JP4128835B2 - Multicolor phosphorescent light emitting sheet - Google Patents

Description

【００７１】
以上の結果より、暗所での色相や紫外線蛍光灯照射時について本発明の多色蓄光発光シートは、比較例の多色蓄光発光シートに比較して、優れた効果が得られることが明らかである。
【図面の簡単な説明】
【図１】図１は、本発明の多色蓄光発光シートで２層であるシートの形態を示す概略断面図である。
【図２】図２は、本発明の多色蓄光発光シートで３層以上であるシートの形態を示す概略断面図である。
【図３】図３は、本発明の多色蓄光発光シートで透明表面層を有する３層以上ののシートの形態を示す概略断面図である。
【符号の説明】
１：透明微小球
２：樹脂層１（着色樹脂層）
３：樹脂層２（蓄光樹脂層）
４：樹脂層３（蓄光樹脂層）
５：透明表面層[0001]
[Industrial application fields]
The present invention relates to a multicolor phosphorescent light emitting sheet for forgery prevention used for anticounterfeiting and copy prevention measures, and more specifically, multicolor phosphorescent light capable of preventing forgery and copying without using a special detection device. The present invention relates to a light emitting sheet.
[0002]
[Prior art]
In recent years, with the advancement of product imitation technology, so-called copy products that analyze and analyze existing products and faithfully reproduce their structures and shapes have been put on the market, and these copy products are indistinguishable from the real product by appearance alone. It has developed into a big social problem. For example, in the toner cartridge market, it is said that more than 60% of them are non-genuine products, but it is very difficult to tell whether they are genuine products, and there is only a method of taking out the toner and analyzing the components. Is the current situation.
[0003]
In order to distinguish genuine products that cannot be distinguished from these appearances from copy products or non-genuine products, a thin label (security label) that is difficult to counterfeit and difficult to peel off is attached to the genuine product, and the genuine product is A method of identifying is widely used.
[0004]
Conventionally, a hologram seal or a brittle film is often used as a security label used to prevent counterfeiting or copy product measures (see, for example, Patent Documents 1 to 3).
[0005]
As described in the above-mentioned document, a hologram is a technique for recording and reproducing interference fringes between an object beam and a reference beam by using a laser beam, and is mainly intended for forgery and copy prevention. Are used to identify genuine products by reproducing recorded real images.
[0006]
On the other hand, the brittle film is intended to prevent alteration due to reattachment, and as shown in Patent Document 4 and the like, when an attempt is made to peel off a sticker once attached, there is a film with an adhesive that destroys the seal itself. in use.
[0007]
[Patent Document 1]
JP 09-31616 A
[Patent Document 2]
JP-A-10-333574
[Patent Document 3]
Japanese Patent Laid-Open No. 11-254868
[Patent Document 4]
JP 2000-072910 A
[0008]
[Problems to be solved by the invention]
The hologram sticker is advantageous in that it is difficult to forge and can record many objects on one hologram, but a special device is required to record information, and a recording material with high resolution is required. Therefore, it has to be expensive. Furthermore, in order to read the recorded image, an image forming device (hologram reader, viewer) consisting of a light source (laser beam irradiator), multiple mirrors, lenses, etc. is necessary, and it is used in large quantities as labels for general-purpose products. Was limited.
[0009]
Furthermore, in recent years, forgery technology has progressed, and a single technology is insufficient to prevent forgery, and there is a need for a security label that has both effects of preventing forgery and preventing replacement, but the structure itself is complicated. As a result, recording devices and reading devices have become more complex and expensive, making it increasingly difficult to use them in large quantities as general-purpose labels.
[0010]
The present invention has been made to solve the above-mentioned problems, and the problem of the present invention is that it does not require a special tool for detection, and can be detected only by simple tools such as visual observation and black light. Another object of the present invention is to provide an inexpensive and versatile multicolor phosphorescent light emitting sheet for use in security labels, which has both a forgery prevention effect and a replacement prevention effect.
