JP2004148782A - Method for marking sheetlike substrate, sheetlike substrate and marking utensil - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prevent the contamination of the hand or clothing by the non-adhesion of an ink liquid to be used when marking is applied to a thermal magnetic recording medium such as a ticket or the like by the ink liquid and to change the color of an applied mark optionally. <P>SOLUTION: In a method for marking a sheetlike substrate, the developer layer of the sheetlike substrate having the developer layer formed in at least a part of the surface is marked with a colorless leuco dye. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for marking a sheet-like substrate including a ticket, and particularly to a novel marking method including applying a colorless color former to a color developer layer formed on the surface of the sheet-like substrate. . The invention also relates to a sheet-like substrate and a marking tool used in this method.
[0002]
[Prior art]
At present, many tickets issued by many public transportation such as railways have a heat-sensitive recording layer on the surface where the price, usable section, transportation name and getting on and off station name etc. can be thermally transferred at the time of ticketing. It has a magnetic recording layer on the back for reading and writing with an automatic ticket collection machine. Due to the presence of the magnetic recording layer, a collection ticket is made by an automatic collection machine. However, in the case of a ticket collection at a station where an automatic ticket collection machine is not installed or a ticket inspection inside a train, as before, staff members cut or make holes with ticket scissors or ticket scissors, or use stampers etc. This is done by engraving a ticket for a collection or inspection stamp. According to the former, it is easy to visually judge whether or not a proper collection ticket or ticket inspection has been performed, but there is a possibility that a problem may occur in the thermosensitive recording characteristics or thermosensitive magnetic recording characteristics of the ticket. Therefore, recently, the latter method of stamping is often used because it can be used in combination with an automatic ticket collection machine and can visualize a station name, date and time, and the like.
However, the latter method has a problem that if a ticket is touched immediately after engraving, hands and clothes are stained by undried ink. In order to overcome this problem, quick-drying inks have also been developed (for example, see Patent Documents 1 and 2).
[0003]
[Patent Document 1]
Patent No. 3215555 (specification paragraph [0002]
[0003]
[Patent Document 2]
Japanese Patent Application Laid-Open No. 2000-239592 (specification paragraph [0003] and abstract [problem])
[0004]
[Problems to be solved by the invention]
Since the colored ink described in the patent document is quick-drying, it does not stain hands and clothes even if the stamp is touched immediately after the stamp, but it may accidentally touch the surface of the stamping tool where the ink is infiltrated, Alternatively, when refilling the marking tool with ink, there is a danger that the ink will adhere and cause contamination of hands and clothes.
[0005]
[Means for Solving the Problems]
The inventors of the present invention have conducted studies on an ink that does not cause contamination of hands and clothes, and as a result, have wondered if a leuco dye known in the thermal recording field can be used as a substitute for a colored ink. Leuco dyes usually used in the production of thermal paper are colorless before coloring and develop color by the action of a developer. In other words, such a colorless leuco dye does not develop color unless affected by a developer. That is, it is considered that the leuco dye and the developer are separately provided, and they are brought into contact with each other as required to cause the color to be developed only at a necessary portion. Therefore, the present inventors apply a color developer in advance to the recording surface of the sheet-shaped base material and dry it, and apply a separately prepared colorless leuco dye thereto in a desired image form. It was confirmed that the leuco dye developed a desired image form by acting with the coloring agent, and the present invention was completed.
[0006]
Therefore, the present invention provides a method for marking a sheet-like substrate, in which a colorless leuco dye is used to mark the developer layer of the sheet-like substrate having a developer layer on at least a part of its surface.
[0007]
In order to carry out the recording method of the present invention, a sheet-like substrate previously coated with a developer and dried, and a marking tool for applying a leuco dye to the sheet-like substrate in a desired image form are used. Required.
That is, the present invention provides a sheet-like base material having a color developer layer on its surface, and a handle portion, and a stamp attached to the handle portion, for use in the method of the present invention. Marking implements are also provided, including those having a stamped surface for applying the leuco dye on the side opposite to the binding site for the hand.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
The method for marking a sheet-like substrate of the present invention is most preferably achieved by using a sheet-like substrate and a marking tool described in detail below.
