JP2000141884A - Recording sheet having light storing properties and displayed material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording sheet having light storing properties capable of manufacturing a displayed material having light storing properties simply from a printing/image pattern formed by using a personal computer or the like, eliminating sticking of a light storing sheet to an output sheet, and also provide a displayed material thereof. SOLUTION: A recording sheet having light storing properties is provided with a light storing layer formed of a thermosetting resin and a light storing pigment at least on one face of a base film, and a recorded layer to be recorded by a toner or an ink is laminated on the light storing layer or on a face opposite to the light storing layer. A displayed material is provided with a light storing layer composed of a thermosetting resin and a thermosetting pigment and formed at least on one face of the base film, and an image layer of 200-1400 dpi resolution is formed on the light storing layer or on a face on its opposite side.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a luminous recording sheet having excellent visibility and a display having luminous properties, which can be suitably used as a guide plate, a poster or the like in a dark place.

[0002]

2. Description of the Related Art Conventionally, as a sheet having good visibility in a dark place, (1) a sheet in which a retroreflective agent or a phosphorescent pigment is contained in a resin (particularly, vinyl chloride resin), or (2) an ordinary sheet is used. There is a sheet in which an image is formed with an ink containing a luminous agent. In each of these methods, the luminous agent absorbs sunlight or light from indoor lighting, emits its energy at night or in a dark place, and emits light to provide visibility in a dark place. However, in the sheet of the above (1), since the phosphorescent pigment is kneaded into the resin and formed into a film, the obtained sheet is still not satisfactory in mechanical properties, productivity and price. Absent. Further, in the case of the sheet (2), since the sheet is of a single-wafer type, productivity is low, and in order to obtain a certain level of luminance, it is necessary to apply a plurality of layers, which causes There is a disadvantage that the surface properties and productivity are reduced. Further, in this case, since screen printing must be performed to form an ink image, a screen printing plate must be prepared, which is not suitable for preparing a small variety of products.

[0003]

According to the present invention, it is possible to easily produce a display having a luminous property from a print / image pattern prepared by using a personal computer or the like, and it is not necessary to attach a luminous sheet and an output sheet. It is an object of the present invention to provide a recording sheet and a display having luminous properties.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, a light-storing layer made of a thermosetting resin and a light-storing pigment is provided on at least one surface of the base film, and can be recorded with toner or ink on the surface or on the opposite surface. There is provided a recording sheet having a luminous property, wherein a recording layer is laminated.
According to the present invention, a luminous layer composed of a thermosetting resin and a luminous pigment is provided on at least one surface of the base film, and an image having a resolution of 200 to 1400 dpi is further provided thereon or on the surface on the opposite side. There is provided an indicator characterized by forming a layer.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The recording sheet having luminous properties of the present invention is provided with a luminous layer composed of a thermoplastic resin and a luminous pigment on at least one surface of the base sheet, and further with toner or ink on the surface or on the surface on the opposite side. It is characterized in that a recordable recording layer is provided.

The base sheet used in the present invention includes paper,
A base sheet usually used for a thermal transfer printer, a hot-melt transfer printer, an ink jet printer, a PPC printer or the like can be used such as a synthetic paper and a plastic sheet. When the recording layer is provided on the luminous layer, it is advantageous in terms of luminance to use a substrate sheet that blocks light. As a substrate sheet that blocks light, there is a plastic sheet such as a thermoplastic resin to which a white pigment such as titanium oxide, calcium carbonate, or synthetic silica is added. As the thermoplastic resin, polyester resin,
Known ones such as acrylic resin, polycarbonate resin, polyether sulfone resin, and polyolefin resin can be used. Among them, a biaxially stretched polyethylene terephthalate sheet is preferable in terms of dimensional stability, flatness, and heat resistance. Also, a laminate of a plastic sheet and paper can be used. When the recording layer and the luminous layer are provided on opposite surfaces, the substrate sheet needs to have transparency, and a transparent plastic sheet is preferable. As such a transparent plastic sheet, polyester resin, acrylic resin, polycarbonate resin,
Examples thereof include those made of known plastic materials such as polyethersulfone resin and polyolefin resin. The thickness of the base sheet is usually 25 to 250 μm, and preferably 38 to 100 from the viewpoint of workability and printer suitability.
It is in the range of μm.

