JP2009142998A - Luminous decorative material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a luminous decorative material capable of effectively visually confirming luminosity from the luminous coating layer of a part not covered with a partial shading layer at a dark place though visually confirmed like a monochromatic color at a bright place, having high emission intensity and a long afterglow time and excellent in design properties. <P>SOLUTION: In the luminous decorative material constituted of a base material 1, the luminous coating layer 2 and the partial shading layer 3, the partial shading layer 3 contains a shading agent for shading light which has a wavelength shorter than a wavelength at the crossing point of the long wavelength side of the exciting spectrum of the luminous pigment used in the luminous coating layer 2 and the short wavelength side of an emission spectrum, and a color difference ΔE with the luminous coating layer 2 is set to 0.1≤ΔE≤1.0. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a phosphorescent decorative material, and in particular, interior materials for buildings such as general houses and buildings, interior materials for stores, induction blocks and wall materials for underground malls and department stores, interior materials for vehicles, surface materials for residential equipment, etc. The present invention relates to a phosphorescent decorative material and a phosphorescent decorative board suitable for the above.

  Cosmetic materials used for interior materials such as ordinary houses and buildings are obtained by printing patterns on substrates such as paper and plastic films by various printing methods. A decorative board or the like is produced by laminating on the top.

  There are gravure method, flexo method, silk screen method, and ink jet printing method as the pattern pattern printing method, and they are selected according to their purpose.

  For example, screen printing has advantages such as thick printing and suitability for small lot production, and some cosmetics are made using this advantage, but it is limited to very few fields such as wallpaper. The design is limited to solid patterns with no tone (tone, tone, etc.).

  Thus, among these printing methods, most of the cosmetic materials are made by the gravure printing method because a highly designable design is obtained and the productivity is excellent.

  By the way, these decorative materials are not only those printed with paints but also those using phosphorescent paints that shine in the night or in the dark for imparting design or guiding.

  Cosmetic materials made using phosphorescent paints and phosphorescent inks (hereinafter collectively referred to as phosphorescent paints) have such characteristics as high visibility in the dark. It is used for media, show windows, display boards, safety guidance signs, etc.

  As such a phosphorescent cosmetic material, for example, a cosmetic material in which a color phosphorescent layer is partially laminated by silk screen printing on a retroreflective sheet (see Patent Document 1), and a fluorescent layer and a phosphorescent layer are combined and produced by silk printing. Cosmetic materials (see Patent Document 2), cosmetic materials produced by combining gravure pigments and fluorescent pigments (see Patent Literature 3), cosmetic materials produced only by screen phosphor printing (see Patent Literature 4), etc. Various things have been proposed.

However, the printed matter using this phosphorescent paint has the property that it emits light when it is in a dark place. However, the light emission intensity is increased as much as possible, and the afterglow time (the time from when the light goes dark until the light emission disappears). Since it is necessary to make it as long as possible, particularly when it is used for a safety-inducing sign or the like, it has not been possible to secure sufficient light emission intensity as various cosmetic materials as described above.
Japanese Patent Laying-Open No. 2003-287613 (FIG. 4) JP 2001-31235 A (paragraphs [0018] to [0020], FIG. 1) Japanese Patent No. 3464476 Japanese Patent No. 3684207

  An object of the present invention is to provide a decorative material having excellent design properties, which can increase the emission intensity and maintain a long afterglow time.

  As a result of intensive studies to achieve the above object, the present inventors have made the basic structure of the phosphorescent cosmetic material a base material / phosphorescent paint layer / partial light blocking layer, and the phosphorescent material used for the phosphorescent paint layer Adopting a partial light blocking layer that blocks light below the wavelength at the intersection between the long wavelength side of the pigment excitation spectrum and the short wavelength side of the emission spectrum, and the hue of this partial light blocking layer is phosphorescent By combining with the paint layer, it is possible to effectively store the light from the phosphorescent paint layer of the part that is not covered with the partial light-blocking layer in the dark place even though it is visually recognized as a single color. Design that can be visually recognized and that can suppress the light accumulation (light emission) from the light-storing paint layer in the portion located under the partial light-blocking layer, has a strong light emission intensity and a long afterglow time, That cosmetics that are superior to Out was.

