JP2009208367A - Laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate excellent in design properties showing various fluorescent emissions by the irradiation with ultraviolet rays. <P>SOLUTION: The laminate showing various fluorescent emissions by the irradiation with ultraviolet rays is constituted by providing a phosphor layer (A) containing a fluorescent material on a base material and forming a coating film (B), which reflects and/or absorbs a part of irradiated ultraviolet rays and permits the remainder of ultraviolet rays to transmit, on the phosphor layer (A) and characterized in that the coating film (B) covers at least a part of the phosphor layer (A) and permits the emission from the phosphor layer (A) to transmit. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a laminate that exhibits fluorescence.

Conventionally, a molded article containing a phosphor 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, a fluorescent light emitting tile (for example, Patent Document 1) in which a colored layer (fluorescent light emitting layer) containing a fluorescent pigment is laminated on a ceramic tile is known. However, only by laminating the phosphor on the substrate as described above, when irradiated with ultraviolet rays, it can only have fluorescence emission with uniform luminance, which may result in a monotonous design. In such a laminate, the brightness of the fluorescent light emitting layer can be changed by setting the fluorescent pigment concentration of the fluorescent light emitting layer, the thickness of the fluorescent light emitting layer, partially irradiating ultraviolet rays, and various other devices. Was necessary.

On the other hand, laminates (for example, Patent Document 2 and Patent Document 3) in which a plurality of fluorescent pigments having different hues are used on the substrate surface and fluorescent light-emitting layers are applied in various forms and patterns are known. . However, in the case of such a laminated body, it is necessary to laminate a plurality of fluorescent light emitting layers in various forms and patterns, and the process may be complicated.

JP-A-4-160082 Japanese Patent Laid-Open No. 3-122363 JP-A-3-290380

  The present invention has been made in view of the above-described problems, and an object of the present invention is to obtain a laminate having excellent design properties that exhibits various fluorescent emissions by ultraviolet irradiation.

As a result of intensive studies to achieve the above object, the present inventor has provided a phosphor layer on a substrate, and a film having specific light characteristics is formed on the phosphor layer. As a result, the present invention has been completed.
That is, this invention laminated body has the following characteristics.

1. A laminate that exhibits various fluorescence emission by ultraviolet irradiation,
On the base material, a phosphor layer (A) containing a fluorescent material is provided,
On the phosphor layer (A), a film (B) that reflects and / or absorbs part of the irradiated ultraviolet rays and transmits the remaining ultraviolet rays is formed,
The laminated body characterized in that the coating (B) covers at least a part of the phosphor layer (A) and transmits light emitted from the phosphor layer (A).
2. The coating (B) has at least two coatings having different ultraviolet reflectivity and / or ultraviolet absorption properties. The laminated body of description.

  In the laminate of the present invention, a phosphor layer (A) containing a phosphor material is provided on a base material, and a coating (B) having specific light characteristics is formed on the phosphor layer (A). Thus, various fluorescent emissions can be exhibited by ultraviolet irradiation. The laminate of the present invention is usually monochromatic (when irradiated with visible light), but can exhibit various fluorescent emissions when irradiated with ultraviolet light.

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

The present invention is a laminate that exhibits various fluorescence emission upon irradiation with ultraviolet rays, and a phosphor layer (A) is provided on a substrate, and a coating (B) having specific light characteristics on the phosphor layer. It is the laminated body characterized by forming. The various fluorescent emission in the present invention means having at least two fluorescent emission having different emission luminances even when one kind of fluorescent emission layer is uniformly laminated.

