JP2010247526A - Laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate which displays different under the irradiation conditions of visible light and ultraviolet rays, is enhanced in the luminescence efficiency of a fluorescence emitting display part, expresses a dark luminescent color and is excellent in design properties. <P>SOLUTION: The laminate is irradiated with the ultraviolet rays from an ultraviolet source to emit light and a fluorescence emitting layer (A) showing the emission of fluorescence, an ultraviolet ray reflecting layer (B) being transparent or translucent when the ultraviolet reflectivity in the whole region of a wavelength region of 300-400 nm is 10% or above and a colored layer (C) are laminated from the side irradiated with ultraviolet rays of the laminate. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a laminate that exhibits fluorescence.

Conventionally, a molded product containing a fluorescent material such as a fluorescent pigment that emits light when irradiated with ultraviolet rays is known. Such phosphors are used as high-design materials in various fields because they exhibit different hues when irradiated with ultraviolet rays and when not irradiated. For example, Patent Document 1 describes a decorative lighting device having a light emitting part drawn with a fluorescent paint and an ultraviolet light source that irradiates ultraviolet light from the light emitting part to a light emitting part provided across a travel path. . However, the light emitted from the light source may be diffused before being applied to the light emitting unit, or ultraviolet light that is not used for fluorescent light emission in the light emitting unit may be leaked, and the light emission efficiency may be reduced. .

On the other hand, in Patent Document 2, in order to improve the visibility of the fluorescent light emitting layer, a reflective layer mirrored behind the light source is provided to prevent external leakage of ultraviolet rays and to achieve a fluorescent display with high luminance. It has been broken. However, if only a reflective layer is provided behind the light source, ultraviolet light that has not been used for fluorescent light emission in the fluorescent layer of the display unit is leaked, so that the light emission efficiency may be reduced.
Further, as a method for increasing the light emission luminance of the fluorescent light emitting layer, it is known to increase the concentration of a fluorescent material such as a fluorescent pigment. In this case, however, the color tends to be lightened.

JP-A-6-314505 JP 2003-29676 A

  The present invention has been made in view of the above-described problems. In a fluorescent light-emitting laminate that exhibits a light emission color under ultraviolet irradiation, the light emission efficiency of the fluorescent light-emitting display portion is improved, and a deep light emission color is further provided. It aims at obtaining the laminated body excellent in the designability which can express.

As a result of intensive studies to achieve the above object, the present inventor is a laminate that emits light by irradiation with an ultraviolet light source, and exhibits a fluorescence emission layer (A) that exhibits fluorescence emission, and has a wavelength region of 300 nm to 400 nm. The inventors have conceived of a laminate having an ultraviolet reflectance in a region of 10% or more and having a transparent or translucent ultraviolet reflecting layer (B) and a colored layer (C), and have completed the present invention. That is, the fluorescent light-emitting laminate of the present invention has the following characteristics.

1. A laminate that emits light when irradiated with an ultraviolet light source,
Fluorescent light emitting layer (A) showing fluorescence emission from the side irradiated with ultraviolet light, a transparent or translucent ultraviolet reflective layer (B) having an ultraviolet reflectance of 10% or more in the entire wavelength region of 300 nm to 400 nm, and 1. A laminate having a colored layer (C) laminated thereon. The colored layer (C) is similar in color to the fluorescent color emitted by the fluorescent layer (A). 2. Laminate described in 3. A laminate that emits light when irradiated with an ultraviolet light source,
From the side irradiated with ultraviolet rays, there is a fluorescent light emitting layer (A) that exhibits fluorescent emission, and a transparent or translucent ultraviolet reflective colored layer (D) that has an ultraviolet reflectance of 10% or more in the entire wavelength region of 300 nm to 400 nm. 3. Laminated body characterized by being laminated. 2. The ultraviolet reflective coloring layer (D) is similar in color to the fluorescence emission color exhibited by the fluorescence emission layer (A). 5. Laminate described in 5.1. ~ 4. A light emitting structure comprising the laminate according to any one of the above and an ultraviolet light source (X) on the fluorescent light emitting layer (A) side of the laminate.

The laminate of the present invention is a laminate that emits light when irradiated with an ultraviolet light source, and is a fluorescent light-emitting layer (A) that emits fluorescence from the side irradiated with ultraviolet light, and ultraviolet light in the entire wavelength region of 300 nm to 400 nm. By laminating a transparent or translucent ultraviolet reflective layer (B) and a colored layer (C) with a reflectance of 10% or more, the luminous efficiency of the fluorescent light emitting display portion is high, and a dark luminescent color can be expressed. It is excellent in design.

