JPH025195B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a heat-sensitive magnetic ticket sheet that can record in multiple colors and is suitable for commuter passes, coupon tickets, various types of train tickets, and the like. In recent years, automatic ticket vending machines and automatic ticket gates using magnetic ticket sheets have become extremely popular in areas with well-developed urban transportation networks, such as Tokyo, Osaka, and Saba. The purpose is to rationalize and simplify business operations, and for this purpose, it can be said that the thermal recording method is currently the best recording method on the other side of the magnetic recording layer. This is because the printing method uses chemical or physical changes in substances due to heating to record images.
It does not require development and fixing, nor does it require replenishment of printing ink. That is, it is possible to downsize and simplify the machine, speed up recording, and there is no fear of ink staining hands or clothes or ink fading. However, commuter passes, coupon tickets, various types of tickets, etc. have a plurality of entries, and multicolor records that are easy to read for users and station operators are required. Conventionally, there are many examples of multicolor thermal paper. Generally, it is possible to apply two or three heat-sensitive layers having different coloring temperatures and coloring hues. For example, a phenolic substance or an organic acid and two or more dye precursors that develop color with the phenolic substance or organic acid are used, and a single color is obtained by heating at a low temperature by utilizing the difference in melting point between the layers by laminating them.
A so-called mixed color system that produces different hues by mixing colors at high temperatures. (Japanese Patent Publication No. 15540-15540
In addition, a phenolic substance or an organic acid and two or more dye precursors that develop color with the phenolic substance or organic acid are used, and the phenolic substance or organic acid is added to the laminated heat-sensitive layer or the adjacent layer. By containing an organic base that melts at a higher temperature, we take advantage of the fact that once a color develops when heated, it fades or disappears at a temperature higher than the melting temperature of the organic base, and by reducing the degree of color mixing, we can create a different color that is close to a single color. A so-called decolorizing type that develops the hue. (Unexamined Japanese Patent Publication No. 1982-8251, Unexamined Japanese Patent Publication No. 1982-8251)
-139290, JP-A-55-161688) Furthermore, by coexisting in such a system a dye precursor that can develop a different color with the organic base,
The so-called simultaneous decoloring and coloring system (Special Publication Publication No. 51), which simultaneously develops different hues of a single color,
-37542). However, in the case of mixed color systems, the single color obtained by low-temperature color development has the disadvantage that the hue is limited to a much lighter hue than the mixed color obtained by high-temperature color development. i.e. red (low temperature)
- Black (high temperature), blue (low temperature) - black (high temperature), yellow (low temperature) - black (high temperature), etc., and a large amount of heat is required to print the black color that occupies the majority of the recorded area, making it difficult to save energy. This is not practical as it goes against speed. In addition, color separation is difficult, and the difference in melting point between layers must be sufficiently widened, resulting in a decrease in color development speed and a large amount of heat, which causes trouble during recording. In addition, in the case of color erasing systems, a basic substance is simply used as a color erasing agent, and when coloring at high temperatures, coloring is again done with phenolic substances or organic acids in the same way as low temperature coloring, resulting in high costs and interlayer formation. At present, there are many problems such as difficulty in balancing the mixture and a large amount of heat required. Therefore, the color erasing and color development simultaneous system was invented to solve the above two problems, and high temperature color development progresses quickly using a basic substance that erases the low temperature color development, making it extremely efficient and Vivid multicolors are obtained, of course black (low temperature) - red (high temperature), blue (low temperature)
- Red (high temperature), black (low temperature) - Yellow (high temperature), etc. The advantage of being able to print frequently recorded characters at low temperatures is also suitable for energy saving and speeding up of recording, and is unique to thermal pens. As we moved from an era when colors could not be realized to an era when thermal printers and thermal facsimiles were desired to have multiple colors, it has come to be said to be the system that can best meet expectations. However, the qualities required for heat-sensitive magnetic ticket sheets include: (1) the coating layer does not peel off and the recorded area remains clear even when the sheet gets wet from water or rain; (2)
Even if your hands are covered with hand cream or hair styling oil, or if you come in contact with a PVC commuter pass or wallet containing a large amount of plasticizer for a long period of time (1, 3, or 6 months), the recording section may fade or disappear. shall not become difficult or impossible to decipher. There are two points to mention. In order to meet the requirement (1), it is possible to improve the effect to some extent by adding a water-resistant agent or water repellent to the water-soluble polymer compound used as a binder in the heat-sensitive coating layer, but the pigment contained in the coating layer It is impossible to form a complete film-like coating due to the influence of agents, dye precursors, etc.Also, increasing the amount of binder may be considered, but this results in a decrease in color development sensitivity. Therefore, as a result of investigation, we found that it is possible to provide a film-like coating (overcoat layer) containing a water-resistant agent and a water-repellent agent to impart water resistance to the surface of the heat-sensitive layer.