  That is, the present invention relates to a decorative material constituted by a base material / luminescent coating layer / partial light blocking layer, wherein the partial light blocking layer is on the long wavelength side of the excitation spectrum of the luminous pigment used in the luminous coating layer. Is a layer containing a light blocking agent that blocks light having a wavelength equal to or shorter than the wavelength at the intersection of the emission spectrum with the short wavelength side, and the color difference ΔE from the phosphorescent paint layer is 0.1 ≦ ΔE ≦ 1.0 A cosmetic material characterized by being provided is provided.

  According to the present invention, the intensity of light emitted from the phosphorescent paint layer provided on the substrate can be increased, the afterglow time can be maintained for a long time, and the partial light blocking layer provided on the phosphorescent paint layer. Therefore, it is possible to provide a gradation and a design pattern, so that it is possible to provide a cosmetic material having excellent design properties.

  Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic cross-sectional view of a decorative material according to the present invention, and FIGS. 2 to 4 are diagrams showing excitation spectra and emission spectra of various phosphorescent pigments used in the phosphorescent paint layer.

  As shown in FIG. 1, the decorative material 4 according to the present invention basically has a configuration in which a phosphorescent paint layer 2 is provided on the entire surface of a substrate 1 and a partial light blocking layer 3 is provided on the phosphorescent paint layer 2. However, between the base material 1 and the phosphorescent paint layer 2 and between the phosphorescent paint layer 2 and the partial light blocking layer 3, it is necessary for the purpose of improving adhesion, strength, durability, etc. Depending on the above, these intermediate layers may be provided.

  The material of the substrate 1 is not particularly limited, and may be a plastic substrate, a paper substrate, or a wood substrate. For example, it is possible to produce the decorative material 4 by using a plastic base material such as a plastic film or a plastic sheet, and attach this to a substrate to form a decorative board. It can also be used for interior decoration by sticking to a wall. It is also possible to provide a decorative board by providing a phosphorescent paint layer and a partial light blocking layer directly on a wooden substrate.

  The phosphorescent paint used for the phosphorescent paint layer 2 is a resin binder made of a color phosphorescent pigment mixed or dispersed in a resin binder with a phosphorescent pigment alone or in combination of two or more, or a fluorescent pigment mixed with a phosphorescent pigment. It can be produced by mixing and dispersing.

As a phosphorescent pigment, [M _x Al _y O _z ] (wherein M is one of Ca, Sr, and Ba, and lowercase letters x, y, and z represent natural numbers, from the viewpoint of color tone and luminous efficiency. The compound represented by) is preferably an aluminate-based or silicon-based compound containing an element belonging to a lanthanoid (Eu, Dy, Nd, etc.) as a co-activator (including a co-activator aid). Can be used.

Specific examples include [SrAl ₂ O ₄ ; Eu, Dy], [Sr ₄ Al ₁₄ O ₂₅ ; Eu, Dy], [CaAl ₂ O ₄ ; Eu, Nd ⁽⁺⁾ ] and the like. Or two or more types can be used together. In addition, “ZnS; Cu”, [(Sr, Ca) S; Bi], and the like can be used, and these may be used alone or in combination of two or more.

  The particle diameter of the phosphorescent pigment is preferably 5 μm or more from the viewpoint of light emission intensity and afterglow time, and is preferably 150 μm or less from the viewpoint of printing suitability and surface smoothness in coating, particularly in the range of 10 to 50 μm. Those are preferred.

This phosphorescent pigment has a strong light emission intensity and a long afterglow time (the time it takes for the brightness of the light emission to drop to 0.32 mcd / m ² after the light supply is stopped). In order to obtain colored light in a wide range of colors including warm colors such as yellow and red, it is mixed with fluorescent pigments or organic fluorescent dyes (rhodamine 6G, rhodamine B, kitten, etc.). May be used.

  When mixing and dispersing phosphorescent pigments, add light-transmitting powder (glass beads, plastic beads, mica, etc.) to increase luminous efficiency, and use additives to prevent sedimentation of phosphorescent pigments You can also.

  As the resin used for the resin binder, conventionally known resins used in the fields of paint and ink can be used. Specifically, vinyl chloride resin, polyester resin, alkyd resin, epoxy resin, vinyl acetate resin, vinyl acetate / vinyl chloride copolymer resin, fluorine resin, urethane resin, polyamide resin, silicon resin Resins, rubber-based and acrylic-based resins may be mentioned, and these may be any type of non-curable type, room temperature curable type, and thermosetting type.

