JPH03205183A - Method for preventing erasure of image of thermal recording type magnetic ticket paper - Google Patents

Abstract

PURPOSE:To improve the fading resistance and water resistance of magnetic ticket paper by providing a magnetic recording layer consisting of a ferromagnetic material and a binder to one surface of a support and providing a thermal color forming layer and a coating layer of a water-soluble resin treated with a water resistance imparting agent to the other surface thereof. CONSTITUTION:A ferromagnetic powder of gamma-Fe2O3 and a binder such as a vinyl chloride resin or a polyurethane resin are uniformly dispersed in a solvent such as toluene or methyl isobutyl ketone to prepare a coating solution for a magnetic recording layer while a coating solution for a thermal recording layer wherein a colorless or slightly light-colored leuco compound and an acidic substance allowing the leuco compound to form a color at the time of heating are compounded along with a binder and a coating solution for an aqueous coating layer compounded with a water soluble resin and a water resistance imparting agent are prepared. The coating solution for the magnetic recording layer is applied to one surface of a support and dried to provide the magnetic recording layer and the coating solution for the thermal recording layer is applied to the other surface of the support to be dried to form the thermal recording layer and, further, the coating solution for the aqueous coating layer is applied to be dried to form the thermal recording layer and the aqueous coating layer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for preventing image loss on heat-sensitive recording magnetic ticket paper useful for train tickets, coupon tickets, commuter passes, and the like.

[Prior art] In recent years, the number of users of train tickets, coupon tickets, commuter passes, etc. has been increasing for travel and commuting, especially in the Tokyo metropolitan area and Osaka area where urban transportation networks such as national railways, private railways, and subways are well-developed. The increase is remarkable.

For this reason, the number of people and time required to create tickets, such as train tickets, coupon tickets, and commuter passes, has increased dramatically, and for this reason, automatic vending of these tickets is being considered, and in some cases it is already in progress. It has been put into practical use.

Conventional printing and recording methods for tickets have been an electrophotographic method, an electrostatic recording method, a diazo copying method using a chemical reaction caused by two-part printing, a chelate method, and a printing method using ink.

However, when these conventional recording methods are adopted for vending machines, developing and fixing processes are required, which makes the printing mechanism of the vending machine complicated and large, and the machine body that houses it also becomes large and costly. They are expensive, and those using printing methods use ink, which has the disadvantage that half-dry ink sticks to your hands and stains your clothes.

Furthermore, vending machines generally use high-quality paper as a support for the tickets, which has the disadvantage that if the support gets wet, it will fold or wrinkle, causing the mechanical device to stop working.

Although there are many unresolved issues, the automatic sale of tickets is being promoted due to the advantages of automation, such as increased efficiency of personnel and shortened production time, and future improvements are expected. has been done.

[Problem to be solved by the invention] In view of the current situation, the inventors have been conducting research on the recording method of these tickets, and as a result, they have developed a thermal recording material that can be recorded simply by heating. If this method is adopted, the process can be simplified by eliminating the complicated developing and fixing processes required by the conventional method or the printing process that tends to get dirty, and what is more, it is possible to simplify the process by simply installing a heating element that can generate heat inside the vending machine. Since it is possible to record, the printing mechanism can be simplified and the machine itself can be made more compact, and costs can also be reduced.For example, even in the case of price revisions, corrective printing can be done simply by changing the electrical signal, making it possible to simplify the printing mechanism and machine. We developed a thermosensitive recording type magnetic ticket paper, focusing on the fact that it has many advantages such as not requiring any replacement of the device.

That is, the present invention employs a thermal recording method for tickets such as train tickets, coupon tickets, commuter passes, etc., and in particular, thermal recording is applied to the magnetic ticket paper of the tickets, which has a magnetic recording layer on one side. This is an application of the method.

Dye-based materials and metal chelate-based materials have been known as the thermosensitive color-forming components of thermal recording materials used in thermal recording methods, but dye-based materials, especially usually colorless or light-colored leuco bodies and acidic substances, are known. It is widely used because the color tone of the obtained record is clear and the storage stability is excellent. Therefore, in the present invention, a heat-sensitive recording type magnetic ticket paper was created using a dye 4-based material consisting of a leuco body and an acidic substance that reacts with the leuco body under heat to develop color, and the recording was clear at the beginning. However, when these tickets were placed in wallets, commuter pass holders, etc. normally used for these tickets and stored for 3 or 6 months, the records on the colored parts faded and became unreadable. This is a plasticizer, such as dioctyl phthalate (DOP), which is contained in the transparent resin film of a wallet or commuter pass that is in contact with the heat-sensitive coloring layer.
This is due to the penetration of dioctia adipate (DOA) into the heat-sensitive coloring layer.In order to improve this, color-forming properties are added to the heat-sensitive recording layer as disclosed in, for example, JP-A-53-19840 and JP-A-53-137155. Although an attempt was made to provide an organic resin coating layer that is soluble in a H organic solvent that does not substantially dissolve the components, it was not possible to prevent the colored portion from discoloring due to the action of the plasticizer described above.