It turned out to be the most effective. This method also satisfies requirement (2). That is, it has been proposed that such a phenomenon will not occur if a plasticizer such as dibutyl phthalate or dioctyl phthalate forms a film for the purpose of preventing penetration into the heat-sensitive layer. (Unexamined Japanese Patent Publication No. 128347, No. 128347,
-3549) The present inventors also developed an overcoat agent with chemical resistance, and
An application has been filed in Japanese Patent Application No. 1981-981. However, when printing or stamping different hues on monochromatic thermal paper with an overcoat layer, the ink sets poorly because there is almost no penetration into the paper surface, resulting in stains on hands and clothing, and poor legibility. The drawback was that it became impossible. As a result of investigation, it has been found that when an overcoat is provided on a heat-sensitive recording sheet capable of multicolor printing, thermal printing and stamping can be easily and clearly performed in multiple colors. Based on these backgrounds, the inventors of the present invention have conducted intensive studies on a heat-sensitive magnetic ticket sheet that can perform multicolor recording without staining printing marks, with the aim of satisfying the requirements (1) and (2). As a result, we have arrived at the present invention. That is, the present invention provides a support provided with a magnetic recording layer containing a ferromagnetic material as a main component, a multicolor coloring heat-sensitive layer of simultaneous decoloring and coloring system on the other side, and alginate alone or alginic acid on the surface thereof. To provide a heat-sensitive magnetic ticket sheet capable of multicolor recording, characterized in that it has a film-like coating layer containing salt as an essential component and one or more other water-soluble polymer compounds in combination. be. The main components used in the present invention will be explained in detail below, but the present invention is not limited thereto unless it exceeds the gist of the present invention. Note that the support may be paper, synthetic paper, synthetic resin film, or the like. Table 1 shows typical examples of dye precursors that develop color with phenolic substances or organic acids. Table 1 (1) Crystal violet lactone (2) 3-indolino-3-p-dimethylaminophenyl-6-dimethylaminophthalide (3) 3-diethylamino-7-chlorofluorane (4) 3-diethylamino -7-Cyclohexylaminofluorane (5) 3-diethylamino-5-methyl-7-t-
Butylfluorane (6) 3-diethylamino-6-methyl-7-anilinofluorane (7) 3-diethylamino-6-methyl-7-p-
Butylanilinofluorane (8) 2-(N-phenyl-N-ethyl)aminofluorane (9) 3-diethylamino-7-dibenzylaminofluorane (10) 3-cyclohexylamino-6-chlorofluorane ( 11) 3-diethylamino-6-methyl-7-xylidinofluorane (12) 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluoran (13) 3-pyrrolidino-6-methyl- 7-anilinofluorane (14) 3-pyrrolidino-7-cyclohexylaminofluorane (15) 3-piperidino-6-methyl-7-toluidinofluorane (16) 3-pyrrolidino-6-methyl-7- (p-
Toluidino) fluorane (17) 3-piperidino-6-methyl-7-anilinofluorane (18) 3-N-methylcyclohexylamino-6
-Methyl-7-anilinofluorane (19) 3-diethylamino-7-(m-trifluoromethylanilino)fluorane (20) 3-diethylamino-6-methyl-7-chlorofluorane In addition, in the present invention Dye precursors that develop color with organic bases include PH indicators that develop color or change color in alkalinity, fluorescein derivatives, phenolphthalein derivatives, and oxidation or reduction in a broad sense due to a change in pH value to the alkaline side. Substances such as ninhydrin derivatives that cause discoloration are used. Typical examples are shown in Table-2. Next, Table 3 shows a representative list of phenolic substances or organic acids (color developers) used in the present invention. Table 3 (1) 4.4′-isopropylidene diphenol (2) 4.4′-isopropylidene bis(2-chlorophenol) (3) 4.4′-isopropylidene bis(2-tertiary-butylphenol) (4) 4.4′ -Secondary-butylidene diphenol (5) 4.4'-(1-methyl-n-hexylidene) diphenol (6) 4-phenylphenol (7) 4-hydroxydiphenoxide (8) Methyl-4-hydroxybenzoate (9) ) Phenyl-4-hydroxybenzoate (10) 4-hydroxyacetophenone (11) Salicylic acid anilide (12) 4.4'-Cyclohexylidene diphenol (13) 4.4'-Cyclohexylidene bis(2-methylphenol) (14) 4.4′-benzylidene diphenol (15) 4.4′-thiobis(6-tert-butyl-3-methylphenol) (16) 4.4′-isopropylidene bis(2-methylphenol) (17) 4.4′-ethylene bis(2 -Methylphenol) (18) 4.4'-Cyclohexylidenebis(2-isopropylphenol) (19) 2.2'-Dihydroxydiphenyl(20) 2.2'-Methylenebis(4-chlorophenol) (21) 2.2'-Methylenebis( 4-methyl-6-t