[0011]
[Means for Solving the Problems]
The present invention solves the above-described problem, and is a sheet in which two or more resin layers having different color development including at least one phosphorescent resin layer are laminated, and the transparent microsphere is a part of the sphere. A multicolor phosphorescent light emitting sheet characterized by protruding from the resin layer surface and in contact with two or more colored layers,
[0012]
Preferably, the multicolor phosphorescent light emitting sheet in which transparent microspheres are embedded in an area of 50% or more with respect to the total surface area of the sheet,
[0013]
Preferably, the multicolor phosphorescent light emitting sheet is provided in which the breaking elongation of the sheet is 1 to 50%,
[0014]
Preferably, the multicolor phosphorescent light emitting sheet, wherein the transparent microspheres are glass beads,
[0015]
An anti-counterfeit sheet using the multicolor phosphorescent light emitting sheet is provided.
[0016]
Hereinafter, the multicolor phosphorescent light emitting sheet of the present invention will be described in more detail.
[0017]
As shown in FIGS. 1 and 2, the multicolor phosphorescent light emitting sheet of the present invention comprises a resin layer 2, a resin layer 3 (4) transparent microspheres 1, and at least one of the resin layers is a phosphorescent resin layer. It is preferable that the plurality of resin layers are phosphorescent resin layers, and it is particularly preferable that all the resin layers are phosphorescent resin layers. However, considering distinguishability, the phosphorescent properties of two or more different hues It is particularly preferable to have a resin layer.
[0018]
The phosphorescent resin layer of the present invention comprises a phosphorescent resin composition containing 5 to 900 parts by weight, preferably 10 to 800 parts by weight, and more preferably 20 to 700 parts by weight of a phosphorescent pigment with respect to 100 parts by weight of the resin component. It is formed. If the amount of phosphorescent pigment added is not less than the lower limit, a sufficient phosphorescent light emitting function can be obtained and excellent distinguishability and visibility can be obtained, and if it is not more than the upper limit, the phosphorescent light emitting layer becomes too hard. This is preferable because it does not cause inconvenience and the characteristics such as flexibility are not impaired.
[0019]
The phosphorescent pigment is not particularly limited as long as it accumulates light such as daytime sunlight or nighttime fluorescent light and emits light even in the dark and has a light emitting performance necessary for product identification. However, from the viewpoint of good phosphorescent performance, oxide-based phosphorescent pigments, particularly metal oxides represented by the general formula MAl2O4 (wherein M represents at least one alkaline earth metal) are used as mother crystals, and activators A luminous pigment containing rare earth metal atoms in a proportion of 1 × 10 −6 to 0.2 (where the total number of metal M atoms and rare earth metal atoms is 1) is preferred.
[0020]
The alkaline earth metal is preferably at least one metal selected from the group consisting of Ca, Ba and Sr. The rare earth metal is Sc, Y, La, Ce, Pr, Nd, Sm, It may be at least one metal selected from the group consisting of Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. Such phosphorescent pigment further contains at least one metal selected from the group consisting of Mn, Sn and Bi as a co-activator in a proportion of 1 × 10 −6 to 0.2 (provided that metal M atom, It is preferable that the phosphorescent pigment contains a rare earth metal atom and a co-activator metal with a total atom number of 1).
