, from the viewpoint of expressing high brightness and maintaining good adhesion. More preferably 40 to 90 mass %, still more preferably 50 to 88 mass %.
The content of the component (B) in the light-emitting film of the present invention is preferably 1 to 50 parts by mass, more preferably 100 parts by mass of the solid content of the component (A), from the viewpoint of expressing high brightness. 2 to 40 parts by mass, more preferably 3 to 30 parts by mass.
The content of the component (C) in the luminescent film of the present invention is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, based on 100 parts by mass of the solid content of the component (A). parts, more preferably 0.5 to 30 parts by mass. If the content is 0.01 parts by mass or more, the adhesion is good, and if it is 50 parts by mass or less, the brightness and color tone are good. Further, when both the (c1) component and (c2) component are included as the (C) component, from the viewpoint of obtaining excellent adhesion, the content ratio of the (c1) component and the (c2) component is the mass ratio and (c1)/(c2) is preferably 0.2 or more, more preferably 0.5 or more, and even more preferably 1 or more. In addition, the value of (c1)/(c2) in mass ratio is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.

The total content of the components (A), (B), and (C) in the light-emitting film of the present invention is preferably 80% by mass from the viewpoint of achieving high brightness even when the light-emitting film is thinned. Above, more preferably 90% by mass or more, still more preferably 95% by mass or more. Moreover, an upper limit is 100 mass %.

The thickness of the luminescent film of the present invention is preferably 0.1 to 50 μm, more preferably 1.0 to 40 μm, even more preferably 3.0 to 30 μm, still more preferably 5.0 to 25 μm. If the thickness of the light-emitting film is 0.1 μm or more, high luminance can be obtained, and if it is 50 μm or less, it is advantageous in terms of thinning.
Specifically, the thickness of the light-emitting film can be measured by the method described in Examples.

[Method for producing light-emitting film]
The method for producing a light-emitting film of the present invention (hereinafter sometimes referred to as "the production method of the present invention") is characterized by comprising the following steps (I) and (II).
Step (I): Vanadium oxide particles (A) represented by the composition formula MVO ₃ (M is one or more atoms selected from the group consisting of K, Rb, and Cs), organic acid potassium salt, organic acid One or more organic acid metal salts (b1) selected from the group consisting of rubidium salts and organic acid cesium salts, organic acid vanadium salts (b2), and the group consisting of organic acid zirconium salts and organic acid titanium salts A step of applying a coating liquid containing one or more additives (C) selected from the group consisting of one or more organic acid metal salts (c1) and silane coupling agents (c2) to form a coating film. (II): A step of maintaining the coating film at a temperature of 10° C. to 450° C. and then irradiating it with ultraviolet rays having a wavelength of 400 nm or less. can do. In particular, by irradiating the coating film obtained by applying the coating liquid containing the components (b1) and (b2) in the step (I) with ultraviolet rays in the step (II), the above-mentioned component (b1) The vanadium oxide crystal (B) represented by the composition formula MVO ₃ formed from M and vanadium in the component (b2) can be grown to produce the light-emitting film of the present invention described above. .

<Step (I)>
Step (I) comprises vanadium oxide particles (A) represented by the composition formula MVO ₃ (M is one or more atoms selected from the group consisting of K, Rb, and Cs), an organic acid potassium salt, an organic One or more organic acid metal salts (b1) selected from the group consisting of acid rubidium salts and organic acid cesium salts, organic acid vanadium salts (b2), and the group consisting of organic acid zirconium salts and organic acid titanium salts A step of applying a coating liquid containing one or more additives (C) selected from the group consisting of one or more selected organic acid metal salts (c1) and silane coupling agents (c2) to form a coating film. is. By carrying out step (I), a coating film containing at least components (A), (b1), (b2) and (C) is formed. Furthermore, the coating film may contain other components.

(Coating liquid)
The coating liquid used in step (I) contains at least the components (A), (b1), (b2) and (C), and may further contain other components. Examples of each component and preferred embodiments thereof are the same as above. Moreover, a solvent such as toluene or xylene may be included as necessary.
The contents of component (A), component (b1), component (b2), and component (C) in the coating liquid are within the range in which the content of each component in the light-emitting film is the preferred content described above. Adjustable. That is, the preferable content of each of the above components in the coating liquid is as follows.
The content of component (A) is preferably 30 to 95% by mass, more preferably 35 to 90% by mass, and still more preferably 40 to 90% by mass, from the viewpoint of expressing high brightness and maintaining good adhesion. , and more preferably 50 to 85% by mass.
The content of component (b1) is preferably 0.5 to 25 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the solid content of component (A), from the viewpoint of obtaining high brightness and excellent adhesion. parts by mass, more preferably 1.5 to 15 parts by mass. Further, the content ratio of the (b1) component and the (b2) component in the coating liquid is M (M is one or more atoms selected from the group consisting of K, Rb, and Cs in the (b1) component. ) and vanadium in the component (b2) preferably have an atomic ratio of 1:0.5 to 1:2, more preferably 1:0.8 to 1:1.2. : 0.95 to 1:1.05 is more preferable. Particularly preferably, the content ratio of the component (b1) and the component (b2) in the coating solution is such that the atomic ratio is 1:1.
The content of component (C) is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, more preferably 0.5 to 50 parts by mass, based on 100 parts by mass of the solid content of component (A). 30 parts by mass. If the content is 0.01 parts by mass or more, the adhesion is good, and if it is 50 parts by mass or less, the brightness and color tone are good. Further, when both the (c1) component and (c2) component are included as the (C) component, from the viewpoint of obtaining excellent adhesion, the content ratio of the (c1) component and the (c2) component is the mass ratio and (c1)/(c2) is preferably 0.2 or more, preferably 0.5 or more, and even more preferably 1 or more. In addition, the value of (c1)/(c2) in mass ratio is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.

The method for preparing the coating liquid is not particularly limited, and the coating liquid can be prepared by mixing each component contained in the coating liquid using a conventionally known method. There are no particular restrictions on the order in which the components are mixed, but it is preferable to prepare a solution by previously mixing the components (b1) and (b2), and then mix the solution with the other components. In this case, the reaction with the oxide represented by the composition formula MVO ₃ is likely to occur, and from the viewpoint of manufacturing a high-quality light-emitting film, after preparation of the coating solution (after mixing the components (b1) and (b2)), It is preferable to form a coating film by coating quickly.
The coating method of the coating liquid is also not particularly limited, and a conventionally known method can be used for coating. Examples of coating methods include bar coating, wire coating, spin coating, roll coating, spray coating, die coating, slit coating, gravure coating and the like.
The object to which the coating liquid is applied can be appropriately selected according to the layer structure and application of the luminescent film and the ultraviolet irradiation type luminescent sheet having the same. For example, when applying a coating liquid onto a substrate, both inorganic substrates and organic substrates can be used. In the case of inorganic substrates, substrates that do not melt at room temperature or are dissolved by atmospheric humidity. If it is Further, in the case of the organic substrate, the substrate temperature may be heated to about 60 to 70° C. for about 10 minutes when the ultraviolet irradiation is performed in step (II) to be described later. Therefore, it is preferable to use an organic substrate made of a material that does not melt near this temperature. Examples of organic substrates include transparent substrates used for light-emitting sheets described later.