It is an example of the structural drawing of this invention laminated body and a light emitting structure. It is an example of the structural drawing of this invention laminated body and a light emitting structure. It is an example of the structure figure of this invention light emission structure.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

(Laminate)
The present invention is a laminate that emits light when irradiated with ultraviolet light, and is a laminate that emits light when irradiated with an ultraviolet light source. , Simply referred to as “(A) layer”), a transparent or translucent ultraviolet reflective layer (B) (hereinafter simply referred to as “(B)”) having an ultraviolet reflectance of 10% or more in the entire wavelength region of 300 nm to 400 nm. And a colored layer (C) (hereinafter also simply referred to as “(C) layer”) (FIG. 1).

The fluorescent light emitting layer (A) of the present invention is a pigment, dye or the like (hereinafter referred to as “fluorescent material”) that exhibits fluorescent light emission on a light transmitting material (hereinafter referred to as “translucent material”). Is included.

  As the translucent material, any of an inorganic material and an organic material may be used as long as it has translucency. For example, examples of the inorganic material include glass, water glass, low-melting glass, silicon resin, and alkoxysilane. Organic materials include acrylic resin, acrylic-styrene resin, cellulose acetobutyrate resin, cellulose propionate resin, polymethylpentene resin, polycarbonate resin, polystyrene resin, polyester resin, etc., or reaction-curing type epoxy resin , Acrylic resin, methacrylic resin, urethane resin and the like. In addition, “translucency” is excellent in visible light transparency and has transparency.

The fluorescent material is not limited as long as it exhibits fluorescence emission under ultraviolet irradiation, and known fluorescent dyes, fluorescent pigments, and the like can be used. In the present invention, those that do not exhibit fluorescence emission under visible light are preferred, and among these phosphors, inorganic fluorescent pigments that are excellent in fluorescence emission durability and weather resistance are particularly preferred.

The (A) layer is formed by molding a composition containing the light-transmitting material and the fluorescent material (hereinafter referred to as “fluorescent light-emitting layer composition”) into a film shape or a plate shape. The thickness is usually 0.01 mm to 10 mm, more preferably 0.05 to 5 mm, and the thickness may be partially changed within this range. By changing the thickness partially, the luminance of the fluorescence emission can be changed. In the composition for a fluorescent light emitting layer, it is preferable to mix 0.5 to 50 parts by weight, further 1 to 30 parts by weight of the fluorescent material with respect to 100 parts by weight of the translucent material (solid content). When the amount is less than 0.5 part by weight, the luminance of the fluorescent light emitting layer is lowered and the visibility may be inferior. Moreover, even if it adds more than 50 weight part, there exists a possibility that the improvement of a brightness | luminance cannot be confirmed.

  The ultraviolet reflection layer (B) having an ultraviolet reflectance of 10% or more (preferably 25% or more) in the entire wavelength region of 300 nm to 400 nm has an ultraviolet reflectance of 10% or more in the entire wavelength region. It is. In addition, when the laminate of the present invention is irradiated with ultraviolet rays from the (A) layer side, it is a layer that is transparent or translucent to such an extent that light emission from the fluorescent light emitting layer can be visually recognized from the side opposite to the (A) layer. preferable.

Specifically, the concealment rate of the layer (B) is preferably 70% or less (preferably 15% to 60%). If it exceeds 70%, the visibility of fluorescent emission may be reduced. Further, by setting the concealment rate to 15% or more, the shape of the light source on the (A) layer side can be made difficult to be visually recognized through the (B) layer.
As a method for measuring the concealment rate, there is a method of placing the layer (B) on the concealment rate test paper and calculating the concealment rate from the luminous reflectance of the white ground and the black ground.
The luminous reflectance can be measured and calculated using a color difference meter (“CR-300” manufactured by Minolta Co., Ltd.).

In addition, since the (B) layer has an ultraviolet reflectance of 10% or more in the entire wavelength region of 300 nm to 400 nm, the (B) layer reflects ultraviolet rays that are about to be emitted without being used for excitation of the phosphor. The light emission efficiency can be improved by irradiating the layer (A) with ultraviolet rays again and repeating fluorescence. In this case, the irradiated ultraviolet rays hardly pass through the layer (B) and are released.
When the ultraviolet reflectance is less than 10%, the ultraviolet rays may leak out, and the effect of improving the luminous efficiency of the layer (A) may be hindered.
The ultraviolet reflectance is a value measured with a spectrophotometer (manufactured by Shimadzu Corporation, UV-3100).
Such a (B) layer should just satisfy | fill the said range, and a resin board, a resin film, a glass plate, a ceramic board, a nonwoven fabric, a woven fabric, paper etc. are mentioned.

In particular, in the present invention, as the layer (B), a layer containing a powder that reflects (scatters) ultraviolet rays in the wavelength region of 300 nm to 400 nm (hereinafter referred to as “ultraviolet reflective powder”) and a translucent material is used. Is preferred.