The luminous layer in the recording sheet of the present invention comprises:
It consists of a resin and a luminous pigment. As the luminous pigment used in the luminous layer in the present invention, for example, metal sulfides such as barium, strontium, cadmium, calcium, zinc and fluorescent dyes are dissolved together with the initial condensate of the condensable synthetic resin, and the condensation is promoted in the resin. Pigments obtained by fixing dyes on the surface, and the following general formula (1)

## STR1 ## MAl ₂ O ₄
(1) (wherein M is at least one selected from the group consisting of calcium, strontium and barium)
A compound obtained by using an oxide-based compound represented by the following formula) as a mother crystal, or a magnesium-added oxide-based compound obtained by adding a compound obtained by adding magnesium to this oxide-based compound to a mother crystal, or these oxide-based compounds or Activated phosphor compounds to which europium, dyspronium, and neodymium are added as an activator for the magnesium-added oxide-based compound are exemplified. Specific examples include N-Night G-300M manufactured by Nemoto Special Science Co., Ltd.

In order to obtain a clearer image as a display, it is preferable to use, as the luminous agent, those which appear white under ordinary visible light. As such a phosphor, a phosphorescent phosphor composed of SrAl ₂ O ₄ : Eu, Dy to which Eu ₂ O ₃ is added (Japanese Unexamined Patent Publication No.
No. 3028) and those obtained by adhering calcium carbonate, silica, or the like to the surface of a luminous pigment, and are available as “WA-300” manufactured by Nemoto Special Chemical Co., Ltd.

As the resin used for the light storage layer of the present invention, various conventionally known resins are used. Such materials include thermoplastic resins, curable resins, rubbers, and the like.
In the present invention, it is particularly preferable to use a curable resin. As the curable resin, various types of conventionally known thermosetting and photocurable resins can be used. The thermosetting resin includes various types such as urethane-based, epoxy-based, polyester (alkyd-based), silicon-based, and thermosetting acrylic-based resins. Also, as the photo-curable resin,
Conventionally known ones such as an acrylic resin can be used. By using such a curable resin as the resin binder, a luminous film excellent in heat resistance and durability can be obtained.

The thermosetting resin is preferably used as a two-component composition comprising a main component comprising a thermosetting resin component and a curing agent. In the present invention, it is particularly preferable to use an aliphatic (non-aromatic) thermosetting resin containing no aromatic component as the resin binder. Among them, aliphatic urethane resins and thermosetting acrylic resins are particularly preferred because of their excellent weather resistance, heat resistance, and adhesion to the base film. As the aliphatic urethane-based resin in this case, it is preferable to use a two-component composition in which a main agent composed of an aliphatic acrylic polyol and an auxiliary composed of a non-yellowing aliphatic isocyanate (curing agent) are combined. The aliphatic acrylic polyol is a polymer in which a hydroxyl group has been introduced into an acrylic polymer or copolymer. The introduction of the hydroxyl group can be achieved by copolymerizing an acrylic ester monomer having a hydroxyl group such as β-hydroxyethyl methacrylate with a non-aromatic acrylic monomer such as acrylic acid or methyl methacrylate.
Non-yellowing aliphatic isocyanates include water additives such as hexamethylene diisocyanate, isophorone diisocyanate and meta-xylene diisocyanate, non-aromatic diisocyanates such as norbonene diisocyanate, and polyols such as trimethylolpropane, glycerin and glycol. Are reacted to form an adduct, and excess isocyanate is removed. When the composition comprising the aliphatic acrylic polyol and the non-yellowing isocyanate is used as a resin binder, when it is used as a cured resin film, it is easy to adjust the glass transition point and elongation of the obtained film. Top, durability,
A luminous layer coating film having good heat resistance and mechanical strength can be obtained.