<Step (II)>
Step (II) is a step in which the coating film obtained in step (I) is maintained at a temperature of 10° C. to 450° C. and then irradiated with ultraviolet rays having a wavelength of 400 nm or less. By performing this step, M in the component (b1) contained in the coating film obtained in step (I) (M is one or more atoms selected from the group consisting of K, Rb, and Cs) and vanadium in the component (b2), the vanadium oxide crystal (B) represented by the composition formula MVO ₃ is grown to obtain the light-emitting film of the present invention.

The coating film obtained in step (I) is kept at a temperature of 10°C to 450°C. This allows the coating to dry and the solvent to be removed. The holding temperature is preferably 15° C. to 200° C., more preferably 20° C. to 150° C., still more preferably 20° C. to 150° C., from the viewpoint of efficiently forming and growing vanadium oxide crystals (B) and suppressing coloration and brightness reduction. 20°C to 100°C.
The retention time of the coating film can be appropriately selected depending on the retention temperature, application, etc., but from the viewpoint of productivity and suppression of coloration and brightness reduction, it is preferably 1 minute to 400 hours, more preferably 1 minute to 400 hours. 3 minutes to 200 hours.

Next, the coating film held at the above temperature is irradiated with ultraviolet light having a wavelength of 400 nm or less. As a result, the growth of the vanadium oxide crystals (B) can be promoted, and the light-emitting film of the present invention capable of exhibiting high brightness can be efficiently produced.
In the ultraviolet irradiation, it is preferable to use an ultraviolet laser or an ultraviolet lamp.
An excimer laser, a pulse laser, or the like can be used as the ultraviolet laser. Moreover, as an ultraviolet lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a carbon arc, or the like can be used.
When using an ultraviolet laser with a wavelength of 400 nm or less, for example, the coating film obtained in step (I) is maintained at the above temperature, and then irradiated with an ultraviolet laser at room temperature under low energy conditions. Specifically, it is preferable to irradiate ultraviolet rays under the condition that the irradiation energy is 15 to 100 mW/m ² .
When an ultraviolet lamp having a wavelength of 400 nm or less is used, for example, the coating film obtained in step (I) is maintained at the above temperature and then irradiated with ultraviolet rays at room temperature under low energy conditions. In this case, in order to promote crystallization of the vanadium oxide crystals (B), it is preferable to irradiate the ultraviolet rays under the condition of irradiation energy of 15 to 50 mW/cm ² .
In the production method of the present invention, an ultraviolet laser with a wavelength of 400 nm or less and an ultraviolet lamp with a wavelength of 400 nm or less may be used in combination during ultraviolet irradiation. In the present invention, when the purpose is to shorten the crystallization time, the coating film obtained in step (I) may be irradiated with ultraviolet rays for a short period of time using an ultraviolet lamp and then irradiated with ultraviolet rays using an ultraviolet laser. preferable.

[Ultraviolet light-emitting sheet]
The ultraviolet irradiation type light-emitting sheet of the present invention (hereinafter sometimes simply referred to as "light-emitting sheet") has the above-described light-emitting film of the present invention. Since the luminescent film can maintain high luminance even if it is made thin, the luminescent sheet of the present invention having this can maintain high luminance while reducing the overall thickness.

<Layer structure of light-emitting sheet>
The luminescent sheet of the present invention may have at least the luminescent film of the present invention. When the luminescent sheet of the present invention is applied to a highway signage device or the like, the luminescent sheet of the present invention preferably has an antifouling layer, a luminescent film, and a reflective layer in this order from the viewpoint of antifouling properties. The reflective layer may be an adhesive reflective layer. Further, the luminescent sheet having the antifouling layer, the luminescent film, and the reflective layer in this order may further have an adhesive layer on the side of the reflective layer.

Examples of the luminescent sheet of the present invention include a sheet having the following layer structure. In the description below, for example, the notation A/B/C indicates that A, B, and C are laminated in this order from above (or from below). Also, the release sheet is optional.
(a) Luminous film/transparent substrate (b) Luminous film/reflective layer (/release sheet)
(c) Antifouling layer/luminescent film/transparent substrate (d) Antifouling layer/luminescent film/reflective layer (/release sheet)
(e) antifouling layer/adhesive layer/luminescent film/reflective layer (/release sheet)
(f) antifouling layer/light-emitting film/reflective layer/adhesive layer (/release sheet)
(g) antifouling layer/adhesive layer/luminescent film/reflective layer/adhesive layer (/release sheet)
Examples of the structure having the antifouling layer, the light-emitting film, and the reflective layer in this order include the light-emitting sheets having the layer structures (d) to (g) described above.

1 to 7 are cross-sectional schematic diagrams showing an example of the configuration of the luminescent sheet of the present invention. FIG. 1 is a schematic sectional view showing a luminescent sheet having the layer structure of (a) above. A luminescent sheet 110 is obtained by laminating a luminescent film 1 on a transparent substrate 2 . FIG. 2 is a schematic cross-sectional view showing a luminescent sheet having the layer structure of (b) above, and the luminescent sheet 120 is obtained by laminating the luminescent film 1 and the reflective layer 3 in this order. A release sheet 4 (not shown) may be provided on the surface of the light-emitting sheet 120 on the reflecting layer 3 side. In particular, when the reflective layer is the adhesive reflective layer 3', it is preferable to have the release sheet 4. FIG. 3 is a schematic cross-sectional view showing a luminescent sheet having the layer structure of (c) above, and the luminescent sheet 130 is obtained by laminating the antifouling layer 5, the luminescent film 1 and the transparent substrate 2 in this order.
FIG. 4 is a schematic cross-sectional view showing a light-emitting sheet having the layer structure of (d) above. In the light-emitting sheet 140 of the present invention, the antifouling layer 5, the light-emitting film 1, and the reflective layer 3 are laminated in this order.
FIG. 5 is a schematic cross-sectional view showing a luminescent sheet having the layer structure of (e) above. In the luminescent sheet 150, an antifouling layer 5, an adhesive layer 6, a luminescent film 1, and a reflective layer 3 are laminated in this order. .
Also in the layer structures (d) and (e), when the reflective layer is the adhesive reflective layer 3', it is preferable to have a release sheet 4 on the reflective layer side.
FIG. 6 is a schematic cross-sectional view showing a light-emitting sheet having the layer structure of (f) above. Laminated.
FIG. 7 is a schematic cross-sectional view showing a luminescent sheet having the layer structure of (g) above. and release sheet 4 are laminated in order.