[0009]
Sheet-like substrate The sheet-like substrate of the present invention has a developer layer formed on at least a part of its surface. That is, for example, the color developer layer 30 may be partially formed on the surface of the sheet-shaped substrate 10 as shown in FIG. 1 or may be formed on the entire surface of the sheet-shaped substrate. . If necessary, even if the heat-sensitive coloring layer 20 is formed between the surface of the sheet-shaped base material 10 and the color-developing agent layer 30, and / or the back surface of the sheet-shaped base material 10, that is, the color-developing layer 30 The magnetic recording layer 40 may be formed on the surface opposite to the surface having.
[0010]
The sheet-like substrate 10 may be made of paper, synthetic paper or plastic.
[0011]
The thickness of the sheet-shaped substrate 10 may generally be in the range of 30 to 200 μm.
[0012]
On the front and back surfaces of the sheet-like substrate 10, before or after formation of a color developer layer, a thermosensitive coloring layer, and / or a magnetic recording layer, which will be described later, using a commonly used ink and a device, etc. Necessary information such as conditions and qualifications (for example, if the sheet-shaped base material is a ticket, the issuer, and the type of ticket such as a ticket or an express ticket) may be printed in at least one color.
[0013]
(1) Developer Layer A developer layer 30 containing a developer 35 is formed on the surface of the sheet-like base material 10, for example, as shown in FIG. The color developer layer 30 may be formed on the entire surface of the sheet-like substrate 10 as illustrated in FIG. 1, or may be formed only on a part of the surface of the sheet-like substrate 10 as necessary. May be.
The developer may be any as long as it causes the leuco dye to be separately prepared and applied. Examples of suitable developers include phenolic substances such as 2,2-bis (p-hydroxyphenyl) propane [ie, bisphenol A] or 4-hydroxy-4'-isopropoxyphenylsulfone, zinc of a salicylic acid derivative Salts, especially zinc salts of 3,5-di-α-methylbenzyl-salicylic acid, or mixtures thereof.
[0014]
The developer layer is, for example, a developer layer obtained by finely dispersing the developer in an aqueous solution containing a latex such as SBR latex, NBR latex, PSBR latex or a binder resin such as starch and polyvinyl alcohol. The coating solution is applied to the exposed surface of the heat-sensitive coloring layer by a conventional method such as flexo, gravure, air knife, meaber, curtain coat or the like in a dry coating weight range of 2.0 to 4.0 g / m ² and dried. May be formed.
[0015]
(2) Thermosensitive Coloring Layer The sheet-like substrate 10 of the present invention may have a thermosensitive coloring layer 10 between the surface thereof and the developer layer 30 as needed. In this case, after the heat-sensitive coloring layer 20 is formed on the surface of the sheet-shaped base material 10, the color developer layer 30 is formed by the above-described method so as to partially or entirely cover the heat-sensitive coloring layer 10.
The heat-sensitive color-forming layer 10 is prepared by applying a coating solution for a heat-sensitive color-forming layer containing a color former, a color developer, and, if desired, various additives such as a binder, an inorganic pigment, and a sensitizer to the surface of the sheet-like substrate 10 by an appropriate method. It is formed by coating and drying.
[0016]
Coloring agents suitably used in the heat-sensitive coloring layer include leuco dyes usually used in the heat-sensitive recording field (for example, triarylmethane, diphenylmethane, xanthene, thiazine, and spiropyran compounds, lactam dyes, and fluoran dyes). It may be. The developer contained in the heat-sensitive coloring layer may also be one suitable for heat-sensitive recording, like the color-forming agent.For example, activated clay, acid clay, attapulgite, bentonite, colloidal silica, and inorganic acidic substances such as aluminum silicate Phenol, triphenylmethane, sulfur-containing phenol, carboxylic acid, urea or thiourea compounds, polyvalent metal salts of aromatic carboxylic acids, condensation reaction products of aromatic carboxylic acids and polyhydric alcohols, diphenyl sulfone System compounds and the like.
When the color former is heated in the presence of the developer contained in the thermosensitive color developing layer, it gives a unique color hue such as black, red, magenta, orange, blue, green, and yellow, respectively. In the present invention, the thermosensitive coloring layer may contain a combination of one or two or more different coloring agents having different hues.