  The film thickness of the phosphorescent paint layer 2 is preferably 10 μm or more from the viewpoint of light emission intensity and afterglow time. However, even if it is extremely thick, the light emission intensity and afterglow time are not affected so much, so the cost is taken into consideration. Then, 500 micrometers or less are preferable and the range of 20-100 micrometers is especially preferable.

  As a means for forming the phosphorescent paint layer 2, a coating method such as a gravure coater, a roll coater, a knife coater, and a silk screen, a film film forming method such as a calendar roll method and an extrusion method can be adopted. In consideration of thick coating and surface smoothness as described above, screen coating (screen printing) is preferable.

  Specifically, the phosphorescent paint is desired by screen printing by setting the ratio of phosphorescent pigment (particle diameter 10 to 50 μm) to resin to about 50:50 (mass%) and the viscosity to 3000 to 7000 mPa · s. The thick phosphorescent coating layer (20 to 100 μm) can be formed.

  A partial light blocking layer 3 is further formed on the phosphorescent paint layer 2 formed on the entire surface of the substrate 1, and this partial light shield layer 3 is a phosphorescent pigment used for the phosphorescent paint layer 2. It is a layer containing a light blocking agent that blocks light having a wavelength less than or equal to the wavelength at the intersection of the long wavelength side of the excitation spectrum and the short wavelength side of the emission spectrum, and the phosphorescent pigment of the phosphorescent paint layer 2 located therebelow In addition to suppressing the application of excitation energy, it also has a function of suppressing light emission in a dark place.

For example, as can be seen from FIG. 2, in the phosphorescent pigment [SrAl ₂ O ₄ ; Eu, Dy], the peak of the excitation spectrum is about 360 nm, but since it is relatively broad, it is excited even with light having a wavelength of 470 nm or less. Will be. On the other hand, the peak of the emission spectrum is about 520 nm, but because of the spectral distribution, light having a wavelength of 470 nm or less is also emitted. Therefore, the partial light blocking layer 3 contains a light blocking agent that blocks light having a wavelength of 470 nm or less, which is the intersection of the long wavelength side of the excitation spectrum and the short wavelength side of the emission spectrum, thereby providing a phosphorescent pigment. Since the excitation light is blocked and light emission is also suppressed, a good contrast can be obtained.

In addition, as can be seen from FIG. 3, even in the phosphorescent pigment [Sr ₄ Al ₁₄ O ₂₅ ; Eu, Dy], the peak of the excitation spectrum is about 360 nm, but since it is relatively broad, it has a wavelength of 460 nm or less. But it will be excited. On the other hand, the peak of the emission spectrum is about 490 nm, but light having a wavelength of 460 nm or less is emitted due to the spectral distribution. Therefore, by blocking light with a wavelength of 460 nm or less, which is the intersection of the long wavelength side of the excitation spectrum and the short wavelength side of the emission spectrum, the excitation light of the phosphorescent pigment is blocked and light emission is also suppressed. Therefore, good contrast can be obtained.

Further, as can be seen from FIG. 4, even with the phosphorescent pigment [CaAl ₂ O ₄ ; Eu, Nd], the excitation spectrum peak is about 330 nm, but it is relatively broad, so it is excited even with light having a wavelength of 410 nm or less. Will be. On the other hand, the peak of the emission spectrum is about 440 nm, but due to the spectral distribution, light with a wavelength of 410 nm or less is also emitted. Therefore, by blocking light with a wavelength of 410 nm or less, which is the intersection of the long wavelength side of the excitation spectrum and the short wavelength side of the emission spectrum, the excitation light of the phosphorescent pigment is blocked and light emission is also suppressed. Therefore, good contrast can be obtained.

  Of course, in the case where it is difficult to specify exactly the wavelength that is the intersection between the long wavelength side of the excitation spectrum of these phosphorescent pigments and the short wavelength side of the emission spectrum, about ± 10 nm of this intersection point is used as a reference. Even if the partial light blocking layer is adjusted so as to block light having a wavelength shorter than that, the above-described effects can be sufficiently obtained in practice.