[0021]
As such phosphorescent pigment, for example, SrAl ₂ O _Four : Eu, SrAl ₂ O _Four : Eu, Dy, SrAl ₂ O _Four : Eu, Nd, SrAl ₂ O _Four : Eu, Pr, SrAl ₂ O _Four : Eu, Sm, SrAl ₂ O _Four : Eu, Tb, SrAl ₂ O _Four : Eu, Ho, SrAl ₂ O _Four : Eu, Mn, SrAl ₂ O _Four : Eu, Sn, SrAl ₂ O _Four : Eu, Bi, CaAl ₂ O _Four : Eu, Nd, CaAl ₂ O _Four : Eu, Sm, CaAl ₂ O _Four : Eu, Tm, CaAl ₂ O _Four : Eu, Nd, La, CaAl ₂ O _Four : Eu, Nd, La, CaAl ₂ O _Four : Eu, Nd, Ce, CaAl ₂ O _Four : Eu, Nd, Pr, CaAl ₂ O _Four : Eu, Nd, Sm, CaAl ₂ O _Four : Eu, Nd, Gd, CaAl ₂ O _Four : Eu, Nd, Tb, CaAl ₂ O _Four : Eu, Nd, Dy, CaAl ₂ O _Four : Eu, Nd, Ho, CaAl ₂ O _Four : Eu, Nd, Er, CaAl ₂ O _Four : Eu, Nd, Tm, CaAl ₂ O _Four : Eu, Nd, Yb, CaAl ₂ O _Four : Eu, Nd, Lu, CaAl ₂ O _Four : Eu, Nd, Mn, CaAl ₂ O _Four : Eu, Nd, Sn, CaAl ₂ O _Four : Eu, Nd, Bi, Ca _0.9 Sr _0.1 Al ₂ O _Four : Eu, Nd, La, Ca _0.9 Sr _0.1 Al ₂ O _Four : Eu, Nd, Dy, Ca _0.7 Sr _0.3 Al ₂ O _Four : Eu, Nd, Dy, Ca _0.9 Sr _0.1 Al ₂ O _Four : Eu, Nd, Ho, Ca _0.7 Sr _0.3 Al ₂ O _Four : Eu, Nd, Ho and the like. These may be used alone or as a mixture of two or more.
[0022]
The afterglow characteristics of these phosphorescent pigments are not particularly limited. However, considering the visibility, they are generally 150 mcd / m 2 or more, preferably 200 mcd / m 2 or more, more preferably 250 mcd / m 2 or more. Is good.
[0023]
The resin constituting the phosphorescent resin layer is not particularly limited as long as it can disperse the phosphorescent pigment and can form at least two resin layers. For example, acrylic resin, urethane resin, polyester resin Fluorine-based resin, vinyl chloride-based resin, vinyl acetate-based resin, polyethylene-based resin, polypropylene-based resin, polycarbonate-based resin, and the like. These are used alone or in a copolymerized form or blended.
[0024]
Among these resins, acrylic resins, urethane resins, polyester resins, fluorine resins, and the like, which are excellent in weather resistance and suitable for processing, are preferable, and acrylic resins are most preferable.
[0025]
Examples of such acrylic resins include ethyl (meth) acrylate (Note: (meth) acrylate means ethyl methacrylate or ethyl acrylate, the same applies hereinafter), n-propyl (meth) acrylate, n- Butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, 2-methylbutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) C of acrylic acid such as acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, and isononyl (meth) acrylate ₂ ~ C ₁₂ At least one alkyl ester (monomer A) and at least one functional group-containing acrylic monomer such as acrylic acid, methacrylic acid, acrylamide, N-methylol acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (monomer B) ) And a copolymer obtained by copolymerization.
[0026]
In addition to the resin component and the phosphorescent pigment, the phosphorescent resin layer may contain other colorants such as ordinary colorants and fluorescent colorants, light stabilizers, heat stabilizers, fillers, and crosslinkers as necessary. You may mix | blend various additives, such as.
[0027]
The resin layer other than the phosphorescent resin layer of the present invention is not particularly limited as long as it does not prevent the light from reaching the transparent microspheres and can adhere to the phosphorescent resin layer and other layers (in the case of three or more layers). For example, acrylic resins, urethane resins, polyester resins, fluorine resins, vinyl chloride resins, vinyl acetate resins, polyethylene resins, polypropylene resins, polycarbonate resins, etc. Alternatively, they are used in a copolymerized form or blended.
[0028]
Among these resins, (meth) acrylic resins, urethane resins, polyester resins, fluorine resins, and the like that are excellent in weather resistance and suitable for processing are preferable, and acrylic resins are most preferable.
[0029]
The phosphorescent light emitting sheet of the present invention is a sheet in which at least one layer of the phosphorescent light emitting resin layer and other resin layers are laminated, and transparent microspheres are embedded therein. Part of the transparent microspheres protrudes from the surface of the resin layer, and it is particularly preferable that the microspheres are embedded over at least two layers and embedded so as to contact two or more layers including the phosphorescent layer.