As the translucent material, the same material as the layer (A) can be used.
In addition, the ultraviolet reflective powder has an ultraviolet reflectance of 50% or more and a refractive index of 1.5 to 2.4 (preferably 1.5 to 1.8) in the entire wavelength region of 300 nm to 400 nm. It is preferable. The particle size is not particularly limited, but is usually preferably 0.2 μm or less, or 0.4 μm or more and 10 μm or less. By setting it as the said range, while reflecting an ultraviolet-ray efficiently and diffusing fluorescence emission (visible light), the outstanding light-emitting luminance can be obtained. As such an ultraviolet reflective powder, for example, alumina, zirconium oxide, barium sulfate, calcium carbonate, or the like can be used.

The ultraviolet reflecting layer (B) is a transparent or semi-transparent composition containing the above translucent material and the above ultraviolet reflecting powder (hereinafter referred to as “ultraviolet reflecting layer composition”) and has a wavelength region of 300 nm. What was shape | molded in the film form or plate shape etc. so that an ultraviolet-ray reflectivity may become 10% or more in the whole area of -400 nm can be used. The thickness is transparent or translucent, and may be set as appropriate within a range that satisfies the above-described ultraviolet reflectance, and is usually 0.01 mm to 10 mm, more preferably 0.05 to 5 mm. The thickness may be partially changed. By changing the thickness partially, the luminance of the fluorescence emission can be changed.
Although the composition for ultraviolet reflective layer depends on the type of ultraviolet reflective powder used and the thickness of the ultraviolet reflective layer to be molded, the ultraviolet reflective powder with respect to 100 parts by weight of the translucent material (solid content). Is preferably 10 to 400 parts by weight, more preferably 30 to 300 parts by weight. If it is such a range, the effect of this invention will be easy to be acquired.

The colored layer (C) is obtained by molding a composition containing a translucent material and a pigment and / or dye (hereinafter referred to as “colored layer composition”) into a film shape or a plate shape. In particular, the colored layer (C) preferably has a similar color to the fluorescent color emitted by the fluorescent layer (A). Further, the colored layer (C) is preferably a colored clear layer having translucency. By using the colored clear layer, light emission of the fluorescent layer (A) can be visually recognized not only from the side irradiated with the light source but also from the opposite side. The (C) layer of the present invention cuts off excess light other than light having a specific wavelength in the visible light region, and effectively extracts only specific light. Specifically, in the laminate of the present invention, when the (A) layer is irradiated with ultraviolet rays from a light source, the phosphor in the (A) layer is excited and converted to a wavelength in the visible light region. In the laminate of the present invention, since the (A) layer and the (B) layer have translucency, the converted light in the visible light region reaches the (C) layer. Only the light is extracted and excess light is absorbed. Thereby, the fluorescence emission color can be changed to a brighter and darker emission color.
The above-mentioned similar color means three elements represented by color characteristics, that is, hue, brightness, and saturation, which are close in hue, and with respect to the fluorescence emission color exhibited by the fluorescence emission layer (A). That is, the color selected from the colors in which the difference in hue angle in the L ^* C ^* h color system falls within the range of Δh = ± 45 ° (preferably Δh = ± 30 °). . The L ^* C ^* h color system here is defined by the International Commission on Illumination in 1976 and is JIS.
The L ^* a ^* b ^* color system used in Z 8729 is displayed in polar coordinates, where L ^* represents lightness, C ^* represents saturation as a distance from the origin, and h represents L ^* The a ^* b ^* color system represents the hue angle shifted from the a counterclockwise hue from 0 to the a ^* red axis.

(C) As a translucent material which can be used for a layer, the thing similar to a fluorescence light emitting layer (A) can be used.
The pigment and / or dye is not particularly limited, and general pigments can be used. Examples of the pigment include titanium oxide, zinc oxide, iron oxide, carbon black, molybdenum red, cobalt blue, manganese violet, petal, bitumen, ultramarine blue and other inorganic pigments; phthalocyanine blue, phthalocyanine green and other phthalocyanine pigments, monoazo Azo pigments such as red, first yellow, permanent yellow and disazo yellow, perylene pigments such as perylene red, quinacridone pigments such as quinacridone red, isoindolinone pigments, methine / azomethine pigments, benzimidazolone pigments, Organic pigments such as dioxazine pigments; metal powder pigments such as aluminum, nickel, and stainless steel; special pigments such as pearl pigments, fluorescent pigments, and phosphorescent pigments.
As the dye, various dyes such as a basic dye, an acid dye, a direct dye, a vat dye, a disperse dye, and a reactive dye can be used.
These may be selected as appropriate according to the desired hue, and may be used alone or in combination of two or more.