  As light blocking agents, there are those that block predetermined light by absorption and those that block by reflection, but in order to make it easy to match the hue with the phosphorescent paint layer, it is possible to use a light blocking agent by light absorption. An ultrafine metal oxide of several tens of nm or less is particularly preferable. In terms of light blocking efficiency, if 90 to 95% of light can be blocked practically, the function can be sufficiently exhibited as a partial light blocking layer.

  Specifically, examples of the inorganic light blocking agent include tungsten oxide, zinc oxide, titanium oxide, and cerium oxide. From the viewpoint of surface smoothness and light blocking efficiency, those having a particle diameter of 50 nm or less. Is preferred.

  In addition to such light blocking agents, organic ultraviolet absorbers, colored pigments and the like can be used alone or in combination of two or more.

  Specifically, as the organic ultraviolet absorber, a salicylic acid ester system, a benzophenone system, a benzotriazole system, a benzoate system, a cyanoacrylate system, a hydroxyphenyl triazone system, and the like are suitable.

  Colored pigments include organic pigments such as condensed azo, phthalocyanine, dioxazine, isoindolinone, and selenium, titanium dioxide, petal, iron yellow, iron black, carbon black, pearl pigment, aluminum Inorganic pigments such as powder, copper powder, barium sulfate and calcium carbonate can be used and are not particularly limited.

  In addition, the partial light blocking layer uses colored pigments for color tone adjustment because the design is improved if the shape and hue of the pattern in the dark place of the phosphorescent paint layer cannot be discriminated in the bright place. It is important to do.

  The hue, saturation, brightness, and the like of the partial light blocking layer can be made difficult to distinguish by using ink containing a colored pigment to approximate the hue, saturation, brightness of the phosphorescent paint layer. In this case, the color difference ΔE between the partial light blocking layer and the phosphorescent paint layer is set to 0.1 to 1.0, preferably 0.3 to 0.5 from the viewpoint of color matching.

  The light blocking agent as described above is mixed with a resin binder to form a partial light blocking layer. As the resin used for this resin binder, conventionally known ones used in the field of paints and inks are used. Can be used.

  Specifically, vinyl chloride resin, polyester resin, alkyd resin, epoxy resin, vinyl acetate resin, vinyl acetate / vinyl chloride copolymer resin, fluorine resin, urethane resin, polyamide resin, silicon resin Resins, rubber-based and acrylic-based resins can be mentioned, and these may be any type of non-curing type, room temperature curing and thermosetting. The same resin can be used for the colored pigment.

  As described above, the partial light blocking layer is an ink layer containing a material composed of an inorganic light blocking agent, an organic ultraviolet absorber, and a colored pigment alone or in combination of two or more. When the thickness of the dried film differs, the light blocking efficiency varies, and the pattern and shape of the phosphorescent paint layer due to the afterglow luminance emission change over time.

  For example, in the case of printing with a gravure plate created by a plate making method such as the conventional method or the helio method, since the film is thin in the light density part and the film is thick in the dark density part, The shape may change with time, and the contrast between the light emitting portion and the non-light emitting portion may be blurred.

  On the other hand, according to the printing on the gravure plate created by the mesh gravure plate making method, the thickness of the dry film is the same, and the gradation can be adjusted by the interval of the gravure plate. There is no change in shape with time (see FIG. 5).

  Therefore, when the cosmetic material according to the present invention is used as a normal cosmetic material, the method for forming the partial light blocking layer is not particularly limited. In particular, a method using a gravure plate which does not change with time and shape is particularly preferable.

  In addition, as various gravure plate making methods, there are conventional methods, mesh screen (TH method, etc.) methods, corrosion methods such as screen gravure methods, engraving methods, etc., but they are produced by a screen gravure (screen dot plate making method) method. The partial light blocking layer printed by the gravure plate can form the same dry film thickness from light to dark to dark areas, and the light emission pattern in the dark does not change over time. Is particularly preferred.

  The depth of the gravure plate obtained by the net gravure method can be determined by the blending amount of inorganic light blocking material, organic ultraviolet absorber, colored pigment, etc. Generally, when the depth of the gravure plate is shallow, the film Since the thickness is extremely thin (for example, around 0.1 μm), the light blocking efficiency is lowered even if the hue is black. On the other hand, if the depth of the gravure plate is too deep, ink transfer is not performed normally, resulting in spot-like printing, and so-called ink mottling occurs. Therefore, the depth of the gravure plate is preferably 5 to 70 μm or less, particularly preferably 25 to 45 μm.