[Means for Solving the Problems] Therefore, the present inventors provided a coating layer of a water-soluble resin in place of the above-mentioned organic solvent-soluble resin coating layer, and were able to obtain a considerable anti-fading effect. Ta. However, the discoloration resistance of such a water-soluble resin coating layer is sufficient when the heat-sensitive magnetic recording paper is handled in a dry place, but when it is handled in the rain or with wet hands, it loses moisture. If the coating layer is colored, the coating layer melts or peels off, making it impossible to prevent discoloration and resulting in unsatisfactory results.

As a result of further research, we found that adding a water-resistant agent to the aforementioned water-soluble resin coating layer solved the above-mentioned drawbacks at once, and produced a thermo-recordable magnetic ticket paper with excellent fade resistance and water resistance. It has been found that a method for preventing image decolorization can be obtained.

That is, in the present invention, a magnetic recording layer mainly composed of a ferromagnetic material and a binder is provided on one surface of a support, and a normally colorless or slightly light-colored leuco material is provided on the other surface of the support. , heat-printing a heat-sensitive recording magnetic ticket paper provided with a heat-sensitive color-forming layer containing as a color-forming component an acidic substance that reacts with the leuco substance to form a color when heated, and a coating layer made of a water-soluble resin; A method for preventing an image formed on a paper from disappearing due to a plasticizer, which comprises making a water-soluble resin covering the coloring layer amphoteric with a water-resistance agent. This is a method of preventing disappearance.

To further explain the heat-sensitive recording magnetic ticket paper according to the present invention, the magnetic recording layer is formed in the same manner as Koya's magnetic ticket paper, for example, using ferromagnetic powder of γ-Fe20x and vinyl chloride resin. , a polyurethane resin may be uniformly dispersed in a solvent such as toluene or methyl isobutyl ketone, then coated on a paper support and dried, or a white magnetic material laminate may be bonded.

The heat-sensitive recording layer is also formed according to conventional formulations, but the colorless or slightly pale leuco dyes used here include triphenylmethane, fluoran, phenothiazine, aurami, and spirobilane dyes. Examples include 3,3-bis(p-dimethylaminophenyl)6-dimethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)phthalide, and 3,3-bis(p-dimethylaminophenyl)phthalide. p-dimethylaconophenyl)6-diethylaminophthalide, 3.3-bis(p-dimethylaminophenyl)6-chlorophthalide, 3-(N-p-toly-N-ethylamino)6
-Methyl-7-(N-phinidylamino)fluorane, 3-diethylamino-B-methyl-7-anilinofluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-7-(3-fluoro methyl)phenylaminofluorane, penzoylleucomethylene blue 6゜-chloro8゜-methoxybenzoindolinobirilosbiran, 6゛-bromo8''-methoxybenzoindolinobilichospiran, 2-[3,8- Bis(diethylamino) -9 -(o
-chloroanilino)xanthyl], benzoic acid lactam, and the like.

In addition, examples of acidic substances that cause a coloring reaction with the leuco body and cause the leuco body to develop color include, for example, α-naphthol, β-naphthol, 4-t-butylphenol, 4-t-
Octylphenol, 4-phenylphenol, 2.2
-bis(p-hydroxyphenyl)broban (also known as bisphenol A), 2,2-bis(p-hydroxyphenyl)butane, 4,4'-cyclohexylidene diphenol, 2,2-bis(2,5- dibromo-4-hydroxyphenyl)broban, 4,4'-isobropylidenebis(2-t-butylphenol), 2,2'-methylenebis(4-chlorophenol), benzoic acid, salicylic acid,
Examples include tartaric acid and gallic acid.

The above-mentioned color-forming components are prepared as a heat-sensitive recording layer coating solution together with a binder in the conventional manner, and the solution is coated on the other side of a support having a magnetic recording layer on one side, and dried to form a heat-sensitive color-forming layer.

Examples of the binder include the following.

Water-soluble ones such as polyvinymel alcohol, methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, polyvinyvirolidone, polyacrylamide, polyacrylic acid, starch, gelatin, etc., or polystyrene, vinyl chloride-vinyl acetate copolymer , aqueous emulsions such as polybutyl methacrylate, etc.

Note that additives such as fillers and lubricants that are commonly used in the heat-sensitive coloring layer may be used.