Each layer constituting the light-emitting sheet of the present invention will be described below.
<Transparent substrate>
Examples of the transparent substrate used for the light-emitting sheet having the layer structure of (a) and (c) include polyester-based resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyethylene, polypropylene, polybutene, polybutadiene, and polymethyl Polyolefin resins such as pentene, low density polyethylene, linear low density polyethylene; cellulose resins such as triacetylcellulose; acrylic resins such as polymethyl methacrylate; polyurethane resins; polycarbonate resins; cycloolefin resins; Examples thereof include resin films made of vinyl, vinyl chloride copolymer, ethylene-vinyl acetate copolymer, ethylene (meth)acrylic acid copolymer, polystyrene, fluororesin, and the like. Among these, from the viewpoint of weather resistance, heat resistance, and antifouling properties, from the group consisting of polyester-based resins, polyolefin-based resins, cellulose-based resins, acrylic-based resins, polyurethane-based resins, polycarbonate-based resins, and cycloolefin-based resins. A resin film made of one or more selected resins is preferable, and a resin film made of one or more resins selected from the group consisting of polyester resins and acrylic resins is more preferable.
Although the thickness of the transparent base material is not particularly limited, it is preferably 5 to 300 μm, more preferably 10 to 200 μm, from the viewpoint of thinning the luminescent sheet and imparting strength.

<Anti-fouling layer>
When the luminescent sheet of the present invention has an antifouling layer, the antifouling layer is provided on the outermost layer of the luminescent sheet from the viewpoint of imparting antifouling properties. The antifouling layer may be a single layer or a plurality of layers. It is preferably composed of a resin or a photocatalyst layer. Even if the surface layer of the antifouling layer is made of a fluorine-based resin or a silicone resin having a low surface energy, the antifouling property can be imparted. , is more preferable because the adhesive strength of the surface is good when a plurality of luminescent sheets are laminated and used.
When the surface layer of the antifouling layer is any of the above resins, the resin constituting the surface layer may be selected from among the three resins from the viewpoint of weather resistance and antifouling properties. , acrylic resin, acrylic urethane resin, and polyester resin in that order.

As the acrylic resin, polymethyl methacrylate resin is preferable, as the acrylic urethane resin, a resin obtained by the method described below can be used, and as the polyester resin, polyethylene terephthalate resin is generally used.

This acrylic urethane resin is obtained by subjecting a vinyl compound having an active hydrogen group such as a hydroxyl group or a thiol group to a polyaddition reaction with a polyol or an isocyanate compound to obtain a vinyl group-containing urethane polymer, followed by radical polymerization with an acrylic monomer. to obtain an acrylic-urethane copolymer. Furthermore, a polyisocyanate compound is added and crosslinked by molding to form a surface layer portion made of an acrylic urethane resin.

When the antifouling layer consists of a plurality of layers, the material of the layers other than the surface layer constituting the antifouling layer (hereinafter sometimes referred to as the "lower layer") is not particularly limited, but thermoplastic resin. Preferably. Further, the surface layer portion and the lower layer portion may be layers made of the same material, or may be layers made of different kinds of materials.

(Photocatalyst layer)
When the surface layer of the antifouling layer is a photocatalyst layer, a layer containing a photocatalyst accelerator and an inorganic binder is provided as the photocatalyst together with a photocatalyst active material.
The photocatalytically active material is not particularly limited, and conventionally known materials such as titanium dioxide, strontium titanate (SrTiO ₃ ), barium titanate (BaTi ₄ O ₉ ), sodium titanate (Na ₂ Ti ₆ O ₁₃ ), and dioxide. Zirconium, α-Fe ₂ O ₃ , tungsten oxide, K ₄ Nb ₆ O ₁₇ , Rb ₄ Nb ₆ O ₁₇ , K ₂ Rb ₂ Nb ₆ O ₁₇ , cadmium sulfide, zinc sulfide and the like. These may be used alone or in combination of two or more. Among them, titanium dioxide, particularly anatase-type titanium dioxide, is useful as a practical photocatalytic active material. This titanium dioxide exhibits excellent photocatalytic activity by absorbing light of a specific wavelength in the ultraviolet region contained in daily light such as sunlight.

On the other hand, as the photocatalyst promoter, platinum group metals such as platinum, palladium, rhodium and ruthenium are preferably used. These may be used alone or in combination of two or more. The amount of the photocatalyst promoter added is usually selected in the range of 1 to 20% by mass based on the total weight of the photocatalyst active material and the photocatalyst promoter from the viewpoint of photocatalytic activity. Moreover, as an inorganic binder, a silica-type binder etc. are mentioned, for example.
When forming such a photocatalyst layer, for example, TOTO Co., Ltd. containing commercially available titanium dioxide, product name "Hydrotect Clear Coat", and Ishihara Sangyo Co., Ltd. containing anatase type titanium oxide, product name "STS -11” or “ST-K211” can be used.

Such a photocatalyst layer is excited by irradiation with ultraviolet rays, and the surface of the photocatalyst layer becomes superhydrophilic with a contact angle with water of 10 degrees or less, exhibiting an excellent antifouling effect.
When this photocatalyst layer is excited by ultraviolet rays, it exerts a strong oxidative decomposition function by means of reactive active oxygen species. It is preferable to interpose a silicone resin, an acryl-modified silicone resin, or the like therebetween.

The thickness of the entire antifouling layer is preferably 3 to 50 μm. If the thickness of the entire antifouling layer is 3 μm or more, the antifouling property is sufficient and uniform film formation is facilitated. On the other hand, if the thickness is 50 μm or less, it is possible to avoid a decrease in luminance of the light-emitting sheet. From the viewpoint of maintaining high brightness, the thickness of the antifouling layer is more preferably in the range of 5 to 40 μm, more preferably in the range of 7 to 30 μm.
The haze value of the antifouling layer is preferably 5% or less, more preferably 3% or less, and even more preferably 1% or less from the viewpoint of maintaining good visibility.
The antifouling layer may contain a hindered amine light stabilizer (HALS) or an antioxidant in order to improve weather resistance.

<Reflective layer>
In the luminescent sheet of the present invention, the reflective layer provided below the luminescent film is a layer that reflects ultraviolet rays transmitted through the luminescent film and contains a white pigment or a colored pigment and a matrix resin. is preferably
Examples of the white pigment include titanium oxide, zinc white, white lead, lithopone, barite, precipitated barium sulfate, calcium carbonate, precipitated silica (white carbon), gypsum, and the like. may be used, or two or more may be used in combination.

A green pigment is usually used as the colored pigment. Examples of the green pigment include inorganic pigments such as Viridian, chromium oxide green, cobalt green, cobalt-chromium green, and chromium green. These may be used singly or in combination of two or more. They may be used in combination.