For example, it can be set in the range of (inorganic light blocking agent + organic ultraviolet absorbing agent): colored pigment = 10: 90 to 90:10, but the constituent material of the partial light blocking layer is L ^* a ^*. In the case of an ivory system with a b ^* display system hue of L ^* = 91.89, a ^* = − 1.15, b ^* = 1.62, the depth of the net gravure solid plate is preferably 35 to 40 μm. Yes.

Hereinafter, the decorative material according to the present invention will be described with reference to Examples and Comparative Examples.
Example 1
<Preparation of phosphorescent paint>
Particles that emit light blue ivory in the light (L ^* a ^* b ^* display system L * = 91.9, a * = − 1.2, b * = 1.6), and blue A screen ink (Seiko Advance Co., Ltd .: Super Shine N Blue) using a phosphorescent pigment [Sr ₄ Al ₁₄ O ₂₅ ; Eu, Dy] (see FIG. 3) having a diameter of 25 μm is prepared, and the viscosity is set to 7000 mPa · s with a diluent solvent. Prepared to obtain a phosphorescent paint.

<Formation of phosphorescent paint layer 1>
The phosphorescent paint obtained above was screen-printed on 150-μm thick PET-G (manufactured by Riken Technos Co., Ltd.) using a 100-mesh solid plate to obtain a phosphorescent paint layer-forming member 1. The film thickness of the phosphorescent paint layer 1 was 40 μm in terms of dry film thickness.

(Comparative Example 1)
<Preparation of phosphorescent paint>
In gravure printing, it is impossible to print a pigment having a particle diameter of 25 μm, and therefore, in a bright place, a light ivory hue (L * = 89.0 in the L ^* a ^* b ^* display system, a * = − 2.3) , B * = 0.5), and a screen ink (Easy Bright Co., Ltd.) using a phosphorescent pigment [Sr ₄ Al ₁₄ O ₂₅ ; Eu, Dy] (see FIG. 3) that emits blue light in the dark and has a particle diameter of 2 μm. Manufactured by EGCB02 Blue) and prepared with a diluent solvent to a viscosity of 150 mPa · s to obtain a phosphorescent paint.

<Formation of phosphorescent paint layer 2>
The phosphorescent paint obtained above is gravure-printed using a solid plate with a cell depth of 50 μm made on a 150-μm thick PET-G (manufactured by Riken Technos) using a net gravure method to obtain a phosphorescent paint layer forming member 2. It was. The film thickness of the luminous paint layer 2 was 4.5 μm in terms of dry film thickness.

<Afterglow luminance measurement>
The afterglow luminance of the luminous paint layer forming member 1 and the luminous paint layer forming member 2 was measured with a luminance meter LS-100 (manufactured by Konica Minolta Co., Ltd.) in accordance with JIS Z9107 ¹⁹⁹⁸ (safety sign board). The results are shown in Table 1.

<Evaluation of afterglow brightness>
According to the JIS standard for safety sign boards (JIS Z9107 ¹⁹⁹⁸ ), the luminance after 5 minutes after light blocking is 110 (mcd / m ² ) and the luminance after 60 minutes after light blocking is 7 (mcd / m ² ). ing. From Table 1, the luminous paint layer forming member 1 achieved the safety sign standard shown in the JIS standard from immediately after light blocking until 60 minutes, and maintained a brightness that could be clearly confirmed after 2 hours. . On the other hand, in the phosphorescent paint layer forming member 2, a rapid decrease in luminance was confirmed immediately after the light was blocked, and the JIS standard could not be reached in all ranges from 5 minutes to 60 minutes.