The phosphor layer (A) containing the phosphor material of the present invention (hereinafter also simply referred to as “phosphor layer (A)”) will be described. The phosphor layer (A) includes a light-transmitting material (hereinafter referred to as “translucent material”) including a pigment, a dye or the like (hereinafter referred to as “fluorescent material”) that exhibits fluorescence.
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, alkoxysilane, and silane coupling agent. Organic materials include acrylic resin, acrylic-styrene resin, cellulose acetobutyrate resin, cellulose propionate resin, polymethylpentene resin, polycarbonate resin, polystyrene resin, polyester resin, epoxy resin, methacrylic resin, urethane resin. Etc. Note that “translucency” means excellent transparency to visible light and 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 phosphor layer (A) is obtained by molding the light-transmitting material and a material containing the phosphor material (hereinafter referred to as “phosphor layer material”) into a film shape or a plate shape. The thickness is usually 0.01 mm to 10 mm, more preferably 0.05 mm to 5 mm, and the concealment rate (%) is not particularly limited, but is usually 70% or less, preferably 50% or less. In the case of 70% or less, since the substrate can be visually recognized, the design of the substrate can be utilized. The concealment rate of the phosphor layer is a value calculated by measuring with a color difference meter. Such a phosphor layer material is preferably added in an amount of 0.5 to 50 parts by weight, and more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the light-transmitting 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, a brightness | luminance improvement cannot be confirmed but there exists a possibility that it may become difficult to obtain various fluorescence emission.

Next, the coating film (B) that reflects and / or absorbs part of the irradiated ultraviolet rays and transmits the remaining ultraviolet rays (hereinafter also simply referred to as “coating layer (B)”) will be described.
The coating (B) of the present invention has “ultraviolet ray reflectivity and / or ultraviolet ray absorbability” that reflects and / or absorbs part of the ultraviolet ray irradiated from the light source, and has “ultraviolet ray permeability” that transmits the remaining ultraviolet ray. What is necessary is just to have laminated | stacked so that at least one part of a fluorescent substance layer (A) may be covered.

The above “ultraviolet reflectiveness and / or ultraviolet absorptive” means that the laminated body in which the film (B) is formed so as to cover at least a part of the phosphor layer (A) is irradiated with ultraviolet rays from the direction of the film (B). In the case, it means that the coating (B) has a characteristic of reflecting (diffuse reflection) or absorbing a part of ultraviolet rays.
For example, any one of the portion (p) having a low ultraviolet reflectivity and the portion (q) having a higher UV reflectivity than the (p) may cover at least a part of the phosphor layer (A). Alternatively, it may be discontinuously scattered or have irregularities. However, in the present invention, it is not desirable to cover the entire phosphor layer (A) with either one of the uniform coating (B) of (p) and (q). In the present invention, it is particularly preferable to mix (p) and (q). In this case, at least one (q) is necessary, but two or more may be provided.

The difference in ultraviolet reflectance between (p) and (q) is desirably at least 1% or more (preferably 5% or more). In addition, the ultraviolet reflectance of this invention is the value which measured the reflectance (%) in wavelength range 365nm with the spectrophotometer.

As a method for setting the ultraviolet reflectances of (p) and (q) to be different, for example,
(1) Method of using particles having different ultraviolet reflectances (2) Method of using resins having different ultraviolet reflectances (3) Method of using ultraviolet absorbers (4) Method of changing the thickness of the coating (B) It is done. In the present invention, the methods (1) to (4) can be combined.

Examples of the powder that can be used in (1) above include alumina, zirconium oxide, barium sulfate, precipitated barium sulfate, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, titanium oxide, magnesium oxide, and oxidation. Zinc, boron nitride, bismuth oxychloride, zinc phosphate, mica, cryolite, talc, diatomaceous earth, white clay, kaolin, clay, porcelain clay, barite powder, quartz sand, quartzite powder, white carbon, metal powder, organic resin powder, etc. Can be mentioned. Specifically, a granular material having a low ultraviolet reflectance in (p) may be used. Examples of the granular material having a low ultraviolet reflectance include titanium oxide, zinc oxide, talc, calcium carbonate, diatomaceous earth and the like, and titanium oxide, zinc oxide and the like are particularly preferable. In (q), a powder having a high ultraviolet reflectance may be used. Examples of the powder having a high ultraviolet reflectance include alumina, zirconium oxide, barium sulfate, calcium carbonate, magnesium carbonate and the like. Among these, alumina, barium sulfate and the like are preferable, and alumina is particularly preferable. In the present invention, (p) and (q) may be formed by combining a plurality of powder particles.

