JPS6237750Y2 - - Google Patents

Description

[Detailed Description of the Invention] The present invention relates to a new type of magnetic soft note that can be applied to automatic ticket issuing systems, and more specifically, it has a magnetic recording layer on the back side and a heat-sensitive recording layer that can be fixed with light on the front side. This invention relates to magnetic soft tickets for automatic ticket issuing machines.

In recent years, automatic ticket issuing machines have been introduced to save labor in railway operations. The tickets issued by this automatic ticket issuing machine are printed on the front side using a chelate method, a smear ink method, a thermal method, etc., and a magnetic layer is provided on the back side, allowing both visible and magnetic recording to be used at automatic ticket gates. Types adapted to this are also beginning to be used. These automatic ticket issuance and automatic ticket gate type tickets are actually useful in saving labor in railway operations, but they are still far from satisfactory.
For example, those using electrostatic recording methods have problems such as high manufacturing costs and large ticket issuing machines. There are also examples of using heat-developable photosensitive materials such as silver behenate, but these are still far from satisfactory in terms of cost, stability, ticket issuing speed, etc.

On the other hand, among the surface printing recording methods, the thermal recording method is
Because printing costs are low and maintenance is simple,
It is expected that they will become the mainstream of ticket issuing machines in the future. However, printed records using the thermal method are
Because secondary coloring occurs after issuance due to the instability of the heat-sensitive recording layer, apart from short-distance tickets that are discarded within a relatively short period of time after issuance, they may be used repeatedly or over a relatively long period of time. used,
It was considered unsuitable for medium- and long-distance tickets, coupon tickets, commuter passes, etc. In addition to secondary color development, if the physical durability of the heat-sensitive recording layer is poor, there is a problem in that the durability of printing is reduced. However, since the magnetic recording on the back side required for automatic ticket gates is durable, the durability of the front side printing is insufficient, which limits its use for long-term tickets. is extremely inconvenient.

Therefore, if the surface printing of magnetic soft notes is fixed by some means after thermal recording, it will be possible to improve the secondary color development, and if more durable printing can be obtained, magnetic soft notes can be issued using thermal ticket issuing systems. This makes it possible to take full advantage of the advantages of thermal recording.

The present inventors have previously proposed its use as a light- and heat-sensitive recording material (for example, US Patent No.
Specification No. 2217189, Japanese Patent Publication No. 45-40152, Japanese Patent Publication No. 1973
5582, JP-A No. 51-43926, etc.), we have noticed that there is a system consisting of a combination of diazosulfonate and a coupling agent. The characteristics of these systems are that they themselves have low thermal sensitivity and the thermal energy provided by the thermal head is limited, making them unsuitable as ordinary thermal recording materials. If proper sensitization is carried out, the energy required for thermal recording can be easily applied with a normal thermal head, and after the above combination system is thermally recorded, optical fixing is possible by irradiating the entire surface with light of a decomposed wavelength. be. That is, a diazosulfonate represented by the general formula R-N=N- _SO3M (where R is a substituted or unsubstituted aryl group and M is an alkali metal) is treated with activating light (400-550 nm) in the presence of a coupling agent. ), polarization occurs between the -N-SO ₃ - bonds, making it easier for a coupling reaction to occur, and while an azo dye is formed with less thermal energy, it has a shorter wavelength and more energy. It is thought that when diazosulfonate is irradiated with high fixing light (300 to 450 nm), it generates _N2 and decomposes, and no longer has the ability to form an azo dye. Further, the azo dye formed in the heat-sensitive recording process is not decomposed even when irradiated with fixing light.