[0030]
The ratio of the transparent microsphere protruding portion from the surface varies depending on the relationship between the thickness of the resin layer and the diameter of the microsphere, but the microsphere is embedded in two or more resin layers, and the microsphere About 1 to 50% of the diameter, preferably 5 to 40%, particularly preferably about 10 to 30% should protrude. Even if the bead protruding portion is too small or too large, the color tone of the lower layer is hardly expressed.
[0031]
The material of the transparent microspheres of the present invention is not particularly limited as long as it is transparent. For example, transparent microspheres such as glass, acrylic resin, polycarbonate resin, and polystyrene resin can be raised. Microspheres and acrylic resin microspheres are preferable, and glass microspheres are particularly preferable from the viewpoint of heat resistance, acid resistance, and solvent resistance. The term “transparency” as used herein means transparency that allows the color tone and light emission of the lower layer to be observed from the upper part of the sheet through the microsphere.
[0032]
The particle size of the transparent microspheres may be in the range of 30 to 200 μm from the viewpoint of sheet processing suitability and the degree of embedding in the multilayer, but is preferably in the range of 40 to 180 μm, more preferably 50 μm to 150 μm. If the outer diameter of the microsphere is too large, it becomes difficult to process the sheet, and if it is too small, it is difficult to embed in a multilayer.
[0033]
In order to refract light by using the transparent microsphere and exhibit a complicated appearance, the refractive index of the transparent microsphere is preferably in the range of 1.5 to 2.7, more preferably 1.5 to 2.5. A range of 1.5 to 2.2 is particularly preferable.
[0034]
The ratio of the transparent microspheres embedded on the resin surface that forms the surface of the multicolor phosphorescent light emitting sheet is not particularly limited as long as it is dispersed and embedded to such an extent that a characteristic appearance can be expressed. In general, the transparent microspheres should be dispersed and embedded in an area of 50% or more, preferably 60% or more, particularly preferably 70% or more with respect to the total surface area of the sheet. When the area occupancy of the microspheres is too small, when the surface layer is the first layer, it is difficult to sufficiently recognize the light emission of the resin layer below the second layer, and when the occupied area is too large, Color development and emission color become weak, and it becomes difficult to visually recognize the hue change of the entire sheet.
[0035]
In the present invention, the microspheres are embedded over at least two resin layers. As a method for this, after the resin layers are sequentially coated to produce a laminated sheet, the microspheres are dispersed on the laminated sheet. After heating the sheet and embedding microspheres over several layers (spreading method), after fixing the microspheres to the temporary support, after creating a multicolor phosphorescent light emitting sheet by sequentially coating the resin layer on the temporary support, A method of embedding the microspheres over several layers by peeling the temporary support and further pushing the microspheres into the resin layer under heating (build-up method), fixing the microspheres to the temporary support, After making a laminated sheet by coating sequentially, the microspheres were transferred from the temporary support to the laminated sheet, and the microspheres were embedded in several layers by heating and pressing into the resin layer under pressure. Method for obtaining a laminated sheet ( Utsushiho) like can be listed, without disturbance laminated resin layer interface, application method from the viewpoint which can hold the layers interface transfer method is preferred. Among these, the transfer method is particularly preferable because it is easy to embed transparent microspheres in multiple layers.
[0036]
One useful embodiment of the present invention is shown in FIG. FIG. 1 shows a mode in which transparent microspheres are embedded in two layers of phosphorescent resin layers having different color tones. A part of the glass microsphere 1 is exposed from the surface, penetrates the upper phosphorescent resin layer 2 and passes through the glass microsphere. The lower part reaches the lower phosphorescent resin layer 3. Light that enters the glass microsphere from the exposed surface when exposed to light from a fluorescent lamp, etc., is refracted in the transparent microsphere and reaches each of the upper and lower phosphorescent resin layers with different color tones, causing the phosphorescent resin layer to emit light. Therefore, when the light is blocked, a complex color tone (appearance) in which two types of phosphorescent emission are mixed is expressed.
[0037]
FIG. 2 shows another useful embodiment. As shown in FIG. 2, when there are three or more resin layers, the color tone (appearance) becomes more complicated, and various variations are possible depending on the layer configuration.