On the other hand, the matrix resin constituting the reflective layer differs depending on whether the reflective layer is a non-adhesive reflective layer or an adhesive reflective layer.
As the matrix resin constituting the non-adhesive reflective layer, a urethane-based resin is preferable from the viewpoint of weather resistance, ultraviolet transmittance, mechanical strength, and the like. On the other hand, the matrix resin constituting the adhesive reflective layer is preferably an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive or a polyester-based pressure-sensitive adhesive, and more preferably an acrylic pressure-sensitive adhesive. Details of the acrylic pressure-sensitive adhesive that is preferable as the matrix resin constituting the pressure-sensitive reflective layer will be described later in the section on the pressure-sensitive adhesive layer.
The ratio of the matrix resin to the white pigment or the colored pigment is, from the viewpoint of UV reflectivity, 10 to 100 parts by mass of the white pigment per 100 parts by mass of the matrix resin. It is preferably used in proportions, and more preferably in proportions of 15 to 70 parts by mass. In the case of a colored pigment such as green, the colored pigment is preferably used in a proportion of 2 to 25 parts by mass, more preferably in a proportion of 5 to 20 parts by mass.

In addition, as the non-adhesive reflective layer, it is also possible to use a resin substrate having a concealing property containing a white pigment or a colored pigment, or a resin substrate having a concealing layer containing a white pigment or a colored pigment on at least one surface. can. Examples of white pigments and colored pigments include those mentioned above. In addition, examples of resins constituting these resin substrates include the same resins as those constituting the transparent substrate.

The thickness of the reflective layer is preferably 15-300 μm, more preferably 20-100 μm. By setting the thickness to 15 μm or more, it is possible to prevent the color of the base from appearing mixed due to light transmission through the light-emitting sheet. In addition, by setting the thickness to 300 μm or less, daytime reflection can be moderately suppressed, and good visibility can be imparted.

<Adhesive layer>
Examples of the adhesive layer provided in the luminescent sheet of the present invention include an acrylic adhesive layer, a urethane adhesive layer, a polyester adhesive, and the like. From the viewpoint of adhesiveness, the acrylic adhesive layer is preferable.
(Acrylic adhesive)
The acrylic pressure-sensitive adhesive used as the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer in the present invention preferably contains a (meth)acrylic acid ester-based copolymer as a resin component and a cross-linking agent.
The (meth)acrylic acid ester-based copolymer includes a (meth)acrylic acid alkyl ester having 1 to 18 carbon atoms in the alkyl group of the ester portion, and a crosslinkable functional group-containing ethylenic unit that is used as necessary. Polymers and copolymers with other monomers are preferred.

[Crosslinkable functional group-containing ethylenic monomer]
Examples of the crosslinkable functional group-containing ethylenic monomer used as necessary include ethylenic monomers having functional groups such as hydroxyl group, carboxyl group, amino group, substituted amino group and epoxy group in the molecule. Hydroxy group-containing ethylenically unsaturated compounds and carboxyl group-containing ethylenically unsaturated compounds are preferably used.

[Preparation of (meth)acrylic acid ester copolymer]
First, the (meth)acrylic acid alkyl ester described above, and the crosslinkable functional group-containing ethylenic monomer and other monomers used as necessary are used in predetermined proportions, respectively, and are shared according to a conventionally known method. Polymerization is carried out to produce a (meth)acrylate copolymer having a weight average molecular weight of preferably 500,000 to 1,500,000, more preferably 600,000 to 1,300,000.
In addition, the said weight average molecular weight is a value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.

[Crosslinking agent]
Examples of the cross-linking agent contained in the acrylic pressure-sensitive adhesive include organic polyvalent isocyanate compounds, organic polyvalent epoxy compounds, organic polyvalent imine compounds, metal chelate compounds, and the like. Among these, organic polyisocyanate compounds, organic polyepoxy compounds, and metal chelate compounds are preferred from the viewpoints of increasing cohesive strength and improving adhesive strength, and from the viewpoint of availability.

In addition, you may use these crosslinking agents individually or in combination of 2 or more types.
The content of the cross-linking agent is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, still more preferably 0.01 to 10 parts by mass, with respect to 100 parts by mass of the (meth)acrylate copolymer. 2 to 4 parts by mass. When the amount is 0.01 parts by mass or more, sufficient cohesive force of the adhesive to maintain the shape against stress in the shear direction can be obtained, and when the amount is 10 parts by mass or less, sufficient adhesive strength can be obtained.

[Preparation of acrylic adhesive]
The acrylic pressure-sensitive adhesive contains the above-described (meth)acrylic acid ester copolymer, a cross-linking agent, and other additives used as necessary, such as tackifiers, pigments, dyes, antioxidants, and ultraviolet absorbers. , hindered amine light stabilizers, etc. can be prepared by adding a suitable solvent to a concentration suitable for coating.
The adhesive layer in the luminescent sheet of the present invention is excellent in weather resistance and adhesive performance, and preferably has a thickness of 1 to 40 μm, more preferably 5 to 35 μm, still more preferably 10 to 30 μm.

<Release sheet>
In the luminescent sheet of the present invention, the release sheet used for protecting the above-described adhesive layer and the like includes a release sheet base material provided with a release agent layer on the surface thereof.
Base materials for release sheets include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; and polyolefin resins such as polyethylene, polypropylene, polybutene, polybutadiene, polymethylpentene, low-density polyethylene, and linear low-density polyethylene. Cellulose-based resins such as triacetyl cellulose; Acrylic-based resins such as polymethyl methacrylate; Polyurethane-based resins; Polycarbonate-based resins; Cycloolefin-based resins; Examples include resin films made of ethylene (meth)acrylic acid copolymer, polystyrene, fluororesin, woodfree paper, coated paper, glassine paper, laminated paper, and the like. Among these, a polyethylene terephthalate film is preferable because it is inexpensive and has good stiffness. The thickness of the release sheet substrate is preferably 5 to 300 μm, more preferably 10 to 200 μm.
Examples of the release agent that constitutes the release agent layer provided on the surface of the release sheet substrate include silicone resins, fluorine resins, and long-chain alkyl group resins. A silicone-based resin is preferable because it provides a high performance. The thickness of the release agent layer is preferably 0.05 to 2.0 μm, more preferably 0.1 to 1.5 μm.

<Sheet for film forming process>
The film-forming process sheet can be used as a process sheet for forming an antifouling layer, a light-emitting film, and a reflective layer in the light-emitting sheet of the present invention. It also serves to protect the surface of the outermost layer of the luminescent sheet until the luminescent sheet is used. How to use it will be described later.
The sheet for the film-forming process is not particularly limited, but it is preferable to use the same release sheet as the above-mentioned release sheet in order to easily release from the surface of each layer during use.