In addition, the ultraviolet reflectance of the granular material in the above (1) is a composition in which each granular material is mixed with acrylic resin on an aluminum plate painted in advance so as not to reflect ultraviolet rays (hiding ratio 95%). ) Is a value obtained by measuring the reflectance (%) in a wavelength region of 365 nm with a spectrophotometer using a coated (dry film thickness: 100 μm) and dried sample. The concealment rate is a value obtained by calculating Y _B / Y _W as a percentage in accordance with JIS K 5600-4-1: 1999 method B (concealment rate test paper).

The resin that can be used in the above (2) may be either an inorganic material or an organic material. Examples of the inorganic material include glass, water glass, low-melting glass, silicon resin, alkoxysilane, silane coupling agent, and the like. Is mentioned. Organic materials include acrylic resin, polyester resin, polyether resin, vinyl resin, polyamide resin, phenol resin, urethane resin, epoxy resin, fluororesin, vinyl acetate resin, acrylic-styrene resin, vinyl acetate-vinyl versatate Ester resin, polyvinyl pyrrolidone resin, polyvinyl caprolactam resin, polyvinyl alcohol resin, polycarbonate resin, ABS resin, AS resin, cellulose resin, acrylic-silicon resin, silicon resin, alkyd resin, melamine resin, amino resin, water dispersion type, water Examples of the resin include soluble type, NAD type, solvent soluble type, and solventless type.

Specifically, a resin having a low ultraviolet reflectance in (p) may be used. In the above (2), the difference in ultraviolet reflectance between the resin having the lowest ultraviolet reflectance and the resin having the highest ultraviolet reflectance is 1% or more (preferably 2% or more, more preferably 3% or more, more preferably 5% or more). It is desirable to do. Such a difference in ultraviolet reflectance can be provided, for example, by changing the ratio of ultraviolet absorbing groups in the resin. Examples of the ultraviolet absorbing group include a phenyl group, a benzophenone group, a benzotriazole group, and a triazine group.

Specific examples of the above (2) include a combination in which a resin having a large styrene ratio in the resin is used in (p) and a resin having a small styrene ratio in the resin is used in (q). In this case, the styrene ratio in the resin is desirably different by 10% by weight or more (preferably 35% by weight or more).
In addition, the ultraviolet reflectance in (2) is obtained by applying a composition (a concealment ratio of 95%) in which alumina is mixed with each resin on an aluminum plate painted in black so as not to reflect ultraviolet rays (dry film). (Thickness: 100 μm) The value obtained by measuring the reflectance (%) in a wavelength region of 365 nm with a spectrophotometer using a dried sample as a sample.

In (3) above, the ultraviolet reflectance is changed depending on the presence or absence of the ultraviolet absorber or the difference in concentration. Examples of the ultraviolet absorber usable in the above (3) include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. Among these, as the benzophenone-based ultraviolet absorber, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n -Octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2'-dihydroxy -4-methoxybenzophenone, 2,2'-dihydroxy-4,4'dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4- Methoxy-2'- Carboxymethyl benzophenone, 2-hydroxy-4-stearyloxy benzophenone. As radically polymerizable benzophenone UV absorbers, 2-hydroxy-4-acryloxybenzophenone, 2-hydroxy-4-methacryloxybenzophenone, 2-hydroxy-5-acryloxybenzophenone, 2-hydroxy-5-methacryloxybenzophenone 2-hydroxy-4- (acryloxy-ethoxy) benzophenone, 2-hydroxy-4- (methacryloxy-ethoxy) benzophenone, 2-hydroxy-4- (methacryloxy-diethoxy) benzophenone, 2-hydroxy-4- (acryloxy-triethoxy) ) Benzophenone.

Specifically, an ultraviolet absorber may be blended in (p), and an ultraviolet absorber may not be blended in (q). Alternatively, the concentration of the ultraviolet absorber in (p) may be increased and the concentration of the ultraviolet absorber in (q) may be set low. In the above (3), it is desirable that the difference in ultraviolet reflectance between the portion where the concentration of the ultraviolet absorber is high and the portion where the concentration is low is 2% or more (preferably 5% or more, more preferably 10% or more). In (3), it is desirable that the concentration of the ultraviolet absorber is set to be different by 0.01% by weight or more (preferably 0.05% by weight or more). In addition, the ultraviolet reflectance in (3) is a composition in which alumina and an ultraviolet absorber are mixed in each resin on an aluminum plate painted in black so as not to reflect ultraviolet rays (hiding ratio 95%), This is a value obtained by measuring the reflectance (%) in a wavelength region of 365 nm with a spectrophotometer using a sample that has been applied (dry film thickness: 100 μm) and dried.