Therefore, such a combination system of diazosulfonate and a coupling agent has excellent storage stability before photoactivation, and can also prevent secondary coloring after thermal recording by using photofixing. However, there are many problems in directly using such a heat-sensitive recording material system in the surface printing layer of a magnetic soft ticket capable of automatic ticket issuing and automatic ticket gates as described above. That is, the surface printing layer is repeatedly subjected to a fairly strong surface sliding force due to the sliding movement of a thermal head for automatic ticket issuing or the sliding movement of a magnetic reader for automatic ticket gates. For this reason, the conventional heat-sensitive recording layer, which is formed by applying a solution of diazosulfonate and a coupling agent to the surface of a thermoplastic resin layer and forming it by penetration, cannot withstand such repeated sliding forces. It is something. In addition, the printed surface may become soiled due to contact with alcohol or other chemicals after ticket issuance.
Or records may be lost. However, as a result of further research by the present inventors, it was found that in a homogeneous three-component system of diazosulfonate, coupling agent, and binder resin, the binder resin is not substantially cured by activating light (400 to 550 nm), but is cured by fixing light (300 nm). It has been found that by using a photocurable resin that cures at wavelengths of up to 450 nm), a recording layer with a good balance of durability and heat-sensitive recording properties can be obtained.
In other words, the heat-sensitive recording layer is not yet hardened during thermal recording, so molecular movement of the diazosulfonate and coupling agent molecules necessary for color development easily occurs, but since it is hardened by irradiation with fixing light, mechanical movement Strength and chemical resistance are dramatically improved. Furthermore, since the molecular movement of the color-forming molecules is also suppressed by curing, the fixing effect of the recording and, therefore, the durability are further improved, together with the photodecomposition of the diazosulfonate.

The heat-printable magnetic soft note of the present invention is based on this knowledge, and more specifically, a magnetic recording layer is provided on at least a part of the back side of the paper support, and a diazo-based note is provided on at least a part of the surface of the paper support. sulfonate,
It is characterized by being provided with a heat-sensitive recording layer that contains a coupling agent and a photocurable resin and is capable of photoactivation, thermal recording, and photofixing.

EMBODIMENT OF THE INVENTION Hereinafter, the structure and function of the magnetic soft note of the present invention will be explained in more detail with reference to the drawings.

In its most basic form, the magnetic soft note of the present invention, as shown in FIG. It becomes. magnetic recording layer 2
The heat-sensitive recording layer 3 does not need to be provided on the entire surface of the support 1, and may be provided only on required parts.

As the support 1, any material that is generally called paper and has printability and flexibility can be used, and paper made of vegetable fibers, especially coated paper and art paper, are good, but it is not resistant to heat-sensitive recording. Synthetic paper can also be used as long as it has sufficient heat resistance.

The magnetic recording layer 2 is not special, and is formed by a conventional method such as dispersing magnetic powder and a binder in a suitable solvent and applying it by roll coating or the like.

The photofixable heat-sensitive recording layer 3 of the present invention is prepared by applying a heat-sensitive recording material composition containing diazosulfonate, a coupling agent, a binder made of a photocurable resin, and a suitable solvent by a method such as roll coating or gravure coating. For example, 0.5-3g/
m ² (dry weight).

Generally, the diazosulfonate has the general formula R
An alkali metal salt of an aromatic diazosulfonic acid represented by -N=N-SO ₃ M (wherein R is a substituted or unsubstituted aryl group and M is an alkali metal) is used, and as a coupling agent, for example, resorcinol is used. , phloroglucin, catechol, pyrazolone, naphthoic acid, or derivatives thereof. As mentioned above, the combination of these diazosulfonates and coupling agents has excellent storage stability and correspondingly low thermal sensitivity, but the sensitivity to heat from the thermal head can be maintained high by photoactivation. As the binder, photocurable resins such as cinnamate esters such as polyvinyl cinnamate, azide photopolymers such as polyvinyl-p-azidobenzoate, and other diazo photopolymers are preferably used.

The thermal softening start temperature of photocurable resin is 80 to 200℃.
It is preferable that it is in the range of . Thermal softening start temperature is
If the temperature is below 80℃, the thermal head will momentarily
Since the temperature is between 200 and 350°C, the binder and coloring agent in the recording layer are likely to fuse together, causing smearing of prints and scratches. Also, if printing is performed for a long period of time, printing may stop due to printing residue. Furthermore, if the thermal softening start temperature exceeds 200°C, the molecular motion of the color-forming molecules cannot easily occur with only the amount of heat given from the thermal head, and the color-forming ability decreases. Depending on the type of photocurable resin, this thermal softening start temperature may exceed 200°C. In such cases, thermoplastic resins such as acrylic resins such as polymethacrylic acid esters, cellulose derivative resins such as nitrocellulose, etc., are used in an amount of, for example, 50% by weight based on the photocurable resin.
(based on the total amount) and preferably adjust the thermal softening start temperature.