The mixing ratio of the luminous pigment and the resin is as follows:
The weight ratio is in the range of 5:95 to 95: 5. When the resin solid content is less than 5 parts by weight, the light-storing layer strength cannot be obtained, and when the light-storing pigment is less than 5 parts by weight, sufficient night vision cannot be obtained. From the viewpoint of the coating strength of the light-storing layer and the light-storing performance, particularly from the viewpoint of night vision, the mixing ratio of the light-storing pigment and the resin is 15: 8 by weight.
The range of 5 to 85:15 is more preferable.

The glass transition temperature (hereinafter also referred to as Tg) of the luminous layer of the present invention is preferably from 10 to 60 ° C. in consideration of winding a sheet into a roll at the time of production. If Tg is less than 10 ° C, blocking is inevitable during winding and storage, and if Tg is 60 ° C or more, cracks occur in the coating film during winding. The thickness of the luminous layer is in the range of 20 to 200 μm, preferably 30 to 150 μm.
m. If the thickness of the phosphorescent layer is less than 20 μm, sufficient night vision cannot be obtained, and if it exceeds 200 μm, it is not preferable from the viewpoint of cost and workability. The preferred thickness of the luminous layer is 3 from the viewpoint of luminous performance, in particular, night vision and workability.
The range is from 0 to 70 μm.

In the case where the resin binder is a liquid resin at the time of film formation, it is not always necessary to use a solvent. It becomes a coating solution of 45 to 85%, and a luminous layer is formed by coating and drying according to a conventional method. At this time, various additives conventionally used, for example, a surfactant, an antifoaming agent, a stabilizer and the like can be added to the coating liquid.

In the recording sheet of the present invention, in order to improve the adhesiveness between the base sheet and the luminous layer or the recording layer, the base material and the luminous layer or between the luminous layer and the recording layer may be used, if necessary. A primer layer may be provided between them. As the primer layer, a saturated polyester resin, a urethane resin, or the like is usually used, and particularly, a urethane resin is preferable because of good adhesion between the substrate sheet and the luminous layer or between the luminous layer and the recording layer. The coating amount of this primer layer is usually 0.1.
It is in the range of 5 to ²⁰ g / m ² , preferably 0.5 to ²⁰ g / m ^2.
10 g / m ² . When the coating amount is less than 0.5 g / m ² , uniform adhesion cannot be obtained, and the coating amount is 20 g / m ^2.
If it is larger, it is not preferable in terms of cost and workability. In addition, in order to improve the adhesion between the substrate sheet and the luminous layer or between the substrate sheet and the recording layer, for example, chemical etching treatment such as chromic acid treatment, ionizing radiation treatment such as corona treatment or plasma treatment, exposure to ozone, fire Surface treatment such as chemical or physical treatment for oxidizing the surface by exposure or high-voltage piezoelectric exposure may be performed.