A coating layer made of a water-soluble resin and a water-resistant agent is further formed on the above heat-sensitive coloring layer, and the water-soluble resin constituting this layer is generally known, such as polyvinyl alcohol, methyl cellulose, ethyl cellulose, carboxymethyl cellulose. , polyvinylpyrrolidone, starch,
Examples include gelatin, methoxycellulose, polyacrylamide, and the like.

In addition, as water resistance agents, formalin, glyoxal,
Examples include chromium alum, melamine, melamine formalin, polyamide resin, and polyamide/ebichlorohydrin resin, which are formed into an aqueous coating solution and then applied onto the heat-sensitive coloring layer and dried.

Examples are shown below.

Example 1 The following components were dispersed in a ball mill for 48 hours to form a magnetic recording layer, and coated on commercially available high-quality paper (basis weight 157 g/m2) to a dry coating weight of 40 g/m2, dried to form a magnetic recording layer. Established.

Magnetic recording layer coating liquid Magnetic powder (7-Fe203) 100 parts by weight Lecithin 2 parts by weight Vinyl chloride resin
15 parts by weight polyurethane resin 10
Parts by weight Toluene 120 parts Methyl isobutyl ketone (M.I.B.K.) 100 parts by weight Next, as a heat-sensitive coloring layer, liquids A and B having the following composition were separately dispersed for 12 hours using an attritor. The liquids were thoroughly mixed to obtain a heat-sensitive coloring layer coating liquid.

Part A 3-diethylamino-6-methyl-7-anilinofluorane 15 parts by weight Calcium carbonate 1.0 parts by weight 20% starch oxide aqueous solution 5.0 parts by weight Water 4
2.5 parts by weight Liquid B Bisphenol A 6.0 parts by weight Stearamide 1.0 parts by weight 20% polyvinyl alcohol aqueous solution 5.0 parts by weight Water 38.0 parts by weight Coating amount of the above heat-sensitive coloring layer coating liquid when dry A heat-sensitive coloring layer was provided by coating and drying the coating on the opposite side of the support to the side on which the magnetic recording layer was provided so that the coating weight was 8 g/m 2 .

Next, a coating liquid of the following composition was coated on the above heat-sensitive coloring layer so that the dry coating amount was 2 g/m', and dried to form a coating layer to produce a heat-sensitive recording type magnetic ticket paper of the present invention. did.

Coating layer coating liquid Polyvinyl alcohol 5.0 parts by weight Melamine resin 30% aqueous solution 3.0 parts by weight Water
92.0 parts by weight Example 2 A thermosensitive recording magnetic ticket paper of the present invention was prepared in the same manner as in Example 1 except that glyoxal was used instead of the melamine resin in Example 1.

Example 3 A heat-sensitive recording type magnetic ticket paper of the present invention was produced in the same manner as in Example 1 except that polyamide hydroxide resin was used instead of the melamine resin in Example 1.

Comparative Example A thermosensitive recording type magnetic ticket paper was prepared in the same manner as in Example except that the coating layer was not provided, and this was designated as Comparative Product 1.

Furthermore, a heat-sensitive recording type magnetic ticket paper was prepared in the same manner as in the example except that the melamine resin in the coating liquid of the example was removed, and this was designated as comparative product 2.

The five types obtained above were surface-treated using a super calender, and then measured using a thermal inclinometer (manufactured by Toyo Seiki) at a temperature of 150°C and a pressure of 1.
kg/cm2. After printing with a contact time of 1 sec and measuring the color density at the Macbeth concentration, we tested food containing 5 to 10 times more plasticizer than a regular soft commuter pass as a discoloration resistance test. Bring each wrap into contact with the coloring surface at a pressure of 10 g/CI2, a temperature of 40°C, and a contact time of 1 hour (
This condition corresponds to holding the sample in a soft container for 10 months), and the decrease in concentration due to the plasticizer was measured.

Next, as a water resistance test, each sample immediately after the above color development was
The concentration drop after immersion in water at 0° C. for 1 hour was tested. The results are shown in Table 1.

Table 1 This is a heat-sensitive recording type magnetic ticket paper with excellent durability and water resistance.

Claims (1)

[Claims] A magnetic recording layer mainly composed of a ferromagnetic material and a binder is provided on one side of the support, and a normally colorless or slightly light-colored leuco body is provided on the other side of the support, and the leuco body and the heat An image formed on the thermosensitive coloring layer is printed by heating a thermosensitive recording magnetic ticket paper provided with a thermosensitive coloring layer containing as a coloring component an acidic substance that reacts with a water-soluble resin and a coating layer made of a water-soluble resin. 1. A method for preventing image disappearance of a heat-sensitive recording magnetic ticket paper, which method comprises making a water-soluble resin coating the color forming layer water-resistant using a water-resistant agent.