[0038]
The color tone (appearance) varies depending on the thickness of the resin layer, the material of the microsphere, the size, the refractive index, the particle size distribution, and the like, and further by selecting the afterglow time of the phosphorescent pigment and the contrast of each layer. The hue can be changed. As described above, it is extremely difficult for a third party to duplicate the two types of appearances of the color tone (appearance) before light emission and the color tone (appearance) of phosphorescent light emission, and a security function is imparted to the sheet.
[0039]
Furthermore, two types of appearances, the color tone (appearance) before light emission and the color tone (appearance) of phosphorescent light emission, can be observed simply by covering the sheet with hand under natural light and blocking the light without using a special detection device. Since the color tone of the phosphorescent light emission of the sheet can be confirmed by simple operation and can be identified by two types of color tone, the color tone under natural light and the color tone of the phosphorescent light emission, the phosphorescent light emitting sheet of the present invention has an excellent anti-counterfeit effect. It has a lot of versatility.
[0040]
It is also a useful embodiment of the present invention to provide a layer containing an ultraviolet light-emitting pigment in one or more resin layers other than the phosphorescent layer. Fluorescent light-emitting layers containing ultraviolet light-emitting pigments can express even more complex colors by simple operations such as irradiation with black light, and it becomes much more difficult to replicate these colors. .
[0041]
The thickness of each resin layer forming the phosphorescent light emitting sheet of the present invention is not particularly limited and can be appropriately selected according to the diameter of the glass beads and the desired application. However, it is easy to attach and difficult to peel off. In consideration, it is preferably in the range of 30 to 200 μm, more preferably 40 to 180 μm, and even more preferably 50 to 150 μm.
[0042]
Furthermore, another object of the present invention is that when the sheet is forcibly peeled off after being attached to the base material, the sheet easily breaks and cannot be reattached, and has a further anti-counterfeit function. The object is to provide a color phosphorescent light emitting sheet.
[0043]
In order to make it impossible to reattach the light emitting sheet, the breaking elongation of the light emitting sheet is preferably set to 1 to 50%, more preferably 3 to 40%, and more preferably 5 to 30%. Further preferred.
[0044]
As a final aspect, in the multicolor phosphorescent light emitting sheet of the present invention, an adhesive layer for being attached to the substrate is provided on the back surface of the light emitting sheet.
The thickness of the adhesive layer is not particularly limited, but generally considering the workability when the multicolor phosphorescent light emitting sheet is bonded to the base material, or the initial adhesive strength when bonded, etc. The thickness is set to about 5 to 100 μm, preferably about 10 to 80 μm, more preferably about 15 to 50 μm.
[0045]
Although it does not specifically limit as resin used for an adhesive bond layer, For example, acrylic resin, a silicon-type resin, a rubber-type resin, etc. are used individually or mixed with other resin. Of these, acrylic resins and silicone resins are preferably used due to their weather resistance, heat resistance and other characteristics.
[0046]
The adhesive layer may be a pressure-sensitive type, a heat-sensitive type, or a hot-melt type, but when the multicolor phosphorescent light-emitting sheet is bonded to the substrate, In consideration of workability or the material of the base material, a pressure-sensitive adhesive is most preferably used.
[0047]
Further, a transparent cover sheet may be further adhered to the surface of the phosphorescent light emitting sheet of the present invention and used in the embodiment as shown in FIG. The material and adhesion method of the transparent cover sheet are not particularly limited, and are appropriately selected depending on the application and product within a range satisfying the above properties as a sheet.
[0048]
The above-described phosphorescent light emitting sheet of the present invention has many varieties such as small household appliances and various printer inks, and is effectively used as a security label for products handled in large quantities at mass retailers.
[0049]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
[0050]
Example 1
A temporary support having a polyethylene (PE) layer having a thickness of about 20 μm laminated on paper is heated to about 120 ° C., and glass beads having a particle size of 50 to 100 μm and a refractive index of about 1.9 are uniformly and densely formed thereon. After dispersing in a single layer, a temporary support sheet was produced in which glass beads were embedded in PE by 1/5 of the diameter by pressing with a hand roller.