[0017]
Examples of additives that can be added to the thermosensitive coloring layer include, for example, starch, methylcellulose, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, binders such as polyacrylamide, fatty acid amides, aromatic carboxylic acid esters, fatty acid esters, and aromatic compounds. Sensitizers such as aromatic ethers; and inorganic pigments such as kaolin, clay, calcium carbonate, and finely divided anhydrous silica.
[0018]
The thermosensitive coloring layer can be formed, for example, by the following method. A binder resin such as polyvinyl alcohol or polyacrylamide is previously dissolved separately for the color former and the developer. Each of the two obtained solutions is finely dispersed into fine particles using a ball mill, an attritor, a sand mill or the like. Thereafter, the two are combined and mixed, and then an additive is appropriately added as necessary to prepare a coating solution for a thermosensitive coloring layer. The thermosensitive coloring layer is formed by applying the coating solution for the thermosensitive coloring layer to the surface of the sheet-like substrate by a conventional method such as gravure, flexo, silk screen, air knife, and meaver.
[0019]
In the coating solution for the heat-sensitive coloring layer, the amount of each of the coloring agent, the developer, the binder resin, and any additives used is dependent on the hue, heat energy sensitivity, and recording suitability required for the heat-sensitive coloring layer. Is determined. The coating solution for the heat-sensitive coloring layer preferably used in the present invention is, for example, 3 to 12 parts by weight of a developer, 0 to 12 parts by weight of a sensitizer, 1 to 1 part by weight of a coloring agent, and 1 to 1 part by weight of an inorganic pigment. It contains 20 parts by weight and 10 to 25 parts by weight (solid content) of a binder resin.
[0020]
The amount of the thermosensitive coloring layer coating solution applied to the surface of the sheet-shaped substrate 10 is determined so that the mark provided by the marking has a desired coloration density, sensitivity, and the like, and is, for example, ^{2 to} 12 g / m ² , preferably It may be ³ to 7 g / m ² .
[0021]
(3) Magnetic Recording Layer The sheet-like substrate 10 of the present invention may have a back surface (that is, a surface opposite to the surface having the thermosensitive coloring layer 20 or the developer layer 30), if desired, as illustrated in FIG. 1. (Surface) may have the magnetic recording layer 40. The magnetic recording layer contains a magnetic substance powder and a binder, and, if necessary, various additives such as a wetting agent, a dryer, and an anti-drying agent.
[0022]
The magnetic powder contained in the magnetic recording layer may be any of those commonly used in the art. For example, γ-Fe ₂ O ₃ , Fe ₃ O ₄ , Co-γ-Fe ₂ O ₃ and BaO. 6Fe ₂ O ₃ .
[0023]
As a suitable binder, a material having a good film-forming property such that the magnetic powder can be held in the layer without causing the magnetic powder to fall off or crack is preferable. Such binders include epoxy resins, alkyd resins, urethane resins, cellulose resins, vinyl chloride-vinyl acetate copolymers, phenolic resins, SBR latex, and the like.
[0024]
The magnetic recording layer, for example, the binder is dissolved or dispersed in ethanol, isopropyl alcohol, toluene, methyl ethyl ketone, ethyl acetate, finely disperse the magnetic powder there, if necessary, further mixed with various additives The prepared coating solution for the magnetic recording layer is applied to the back surface of the sheet-like base material by a conventional method such as a measurer, a gravure, an air knife, and a curtain coat in a dry coating weight range of 5.0 to 20.0 g / m ^2. Subsequently, the magnetic powder is formed by subjecting the magnetic powder to an orientation treatment by a commonly used method, followed by drying.
[0025]
The magnetic recording layer only needs to be capable of magnetically writing and reading information. For example, when the sheet-shaped base material of the present invention is a ticket, predetermined information (expiration date, boarding / alighting section, fare, etc.) is written on the magnetic recording layer by an automatic ticketing machine, and then this information is automatically collected. It is read magnetically by a billboard. In the magnetic recording layer, it is also possible to magnetically add new ticket information and the like as needed.