The above (4) is that a material having a low ultraviolet reflectance tends to have a lower ultraviolet reflectance as the thickness is larger, and a material having a higher ultraviolet reflectance tends to have a higher ultraviolet reflectance as the thickness is larger. It is something that takes advantage of something. As the material having a high ultraviolet reflectance, for example, the material forming (q) in the above (1) to (3) can be used. What is necessary is just to set the thickness of a film (B) within the range of 5 micrometers-500 micrometers normally (preferably 10 micrometers-250 micrometers).

In the present invention, in addition to the above (1) to (4), (p) and (q) are provided by a method of changing the concentration of a granular material having a high ultraviolet reflectance, a resin having a high ultraviolet reflectance, or the like. You can also.

In addition, the coating (B) of the present invention can be replaced with, for example, a part (p ′) having a high UV-absorbing property, or a part having a lower UV-absorbing property (p ′) (instead of the above (p) and (q)). q ′) can also be provided.
Specifically, the portion (p ′) having high UV absorption corresponds to the portion (p) having low UV reflectance, and the portion (q ′) having low UV absorption corresponds to the portion (q) having high UV reflectance. These can be used as well. Also in this case, it is preferable that (p ′) and (q ′) are mixed.

Further, the coating (B) has an ultraviolet transparency that transmits the remaining ultraviolet rays (hereinafter also referred to as “ultraviolet transmission”) and a property that transmits light emitted from the phosphor layer (hereinafter referred to as “emission transparency”). Say). The above “ultraviolet ray transmissive” means that when the laminate of the present invention is irradiated with ultraviolet rays from the direction of the coating (B), the phosphor layer (A) emits light through the coating (B) layer. It is to transmit as much ultraviolet rays as possible. “Luminescence transparency” refers to the ability to visually recognize the luminescence of the phosphor layer (A) through the coating (B) layer. Such a coating (B) is preferably transparent or translucent.

In addition, as a method for measuring transparency or translucency, there is a method in which the coating (B) is placed on a concealment rate test paper and the concealment rate is calculated from the luminous reflectance of the white ground and the black ground.
The concealment rate of the coating (B) is usually 70% or less, preferably 60% or less. If the concealment rate exceeds 70%, the visibility of fluorescent emission may be reduced.
The luminous reflectance can be measured and calculated using a color difference meter (“CR-300” manufactured by Minolta Co., Ltd.).

In the phosphor layer (A) or coating (B), for example, a pigment, an aggregate, a plasticizer, a flame retardant, a lubricant, an antiseptic, an antifungal agent, as long as the effect of the present invention is not impaired. It may contain anti-algae agent, antibacterial agent, dispersant, defoaming agent, film-forming aid, adsorbent, crosslinking agent, antioxidant, ultraviolet absorber, catalyst, anti-blocking agent, etc. The components can be uniformly mixed by a conventional method.

  In the present invention, applicable substrates include, for example, 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 plate, aluminum plate, plastic plate, glass plate and the like. The shape of these base materials is not particularly limited, but if the substrate is an uneven substrate, the diversity of fluorescence emission is increased. In addition, the surface of these base materials may have been subjected to some surface treatment (for example, putty, filler, etc.), and has already been coated and colored, or has already been applied with wallpaper. There may be.

  In this invention, it is preferable that the layer (C) with a high ultraviolet reflectance is previously formed on the base material. Specifically, the coating film having a high ultraviolet reflectance is obtained by laminating the layer (C) containing the powder having a high ultraviolet reflectance.