In the present invention, a recording layer having a property of retaining a toner or ink, particularly an ink for ink jet or an aqueous ball-point pen or an aqueous pen, is provided on the phosphorescent layer or on the surface opposite to the phosphorescent layer. Provide. Examples of the recording layer include those conventionally used as an ink receiving layer of an ink jet recording sheet, those having transparency in a toner receiving layer used in a recording material for a PPC, and the like.
In particular, a material having such transparency that the light storage layer can be visually confirmed is used. The ink receiving layer is composed of at least one layer containing, for example, a water-soluble, water-absorbing polymer compound or a water-resistant water-soluble polymer compound as a binder, and optionally containing a pigment or a dye fixing agent, organic or inorganic fine particles, and the like. Is preferred. As the water-soluble, water-absorbing polymer compound, for example, polyvinyl alcohol and its derivatives, polyvinyl acetal, polyvinyl pyrrolidone,
Examples include starch, latex, acrylic resin, melamine resin, cellulose, tannin, and alginic acid. Further, the water-resistant water-soluble polymer compound, the water-soluble polymer compound, a salt bond, a coordination bond, a covalent bond,
It is obtained by insolubilization by a reaction such as hydrogen bonding. As the crosslinking agent for the water-soluble polymer, for example, a fibrous reaction crosslinking agent, such as urea resin, water-soluble melamine,
Isocyanate resins and aziridine compounds are exemplified.
By using this crosslinking agent, water resistance can be imparted to the coating film. Examples of the pigment or dye fixing agent include, for example, pseudo-boehmite, an anionic surfactant, porous silica, and the like.In particular, pseudo-boehmite has excellent water resistance, excellent dye / pigment fixability, and transparency. Is preferred. On the other hand, as the material used for the toner receiving layer, an acrylic resin, a polyolefin-based resin, for example, a polyethylene resin, a polypropylene resin, or the like may be used, but a polyethylene resin is preferably used from the viewpoint of adhesion to the toner. . At this time, the toner receiving layer is selected from those having a melting point equal to or lower than the melting point of the toner, so that the toner receptivity, the color development of the image,
The sharpness of an image can be improved. It is particularly preferable that the ink receiving layer has toner adhesion because it can be used for both purposes.

Further, the recording layer of the present invention may contain organic or inorganic fine particles to such an extent that the light storage properties of the light storage layer are not impaired. By incorporating these fine particles, it is possible to improve the transportability at the time of output and the fixability of the pigment and the toner. Examples of the inorganic and organic fine particles include synthetic silica, natural silica, kaolin, talc, clay, calcium carbonate, titania, alumina, zirconia, zeolite, barium sulfate, magnesium hydroxide,
Inorganic materials such as calcium phosphate, fine powder such as glass, acrylic resin, urethane resin, vinyl chloride resin,
Benzoguanamine resin, benzoguanamine / melamine /
Organic materials such as powders of synthetic resins such as formaldehyde condensates are exemplified. Among them, among inorganic fine particles, silica and calcium carbonate are preferable because they are excellent in ink absorption and blocking resistance. Further, among organic fine particles, acrylic resin and benzoguanamine resin are preferable because they do not impair transparency and are excellent in blocking resistance and printer transportability. In addition, the shape of the particles is preferably spherical for excellent workability during preparation of the coating liquid and excellent ink permeability.

In the recording layer of the present invention, a particle-form roughening agent can be used, and the particle size of the surface-forming agent particles is in the range of 0.5 to 30 μm in weight average particle size. It is. If the particle size of the surface-forming agent particles is smaller than this range, no convex portion will be formed on the surface of the recording layer, the effect of surface roughening will not be exhibited, and the fixability of the pigment ink will not be improved. When the particle size of the particles is larger than this range, the size of the particles on the surface of the recording layer becomes large, transfer unevenness of the toner image occurs, or when the transferred toner image is fixed, the fixing by the roll becomes insufficient, When a print / image pattern is formed by ink jet, the dots are deformed and a clear image cannot be obtained. The particle size of the surface-roughening agent is preferably in the range of 2 to 25 μm from the viewpoints of forming convexities on the surface, fixing the pigment, preventing transfer unevenness, and obtaining a clear image. When the recording layer contains the surface-roughening agent, its content can be appropriately selected within a range that does not impair the transparency of the recording layer and the luminous property of the luminous layer. , In the recording layer in the range of 0.1 to 20% by weight. When the content of the surface-roughening agent is less than 0.1% by weight, blocking occurs, and when it is more than 20% by weight, image reproducibility, transparency and light storage efficiency are undesirably reduced.