The (C) layer is formed by molding a composition containing the above translucent material and the above pigment and / or dye (hereinafter referred to as “colored layer composition”) into a film shape or a plate shape. The thickness is usually 0.01 mm to 5 mm, more preferably 0.01 to 1 mm, and the thickness may be partially changed within this range. By changing the thickness partially, the shade of the emission color can be changed. In the colored layer composition, it is preferable to mix 0.01 to 5 parts by weight, and further 0.03 to 2 parts by weight of pigment and / or dye with respect to 100 parts by weight of the translucent material (solid content). . If the amount is less than 0.01 parts by weight, the emission color may not be darkened. Moreover, when adding more than 5 weight part, there exists a possibility that a luminescent color may become difficult to confirm.

In the present invention, the ultraviolet light reflecting layer (B) and the colored layer (C) are laminated on the fluorescent light emitting layer (A) exhibiting fluorescent light emission from the side irradiated with the ultraviolet light, whereby the layer (B) and ( C) Due to the synergistic effect of the layers, the fluorescent emission color can be made brighter and darker.
Although the (B) layer and the (C) layer may be laminated as separate layers as described above, the ultraviolet ray is irradiated in the entire wavelength region of 300 nm to 400 nm, which has both the effects of the (B) layer and the (C) layer. It can also be laminated as a transparent or translucent ultraviolet reflective colored layer (D) (hereinafter also simply referred to as “(D) layer”) having a reflectance of 10% or more. As the layer (D), for example, a composition containing a translucent material, an ultraviolet reflective powder, and a pigment and / or dye (a composition for an ultraviolet reflective colored layer) is formed into a film shape or a plate shape. Can be used. (Figure 2)

The layer (D) is a film-like or plate-like composition containing the light-transmitting material, the ultraviolet-reflecting powder, the pigment and / or the dye (hereinafter referred to as “ultraviolet-reflective colored layer composition”). Etc. are formed. The thickness is usually 0.01 mm to 10 mm, more preferably 0.01 to 5 mm, and the thickness may be partially changed within this range. By changing the thickness partially, the shade of the emission color can be changed. The composition for ultraviolet reflective coloring layer is composed of 10 to 400 parts by weight (preferably 30 to 300 parts by weight) of ultraviolet reflective powder, pigment and / or dye with respect to 100 parts by weight of the translucent material (solid content). It is preferable to mix 0.01 to 5 parts by weight (preferably 0.03 to 2 parts by weight).

In addition, the layer (D) of the present invention is transparent to the extent that the emission of the fluorescent light emitting layer can be visually recognized from the side opposite to the layer (A) when the laminate of the present invention is irradiated with ultraviolet rays from the (A) layer side. What is necessary is just to be translucent, and it is preferable that the concealment rate of the (D) layer is 70% or less (preferably 15% to 60%). If it exceeds 70%, the visibility of fluorescent emission may be reduced. Further, by setting the concealment rate to 15% or more, the shape of the light source on the (A) layer side can be made difficult to be visually recognized through the (D) layer.

As the laminate of the present invention, the fluorescent light emitting layer (A), the ultraviolet light reflecting layer (B), and the colored layer (C) are laminated in order from the side irradiated with the ultraviolet light, or the fluorescent light emitting layer (A). ), And a laminate Q in which an ultraviolet reflective coloring layer (D) is laminated. In addition, the fluorescent light emitting layer (A), the ultraviolet reflective layer (B), and the ultraviolet reflective are sequentially arranged from the side irradiated with ultraviolet rays. It may be a laminate in which the colored layer (D) is laminated, or a laminate in which the fluorescent light emitting layer (A), the ultraviolet reflective colored layer (D), and the colored layer (C) are laminated. Furthermore, a substrate ((E) layer) or the like can be laminated as long as the effects of the present invention are not impaired.

A base material (E) is not specifically limited, Gypsum board, plywood, concrete, mortar, porcelain tile, fiber mixed cement board, cement calcium silicate board, slag cement pearlite board, ALC board, siding board, extrusion board, steel sheet , Aluminum plate, plastic plate, glass plate and the like. Especially, in this invention, it is preferable that it is a translucent base material (E '), and in the case of a translucent base material (E'), it is visible not only from the side irradiated with a light source but from the opposite side. Therefore, the design is excellent. As such a translucent base material (E ′), the same translucent material as that of the fluorescent light emitting layer (A) is formed into a film or plate, a commercially available glass plate, resin plate, A resin film or the like can be used. The thickness may be appropriately set depending on the type of base material to be used, but is usually preferably 0.05 mm to 10 mm. When it is too thick, there is a possibility that light emission is difficult to visually recognize. In the case of the laminate P, the translucent substrate (E ′) may be laminated so that (E ′) is in contact with at least one of the (A) layer, the (B) layer, and the (C) layer. In the case of the stacked body Q, the stacked body Q may be stacked so that (E ′) is in contact with at least one of the (A) layer and the (D) layer.