The laminate structure of the present invention comprises a phosphor layer (A) containing a fluorescent material on a substrate, and a coating (B) that reflects and / or absorbs part of the irradiated ultraviolet rays and transmits the remaining ultraviolet rays. If is laminated | stacked, it will not specifically limit about the manufacturing method. For example, the coating (B) forms a coating (B) forming material, specifically, a material “low reflection material” for forming a portion (p) having a low ultraviolet reflectance and a portion (q) having a high ultraviolet reflectance. Using the material “highly reflective material”, it can be produced by the following method.

(I) After forming the fluorescent light emitting layer (A) on the entire surface of the base material, a low reflective material and / or a high reflective material is partially laminated on the fluorescent light emitting layer (A) to form a coating (B). how to,
(II) After forming the fluorescent light emitting layer (A) on the entire surface of the substrate, a low reflective material is further laminated on the fluorescent light emitting layer (A), and then a high reflective material is partially laminated to form a coating (B )
(III) After forming the fluorescent light emitting layer (A) on the entire surface of the base material, a high reflective material is further laminated on the fluorescent light emitting layer (A), and then a low reflective material is partially laminated to form a coating (B )
(IV) A method of laminating a high reflection material and a low reflection material at the same time and laminating a film (B) after forming the fluorescent light emitting layer (A) on the entire surface of the substrate,
Etc. can be manufactured.

In the above (I), the low reflection material and / or the high reflection material are partially laminated, and in the above (II) and (III), the low reflection material and the high reflection material are laminated in stages. It becomes possible to form a pattern. In (IV), for example, a method of spraying a low reflection material and a high reflection material at the same time, a method of laminating a composition in which a plurality of low reflection materials and high reflection materials encapsulated or gelled are dispersed Can be formed.
Furthermore, when a base material has an unevenness | corrugation, the recessed part and convex part of a base material can also be painted separately using the method of (I)-(IV).

  In the above (I) to (IV), when laminating the phosphor layer material and the coating (B) forming material, the layers formed in advance are bonded together with an adhesive, or the material before molding is sprayed, roller, trowel , Reciprocation, coater, pouring, screen printing and the like. Further, when the (A) layer or the film (B) forming material is dried, it is usually performed at room temperature, but can be heated.

  In the above (I) to (IV), the material “low reflection material” for forming the portion (p) having a low ultraviolet reflectance and the material “high reflection material” for forming the portion (q) having a high ultraviolet reflectance. Instead, the material “high absorption material” that forms the part (p ′) having a high ultraviolet absorption rate and the material “low absorption material” that forms the part (q ′) that has a low ultraviolet absorption rate are used. A film (B) can be formed.

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

<Phosphor layer material>
・ Phosphor layer material 1
Phosphor layer material 1 was prepared by mixing 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 (dispersant, antifoaming agent, etc.).
Regarding the phosphor layer material 1, a black ground coating film and a white coating on the test body were used by using a test body that was coated on a concealment rate test paper so that the coating thickness was 150 μm (dry film thickness was 80 μm). When the visual reflectance of the ground coating film was measured using a color difference meter (“CR-300”: manufactured by Minolta Co., Ltd.) and the concealment rate (%) was calculated, the concealment rate of the phosphor layer material 1 was 6. 1%.

<Manufacture of film forming material>
・ Film forming material 1
100 parts by weight (solid content) of resin emulsion 1, 40 parts by weight of alumina, and 4 parts by weight of additives (dispersant, antifoaming agent, etc.) were mixed by a conventional method to prepare film forming material 1.
・ Film forming materials 2-7
Based on the formulation shown in Table 1, film-forming materials 2 to 7 were produced in the same manner as film-forming material 1.

The following materials were used as raw materials for the film forming material.
Resin emulsion 1: Acrylic / styrene = 100/0, UV reflectance 83.6%
Resin emulsion 2: Acrylic / styrene = 70/30, UV reflectance 81.5%
Alumina: average particle diameter 1.0 μm, ultraviolet reflectance 83.6%
-Titanium oxide: average particle size 0.2 μm, ultraviolet reflectance 6.5%
-Heavy calcium carbonate: average particle size 2.0 μm, ultraviolet reflectance 45.1%
-UV absorber: benzotriazole UV absorber The UV reflectance of resin emulsions 1 and 2 is a composition in which alumina is mixed with each emulsion (hiding ratio 95%), and also alumina, titanium oxide, heavy The ultraviolet reflectance of calcium carbonate is determined by applying a composition (concealment rate 95%) obtained by mixing each granular material to the resin emulsion 1 onto an aluminum plate painted in black so as not to reflect ultraviolet rays (dry film). (Thickness: 100 μm) The value obtained by measuring the reflectance (%) in a wavelength region of 365 nm with a spectrophotometer using a dried sample as a sample.