The recording layer of the present invention is prepared, for example, by dissolving or decomposing the above-mentioned polymer compound and, if desired, a surface-roughening agent at a predetermined ratio in a solvent to form a coating having a solid content of about 10 to 15% by weight. After the solution is prepared, it can be formed by applying the solution on a base material sheet, a primer layer provided as required, or a phosphorescent layer according to a conventional method, followed by drying. At this time, various additives conventionally used, for example, a surfactant, a lubricant, a stabilizer and the like can be added to the coating liquid.

The recording layer of the present invention has a thickness of 5 to 30 μm,
Preferably it is in the range of 7 to 20 μm. If the thickness of the recording layer is less than 5 μm, the ink absorbency and toner receptivity will be insufficient, and if it exceeds 30 μm, curling of the sheet will occur, and it will be difficult to prevent this, which is not preferable in terms of cost.

In the recording sheet of the present invention, when a base sheet, a luminous layer and a recording layer are sequentially laminated, an adhesive layer may be provided on the surface opposite to the surface on which the luminous layer is provided. . Further, the recording sheet in the present invention is higher by providing a white paint layer on the luminous layer when the luminous layer is laminated on the base sheet and the recording layer is formed on the surface opposite to the luminous layer. Brightness can be obtained, and when a white luminous agent is used, the observation surface of the printed / image pattern can be made whiter. This white paint layer is mainly
It consists of a binder and a white pigment, and the binder can be appropriately selected from thermosetting and thermoplastic resins. For example, it is preferable to use the same kind of binder as used for the light storage layer from the viewpoint of adhesion to the light storage layer.
As the white pigment, inorganic pigments such as titanium oxide, zinc white, talc, clay, calcium carbonate, silica, aluminum hydroxide, aluminum oxide and the like, and organic pigments such as white acrylic resin particles can be used. Among them, titanium oxide is preferable because of its excellent concealing property.
The particle size of the white pigment is 0.1 to 50 in weight average particle size.
It is in the range of μm. Outside of this range, the adhesion to the luminous layer and the whiteness decrease. The particle size of the white pigment is preferably in the range of 0.2 to 30 [mu] m from the viewpoint of the adhesion to the phosphorescent layer and the decrease in luminance due to the decrease in whiteness. The mixing ratio of the white pigment and the binder may be appropriately selected depending on the degree of whiteness to be obtained. For example, the total light transmittance is preferably 30% or less. Furthermore, in the white paint layer,
Organic fine particles such as a powder of a synthetic resin such as an acrylic resin, a benzoguanamine resin, or a benzoguanamine / melamine / formaldehyde condensate may be contained in order to prevent printer transportability and blocking.

When a pattern is formed on a recording layer by various output devices such as a printer using the recording sheet according to the present invention, the printer resolution is 200 to 1400 dp.
It is necessary to output in the range of i. If the printer resolution is less than 200 dpi, the resolution of the output print / image pattern is low, resulting in reduced image clarity and impact. If it exceeds 1400 dpi, a clear image can be obtained during the day, but the output print -The image pattern inhibits the luminous property, the luminous efficiency and the luminous efficiency of the luminous pigment are reduced, and printing in a dark place-the feature that the image pattern can be observed without a light source, the so-called night vision property, is not preferred because it is reduced. . This is because light from the luminous layer is between the dots,
This is to prevent the phenomenon of passing through the translucent portion and appearing on the surface of the pattern, and it is desirable that this printer resolution be appropriately selected according to the sheet size to be output. For example,
When the sheet size exceeds A3, a clear image can be obtained even with a relatively low printer resolution.
In addition, visibility in a dark place can be secured.

According to the display material of the present invention, in the recording sheet, the recording layer has a resolution of 200 to 1400 dpi,
Preferably, it is formed by forming an image of 300 to 1200 dpi. In this case, the image can be formed using various printers as described above, and can also be performed using various printing methods. The display object of the present invention is displayed at a predetermined place as an advertisement medium or the like according to the type of the image.