The shape of these base materials (E) is not particularly limited, but if the base material is an uneven base material, the diversity of fluorescence emission increases. The uneven shape preferably has a difference between the concave and convex portions of about 0.01 mm to 10 mm, and more preferably about 0.05 mm to 5 mm. By being in this range, it is possible to express fantastic light emission, and it is excellent in design and aesthetics.

In the laminate of the present invention, the fluorescent light emitting layer (A), the ultraviolet reflective layer (B), and the colored layer (C) are laminated (laminate P) or the fluorescent light emitting layer (A) in order from the side irradiated with the ultraviolet rays. As long as the ultraviolet reflective coloring layer (D) is laminated (laminated body Q), the shape is not particularly limited, such as a plate shape, a prismatic shape, or a cylindrical shape. Moreover, although the manufacturing method of this invention laminated body is not specifically limited, For example,
(I) A fluorescent light emitting layer (A), an ultraviolet reflective layer (B), a colored layer (C), or an ultraviolet reflective colored layer (D) formed into a plate shape is adhesive as shown in FIG. 1 or FIG. A method of laminating via, etc.
(II) An ultraviolet reflective layer composition, a colored layer composition, or an ultraviolet reflective colored layer composition is applied to the fluorescent light emitting layer (A) formed into a plate shape as shown in FIG. 1 or FIG. The curing method,
Etc.
Moreover, it can also manufacture combining said (I) and said (II).

In the above (I) to (II), when the fluorescent light emitting layer composition, the ultraviolet reflective layer composition, the colored layer composition, and the ultraviolet reflective colored layer composition are formed into a film shape, a plate shape or the like, What is necessary is just to perform by a well-known shaping | molding method, for example, mold forming, injection molding, cast molding, etc. are mentioned.
In the above (II), when applying the fluorescent light emitting layer composition, the ultraviolet reflective layer composition, the colored layer composition, and the ultraviolet reflective colored layer composition, spray, roller, trowel, reciprocating, Means such as a coater and pouring can be used.

Moreover, at the time of molding, for example, coloring materials, plasticizers, flame retardants, lubricants, preservatives, antifungal agents, antialgae agents, antibacterial agents, dispersants, antifoaming agents, film-forming aids, adsorption agents An agent, a crosslinking agent, an antioxidant, a catalyst, an antiblocking agent and the like may be contained, and such a component can be uniformly mixed by a conventional method to produce a molded product.

  When the fluorescent light emitting layer (A) and the ultraviolet reflective layer (B), the colored layer (C), or the ultraviolet reflective colored layer (D) are laminated via an adhesive or the like, the transparent layer does not impair the effects of the present invention. A light adhesive, pressure-sensitive adhesive, pressure-sensitive adhesive tape, or the like can be used. Moreover, although the said fluorescent light emitting layer composition or the composition for ultraviolet reflection layers may be normally dried at normal temperature, it can also be heated.

(Light emitting structure)
In the light emitting structure (R) of the present invention, the ultraviolet light source (X) (light source (X)), the fluorescent light emitting layer (A), the ultraviolet reflective layer (B), and the colored layer (C) are laminated. The laminated body is provided. The ultraviolet light source (X) is disposed on the fluorescent light emitting layer (A) side of the laminate.

The light source (X) may irradiate the entire surface of the layer (A) or may irradiate locally to form a pattern. Further, the display content can be easily changed by switching the light source ON / OFF.
Although the light source used for this invention should just emit an ultraviolet light, what has an emission line in the wavelength range of 300 nm-400 nm is preferable.
The direction of viewing the light emission of the light emitting structure is not particularly limited, but when the (B) layer, (C) layer, and (base material (E)) are translucent, You can also In this case, the shape of the light source installed behind the (A) layer becomes difficult to be visually recognized through the (B) layer.