・ Film forming material 8
A film-forming material 8a was produced by uniformly mixing 11 parts by weight (solid content) of a solvent-soluble acrylic resin, 1 part by weight of titanium oxide, 1 part by weight of a viscosity modifier, and 10 parts by weight of mineral spirit by a conventional method.
Subsequently, 4 parts by weight of polyvinyl alcohol, 3 parts by weight of an acrylic resin emulsion, and 50 parts by weight of water are mixed with an aqueous dispersion medium obtained by uniformly dropping the film-forming material 8a, and then a crosslinking agent. 1 part by weight was mixed.
By the above method, the coating composition 1 in a state in which white particles having a particle diameter of 3 to 5 mm containing titanium oxide were dispersed in an aqueous dispersion medium was obtained.
The coating material 8b was produced according to the above method except that 17 parts by weight of alumina was used instead of titanium oxide, and then the white paint particles having a particle diameter of 3 to 5 mm containing alumina were dispersed in an aqueous dispersion medium. Composition 2 was obtained.
By mixing the coating composition 1 and the coating composition 2 obtained by the above method at a weight ratio of 1: 1, a film forming material 8 in which white particles containing titanium oxide and white particles containing alumina are mixed is obtained. Obtained.

-Film forming material 9
A film-forming material 9a was produced by uniformly mixing 11 parts by weight (solid content) of a solvent-soluble acrylic resin, 1 part by weight of a viscosity modifier, and 10 parts by weight of mineral spirit by a conventional method.
Subsequently, 4 parts by weight of polyvinyl alcohol, 3 parts by weight of an acrylic resin emulsion, and 50 parts by weight of water are mixed with an aqueous dispersion medium obtained by uniformly dropping the film forming material 9a, and then a crosslinking agent. 1 part by weight was mixed.
By the above method, a coating composition 3 was obtained in which clear particles having a particle diameter of 3 to 5 mm were dispersed in an aqueous dispersion medium.
A coating composition in which the film-forming material 9b is produced according to the above method except that 0.1 part by weight of the ultraviolet absorber is added, and the clear particles having a particle diameter of 3 to 5 mm containing the ultraviolet absorber are dispersed in the aqueous dispersion medium. Product 4 was obtained.
The coating composition 3 and the coating composition 4 obtained by the above method were mixed at a weight ratio of 1: 1 to obtain a film forming material 9 in which two kinds of clear particles were mixed.

<Evaluation of film forming material>
・ Evaluation 1
Using the test specimen obtained by coating and curing the prepared film-forming materials 1 to 7, 8a, 8b, 9a, and 9b on the concealment rate test paper to a coating thickness of 150 μm, The visual reflectance of the coating film and the white ground coating film was measured using a color difference meter (“CR-300” manufactured by Minolta Co., Ltd.), and the concealment rate (%) was calculated. The results are shown in Tables 2 and 3.
・ Evaluation 2
A dry film thickness of 80 μm is obtained by mixing 20 parts by weight of carbon black (average particle diameter: 0.02 μm) with 100 parts by weight (solid content) of urethane resin on an aluminum plate (40 mm × 40 mm × 0.6 mm). The substrate was coated and cured as described above. On a base material, using a test body in which the coating compositions 1 to 4 of the film forming materials 1 to 4 and the film forming materials 8 to 9 are applied so as to have a dry film thickness of 100 μm and dried, in a wavelength region of 365 nm. Was measured with a spectrophotometer ("UV-3100": manufactured by Shimadzu Corporation). The results are shown in Table 2. In addition, the reflectance of the base material before apply | coating the composition 1 was 1.5%.
・ Evaluation 3
Since the film forming materials 5 to 7 were transparent, the following evaluation was performed instead of the ultraviolet reflectance in the evaluation 2. The film forming materials 5 to 7 were applied onto the release paper so that the coating thickness was 150 μm and dried, and then the formed coating film was peeled off from the release paper to prepare a film-like test body. The transmittance (%) in the wavelength region 365 nm of the obtained film-like test body was measured with a spectrophotometer (“UV-2200”: manufactured by Shimadzu Corporation).