[0023]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. The physical properties of the recording sheet and the display were evaluated according to the following methods. [Evaluation method] Visibility Using EPSON Prospurt Photo Mach Color Printer PM-2000C, 180, 360, 7
The image was printed at 20, 1440 dpi, and its image quality was visually evaluated from a distance of 1 m during the day and at night. ：: The image can be recognized without any problem during the day and at night. Δ: Images can be recognized during the day, but not at night. ×: Images cannot be recognized during the day or at night. 2. Adhesion The adhesion between the luminous layer and the recording layer is determined by a grid test (JIS k
-5400). 5: Defective part is 0 4: Defective part is within 5% 3: Defective part is 5 to 15% 2: Defective part is 15 to 35% 1: Defective part is 35% or more Ink drying properties EPSON Mach Jet Printer PM700C
, And evaluated according to the following indices. ：: Touch dry time is less than 60 seconds Δ: 60 seconds or more and less than 3 minutes ×: 3 minutes or more Roll winding property The appearance of the coating film surface was visually observed during roll winding. ：: unwound without blocking and no cracking ×: unblocked or cracked Heat Resistance The flatness and printer transportability of the sheet coated with the toner or ink recording layer and dried under a constant drying condition (140 ° C., 3 minutes) were evaluated. ：: No ripples and good printer transportability △: Ripples but good printer transportability ×: Ripples and poor printer transportability After the curl roll product is cut to A4 size, it is placed on a flat table with the surface having the luminous layer facing upward. At this time, the average of the heights of the four corners from the table to the sheet was measured and evaluated by the following indices. ：: height 10 mm or less △: height 10 to 20 mm ×: height 20 mm or more

Example 1 43.5 parts by weight of acrylic polyol (hydroxyl value 17.5), luminous pigment (G-300M, manufactured by Nemoto Special Chemical Co., Ltd.) 4
7.8 parts by weight, additives 4.4 parts by weight, curing agent (NCO%
12.6) 4.3 parts by weight were mixed to prepare a phosphorescent layer forming coating solution. One side of a 50 μm thick white polyethylene terephthalate sheet made of urethane resin on one side
m, the coating liquid was applied on the easy-adhesion layer with an applicator, and dried to a thickness of 50 μm, Tg3.
A luminous layer at 5 ° C. was formed. Next, acetoacetylated polyvinyl alcohol (99 mol% of saponification, polymerization degree of 1,0
00) 6.4 parts by weight, polyvinylpyrrolidone (weight average molecular weight 630,000) 2 parts by weight, acidic colloidal silica solution (Snowtex ST-AK, manufactured by Nissan Chemical Industries, Ltd.)
8 parts by weight, 10 parts by weight of ethanol and 73.6 parts by weight of water were mixed to prepare a recording layer forming coating liquid. After providing a 1 μm-thick easy-adhesion layer made of urethane resin on the light-storing layer, the recording-layer-forming coating liquid is applied onto the easy-adhesion layer with a wire bar, and dried to form a 10 μm-thick recording layer. (Ink receiving layer) was formed, and a recording sheet having a light storing property according to the present invention was prepared.

Example 2 A recording sheet was produced in the same manner as in Example 1, except that the coating liquid for forming a recording layer was changed as follows. 7 parts by weight of polyvinyl alcohol (degree of polymerization 1700, saponification degree 88 mol%), 1 part by weight of polyvinylpyrrolidone (weight average molecular weight 630,000), 2 parts by weight of polystyrene sulfonate (manufactured by Sanyo Chemical Industries, Chemistat 6120), cellulose A recording layer forming coating liquid is prepared by mixing 0.2 parts by weight of dimethylol glyoxal monourein, which is a reactive cross-linking agent, 69.66 parts by weight of water, and 0.04 parts by weight of synthetic silica (average particle size: 6 μm). did. The coating liquid for forming a recording layer was applied onto the easy-adhesion layer with a wire bar and dried to form a recording layer (ink receiving layer) having a thickness of 25 μm.