As described above, an internally illuminating light emitting structure is exemplified as a light emission viewing direction opposite to the light source (X) (FIG. 3). In the case of an internally illuminated structure, external leakage of light emitted from the light source (X) can be prevented. In this case, a reflector (Y) can be provided behind and on the side of the light source. As such a reflective layer, a coating layer made of a metal material such as Ag, Al, Au, Cr, Cu, Ni, Ti, Pt having a high ultraviolet reflective efficiency, or the ultraviolet reflective layer (B) of the present invention, or Examples include those coated with a white paint containing kaolin, talc, silica, etc., porous plates, porous sheets and the like. The shape of the reflecting plate (Y) may be either a flat shape (FIG. 3-1) or a wavy shape (FIGS. 3-2 and 3-3). Particularly, in the present invention, a wave shape is preferable, and in this case, it is preferable that the light source is disposed in the concave portion of the reflection plate. By providing the reflecting plate having such a shape, the light emitted from the light source is irregularly reflected, so that the fluorescent light emitting layer (A) can be irradiated with uniform light. Further, it is preferable that the surface of the reflecting plate has fine irregularities so that the light irregular reflection effect can be further enhanced. The height of the unevenness is preferably 1 to 1000 μm (preferably 5 to 500 μm).
On the other hand, in order to adjust the irradiation intensity near the light source, a shielding plate (Z) can be provided between the light source (X) and the fluorescent light emitting layer (A). The shielding plate (Z) shields part of the light from the light source (X). Thereby, uniform light can be irradiated by the fluorescent light emitting layer (A).

In the light emitting structure of the present invention, the shape of the light source installed behind the (A) layer is difficult to be visually recognized through the (B) layer as described above. A translucent uneven plate (F) can be disposed therethrough. By providing such a concavo-convex plate (F), it becomes difficult to visually recognize the shape of the light source installed behind. Furthermore, it can express fantastic light emission of the laminate, and is excellent in design and aesthetics. As an uneven | corrugated board (F), the thing similar to the translucent base material in the above-mentioned base material (E) can be used.

  Examples are given below to clarify the features of the present invention.

-Composition 1 for fluorescent light emitting layer
100 parts by weight (solid content) of an acrylic resin emulsion, 10 parts by weight of a green inorganic fluorescent pigment, and 4 parts by weight of additives (dispersing agent, antifoaming agent, etc.) are mixed by a conventional method to prepare a composition 1 for a fluorescent light emitting layer. did.
The composition for fluorescent light emitting layer 1 was applied to an acrylic plate (300 mm × 200 mm × 3 mm) so as to have a coating thickness of 150 μm (dry film thickness was about 80 μm) and dried. An ultraviolet light source (6 W ultraviolet lamp: 365 nm) was installed at a distance of 3 cm from the fluorescent light emitting layer, irradiated with ultraviolet rays in a dark room, and the emitted color was measured using a color luminance meter “BM-5A” (manufactured by Topcon Corporation). It was measured. From this result, the hue angle in the L ^* C ^* h color system was calculated to be h = 159.0 °.

-Composition 1 for colored layer
A colored layer composition 1 was prepared by mixing 100 parts by weight (solid content) of an acrylic resin emulsion and 0.2 parts by weight of a phthalocyanine green pigment by a conventional method.
The colored layer composition 1 was applied to standard white paper so that the coating thickness was 150 μm (the dry film thickness was about 80 μm) and dried. The hue of the colored layer was measured using a color difference meter (“CR-300” manufactured by Minolta Co., Ltd.), and the hue angle in the L ^* C ^* h color system was calculated, and h = 182.1 °. It was.
・ Composition 1 for UV reflective colored layer
100 parts by weight of acrylic resin emulsion (solid content), 30 parts by weight of alumina, 5 parts by weight of additives (dispersing agent, antifoaming agent, etc.) and 0.2 parts by weight of phthalocyanine green pigment are mixed in a conventional manner, and ultraviolet reflection coloring Layer composition 1 was prepared.
As with the colored layer composition 1, the hue angle was calculated to be h = 182.1 °.

-Composition 1 for UV reflective layer
100 parts by weight (solid content) of an acrylic resin emulsion, 30 parts by weight of alumina, and 5 parts by weight of additives (dispersant, antifoaming agent, etc.) were mixed by a conventional method to prepare a composition 1 for an ultraviolet reflective layer.
-Compositions for UV reflective layer 2-6
Based on the composition of Table 1, Compositions 2 to 6 for ultraviolet reflection layer were prepared in the same manner as Composition 1 for ultraviolet reflection layer.
In addition, the raw material used is shown below.
Alumina: particle diameter 1 μm, refractive index 1.76
Barium sulfate: particle size 2 μm, refractive index 1.64
-Heavy calcium carbonate: particle size 1.5 μm, refractive index 1.56
Titanium oxide: particle size 0.25 μm, refractive index 2.71
Zinc oxide: particle diameter 1 μm, refractive index 1.95

The following evaluation was implemented regarding the compositions 1-6 for ultraviolet reflective layers. Moreover, the same evaluation was implemented also about the composition 1 for ultraviolet reflective coloring layers. The results are shown in Table 1.
・ Evaluation 1
On the concealment rate test paper, the prepared compositions 1 to 6 for ultraviolet reflection layer and the composition 1 for ultraviolet reflection coloring layer are applied and cured to a coating thickness of 150 μm (dry film thickness is about 80 μm). Using the test specimen, the luminous reflectance of the black ground paint film and the white ground paint film in the test specimen was measured using a color difference meter ("CR-300" manufactured by Minolta Co., Ltd.), and the concealment rate (%) was calculated. Calculated.