-butylphenol) (22) 1.1'-bis(4-hydroxyphenyl)-
Cyclohexane (23) 2.2-bis(4'-hydroxyphenyl)propane (24) Novolak phenolic resin (25) Halogenated novolak phenolic resin (26) α-naphthol (27) β-naphthol (28) 3.5-di -t-Butylsalicylic acid (29) 3.5-di-α-methylbenzylsalicylic acid (30) 3-methyl-5-t-butylsalicylic acid (31) Phthalic acid monoanilide paraethoxybenzoic acid (32) Parahydroxybenzoic acid benzyl ester Furthermore, if the organic base used in the present invention has a too low melting point or a very high water solubility, there is a high possibility that the heat-sensitive layer using it will change color during storage. However, if the basicity is too low, decoloring or coloring of the heat-sensitive layer is difficult to occur, which is not preferred in practice. Among the organic bases used in the present invention, guanidine derivatives are particularly excellent in practical use, and specific examples are listed in Table 4A, but these are not intended to limit the present invention. In the table

[Formula] represents a cyclohexyl group. Organic bases that can be used in the present invention other than the above-mentioned guanidine derivatives are shown in Table 4B, but this is not intended to limit the present invention. Table 4B (49) Phenylthiourea (50) Hexadecylamine (51) Tribenzylamine (52) N, N, N', N'-Tetrabenzyl-ethylenediamine (53) N, N, N', N'- Tetrabenzyl-hexamethylene diamine (54) Decamethylene diamine (55) Tricyclohexylamine (56) N,N'-dibenzylpiperazine (57) Dioctadecylamine (58) 2-Aminobenzoxazole (59) 2-Aminobenzo Thiazole (60) 2-Aminobenzimidazole (61) Quinine (62) Cyclohexyldibenzylamine (63) Octadecyldibenzylamine The thermal recording paper of the present invention can be obtained by the following method. That is, a phenolic substance or an organic acid, a dye precursor that develops color with the phenolic substance or organic acid, an organic base, and a dye precursor that develops a color with the organic base are separately or simultaneously pulverized into fine particles using a pulverizer. A coating liquid is prepared by grinding, dispersing, mixing with a binder, pigment, etc. in an appropriate combination, and adding various additives as necessary. Examples of the binder include water-soluble binders such as starch, hydroxyethylcellulose, methylcellulose, polyvinyl alcohol, styrene-maleic anhydride copolymer, styrene-butadiene copolymer, polyacrylamide, carboxymethylcellulose, gum arabic, and casein. , styrene-butadiene latex, and the like can be used. Examples of pigments include aluminum hydroxide, heavy and light calcium carbonate, zinc oxide, titanium oxide, barium sulfate, silica gel, activated clay, talc, clay, satin white, kaolinite, calcined kaolinite, diatomaceous earth, and synthetic kaolinite. , polyolefin granules, polystyrene granules, urea
Examples include formalin resin particles. Next, regarding the material forming the film-like coating layer in the present invention, water-soluble polymer compounds are generally preferred, among which alginate alone or alginate as essential, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose. It is preferable to use one or more polymer compounds selected from polyvinyl alcohol. (Japanese Patent Application No. 56-152455) Furthermore, water resistance can be achieved by using one or more of the following:
It is preferable to use one that imparts light resistance and prevents the formation of pinholes. In the present invention, the thickness of the overcoat layer as a dry film is 0.5 μm or more, preferably 3 to 3 μm.
A thickness of 12 μm is desirable from the viewpoint of heat-sensitive properties and chemical resistance. If the film thickness is thinner than 0.5 μm, it will not have enough heat-sensitive properties to prevent dust and staining, fingerprint stains, and chemical resistance. However, it tends to cause a decrease in color development sensitivity. Next, the present invention will be specifically explained using the drawings. The figure is a cross-sectional view of the heat-sensitive magnetic ticket sheet of the present invention, in which a support 1 provided with a magnetic recording layer containing a ferromagnetic material as a main component has Tables 4-A and 4-B on the other side. Layer 2 which has the function of a decolorizing agent and a coloring agent when heated at high temperature, the main component being the organic base shown below.