[0026]
The sheet-shaped substrate of the present invention may be, for example, one selected from a ticket, an admission ticket, a bond, a security, and a meal certificate. If the sheet-like base material 10 of the present invention is a ticket, that is, a ticket, an express ticket, a reserved seat ticket, an entrance ticket, or the like, the heat-sensitive coloring layer 10 or the magnetic recording layer 40 may be used at the time of ticketing by an automatic ticketing machine or At the time of automatic ticket collection by automatic ticket collection machines, desired information (date and time, use section, fee, etc.) is printed by a thermal printer incorporated in those machines.
[0027]
Marking tool The marking method of the present invention is achieved by applying a leuco dye to the developer layer of the sheet-like substrate of the present invention using a suitable marking tool.
FIG. 2 shows an example of the marking tool 200 of the present invention. The marking tool 200 of the present invention shown in FIG. 2 basically includes a handle portion 210 and a stamp 220 coupled to the handle portion. Here, the marking tool 200 shown in FIG. 2 shows a form of a stamper, but the present invention is not particularly limited to this form.
The handle portion 210 may be any material having a mechanical strength suitable for being held by a person and imprinting a stamp placed at the tip thereof on a sheet-like base material. Alternatively, it includes one manufactured by processing rubber or the like into a cylindrical shape, a rectangular shape, a spherical shape, or the like.
[0028]
As one mode of the stamp 220 coupled to the handle portion, as shown in FIG. 2, a porous medium 250 in which the leuco dye-containing ink liquid is pre-infiltrated, a leuco dye-containing ink liquid , Which includes a holder 225 for preventing leakage from the outside of the marking tool 200.
The porous medium 250 has on its end a stamped surface 255 for applying the leuco dye-containing ink liquid. The stamp surface 255 has a pattern of concavities and convexities corresponding to a desired mark. Such a porous medium 250 is capable of infiltrating a leuco dye-containing ink liquid in a sufficient amount necessary for at least one printing, and has sufficient strength and elasticity to apply the ink liquid to a sheet-like substrate. It may be manufactured from a material having: Examples of such materials include porous rubber, sponge or felt, and the like.
As shown in FIG. 2, the holder 225 for holding the porous medium 250 surrounds the entire porous medium 250 except for the stamped surface 255, and is made of, for example, a molded product made of a plastic material or rubber, such as aluminum or stainless steel. May be.
[0029]
Marking method The present invention is a marking method for a sheet-like substrate in which a colorless leuco dye is used to mark the developer layer of the sheet-like substrate having a color developer layer on at least a part of its surface. In the method of the present invention, the leuco dye applied to the color developer layer only needs to be one that develops color for the first time by the action of the color developer in the color developer layer, and is preferably 3,3-bis ( 4'-diethylaminophenyl) -6-diethylaminophthalide, 2-anilino-6- (cyclohexylmethylamino) -3-methylfluoran, 3-diethylamino-6-methyl-7-xylidinofluoran, 2- [3 , 6- (Bis-diethylamino) -9- (p-nitroanilino) xanthyl] benzoic acid lactam, 3-dimethylamino-5,6-benzofluoran, 2-chloro-6-diethylaminofluoran, 2-chloro -6-diethylamino-3-methylfluoran, 2-chloro-6-diethylaminofluoran and 2-dihendylamino-6-diethyl Selected from the group consisting of aminofluorans.
[0030]
According to the present invention, the same sheet-like substrate, that is, without changing the developer contained in the developer layer, by appropriately selecting the leuco dye applied to this sheet-like substrate , Marking of a desired coloring hue is possible.
[0031]
The leuco dye may be provided in a state after preparation or in a state encapsulated in microcapsules. In the latter case, by applying the leuco dye-containing microcapsules to the color developer layer and simultaneously applying heat or pressure, the microcapsules are broken, and the leuco dye contained in the microcapsules is deposited on the color developer layer. The leuco dye migrates and acts with a color developer to form a color.
[0032]
In the present invention, the leuco dye is, specifically, an organic solvent or an aqueous solvent usually used for preparing an ink, particularly preferably alkylnaphthalene, N-methyl-2-pyrrolidone, benzyl alcohol, tetrahydrofurfuryl ether, It may be treated as a leuco dye-containing ink liquid dissolved or dispersed at a concentration of 3 to 20%. The leuco dye-containing ink liquid may be used, if necessary, to promote the action of the developer in the color developer layer and the drying after application to the sheet-like substrate, or the desired color hue of the mark to be provided. May be further added to maintain a certain period of time.