The total thickness of the luminescent sheet of the present invention is preferably in the range of 20 to 430 μm, more preferably 45 to 300 μm, from the viewpoint of achieving thinness and maintaining high brightness. In addition, the said total thickness shall mean the sum total of the thickness of the antifouling layer, the light emitting film, the reflective layer, and the adhesion layer among each layer which comprises a light emitting sheet. Specifically, the thickness of the luminescent sheet can be measured by the method described in Examples.

<Method for producing ultraviolet irradiation type luminescent sheet>
Next, an example of the method for producing the ultraviolet irradiation type luminescent sheet of the present invention will be described. It should be noted that the method for manufacturing the luminescent sheet of the present invention is not limited to the following method.
The light-emitting sheet having the layer structure (light-emitting film/transparent substrate) of (a) shown in FIG. It can be manufactured by forming.
As a method for producing the light-emitting sheet having the layer structure (light-emitting film/reflective layer (/release sheet)) of (b) shown in FIG. A method of forming a light-emitting film on the upper surface of a layer; a method of forming a light-emitting film on the release-treated surface of a film-forming process sheet and forming a reflective layer on the upper surface of the light-emitting film; A method for forming the reflective layer will be described later.

As a method for producing the light-emitting sheet having the layer structure (antifouling layer/light-emitting film/transparent substrate) of (c) shown in FIG. a method of forming an antifouling layer on a transparent substrate; a method of forming a luminescent film and an antifouling layer on a transparent substrate by simultaneous multi-layer coating; A method for forming the antifouling layer will be described later.

In the manufacturing method of the luminescent sheet having the layer structure (antifouling layer/luminescent film/reflecting layer (/release sheet)) of (d) shown in FIG. 4, the order of forming the layers is not particularly limited. For example, a luminescent film and a reflective layer may be sequentially formed on the top surface of the antifouling layer, or a luminescent film and an antifouling layer may be sequentially formed on the top surface of the reflective layer. A method of forming an antifouling layer on one surface of the light-emitting film and forming a reflective layer on the other surface can also be used.

In the manufacturing method of the light-emitting sheet having the layer structure (antifouling layer/adhesive layer/light-emitting film/reflective layer (/release sheet)) of (e) shown in FIG. For example, an adhesive layer, a luminescent film, and a reflective layer may be sequentially formed on the top surface of the antifouling layer, or a luminescent film, an adhesive layer, and an antifouling layer may be sequentially formed on the top surface of the reflective layer.
In addition, the method shown in FIG. 8 can also be used to produce a luminescent sheet having the layer structure (e). First, the antifouling layer 5 is prepared, and the adhesive layer 6 is formed on the upper surface of the antifouling layer 5 to produce the laminate 7 . On the other hand, the luminescent film 1 is formed on the release-treated surface of the film 8 for the film-forming process, and the adhesive layer 6 side of the laminate 7 is adhered to the upper surface of the luminescent film 1 .
Next, the film 8 for the film-forming process is peeled off, and the reflective layer 3 is formed or attached to the luminescent film 2 present on the peeled surface. As a result, the luminescent sheet 150 having the layer structure (e) is obtained. When the reflective layer 3 is an adhesive reflective layer 3 ′, it is preferable to form the adhesive reflective layer 3 ′ on the release-treated surface of the release sheet and attach it to the luminescent film 2 .

In the manufacturing method of the light-emitting sheet having the layer structure (f) (antifouling layer/light-emitting film/reflective layer/adhesive layer (/release sheet)) shown in FIG. For example, a method of sequentially forming each layer may be used, or a method of forming an adhesive layer on the release-treated surface of the release sheet and attaching the adhesive layer to the reflective layer side surface of the light-emitting sheet having the layer structure (d). can also be used.

Further, in the method for manufacturing a light-emitting sheet having the layer configuration (g) (antifouling layer/adhesive layer/light-emitting film/reflective layer/adhesive layer (/release sheet)) shown in FIG. There are no particular restrictions. For example, a method of sequentially forming each layer may be used, or a method of forming an adhesive layer on the release-treated surface of the release sheet and attaching the adhesive layer to the reflective layer side surface of the light-emitting sheet having the layer structure (e). can also be used.

(Formation of reflective layer)
A method of forming a reflective layer containing a white pigment or colored pigment and a matrix resin will be described. First, the aforementioned pigment and matrix resin are mixed, an appropriate amount of an appropriate solvent is added, and forced defoaming is performed to prepare a reflective layer-forming coating liquid having a viscosity suitable for coating. Next, the coating liquid for forming the reflective layer is applied to the surface of the release sheet or film for manufacturing process coated with the release agent, or the upper surface of the layer in contact with the reflective layer, using an applicator or the like, so that the thickness after drying reaches a predetermined thickness. Apply and dry to form a reflective layer.
The reflective layer thus formed has a function of reflecting the ultraviolet rays that pass through the light-emitting film, and also has a masking effect of increasing the brightness of the light-emitting film that emits light when irradiated with ultraviolet rays.
Further, as described above, as the reflective layer, a resin substrate having a concealing property containing a white pigment or a colored pigment, or a resin substrate having a concealing layer containing a white pigment or a colored pigment on at least one surface can be used. can also

(Formation of antifouling layer)
As a method for forming the antifouling layer, a case of forming the antifouling layer on the film for manufacturing process will be described below as an example. The same method can be used when the antifouling layer is provided on the upper surface of the layer in contact with the antifouling layer.
For example, when the antifouling layer is a single layer, a coating liquid containing one or more resins selected from the group consisting of acrylic resins, acrylic urethane resins, and polyester resins and a solvent such as methyl ethyl ketone is prepared. An antifouling layer can be formed by coating and drying on the release-treated surface of the film for membrane process so that the thickness after drying becomes a predetermined thickness.

When the antifouling layer is composed of a surface layer portion and a lower layer portion, and the surface layer portion is composed of the above resin, after forming the surface layer portion in the same manner as described above, the An antifouling layer can be formed by forming a resin layer (lower layer portion) positioned below the surface layer portion. The resin layer (lower layer portion) positioned below the surface layer portion may be formed by laminating a resin film on the surface layer portion by heat sealing or the like, and contains a resin constituting the lower layer portion, a solvent, and the like. A coating solution may be prepared, applied on the surface layer so that the thickness after drying becomes a predetermined thickness, and dried to form the coating.
Further, when the antifouling layer is composed of a surface layer portion and a lower layer portion, and the surface layer portion is composed of the photocatalyst layer, for example, a commercially available photocatalyst coating liquid containing titanium dioxide is added to the film forming process. On the release-treated surface of the film for film, it is applied so that the thickness after drying becomes a predetermined thickness, and then dried. A surface layer portion of the antifouling layer can be formed by coating and drying a silicone resin or the like so that the thickness after drying is about several μm. Furthermore, an antifouling layer can be formed by forming a resin layer positioned below the surface layer portion thereon in the same manner as described above.