<Laminated body>
-Base material An aluminum plate (40 mm x 40 mm x 0.6 mm) mixed with 100 parts by weight of acrylic emulsion resin (solid content), 500 parts by weight of alumina, and 5 parts by weight of additives by a conventional method is used as a dry film thickness. Was coated and dried so as to be 100 μm as a substrate.

Example 1
On the said base material, the fluorescent light emitting layer material 1 was apply | coated and dried so that the dry film thickness might be set to 80 micrometers, and the fluorescent light emitting base material was obtained. Next, the film-forming material 1 is applied and dried on the fluorescent light-emitting substrate so that the dry film thickness is 100 μm, and then the film-forming material 2 is spotted using a brush (dry film thickness: average). 80 μm) and dried to obtain a laminate 1.
When the obtained laminated body 1 was visually evaluated under 40 W indoor fluorescent lamp illumination, the laminated body 1 was visually recognized as a substantially uniform white color. In addition, when a 6 W ultraviolet lamp was installed at a distance of 3 cm from the laminate 1 and irradiated with ultraviolet rays, the intensity of brightness was generated on the film forming material 1 and the film forming material 2, and various light emission patterns were recognized. Luminous patterns having lower luminance than the surroundings and partially different luminance were recognized in the coated portion of the film forming material 2.

(Example 2)
A laminate 2 was obtained in the same manner as in Test Example 1 except that the film-forming material 3 was used instead of the film-forming material 2 of Example 1.
When the obtained laminated body 2 was visually evaluated under indoor fluorescent lamp illumination in the same manner as in Example 1, the laminated body 2 was visually recognized as a substantially uniform white color. In addition, under the ultraviolet lamp illumination, brightness intensities are generated on the film forming material 1 and the film forming material 3, and various light emission patterns are recognized. A light emission pattern with partially different brightness was observed.

(Example 3)
A laminate 3 was obtained in the same manner as in Test Example 1 except that the film-forming material 4 was used instead of the film-forming material 2 in Example 1.
When the obtained laminated body 2 was visually evaluated under indoor fluorescent lamp illumination in the same manner as in Example 1, the laminated body 3 was visually recognized as a substantially uniform white color. In addition, under the ultraviolet lamp illumination, brightness intensities occur on the film forming material 1 and the film forming material 4, and various light emission patterns are recognized, and the light emission luminance is higher than the surroundings in the coated portion of the film forming material 1. A light emission pattern with partially different brightness was observed.

Example 4
A laminate 4 was obtained in the same manner as in Test Example 1 except that the film forming material 6 was used in place of the film forming material 5 and the film forming material 2 instead of the film forming material 1 of Example 1. .
When the obtained laminated body 4 was visually evaluated under indoor fluorescent lamp illumination in the same manner as in Example 1, the laminated body 4 was visually recognized as a substantially uniform white color. In addition, under the ultraviolet lamp illumination, brightness intensities occur on the film forming material 5 and on the film forming material 6, and various light emission patterns are recognized, and the light emission brightness is lower than the surroundings at the coated portion of the film forming material 6. A light emission pattern with partially different brightness was observed.

(Example 5)
A laminate 5 was obtained in the same manner as in Example 4 except that the film forming material 7 was used instead of the film forming material 6 in Example 4.
When the obtained laminate 5 was visually evaluated under indoor fluorescent lamp illumination in the same manner as in Example 1, the laminate 5 was visually recognized as a substantially uniform white color. Further, under the ultraviolet lamp illumination, the intensity of brightness was generated on the film forming material 5 and the film forming material 7, and various light emission patterns were observed. However, the difference in luminance between the film forming material 5 and the film forming material 7 was observed. Was small, and it was difficult to identify the pattern.