[0033]
The method of the present invention will be described more specifically with reference to FIGS.
In one embodiment of the method of the present invention illustrated in FIG. 3, the marking surface 255 of the marking tool 200 in FIG. 2 is pressed in the direction of the arrow against the developer layer 30 formed on the entire surface of the sheet-like substrate 10 in FIG. Has been. As a result, the leuco dye-containing ink liquid is applied on the color developer layer 30 in accordance with the concavo-convex pattern of the stamp face 255 formed at the tip of the stamp 220. The leuco dye 215 applied to the color developer layer 30 develops a color when it comes into contact with the color developer 35 contained in the color developer layer 30. As a result, the mark 300 is recorded on the sheet-shaped substrate 10. For example, when the sheet-shaped base material 10 is a ticket such as an admission ticket, a ticket, or a coupon, the mark 300 formed on the sheet-shaped base material 10 is a ticket gate or a ticket inspection mark as illustrated in FIG. May be.
[0034]
In the marking tool 200 shown in FIG. 2, the porous medium 250 may be infiltrated with a sufficient amount of the leuco dye-containing ink liquid necessary for two or more times of printing. By using such a marking tool 200, marking on a plurality of sheet-like substrates becomes possible.
[0035]
Alternatively, the marking tool 200 may sequentially supply ink liquid to the stamp surface 255 using a stamp table in which the leuco dye-containing ink liquid has been infiltrated without previously infiltrating the porous medium 250 with the leuco dye-containing ink liquid. May be. FIG. 5 shows an example of a stamp table 500 suitably used in this case. In FIG. 5, a stamp base 500 has an ink storage unit 540 for infiltrating a leuco dye-containing ink liquid in a hollow portion of a holder part 550, which is a hollow molded product, and a number of fine holes through which the leuco dye-containing ink liquid passes. Are arranged in order, a mesh part 530 spaced at regular intervals, a control part 540 for temporarily storing the leuco dye-containing ink liquid passing through the mesh part 530, and a coating layer 550 covering the whole of the control part 540 are sequentially stored. ing. These parts and layers 510, 520, 530 and 540 are generally housed so as not to be detached from holder part 550.
[0036]
In the stamp stand 500, the ink storage unit 540 is pre-infiltrated with a sufficient amount of the leuco dye-containing ink liquid to supply the leuco dye-containing ink liquid to the marking tool 200 many times. It may be a thick felt or the like. The mesh unit 530 may be a perforated plastic plate, and serves to supply a constant amount of ink liquid from the ink storage unit 540 to the adjustment unit 540 at all times. The adjusting unit 540 is made of, for example, a combination of a nonwoven fabric and a cored felt, and provides the stamp base 500 with elasticity that can hold a constant amount of ink liquid as a whole and can withstand the pressing of the marking tool 200. . The outermost coating layer 550 is disposed for convenience in handling and storage stability.
[0037]
By using the stamp base 500 having such a structure, an appropriate amount of the leuco dye-containing ink liquid is always supplied to the entire stamp surface 255. Next, the stamping surface 255 is pressed against the color developer layer 30 of the sheet-like base material 10, so that a plurality of sheet-like base materials can be marked. In addition, since the leuco dye held on the stamp base 500 is colorless, there is an advantage that even if the cover layer 550 of the stamp base 500 is accidentally touched, there is no risk of contamination of hands and clothes by coloring.
[0038]
【The invention's effect】
According to the method of the present invention, since the colorless leuco dye is used, hands, clothes, a work table, and the like are not stained by coloring. Furthermore, even if the mark is touched immediately after application, the problem of coloring contamination on hands and clothes does not occur.
According to the method of the present invention, the composition of the color developer layer formed on at least a part of the surface of the sheet-like substrate and the characteristics of the sheet-like substrate (for example, thermosensitive recording or thermosensitive magnetic recording characteristics) are changed. Instead, by arbitrarily changing the type of leuco dye to be applied, a desired color hue such as red, black or blue can be marked on the sheet-like substrate.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing one embodiment of a sheet-like substrate of the present invention.
FIG. 2 is a specific example of the marking tool of the present invention.