(Example 2)
<Preparation of paint for forming partial light blocking layer>
A paint for forming a partial light blocking layer was prepared by the following procedure.
(1) Preparation of paint containing light blocking agent that blocks light of 460 nm or less ・ Binder: PVC / vinyl acetate copolymer resin (average polymerization degree 450) / MEK, ethyl acetate, butyl acetate ・ Inorganic light blocking agent: WO ₃ (Manufactured by Nippon Tungsten Co., Ltd .: particle size 13-18 μm)
-Inorganic light blocking agent: ZnO (NANOFINE-50-A manufactured by Sakai Chemical Industry Co., Ltd .: particle size 20 nm)
・ Organic UV absorber: benzotriazole (manufactured by Nagase Sangyo Co., Ltd .: TINUVIN109)
・ Paint with light blocking agent: Binder / WO ₃ / ZnO / TINUVIN109 = 100: 3: 3: 2 (parts by weight)
(2) Preparation of paint containing colored pigment ・ Binder: Vinyl chloride / vinyl acetate copolymer resin (average polymerization degree 450) / MEK, ethyl acetate, butyl acetate ・ Organic transparent pigment ink: (Dainippon Ink Chemical Industries, Ltd .: VD2008 red) NT, VD4300 Tomeiki, VD5700 Genshokuai)
・ Inorganic pigment ink: (Dainippon Ink Chemical Co., Ltd .: VD8500 Sumi, VD7700 Cha NT, VD7900 White, VD40 KiNT)
(3) Preparation of coating material 1 for forming partial light blocking layer 1 The coating material containing the light blocking agent obtained in the above (1) and the coating material containing the colored pigment obtained in the above (2) are used in 60:40 ( The paint for forming the partial light blocking layer 1 was obtained. In addition, this paint is adjusted so that the color difference ΔE = 0.5 with a paint containing a colored pigment, using the solid hue of the phosphorescent paint layer 1 as a standard, and further with a dilution solvent (MEK / ethyl acetate). It was adjusted to 150 mPa · s.

<Formation of partial light blocking layer 1>
The coating 1 for forming the partial light blocking layer 1 obtained in the above (3) is applied to the easy-adhesion surface of a transparent PET film (A4100 manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm on one side. Gravure printing was carried out using the solid plate having a cell depth of 50 μm made in step 1 to obtain a partial light blocking layer forming member 1. The film thickness of the partial light blocking layer 1 was 4.5 μm in terms of dry film thickness.

<Manufacture of phosphorescent cosmetic material 1>
The phosphorescent paint layer forming member 1 and the partial light blocking layer forming member 1 obtained in Example 1 were laminated by a dry laminating machine so that the respective printing surfaces were in contact with each other via a urethane adhesive, and the phosphorescent property A decorative material 1 was obtained.

(Comparative Example 2)
<Preparation of paint for forming partial light blocking layer>
A paint for forming a partial light blocking layer was prepared by the following procedure.
(1) Preparation of paint containing light blocking agent that blocks light of 360 nm or less ・ Binder: PVC / vinyl acetate copolymer resin (average polymerization degree 450) / MEK, ethyl acetate, butyl acetate ・ Organic UV absorber: benzotriazole Series (Nagase Sangyo Co., Ltd .: TINUVIN109)
・ Paint with light blocking agent: Binder / TINUVIN109 = 100: 8 (parts by weight)
(2) Preparation of paint containing colored pigment ・ Binder: Vinyl chloride / vinyl acetate copolymer resin (average polymerization degree 450) / MEK, ethyl acetate, butyl acetate ・ Organic transparent pigment ink: (Dainippon Ink Chemical Industries, Ltd .: VD2008 red) NT, VD4300 Tomeiki, VD5700 Genshokuai)
・ Inorganic pigment ink: (Dainippon Ink Chemical Co., Ltd .: VD8500 Sumi, VD7700 Cha NT, VD7900 White, VD40 KiNT)
(3) Preparation of coating material 2 for forming partial light blocking layer 2 The coating material containing the light blocking agent obtained in the above (1) and the coating material containing the colored pigment obtained in the above (2) are used in 60:40 ( The paint for forming the partial light blocking layer 2 was obtained. This paint has a solid hue of the phosphorescent paint layer 1 (Ivory with L * = 91.9, a * = − 1.2, b * = 1.6 in the L ^* a ^* b ^* display system). ) With a colored pigment so that the color difference ΔE = 0.5, and a viscosity of 150 mPa · s with a diluting solvent (MEK / ethyl acetate).

<Formation of partial light blocking layer 2>
The paint 2 for forming the partial light blocking layer 2 obtained in the above (3) is applied to the easy-adhesion surface of a transparent PET film (A4100 manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm on one side. Gravure printing was carried out using the solid plate having a cell depth of 50 μm made in step 1 to obtain a partial light blocking layer forming member 1. The film thickness of the partial light blocking layer 1 was 4.5 μm in terms of dry film thickness.