(Example 6)
On the same fluorescent light-emitting substrate as in Example 1, the film-forming material 8 was spray-coated at a coating amount of 200 g / m ³ and dried, and an overcoat layer was laminated to obtain a laminate 6.
The obtained laminate 6 was visually evaluated under indoor fluorescent lamp illumination in the same manner as in Example 1. As a result, the laminate 6 was visually recognized as a substantially uniform white color, and was randomly painted under ultraviolet lamp illumination. The luminance was different between the coating portions of the film forming material (8a) and the film forming material (8b), and a complicated light emission pattern was recognized.

(Example 7)
Instead of the film-forming material 8 of Example 6, the film-forming material 9 was spray-coated at a coating amount of 200 g / m ³ and dried, and the film was laminated to obtain a laminate 7.
The obtained laminate 7 was visually evaluated under indoor fluorescent lamp illumination in the same manner as in Example 1. As a result, the laminate 7 was visually recognized as a substantially uniform white color, and was randomly painted under ultraviolet lamp illumination. The brightness was different between the coating portions of the film forming material (9a) and the film forming material (9b), and a complicated light emission pattern was observed.

(Example 8)
On the same fluorescent light-emitting substrate as in Example 1, the film forming material 2 was applied at a coating amount of 100 g / m ³ using a design roller and dried, and a discontinuous film was laminated to obtain a laminate 8. .
The obtained laminate 8 was visually evaluated under indoor fluorescent lamp illumination in the same manner as in Example 1. As a result, the laminate 8 was visually recognized as a substantially uniform white color, and was applied with a design roller under ultraviolet lamp illumination. In the designed part, the emission luminance was lower than the surroundings, and a light emission pattern with partially different luminance was recognized.

Example 9
A laminated body 9 was obtained in the same manner as in Example 8, except that the film forming material 7 was used instead of the film forming material 2 in Example 8.
The obtained laminate 9 was visually evaluated under indoor fluorescent lamp illumination in the same manner as in Example 1. As a result, the laminate 9 was visually recognized as a substantially uniform white color, and was applied with a design roller under ultraviolet lamp illumination. In the designed part, the emission luminance was lower than the surroundings, and a light emission pattern with partially different luminance was recognized.

(Example 10)
A laminate 10 was obtained in the same manner as in Example 8, except that the film forming material 8 was used instead of the film forming material 2 in Example 8.
The obtained laminate 10 was visually evaluated under indoor fluorescent lamp illumination in the same manner as in Example 1. As a result, the laminate 10 was visually recognized as a substantially uniform white color, and was applied with a design roller under ultraviolet lamp illumination. In the designed part, the luminance was different between the coating part of the film forming material (9a) and the film forming material (9b), and further around the design part, and light emission patterns with partially different luminance were recognized.

(Reference example)
On the base material (aluminum plate (40 mm × 40 mm × 0.6 mm)) on which the white coating film is formed, the fluorescent light emitting layer material 1 is applied so as to have a dry film thickness of 80 μm and dried to form the fluorescent light emitting layer. It was applied and dried to obtain a fluorescent light-emitting substrate. Next, on this fluorescent light-emitting substrate, the film-forming material 1 was uniformly applied to the whole so as to have a dry film thickness of 100 μm and dried, and a film layer was laminated to obtain a laminate 11.
When the obtained laminate 11 was visually evaluated under illumination of a 40 W indoor fluorescent lamp, the laminate 11 was visually recognized as a substantially uniform white color. Further, when a 6 W ultraviolet lamp was installed at a distance of 3 cm from the laminate 1 and irradiated with ultraviolet rays, uniform light emission was obtained.

Claims (2)

A laminate that exhibits various fluorescence emission by ultraviolet irradiation,
On the base material, a phosphor layer (A) containing a fluorescent material is provided,
On the phosphor layer (A), a film (B) that reflects and / or absorbs part of the irradiated ultraviolet rays and transmits the remaining ultraviolet rays is formed,
The laminated body characterized in that the coating (B) covers at least a part of the phosphor layer (A) and transmits light emitted from the phosphor layer (A). The laminate according to claim 1, wherein the coating (B) has at least two coatings having different ultraviolet reflectivity and / or ultraviolet absorbability.