FIG. 3 is a schematic cross-section showing a step of pressing the marking surface 255 of the marking tool 200 of FIG. 2 onto the developer layer 30 of the sheet-like substrate 10 of FIG. 1 according to the method of the present invention to perform marking. FIG.
FIG. 4 is a top view illustrating a specific example of a mark marked on a sheet-like substrate by the method of the present invention.
FIG. 5 is a schematic cross-sectional view illustrating a stamp base used to supply a leuco dye to the stamp surface of the marking tool of FIG. 2;
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 10 ... sheet-like base material, 20 ... thermosensitive coloring layer, 30 ... developer layer, 35 ... developer, 40 ... magnetic recording layer, 200 ... marking tool of this invention, 210 ... handle, 220 ... stamping board, Reference numeral 225: holder, 250: porous medium, 255: stamped surface, 300: mark, 500: stamp stand, 510: coating layer, 520: adjustment unit, 530: mesh unit, 540: ink storage unit, 550: holder unit

Claims (15)

A marking method for a sheet-like base material, wherein marking is performed with a colorless leuco dye on a developer layer of a sheet-like substrate having a developer layer on at least a part of its surface. The method for marking a sheet-like substrate according to claim 1, wherein the sheet-like substrate further comprises a thermosensitive coloring layer between the surface thereof and the color developer layer. 3. The method for marking a sheet-like substrate according to claim 1, wherein the sheet-like substrate further has a magnetic recording layer on a back surface thereof. The leuco dye is 3,3-bis (4′-diethylaminophenyl) -6-diethylaminophthalide, 2-anilino-6- (cyclohexylmethylamino) -3-methylfluoran, 3-diethylamino-6-methyl-7 -Xylidinofluoran, 2- [3,6- (bis-diethylamino) -9- (p-nitroanilino) xanthyl] benzoic acid lactam, 3-dimethylamino-5,6-benzofluoran, 2-chloro 2. The method of claim 1, wherein said compound is selected from the group consisting of -6-diethylaminofluoran, 2-chloro-6-diethylamino-3-methylfluoran, 2-chloro-6-diethylaminofluoran, and 2-dihendylamino-6-diethylaminofluoran. The method for marking a sheet-like substrate according to the above. The method according to claim 1, wherein the color developer contained in the color developer layer is a phenolic substance, a zinc salt of a salicylic acid derivative, or a mixture thereof. A sheet-like base material having a color developer layer on at least a part of its surface for use in the method for marking a sheet-like base material according to claim 1. The sheet-like substrate according to claim 6, wherein the sheet-like substrate further has a thermosensitive coloring layer between the surface thereof and the color developer layer. The sheet-like substrate according to claim 6 or 7, wherein the sheet-like substrate further has a magnetic recording layer on a back surface thereof. The sheet-like substrate according to claim 6, wherein the color developer contained in the color developer layer is a phenolic substance, a zinc salt of a salicylic acid derivative, or a mixture thereof. The sheet-like base material according to claim 6, wherein the base material is selected from a ticket, an admission ticket, a bond, a security, and a meal certificate. A marking tool including a handle portion and a stamp attached to the handle portion, the stamp plate having a stamp surface for applying a leuco dye on a surface opposite to a binding portion with the handle portion. The leuco dye is 3,3-bis (4′-diethylaminophenyl) -6-diethylaminophthalide, 2-anilino-6- (cyclohexylmethylamino) -3-methylfluoran, 3-diethylamino-6-methyl-7 -Xylidinofluoran, 2- [3,6- (bis-diethylamino) -9- (p-nitroanilino) xanthyl] benzoic acid lactam, 3-dimethylamino-5,6-benzofluoran, 2-chloro 12. The composition of claim 11, wherein the composition is selected from the group consisting of -6-diethylaminofluoran, 2-chloro-6-diethylamino-3-methylfluoran, 2-chloro-6-diethylaminofluoran, and 2-dihendylamino-6-diethylaminofluoran. Marking tool as described. The marking tool according to claim 11, which is a stamper. The marking tool according to claim 11, wherein the stamp surface has irregularities corresponding to a ticket gate or a ticket inspection mark. The method for marking a sheet-like substrate according to any one of claims 1 to 5, wherein the sheet-like substrate is a ticket, and the collection ticket or the ticket inspection mark is marked with a colorless leuco dye.

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