Example 3 Acrylic polyol (hydroxyl value 17.5) 43.5 weight
Part, phosphorescent pigment (G-300M, manufactured by Nemoto Special Chemical Co., Ltd.) 4
7.8 parts by weight, additives 4.4 parts by weight, curing agent (NCO%
 12.6) 4.3 parts by weight are mixed to form a phosphorescent layer coating
A liquid was prepared. 50 μm thick with easy adhesion treatment on both sides
On one side of a transparent polyethylene terephthalate sheet
Apply the coating solution on the easy-adhesion layer with an applicator and dry
Then, a phosphorescent layer having a thickness of 50 μm and a Tg of 35 ° C. was formed. Next
, Acetoacetylated polyvinyl alcohol (saponification degree
99 mol%, degree of polymerization: 1,000) 6.4 parts by weight, polyvinyl chloride
Nilpyropidone (weight average molecular weight 630,000) double
Parts, colloidal silica acid solution (Snowtex ST-
AK, manufactured by Nissan Chemical Industries) 8 parts by weight, ethanol 10 parts
Parts of water and 73.6 parts by weight of water,
Was prepared. On the surface opposite to the surface provided with the light storage layer,
The recording layer forming coating solution is coated on the easily adhesive layer with a wire bar.
Coated and dried, 10 μm thick recording layer (ink receiving layer)
To form a recording sheet having luminous properties according to the present invention.
Created. The luminous layer at this time is 1000 LX (lux)
After irradiation for 10 minutes, a luminance meter (product name: BM-
8. The surface of the sample table was black.)
Brightness at time (mcd / m ^Two) Is 400 (one minute value)
Was.

Comparative Example 1 In Example 1, a sheet (trade name: Luminova, manufactured by Nemoto Special Chemical Co., Ltd.) in which a luminous pigment was kneaded with a vinyl chloride resin was used in place of the luminous layer according to the present invention.
In the same manner as in Example 1, a recording layer forming solution having the composition shown in Example 1 was applied to obtain a recording sheet.

Example 4 In Example 3, a phosphorescent agent (WA-300, manufactured by Nemoto Special Chemical Co., Ltd.) was used instead of the phosphorescent agent (G-300M, manufactured by Nemoto Special Chemical Co., Ltd.) used in the coating solution for forming the phosphorescent layer. A recording sheet was manufactured in the same manner as in Example 3 except that the recording sheet was used. The brightness (mcd / m ² ) of this recording sheet was 200 (one minute value), and the EPSON Mach Jet Printer PM
When an image pattern was formed on the recording layer at -700 C, the images were clearer than in Examples 1 to 3 under normal visible light. The physical properties of this product were evaluated by the above-mentioned evaluation methods.

Example 5 A white layer forming coating solution having the following composition was applied on the luminous layer of Example 4 and dried to form a 20 μm thick white layer. A recording sheet was produced in the same manner as in Example 4. At this time, the total light transmittance of the white layer is 2
5%, luminance of recording sheet (mcd / m ² ) is 300
(1 minute value), and when an image pattern was formed on the recording layer with the EPSON Mach Jet Printer PM-700C, the image was clearer than that in Example 4 under ordinary visible light. The physical properties of this product were evaluated by the above-mentioned evaluation methods.

<Coating solution for forming white layer> Acrylic polyol (hydroxyl value: 17.5) 60 parts by weight, white pigment (Taipec R-680, manufactured by Ishihara Sangyo Co., Ltd.) 12 parts by weight, additive 1.
2 parts by weight, 3.8 parts by weight of a curing agent (NCO% 12.6), 14 parts by weight of toluene, and 9 parts by weight of methyl cellosolve acetate were mixed to prepare a white layer forming coating liquid.