・ Evaluation 2
A coating composition in which 20 parts by weight of carbon black is mixed with 100 parts by weight (solid content) of urethane resin on an aluminum plate (40 mm × 40 mm × 0.6 mm) is applied and cured to a coating thickness of 150 μm. Was used as a base material. Using the test specimens that were applied to the substrate with the prepared UV reflecting compositions 1 to 6 and UV reflecting colored layer composition 1 so that the coating thickness was 150 μm (dry film thickness was about 80 μm) and dried, The reflectance (%) was measured with a spectrophotometer (“UV-3100” manufactured by Shimadzu Corporation) in the entire wavelength region of 300 nm to 400 nm.
As a result, in the compositions 1 to 4 for the ultraviolet reflective layer and the composition 1 for the ultraviolet reflective colored layer, the ultraviolet reflectance was 10% or more in the entire wavelength region of 300 nm to 400 nm. Table 1 shows the ultraviolet reflectance at a wavelength of 365 nm as a representative value. (The reflectance of the substrate at a wavelength of 365 nm was 1.5%.)

(Manufacture of laminates)
Example 1
The fluorescent light emitting layer composition 1 was applied on a release paper at a coating thickness of 150 μm (dry film thickness was about 80 μm) and dried to form a fluorescent light emitting layer (A-1). Next, the composition 1 for ultraviolet reflecting layer 1 is applied onto the fluorescent light emitting layer (A-1) so that the coating thickness is 150 μm (dry film thickness is about 80 μm), and dried to form the ultraviolet reflecting layer (B-1). Were laminated. Furthermore, the colored layer composition 1 was applied at a coating thickness of 150 μm (dry film thickness was about 70 μm) and dried, and the colored layer (C-1) was laminated to obtain a laminate 1.

  The following evaluation was performed on the obtained laminate 1. The results are shown in Table 2.

・ Evaluation 3
In the laminate 1, an ultraviolet light source (6 W ultraviolet lamp: 365 nm) is installed at a distance of 3 cm from the fluorescent light emitting layer (A-1), irradiated with ultraviolet rays in a dark room, and the emission luminance (cd / m ² ) of the laminate 1. ) Was measured using a color luminance meter “BM-5A” (manufactured by Topcon Corporation). The results are shown in Table 2.

(Example 2)
The colored layer composition 1 is applied to one surface of an acrylic plate (300 mm × 200 mm × 3 mm) with a coating thickness of 150 μm (dry film thickness is about 70 μm) and dried to form a colored layer (C-1). Laminated. Subsequently, the composition 1 for ultraviolet reflective layers was applied with a coating thickness of 150 μm (dry film thickness was about 80 μm) and dried, and an ultraviolet reflective layer (B-1) was laminated. Further, the fluorescent light emitting layer composition 1 is applied onto the ultraviolet reflective layer (B-1) so that the coating thickness is 150 μm (the dry film thickness is about 80 μm), and dried to obtain the fluorescent light emitting layer (A-1). ) To obtain a laminate 2. Evaluation similar to Example 1 was implemented regarding the obtained laminated body 2. FIG. The results are shown in Table 2.

(Example 3)
A laminated body 3 is produced in the same manner as in Example 2, except that the composition 2 for ultraviolet reflection layer is used instead of the composition 1 for ultraviolet reflection layer of Example 2 and the ultraviolet reflection layer (B-2) is laminated. The same evaluation was conducted. The results are shown in Table 2.

Example 4
A laminated body 4 is produced in the same manner as in Example 2 except that the composition 3 for ultraviolet reflection layer is used in place of the composition 1 for ultraviolet reflection layer of Example 2 and the ultraviolet reflection layer (B-3) is laminated. The same evaluation was conducted. The results are shown in Table 2.

(Example 5)
A laminated body 5 is produced in the same manner as in Example 2 except that the ultraviolet reflective layer composition 4 is used in place of the ultraviolet reflective layer composition 1 of Example 2 and the ultraviolet reflective layer (B-4) is laminated. The same evaluation was conducted. The results are shown in Table 2.

(Example 6)
A laminate 6 was prepared in the same manner as in Example 2 except that the ultraviolet reflective layer (B-5) was laminated in place of the application thickness of the composition 1 for ultraviolet reflective layer of Example 2 at 250 μm, and the same evaluation was made. Carried out. The results are shown in Table 2.