In addition, as the antifouling layer, a resin film made of one or more resins selected from the group consisting of acrylic resins, acrylic urethane resins and polyester resins, or a resin film having at least these resins on the surface layer is used. good too.

(Formation of adhesive layer)
For the adhesive layer, apply an adhesive (containing a cross-linking agent) for forming the adhesive layer to the surface of the release sheet coated with the release agent or the upper surface of the layer in contact with the adhesive layer. It can be formed by coating and drying so as to have a thickness.

<Application>
Since the luminescent film and luminescent sheet of the present invention contain the vanadium oxide phosphor represented by the composition formula MVO ₃ , the excitation spectrum is in the range of 250 to 390 nm, which can be excited by the ultraviolet-near-ultraviolet LED, which is the excitation light source of the white LED. have. The fluorescence spectrum emitted by this excitation light extends from 390 to 680 nm and emits white light. Therefore, for example, it is suitable as a phosphor for white LEDs other than ultraviolet rays. Since the peak of the emission spectrum is in the range of 490 to 502 nm, the color temperature is relatively high, but a warm white color can be obtained by combining with a phosphor that emits strong light on the long wavelength side. Moreover, since it does not contain mercury, lead, etc., it has little adverse effect on the environment and the human body.
Therefore, the luminescent film and luminescent sheet of the present invention can be used, for example, as lighting fixtures such as daily lights that require white light, ultraviolet irradiation type signage devices for highways and the like, backlights for other various display devices, and the like. can be done.

An example in which the luminescent sheet of the present invention is applied to an ultraviolet irradiation type labeling device, which is one of the applications of the luminescent film and the luminescent sheet of the present invention, will be described below.
(Ultraviolet irradiation type labeling device)
The light-emitting sheet of the present invention having the above-described structure emits fluorescent color when irradiated with ultraviolet rays, and has good visibility, readability, and attractiveness. can give.
The ultraviolet irradiation type labeling device is composed of, for example, a plurality of luminescent sheets having a layer structure shown in FIG. can also be used as
In the case of superimposing, the release sheet 4 in the light-emitting sheet 160 shown in FIG. 6 is peeled off, and superimposition is performed so that one exposed antifouling layer surface and the other exposed adhesive layer surface are in contact with each other.
Also, the number of sheets to be superimposed is preferably in the range of 2 to 5 sheets.

FIG. 9 is a schematic cross-sectional view (partially enlarged view) showing an example of an ultraviolet irradiation type marking device in which two luminescent sheets of the present invention are stuck together, and FIG. 10 is a marking portion of the ultraviolet irradiation type marking device. It is a plane schematic diagram which shows an example.
In FIG. 9, 9 indicates an ultraviolet irradiation type label body (hereinafter sometimes simply referred to as "label body"), and the label body 9 is supported by a support (not shown). The label main body 9 includes a label portion 10 that emits light when irradiated with ultraviolet light from an irradiation device (not shown). The label portion 10 is composed of a light-emitting sheet 200 and a light-emitting sheet 300 overlaid on a part of the surface layer of the light-emitting sheet 200 .
As shown in FIG. 9, the luminescent sheet 200 has an antifouling layer 5A, a luminescent film 1A, a reflective layer 3A, and an adhesive layer 6A in this order, and a luminescent sheet 300 has an antifouling layer 5B, a luminescent film 1B, and a reflective layer. It has a layer 3B and an adhesive layer 6B in order. The luminescent sheet 300 is attached to part of the surface layer of the luminescent sheet 200 via the adhesive layer 6B and the antifouling layer 5A. The luminescent sheet 300 used has the same configuration as the luminescent sheet 200 .

By laminating the light-emitting sheet 300 on the light-emitting sheet 200, as shown in FIG. 10, the label portion 10 having characters and patterns formed thereon can be obtained.
In this embodiment, an adhesive labeling sheet 200 that is colored substantially green (indicated by halftone dots in FIG. 10) and emits light is attached to the label main body 9 via the adhesive layer 6A. A substantially white colored light-emitting sheet 300 (indicated by a non-dotted area in FIG. 10) is adhered through the antifouling layer 5A to form an ultraviolet irradiation type labeling device.

In the ultraviolet irradiation type labeling device obtained by stacking such luminescent sheets, one sheet (for example, approximately It is eye-catching that the brightness of the light-emitting sheet 300 that is colored in white and emits light has a contrast ratio that is three times or more than the brightness of the other sheet (for example, the light-emitting sheet 200 that is colored in substantially green and emits light). It is preferable from the viewpoint of readability and visibility.
Note that the attractiveness refers to the degree of eye-catching (the degree of conspicuousness), and the legibility refers to the degree to which characters can be identified even from a distance. Visibility, on the other hand, refers to the ability to clearly recognize visual objects and characters.
As ultraviolet rays in the ultraviolet irradiation type labeling device, for example, black light (near ultraviolet rays) emitted from a mercury lamp equipped with a TaO ₅ sputter filter manufactured by Iwasaki Electric Co., Ltd. is suitable.

The ultraviolet irradiation type marking device is a marking device that fluoresces when irradiated with ultraviolet rays and has good visibility, readability, and attractiveness. play.
(1) Black lights are used as exterior lighting, reducing the risk of obstructing the visibility of drivers in oncoming lanes due to strong visible light from lighting fixtures or diffuse reflection of visible light due to fog.
(2) Unlike the conventional floodlight illumination method that uses a reflective sheet, the film attached to the sign itself emits light in response to black light. never
(3) Since the sign part and the lighting equipment are not integrated, installation and maintenance can be easily performed without closing the road or restricting the lane.
(4) It is possible to reduce the weight of sign equipment, and to reduce initial costs and maintenance costs.

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited by these examples.
Various properties of the luminescent film or ultraviolet irradiation type luminescent sheet obtained in each example were determined by the methods described below.

<Method for measuring average secondary particle size>
The average secondary particle size of the vanadium oxide particles (A) was measured with a laser diffraction particle size distribution meter.

<Thickness measurement method>
The thickness of the light-emitting film, layers other than the light-emitting film, and the ultraviolet irradiation type light-emitting sheet was measured using a constant pressure thickness measuring instrument manufactured by Teclock Co., Ltd. was measured using

<Brightness measurement method (measurement method 1)>
The light-emitting surface of the ultraviolet irradiation-type light-emitting sheet obtained in each example is irradiated with ultraviolet rays by a 400 W ultraviolet irradiation tool, and in this state, the luminance of arbitrary multiple points is measured with a luminance meter (manufactured by Konica Minolta, Inc., product name "Luminance meter LS-100") was used to obtain the average luminance.

<Brightness measurement method (measurement method 2)>
The light-emitting surface of the ultraviolet irradiation-type light-emitting sheet obtained in each example is irradiated with light having a wavelength of 350 nm from a light source device (manufactured by Asahi Spectrosco Co., Ltd., product name "MAX-302"), and in this state, at any plurality of locations. was measured using a luminance meter (manufactured by Topcon Corporation, product name “SR-UA1”) to obtain an average luminance.