[0051]
Next, the acrylic resin solution A [52% by weight of ethyl acrylate (EA), 46% by weight of methyl methacrylate (MMA), 2-hydroxyethyl methacrylate (2-HEMA) 2 on a 90 μm-thick process paper subjected to the peeling treatment. 170% ethyl acetate (EAc) / toluene / methyl isobutyl ketone (MIBK) solution with a solid content of 30% by weight and acrylic resin solution B [EA 67% by weight, MMA 32% by weight, AA 1.0% by weight % EAC / toluene / MIBK solution having a solid content of 40% by weight copolymerized] 130 parts by weight, structural formula SrAl ₂ O _Four : Green phosphorescent pigment represented by Eu, Dy [N Nightlight G-300M manufactured by Nemoto Special Chemical Co., Ltd.] 500 parts by weight, cellulose acetate butyrate (CAB) solution C [solid content 15 wt% MIBK solution] 40 A green phosphorescent light emitting layer having a thickness of about 80 μm was formed by applying and drying a mixed solution obtained by mixing 100 parts by weight of EAc as a weight adjusting agent.
[0052]
Furthermore, 170 parts by weight of an acrylic resin solution A and 130 parts by weight of an acrylic resin solution B on the green phosphor layer, structural formula Y ₂ O _Three Mixing 500 parts by weight of red phosphorescent pigment represented by S: Eu, Mg, T (“N Night Light R-300M” manufactured by Nemoto Special Chemical Co., Ltd.), CAB solution C, and 100 parts by weight of EAc as a viscosity modifier. The obtained mixed solution was applied and dried to form a red phosphorescent layer having a thickness of 20 μm, thereby forming a red / green laminated phosphorescent layer.
[0053]
Next, the exposed glass beads on the temporary support made earlier and the red / green laminated phosphorescent layer on the red phosphorescent layer side are overlapped and pressurized while heating to 120 ° C. About 1/3 was embedded in the red / green laminated luminous layer (intermediate form). Next, the temporary support was peeled off from the temporary support / red / green laminated phosphorescent layer.
[0054]
The obtained glass beads / red / green laminated phosphorescent light emitting layer is pressurized again while heating at 80 ° C., and the glass beads are embedded until reaching the green phosphorescent layer, and transparent microspheres are embedded across the two colored layers. A multicolor phosphorescent light emitting sheet was obtained (final form).
As shown in Table 1, the obtained multicolor phosphorescent light emitting sheet was a sheet excellent in visibility.
[0055]
Example 2
In Example 1, instead of the red phosphorescent pigment, the structural formula Y ₂ O ₂ A multicolor phosphorescent light emitting sheet was obtained in the same manner as in Example 1 except that 500 parts by weight of a red ultraviolet light emitting pigment represented by S: Eu [Nemoto Special Chemical Co., Ltd. “MB-710”] was used.
As shown in Table 1, the obtained multicolor phosphorescent light emitting sheet was a sheet excellent in visibility.
[0056]
Example 3
Example 1 was the same as Example 1 except that 286 parts by weight of a red colored resin solution [special colorant industry "AR-4094"] colored with a perylene pigment was used instead of the red phosphorescent pigment. Thus, a multicolor phosphorescent light emitting sheet was obtained.
As shown in Table 1, the obtained multicolor phosphorescent light emitting sheet was a sheet excellent in visibility.