(Example 7)
On one surface of an acrylic plate (300 mm × 200 mm × 3 mm), the composition 1 for ultraviolet reflective colored layer is applied with a coating thickness of 150 μm (dry film thickness is about 70 μm) and dried to form an ultraviolet reflective colored layer (D -1) was laminated. Further, the fluorescent light emitting layer composition 1 is applied on the ultraviolet reflective colored layer (D-1) so that the coating thickness is 150 μm (the dry film thickness is about 80 μm), dried, and then the fluorescent light emitting layer (A- 1) was laminated to obtain a laminate 7. Evaluation similar to Example 1 was implemented regarding the laminated body 7, and the result was shown in Table 2.

(Comparative Example 1)
A laminated body 8 is produced in the same manner as in Example 2 except that the composition 5 for ultraviolet reflecting layer is used in place of the composition 1 for ultraviolet reflecting layer of Example 2 and an ultraviolet reflecting layer (B-6) is laminated. The same evaluation was conducted. The results are shown in Table 2.

(Comparative Example 2)
A laminated body 9 is produced in the same manner as in Example 2, except that the composition 6 for ultraviolet reflecting layer 6 is used instead of the composition 1 for ultraviolet reflecting layer of Example 2 and the ultraviolet reflecting layer (B-7) is laminated. The same evaluation was conducted. The results are shown in Table 2.

(Comparative Example 3)
The ultraviolet reflective layer composition 1 is applied to one surface of an acrylic plate (300 mm × 200 mm × 3 mm) with a coating thickness of 150 μm (dry film thickness is about 80 μm), dried, and the ultraviolet reflective layer (B-1 ) Was laminated. Further, the fluorescent light emitting layer composition 1 is applied onto the ultraviolet reflective layer (B-1) so that the coating thickness is 150 μm (the dry film thickness is about 80 μm), and dried to obtain the fluorescent light emitting layer (A-1). ) To obtain a laminate 10. Evaluation similar to Example 1 was implemented regarding the laminated body 10, and the result was shown in Table 2.

(Comparative Example 4)
On one surface of an acrylic plate (300 mm × 200 mm × 3 mm), the fluorescent light emitting layer composition 1 is applied to a thickness of 150 μm (dry film thickness is about 80 μm) and dried to obtain a fluorescent light emitting layer (A -1) was laminated and the laminated body 11 was obtained. Evaluation similar to Example 1 was implemented regarding the laminated body 11, and the result was shown in Table 2.

(Evaluation of luminous hue)
Regarding the laminates 1 to 12, an ultraviolet light source (20 W black light fluorescent lamp) was installed at a distance of 30 cm from the fluorescent light emitting layer, and the emitted color was evaluated by irradiating the ultraviolet light. As a result, the laminates 1 to 7 had high emission luminance and a deep green emission color. On the other hand, although the laminated bodies 8-9 were the deep green luminescent color, they were inferior to luminescent property. Moreover, the laminated bodies 10 and 11 were light emission color lightened.

(Example 8)
Using the laminate 2 of Example 2, an internally-illuminated light emitting structure shown in FIG. 3-2 was produced. When an ultraviolet light source (6W ultraviolet lamp: 365 nm) was installed at a distance of 3 cm from the fluorescent light emitting layer (A-1) and irradiated with ultraviolet light, the fluorescent light emitting layer (A-1) showed uniform light emission and was deep. It was a green emission color.

(A) Viewing direction (direction of light emission)
(P), (Q) Laminate (R) Light emitting structure (A) Fluorescent light emitting layer (B) Ultraviolet reflective layer (C) Colored layer (D) Ultraviolet reflective colored layer (X) Light source (Y) Reflector (Z )Shield

Claims (5)

A laminate that emits light when irradiated with an ultraviolet light source,
Fluorescent light emitting layer (A) showing fluorescence emission from the side irradiated with ultraviolet light, a transparent or translucent ultraviolet reflective layer (B) having an ultraviolet reflectance of 10% or more in the entire wavelength region of 300 nm to 400 nm, and Laminated body in which colored layer (C) is laminated   The layered product according to claim 1, wherein the colored layer (C) has a color similar to the fluorescent color emitted by the fluorescent layer (A). A laminate that emits light when irradiated with an ultraviolet light source,
From the side irradiated with ultraviolet rays, there is a fluorescent light emitting layer (A) that exhibits fluorescent emission, and a transparent or translucent ultraviolet reflective colored layer (D) that has an ultraviolet reflectance of 10% or more in the entire wavelength region of 300 nm to 400 nm. Laminated body characterized by being laminated   4. The laminate according to claim 3, wherein the ultraviolet reflective coloring layer (D) has a color similar to the fluorescent color emitted by the fluorescent light emitting layer (A). A light emitting structure comprising the laminate according to any one of claims 1 to 4 and an ultraviolet light source (X) on the fluorescent light emitting layer (A) side of the laminate.

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