<Method for measuring chromaticity when emitting light>
The light-emitting surface of the ultraviolet irradiation-type light-emitting sheet obtained in each example is irradiated with ultraviolet rays by an ultraviolet irradiation tool of 400 W, and in this state, the chromaticity of arbitrary multiple points is measured with a luminance meter (manufactured by Konica Minolta Co., Ltd., product (named "Luminance Meter LS-100") to obtain the average luminance.

<Adhesion evaluation method>
A finger was pressed against the luminescent film surface of the ultraviolet irradiation type luminescent sheet obtained in each example to confirm whether or not the luminescent film was transferred to the finger side, and the adhesion was evaluated.
A: The light-emitting film did not transfer even when pressed with a finger or rubbed back and forth twice.
F: The luminescent film was transferred only by pressing a finger.

Production Example 1 (Preparation of CsV solution)
(b1) component cesium octylate (“Nikka Octix Cesium” manufactured by Nihon Kagaku Sangyo Co., Ltd.) 1.5 ml, (b2) component vanadium octylate (“Nikka Octix Vanadium” manufactured by Nihon Kagaku Sangyo Co., Ltd.) A CsV solution was prepared by mixing 1.5 ml (an amount of which the atomic ratio of cesium and vanadium was =66.6:33.4).

Example 1
(Preparation of coating liquid)
7.5 g of CsVO ₃ particles (manufactured by N-Luminescence Co., Ltd., average secondary particle size: 24 μm), 3 mL of the CsV solution obtained in Production Example 1, and zirconium octylate (c1) component (manufactured by Nippon Kagaku Sangyo Co., Ltd. "Nikka Octix Zirconium") 1 mL and 0.15 mL of 3-glycidoxypropyltrimethoxysilane ("Z-6040" manufactured by Dow Corning Toray Co., Ltd.), which is the component (c2), are blended, and an ultrasonic cleaner is used. A coating liquid was prepared by vibrating with ultrasonic waves (42 kHz, 125 W) for 15 minutes for dispersion.

(Production of luminescent film and UV irradiation type luminescent sheet)
The prepared coating solution is applied to a polyethylene terephthalate base material (“Cosmoshine A4100” manufactured by Toyobo Co., Ltd., thickness 50 μm) by a wire coating method so that the thickness of the coating film after drying is 20 μm. was formed (step (I)). After holding this coating film at 60 ° C. for 5 minutes, at room temperature (23 ° C.) in the atmosphere, an excimer lamp with a wavelength of 172 nm (manufactured by Hamamatsu Photonics Co., Ltd., product name “FLAT EXCIMER EX-mini”) was used with an illuminance of 50 mW. /m ² for 10 minutes with ultraviolet lamp light (step (II)). As a result, CsVO ₃ crystals ((B) component) formed from the (b1) component and (b2) component in the CsV solution are grown to form the light emitting film of the present invention, and on the polyethylene terephthalate substrate Thus, an ultraviolet irradiation type light-emitting sheet having the light-emitting film was obtained. The obtained luminescent film and UV irradiation type luminescent sheet showed white fluorescence by UV excitation.
Moreover, the above evaluation was performed on the obtained luminescent film and the external irradiation type luminescent sheet. Table 1 shows the results.

Example 2
A luminescent film and an ultraviolet irradiation type luminescent sheet were produced in the same manner as in Example 1, except that the thickness of the coating film after drying was changed as shown in Table 1, and the above evaluation was performed. Table 1 shows the results.

Comparative example 1
Table 1 shows that the coating solution did not contain CsVO ₃ particles as component (A) and 3-glycidoxypropyltrimethoxysilane as component (c2), and the thickness of the coating film after drying. A luminescent film and an ultraviolet irradiation type luminescent sheet were produced in the same manner as in Example 1, except that changes were made as shown, and the above evaluation was performed. Table 1 shows the results.

Example 3
5 g of CsVO ₃ particles, 3 mL of the CsV solution obtained in Production Example 1, and 0.0025 mL of 3-glycidoxypropyltrimethoxysilane (“Z-6040” manufactured by Dow Corning Toray Co., Ltd.), which is the component (c2) were blended and dispersed by applying ultrasonic vibration for 15 minutes with an ultrasonic cleaner (42 kHz, 125 W) to prepare a coating solution.

(Production of luminescent film and UV irradiation type luminescent sheet)
The prepared coating solution is applied to a polyethylene terephthalate base material (“Cosmoshine A4100” manufactured by Toyobo Co., Ltd., thickness 50 μm) by a wire coating method so that the thickness of the coating film after drying is 10 μm. was formed (step (I)). After holding this coating film at room temperature (23° C.) for 3 days, it was irradiated with ultraviolet rays for 10 minutes at room temperature in the atmosphere using a high-pressure mercury lamp (step (II)). As a result, CsVO ₃ crystals formed from the (b1) component and (b2) component in the CsV solution are grown to form the light-emitting film of the present invention, and the ultraviolet light having the light-emitting film on the polyethylene terephthalate substrate An irradiation type luminescent sheet was obtained. The obtained luminescent film and UV irradiation type luminescent sheet showed white fluorescence by UV excitation.
Moreover, the above evaluation was performed on the obtained luminescent film and the external irradiation type luminescent sheet. Table 1 shows the results.

Examples 4-15
A luminescent film and an ultraviolet irradiation type luminescent sheet were produced in the same manner as in Example 3, except that the composition of the coating liquid was changed as shown in Table 1, and the above evaluation was performed. Table 1 shows the results.

Comparative example 2
A luminescent film and an ultraviolet irradiation type luminescent sheet were produced in the same manner as in Example 3, except that the composition of the coating liquid was changed as shown in Table 1 and the coating liquid did not contain the component (C). made an evaluation. Table 1 shows the results.

The components shown in Table 1 are as follows.
(A) CsVO ₃ particles; manufactured by N-Luminescence Co., Ltd., average secondary particle size: 24 μm
(b1) Cesium octylate; Nikka Octix Cesium manufactured by Nippon Kagaku Sangyo Co., Ltd.
(b2) Vanadium octylate; "Nikka Octix Vanadium" manufactured by Nippon Kagaku Sangyo Co., Ltd.
(c1) Zirconium octylate; "Nikka Octix Zirconium" manufactured by Nippon Kagaku Sangyo Co., Ltd.
(c2-1) 3-glycidoxypropyltrimethoxysilane; "Z-6040" manufactured by Dow Corning Toray Co., Ltd.
(c2-2) 3-methacryloxypropyltrimethoxysilane; "Z-6030" manufactured by Dow Corning Toray Co., Ltd.
(c2-3) Vinyltrimethoxysilane; "Z-6300" manufactured by Dow Corning Toray Co., Ltd.
(c2-4) Vinyltriethoxysilane; "Z-6519" manufactured by Dow Corning Toray Co., Ltd.