[0057]
Example 4
Acrylic resin solution A and acrylic resin solution B of Example 1 were prepared from acrylic resin solution D [ethyl acrylate (EA) 65 wt%, methyl methacrylate (MMA) 21 wt%, 2-hydroxyethyl methacrylate (2-HEMA) 14 % Of EAC / toluene / MIBK solution having a solid content of 50% by weight copolymerization] and 15 parts by weight of hexamethylene diisocyanate-based crosslinking agent [Nippon Carbide Industries Co., Ltd. “CK-102”] A mixed solution obtained by mixing 170 parts by weight of acrylic resin solution A, 130 parts by weight of acrylic resin solution B, and 100 parts by weight of rutile titanium dioxide on the green luminous layer prepared in the same manner as in Example 1, and 40 parts by weight of CAB solution C And applying and drying a mixed solution obtained by mixing 55 parts by weight of EAc as a viscosity modifier. A white layer having a thickness of about 10 μm was formed, and then the acrylic resin solution A and acrylic resin solution B of Example 1 were applied on the white layer with an acrylic resin solution D and a hexamethylene diisocyanate crosslinking agent [Nippon Carbide Industries, Ltd. ) "CK-102"] By changing to 15 parts by weight, a red phosphorescent layer is formed in the same manner as in Example 1 to form a red / white. / Green laminated phosphorescent light emitting layer to obtain a multicolor phosphorescent light emitting sheet. It was.
As shown in Table 1, the obtained multicolor phosphorescent light emitting sheet was a sheet excellent in visibility.
[0058]
Example 5
In Example 4, instead of the red phosphorescent pigment, Example 4 was used except that 500 parts by weight of the same red ultraviolet light-emitting pigment (Nemoto Special Chemical Co., Ltd. “MB-710”) used in Example 2 was used. Similarly, a multicolor phosphorescent light emitting sheet was obtained.
As shown in Table 1, the obtained multicolor phosphorescent light emitting sheet was a sheet excellent in visibility.
[0059]
Example 6
In Example 4, instead of the red phosphorescent pigment, Example 4 was used except that 286 parts by weight of the same red colored resin solution as used in Example 3 [Special Colorant Industry Co., Ltd. “AR-4094”] was used. In the same manner as above, a multicolor phosphorescent light emitting sheet was obtained.
As shown in Table 1, the obtained multicolor phosphorescent light emitting sheet was a sheet excellent in visibility.
[0060]
Example 7
In Example 4, a multicolor phosphorescent light emitting sheet was prepared in the same manner as in Example 4 except that instead of forming a white layer, aluminum was vacuum-deposited on the green phosphorescent layer to form a metal deposited film having a thickness of about 0.1 μm. Obtained.
As shown in Table 1, the obtained multicolor phosphorescent light emitting sheet was a sheet excellent in visibility.
[0061]
Example 8
In Example 7, instead of the red phosphorescent pigment, Example 4 was used except that 500 parts by weight of the same red ultraviolet light-emitting pigment as used in Example 1 [Nemoto Special Chemical Co., Ltd. “MB-710”] was used. Similarly, a multicolor phosphorescent light emitting sheet was obtained.
As shown in Table 1, the obtained multicolor phosphorescent light emitting sheet was a sheet excellent in visibility.
[0062]
Example 9
In Example 7, instead of the red phosphorescent pigment, Example 4 was used except that 286 parts by weight of the same red colored resin solution as used in Example 3 [Special Colorant Industries Co., Ltd. “AR-4094”] was used. In the same manner as above, a multicolor phosphorescent light emitting sheet was obtained.
As shown in Table 1, the obtained multicolor phosphorescent light emitting sheet was a sheet excellent in visibility.
[0063]
Comparative Example 1
In Example 1, a multicolor phosphorescent light emitting sheet was obtained by simply overlaying the red / green laminated phosphorescent layer on the temporary support glass beads without embedding the glass beads in the red / green laminated phosphorescent layer. It was.
As shown in Table 1, the obtained multicolor phosphorescent light emitting sheet was a sheet having poor visibility.
[0064]
Comparative Example 2
In Example 1, the glass beads of the glass beads / red / green laminated phosphorescent light emitting layer were not embedded again, and a multicolor phosphorescent light emitting sheet in a state where the intermediate form was maintained was obtained.
As shown in Table 1, the obtained multicolor phosphorescent light emitting sheet was a sheet having poor visibility.
[0065]
Comparative Example 3
In Example 1, a multicolor phosphorescent light emitting sheet was obtained in the same manner as in Example 1 except that the thickness of the red phosphorescent layer was 50 μm.
As shown in Table 1, the obtained multicolor phosphorescent light emitting sheet was a sheet having poor visibility.