<Manufacture of phosphorescent decorative material 2>
The phosphorescent paint layer forming member 1 and the partial light blocking layer forming member 2 obtained in Example 1 were laminated with a dry laminating machine so that the respective printing surfaces were in contact with each other via a urethane-based adhesive. A decorative material 2 was obtained.

<Afterglow luminance measurement>
The afterglow brightness of the phosphorescent cosmetic material 1 and the phosphorescent cosmetic material 2 was measured with a luminance meter LS-100 (manufactured by Konica Minolta) in accordance with JIS Z9107 ¹⁹⁹⁸ (safety sign board). The results are shown in Table 2.

<Evaluation of afterglow brightness>
In the phosphorescent decorative material 1, light emission of the printed portion of the partial light blocking layer was hardly confirmed. On the other hand, in the phosphorescent decorative material 2, light emission from the phosphorescent paint layer under the partial light blocking layer was confirmed, and it was found that the light emission of the phosphorescent pigment was not sufficiently blocked.

(Example 3)
<Plate making>
The shape of the partial light-blocking layer is a turtle shell shape, and a gravure with a cell depth of 35μm using a net gravure method using a positive film in which the thickness of the line forming the turtle shell is shaded from the center to the end of the line. Got a version.

<Formation of partial light blocking layer 3>
The paint 1 for forming the partial light blocking layer 1 is gravure-printed on the easy-adhesion surface of a transparent PET film (A4100, manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm on one side using the gravure plate, A light blocking layer forming member 3 was obtained. The partial light blocking layer 3 had a dry film thickness of 4.5 μm.

<Manufacture of phosphorescent decorative material 3>
The phosphorescent paint layer forming member 1 and the partial light blocking layer forming member 3 obtained in Example 1 were laminated by a dry laminating machine so that the respective printing surfaces were in contact with each other via a urethane-based adhesive. A decorative material 3 was obtained.

<Formation of partial light blocking layer 4>
The paint 2 for forming the partial light blocking layer 2 is gravure-printed using the gravure plate on the easy-adhesion surface of a transparent PET film (A4100 manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm. A light blocking layer forming member 4 was obtained. The partial light blocking layer 4 had a dry film thickness of 4.5 μm.

<Manufacture of phosphorescent decorative material 4>
The phosphorescent paint layer forming member 1 and the partial light blocking layer forming member 4 obtained in Example 1 were laminated with a dry laminating machine so that the respective printing surfaces were in contact with each other via a urethane-based adhesive. A decorative material 4 was obtained.

<Visual evaluation>
The phosphorescent decorative material 3 can express the design of a tortoiseshell pattern (see Fig. 5) with a high intensity of blue color that has abundant tones after the light is blocked, and the design shape does not change but the design shape does not change for 8 hours. It was also visible afterwards. On the other hand, in the phosphorescent decorative material 4, the boundary of the turtle shell pattern was blurred due to the light emission from the phosphorescent paint layer below the partial light blocking layer, resulting in a pattern without gradation.

The schematic cross section of the decorative material by this invention. Excitation spectrum and emission spectrum of phosphorescent pigment used in phosphorescent paint layer. Excitation and emission spectra of other phosphorescent pigments used in phosphorescent paint layers. Excitation and emission spectra of other phosphorescent pigments used in phosphorescent paint layers. The schematic cross section and top view of the cosmetics by printing with the gravure plate created with the net gravure plate making method.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base material 2 Luminous paint layer 3 Partial light blocking layer 4 Cosmetic material

Claims (3)

In a decorative material composed of a partial light blocking layer / luminescent coating layer / base material, the partial light blocking layer includes a long wavelength side of an excitation spectrum and a short emission spectrum of a luminous pigment used in the luminous coating layer. A layer containing a light blocking agent that blocks light having a wavelength equal to or less than the wavelength at the intersection with the wavelength side, wherein the color difference ΔE from the phosphorescent paint layer is 0.1 ≦ ΔE ≦ 1.0 Make up cosmetics. The cosmetic material according to claim 1, wherein the light blocking agent is a light blocking agent by light absorption. The cosmetic material according to claim 1 or 2, wherein the partial light blocking layer is a partial light blocking layer formed by printing with a gravure plate prepared by a mesh gravure plate making method.

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