and the phenolic substances or organic acids shown in Table 3, the dye precursors that can develop color when heated with the phenolic substances or organic acids shown in Table 1, and the organic bases shown in Tables 4-A and 4-B. The color-forming layer 3 is sequentially laminated with a color-forming layer 3 which is composed mainly of a dye precursor capable of coloring when heated, and which develops a single color when heated at a low temperature, and develops a different hue when heated at a high temperature. On top of these thermosensitive coloring layers, alginate alone,
Alternatively, a film-like coating layer 4 is provided in which alginate is an essential component and one or more other water-soluble polymer compounds are used in combination. To explain the support in more detail,
Any material such as paper, synthetic paper, or synthetic resin film can be used, and the coated magnetic recording layer is similar to the magnetic ticket sheets currently in use, such as gamma-ferric oxide powder. The body is thoroughly dispersed in a vehicle consisting of a binder such as vinyl chloride-vinyl acetate copolymer and an organic solvent using a ball mill, roller mill, attritor, etc., and additives such as plasticizers, lubricants, and antistatic agents are added as appropriate. In addition, coating liquids and water-based magnetic coating liquids are also used, but the present invention is not limited to any of them. Next, examples of the present invention will be given and described in detail. Example A Liquid 3-diethylamino-6-methyl-7-anilinofluorane...200g Maron MS-25 (manufactured by Daido Kogyo Co., Ltd., styrene)
25 of sodium salt of maleic anhydride copolymer
% aqueous solution)...24g Water...276g Liquid B 4,4'-isopropylidene diphenol
...200g Maron MS-25 ...24g Water ...276g Solution C 2.4.5.7-tetrabromofluorescein (compound (50) in Table 2) ...125g 5% hydroxyethyl cellulose aqueous solution
...125g Water ...373g D Solution 1.3-dicyclohexyl-2-phenylguanidine (compound (7) in Table 4A) ...150g 5% hydroxyethyl cellulose aqueous solution
...150g Water ...200g The above liquids A, B, C, and D were separately ground and dispersed in a ball mill for 48 hours. A heat-sensitive coating liquid was prepared using the liquids A, B, C, and D thus dispersed as follows. Undercoat layer coating liquid: D liquid...10g 10% hydroxyethylcellulose aqueous solution
......12g Water...8g The coating liquid prepared as above was applied to base paper with a basis weight of 50g/ ^m2 so that the coating weight after drying was 3.6g/ ^m2 ,
The undercoated paper was prepared by drying at 60°C for 1 minute. Top coat coating liquid: Ancilex (manufactured by Engelhard KK, calcined kaolin)...20g Solution A...4g Solution B...15g Solution C...6g 20% by weight stearamide emulsion (manufactured by Chukyo Yushi Co., Ltd., Hydrin M-7)
...15g Maron MS-25 ...22g Water ...55g The coating solution prepared as above was applied onto the undercoat paper so that the coating amount after drying was 7.4g/ ^m2 , and the temperature was 60°C.
After drying for 1 minute, a multicolor thermal paper with simultaneous color erasing and color development was produced. The multicolor thermal paper developed a color with a sharp contrast of black when heated at a low temperature and red when heated at a high temperature. The overcoat layer is a mixture of sodium alginate/carboxymethyl cellulose = 1/1 (weight ratio) and an epoxy crosslinking agent (trade name: Epiol G).
-100, manufactured by NOF Corporation) was added at a weight ratio of 0.1, and it was coated on the multicolor thermal paper so that the thickness of the film after drying was 4 μm, and after drying, it was supercalendered to produce the desired multicolor recording. A heat-sensitive magnetic recording sheet was obtained. The thus produced thermosensitive magnetic recording sheet capable of multicolor recording obtained clear black and red images, satisfied water resistance and plasticizer resistance, and was free from cassette kinging during printing.

[Brief explanation of drawings]

The figure is a sectional view of a heat-sensitive magnetic ticket sheet capable of multicolor recording according to the present invention. 1 in the figure is paper with a magnetic recording layer (shaded area);
Supports made of synthetic paper and synthetic resin film, 2 and 3 are examples of combinations of multicolor thermosensitive recording layers, 4
indicates a film-like coating layer. In addition, ○ marks are phenolic substances or organic acids, ◎ marks are dye precursors that develop color when heated due to the phenolic substance or organic acid, × marks are organic bases, and 〓 marks are dyes that develop color when heated due to the organic bases. The precursors are shown respectively.

Claims (1)

[Claims] 1. A support provided with a magnetic recording layer containing a ferromagnetic material as a main component, on the other side, a phenolic substance or an organic acid, a dye precursor capable of developing color when heated by the phenolic substance or organic acid, an organic base, and In combination with a dye precursor that can develop color when heated by the organic base, alginate alone or alginate as an essential component and other water-soluble polymer compounds are applied to the surface of a multicolor heat-sensitive layer formed as a single layer or a multilayer. A heat-sensitive magnetic ticket sheet capable of multicolor recording, characterized in that it is provided with a film-like coating layer using one type or a combination of two or more types.