Example 6 In Example 3, an ink fixing layer forming coating liquid consisting of 30 parts by weight of a polyester resin, 20 parts by weight of toluene, 20 parts by weight of methyl ethyl ketone, and 30 parts by weight of an additive was applied instead of the ink receiving layer. A recording sheet was prepared in the same manner as in Example 3 except that the sheet was dried and an ink fixing layer was provided. Using a thermal transfer printer (MD-2300, manufactured by Alps) on the surface of the recording sheet opposite to the luminous layer with a print / image pattern resolution of 600 dpi, the image was recognized without any problem during the day and night. In particular, a display object in which a clear image can be recognized during the day was obtained.

The evaluation results of the products obtained in Examples 1 to 5 and Comparative Example 1 are shown in Table 1.

[Table 1]

[0033]

As described above, the luminous recording sheet of the present invention can be used to easily output a print / image pattern created by a personal computer or the like using an inkjet printer, an inkjet plotter, a thermal transfer printer, a thermal fusion transfer printer, a laser printer, or the like. And since the luminous layer and the recording layer are laminated, the work of bonding the luminous sheet and the recording sheet is unnecessary,
Work efficiency is good. Further, the printing / image pattern on the luminous recording sheet according to the present invention can be printed at a printer resolution of 2.
When a display object is formed by forming the display object at 00 to 1400 dpi,
Even in a dark place as well as in a bright place, the stored light clearly displays a print / image pattern, so that there is no need to prepare a lighting fixture or the like. For this reason, since fossil fuels such as electricity are not required, it is possible to obtain excellent advertisements and signs such as signboards which are friendly to the global environment. further,
By providing a white paint layer on the light-storing layer, the brightness of the light-storing layer can be improved, and when a white light-storing agent is used, it looks more white under normal visible light, so the pattern of the recording layer Can be clearly reproduced.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Nozomi Nagase Inventor No. 11-2, Ginza 4-chome, Chuo-ku, Tokyo F-term (reference) 2H086 BA12 BA15 BA16 BA24 BA33 BA41 4F100 AK01B AK21 AK25 AK42 AK51G AS00C AT00A BA03 BA04 BA10A BA10B BA10C BA10D CA13B GB41 JA05B JB13B JL10D JL11G JN01D JN13B YY00B YY00D

Claims (10)

[Claims] 1. A light-storing layer comprising a thermosetting resin and a light-storing pigment is provided on at least one surface of a base film, and a recording layer recordable with toner or ink on the light-storing layer further on or on the opposite surface. A recording sheet, comprising: 2. A luminous layer composed of a thermosetting resin and a luminous pigment is provided on one surface of a substrate film, and a recording layer recordable with toner or ink is laminated on the surface opposite to the luminous layer. A recording sheet according to claim 1, wherein a white layer is further laminated on the phosphorescent layer. 3. The luminous pigment is 5 to 95 with respect to the entire luminous layer.
The recording film according to claim 1, which is in terms of% by weight. 4. The recording film according to claim 1, wherein the light storage layer has a thickness of 20 to 200 μm. 5. The glass transition temperature (Tg) of the phosphorescent layer is 10
The recording film according to any one of claims 1 to 4, wherein the temperature is from 60 to 60 ° C. 6. The recording film according to claim 2, wherein the white layer has a light transmittance of 30% or less. 7. A luminous layer made of a thermosetting resin and a luminous pigment is provided on at least one surface of a substrate film, and a resolution of 200 to 1 is further provided on the luminous layer or on the opposite surface.
A display object comprising a 400 dpi image layer. 8. The display according to claim 7, wherein a white layer is laminated on the phosphorescent layer. 9. The phosphorescent layer has a glass transition temperature (Tg) of 10
The display according to claim 7 or 8, wherein the temperature is -60 ° C. 10. The display according to claim 7, wherein the white layer has a light transmittance of 30% or less.