[0066]
Comparative Example 4
In Example 6, 114 parts by weight of a green colored resin solution [“N-3608” manufactured by Special Colorants Co., Ltd.] colored with a phthalocyanine pigment instead of the green phosphorescent pigment was used. A multicolor sheet was obtained in the same manner as in Example 6 without adding the agent [Nippon Carbide Industries Co., Ltd. “CK-102”].
As shown in Table 1, the obtained multicolor phosphorescent light emitting sheet was a sheet having poor visibility.
[0067]
<Measurement method of elongation at break by tensile test>
The multicolor phosphorescent light emitting sheets of Examples 1 to 9 and Comparative Examples 1 to 4 were cut into strips having a width of 25 mm and a length of 150 mm, respectively, and used as test samples.
The measurement conditions are shown below.
Test sample grip interval = 100 mm
Pulling speed = 500mm / min
Measurement atmosphere = 23 ° C x 65% R
[0068]
<Color change in the dark>
Using the multicolor phosphorescent light emitting sheets of Examples 1 to 9 and Comparative Examples 1 to 4 as test samples, placing them under a fluorescent lamp for 30 minutes, placing them in a dark place, observing the colors while changing the direction of the sheets, and visually recognizing The degree of sex was evaluated. The obtained results are shown in Table 1.
A: The phosphorescent color is sufficiently bright, the hue changes depending on the viewing angle, and the visibility is extremely excellent.
(Triangle | delta): The change of a hue is scarce and the difference in hue can be discriminate | determined only by the edge of a sheet | seat.
X: The hue is monotonous or fluorescent color development cannot be confirmed.
[0069]
<Visibility when irradiated with UV fluorescent lamp>
Using the multicolor phosphorescent light emitting sheets of Examples 1 to 9 and Comparative Examples 1 to 4 as test samples, irradiating an ultraviolet fluorescent lamp (“FL15BLB” manufactured by Matsushita Electric Industrial Co., Ltd.) and changing the sheet angle The change was observed and the degree of visibility was evaluated. The obtained results are shown in Table 1.
○: The difference in hue between red and green is remarkably excellent in visibility.
(Triangle | delta): The change of a hue is scarce and the difference in hue can be discriminate | determined only by the edge of a sheet | seat.
X: Hue is monotonous or fluorescent color development cannot be confirmed.
[0070]
[Table 1]

[0071]
From the above results, it is clear that the multicolor phosphorescent light emitting sheet of the present invention can obtain superior effects compared to the multicolor phosphorescent light emitting sheet of the comparative example at the time of hue and irradiation with an ultraviolet fluorescent lamp in a dark place. is there.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing the form of a sheet having two layers in the multicolor phosphorescent light emitting sheet of the present invention.
FIG. 2 is a schematic cross-sectional view showing the form of a sheet having three or more layers in the multicolor phosphorescent light emitting sheet of the present invention.
FIG. 3 is a schematic cross-sectional view showing the form of a sheet of three or more layers having a transparent surface layer in the multicolor phosphorescent light emitting sheet of the present invention.
[Explanation of symbols]
1: Transparent microsphere
2: Resin layer 1 (colored resin layer)
3: Resin layer 2 (phosphorescent resin layer)
4: Resin layer 3 (phosphorescent resin layer)
5: Transparent surface layer

Claims (4)

A sheet in which two or more resin layers having different color development including at least one phosphorescent resin layer are laminated, wherein transparent microspheres project part of the sphere from the surface of the resin layer, and two or more colored layers are formed. An anti-counterfeit label comprising a multicolor phosphorescent light emitting sheet , which is in contact with the sheet. The anti-counterfeit label comprising the multicolor phosphorescent light emitting sheet according to claim 1, wherein transparent microspheres are embedded in an area of 50% or more with respect to the total surface area of the sheet. The anti-counterfeit label comprising the multicolor phosphorescent light emitting sheet according to claim 1, wherein the transparent microspheres are glass beads. The anti-counterfeit label comprising the multicolor phosphorescent light emitting sheet according to any one of claims 1 to 3, wherein the breaking elongation is 1 to 50% .

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