From Table 1, it can be seen that the light-emitting films and light-emitting sheets of the examples of the present application have high luminance even when they are thin, and have good adhesion.
On the other hand, the light-emitting film of Comparative Example 1 did not contain the component (A), so the luminance was lowered. Moreover, since the light-emitting film of Comparative Example 2 did not contain the component (C), the adhesion was lowered.

Reference example 1
A luminescent sheet described in Example 2 of Patent Document 3 was produced and evaluated.
(Composition of light emitting layer forming material)
Polyurethane resin ("Samprene IB-582" manufactured by Sanyo Kasei Co., Ltd.) 100 parts by mass Fluorescent pigment ("YS-A" manufactured by Nemoto Specialty Chemicals Co., Ltd.) 100 parts by mass Solvent (isopropyl alcohol: toluene mass ratio = 1: 4) 40 Parts by mass (composition of material for forming ultraviolet reflective layer)
Polyurethane resin ("Sampren IB-582" manufactured by Sanyo Kasei Co., Ltd.) 100 parts by mass White pigment ("Titanium White A-150" manufactured by Sakai Chemical Co., Ltd.) 80 parts by mass Solvent (isopropyl alcohol: toluene mass ratio = 1: 4) 40 parts by mass (manufacture and evaluation of luminescent sheet)
After kneading each component used for the above material for forming a light emitting layer with a kneader, the mixture was forcibly defoamed to prepare a material for forming a light emitting layer. In addition, after kneading each component used for the above material for forming an ultraviolet reflective layer in a kneader, the mixture was forcibly defoamed to prepare a material for forming an ultraviolet reflective layer.
Then, a process film in which one side of a 50 μm-thick polyester film is coated with a silicone resin is used as a base layer, and a material for forming a light-emitting layer is applied to the coated surface with an applicator to a thickness of about 30 μm (when dry). C. for 10 minutes to form a light-emitting layer.
Further, a material for forming an ultraviolet reflective layer was applied on the light emitting layer with an applicator so as to have a thickness of about 40 μm (dry) and dried at 100° C. for 10 minutes to form an ultraviolet reflective layer. After that, the light-emitting layer and the UV-reflecting layer integrated together were peeled off from the base layer to obtain a light-emitting sheet. It was confirmed that this luminescent sheet exhibited good fluorescent coloration when irradiated with ultraviolet rays from the surface side of the luminescent layer.
When the luminance and chromaticity of the obtained luminescent sheet were measured by the above method (measurement method 1), the luminance was 18.6 (cd/cm ² ), and the chromaticity was x; Met. The luminescent sheet of Reference Example 1 has good luminescent performance, but compared to the luminescent sheet of the Examples of the present application, the amount of the luminescent material (fluorescent pigment) required to exhibit the same level of brightness is large, and , the light-emitting layer must be thicker than the light-emitting film of the present invention.

According to the present invention, a luminescent film that develops fluorescence when irradiated with ultraviolet rays, can maintain high brightness even when thinned, and has excellent adhesion, a method for producing the same, and an ultraviolet irradiation type luminescent sheet having the luminescent film. can be provided. Since the light-emitting film and the ultraviolet irradiation-type light-emitting sheet are thin and have high brightness, when applied to a sign device installed on a highway, for example, dirt does not easily accumulate on the steps caused by the thickness of the sheet, and cleaning is possible. It becomes possible to maintain good visibility without performing for a long period of time.

100 to 170, 200, 300 Ultraviolet irradiation type light-emitting sheets 1, 1A, 1B Light-emitting film 2 Transparent base material 3, 3A, 3B Reflective layer 4 Release sheet 5, 5A, 5B Antifouling layer 6, 61, 62, 6A, 6B Adhesive layer 7 Laminate 8 Film for film forming process 9 Sign body 10 Label part

Claims (13)

Composition formula MVO₃(M isCsis) vanadium oxide particles (A) represented by,
Yescesium saltisA composition formula MVO formed from an organic acid metal salt (b1) and an organic acid vanadium salt (b2)₃(M isCsis) and a vanadium oxide crystal (B) represented by
one or more additives (C) selected from the group consisting of one or more organic acid metal salts (c1) selected from the group consisting of organic acid zirconium salts and organic acid titanium salts and silane coupling agents (c2); a luminescent film containingand
The crystal (B) is 1 to 50 parts by mass with respect to 100 parts by mass of the solid content of the particles (A),
The component (C) is 0.01 to 50 parts by mass with respect to 100 parts by mass of the solid content of the particles (A),
The component (C) contains component (c2) as an essential component,
The light-emitting film, wherein the total content of the components (A), (B) and (C) in the light-emitting film is 80% by mass or more.. 2. The light-emitting film according to claim 1, wherein the organic acid metal salt (b1) is a fatty acid metal salt. 3. The light-emitting film according to claim 1, wherein the organic acid vanadium salt (b2) is a fatty acid vanadium salt. 4. The light-emitting film according to claim 1, wherein the organic acid metal salt (c1) is a fatty acid metal salt. The luminescent film according to any one of claims 1 to 4, wherein the component (A) has an average secondary particle size of 1 to 50 µm. 6. The silane coupling agent according to any one of claims 1 to 5 , wherein the component (c2) is one or more silane coupling agents having a group selected from the group consisting of an epoxy group, a vinyl group, and a (meth)acryloyl group. luminescent film. The light emitting film according to any one of claims 1 to 6 , wherein the component (C) contains both the component (c1) and the component (c2). The luminescent film according to any one of claims 1 to 7 , having a thickness of 0.1 to 50 µm. A method for producing a light-emitting film according to any one of claims 1 to 8,
A method for producing a light-emitting film, comprising the following steps (I) and (II).
Step (I): Composition formula MVO3 (M isCsis) vanadium oxide particles (A) represented by, Yescesium saltisOrganic acid metal salt (b1), organic acid vanadium salt (b2), and one or more organic acid metal salts (c1) selected from the group consisting of organic acid zirconium salts and organic acid titanium salts, and a silane coupling agent ( A step of applying a coating liquid containing one or more additives (C) selected from the group consisting of c2) to form a coating film
Step (II): After maintaining the coating film at a temperature of 10° C. to 450° C., a step of irradiating ultraviolet rays having a wavelength of 400 nm or less. An ultraviolet irradiation type luminescent sheet having the luminescent film according to any one of claims 1 to 8 . 11. The UV irradiation type luminescent sheet according to claim 10 , which has an antifouling layer, the luminescent film, and a reflective layer in this order. 12. The UV irradiation type luminescent sheet according to claim 11 , wherein the reflective layer is an adhesive reflective layer. 12. The UV irradiation type luminescent sheet according to claim 11 , further comprising an adhesive layer on the reflective layer side of the luminescent sheet.

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