If necessary, the heat-sensitive recording material composition may further contain, for example, 0.01 to 1 part by weight of the binder resin.
0.5 parts by weight of lubricant and/or mold release agent may be included. This reduces the thermal head and friction coefficient of the heat-sensitive recording layer, and prevents deterioration of printing quality due to adhesion of printing residue even after printing many times.

An example of the heat-sensitive recording material composition is as follows. All "parts" mean "parts by weight."

Γ Diazosulfonate 1 part Sodium 4-(4'-tolylmercapto)-2,5-diethoxybenzenesulfonate Γ Coupler 1.5 parts 2-hydroxy-3-naphthoic acid
(Generally 0.3 to 5 parts) Γ Solvent 7.5 parts Methyl cellosolve (5 to 15 parts) Γ Binder 2.5 parts Polyvinyl cinnamate ester (Tokyo Ohka)
(1 to 10 parts) Γ Solvent 17 parts Methyl ethyl ketone (5 to 30 parts) Γ Solvent 3.5 parts Toluene (1 to 10 parts) Γ Lubricant 0.2 parts Polyethylene wax Γ Mold release agent 0.1 part Teflon powder Also polyvinyl silica as a binder By replacing a portion of the acid ester, for example 0.5 part by weight, with thermoplastic polymethyl acrylate, the temperature at which thermal softening begins can be adjusted.

As mentioned above, such a liquid composition is applied onto the support 1 using, for example, a roll coater,
After drying, a heat-sensitive recording layer 3 is obtained.

In the heat-sensitive recording layer 3 of the obtained magnetic soft note of the present invention,
After activation by irradiation with light having a wavelength of 400 to 550 nm (0.1 to 5 joules/cm ² ), necessary information (e.g. departure station, destination station, validity period, name, age, Gender, etc.) are printed and recorded, and then irradiated with light having a wavelength of 300 to 450 nm (5 to 15 Joules/cm ² ), which is shorter than the activation light described above, to optically fix the information, and the necessary information is also recorded on the magnetic layer. Tickets will be issued after entering.

In the above, an embodiment of the most basic configuration of the magnetic soft note of the present invention has been described. However, it will be apparent to those skilled in the art that different embodiments of magnetic soft notes may be obtained within the scope of the present invention. For example, in order to improve the adhesion between the support 1 and the heat-sensitive recording layer 3 or the magnetic recording layer 2, the surface of the support 1 may be subjected to a surface treatment such as roughening or corona discharge treatment, or a primer layer may be provided. It is preferable to provide a thermosensitive recording layer 3 or a magnetic recording layer 2. By improving the adhesion between the heat-sensitive recording layer 3 and the support 1 in this manner, it is possible to prevent printing residue from adhering to the thermal head and improve printing quality. Furthermore, in addition to the heat-sensitive recording, a background pattern formed by general printing or drawing may be provided on or below the heat-sensitive recording layer 3 on the surface of the magnetic soft note. FIG. 2 shows an example of the magnetic soft note of the present invention provided with such a primer layer 4 and background pattern 5.

As mentioned above, if the magnetic soft note according to the present invention is used, a light source capable of supplying light with two different wavelengths and a relatively compact automatic ticket issuing machine equipped with a thermal head and a magnetic head can be used to generate light in a short period of time.
Stable thermal image recording and magnetic recording are performed using heat and light, and magnetic soft notes are issued that have stable quality over a long period of time and are capable of automatic ticket gates.

[Brief explanation of the drawing]

1 and 2 are enlarged schematic cross-sectional views of an embodiment of the magnetic soft note of the present invention, respectively. 1...Paper support, 2...Magnetic recording layer, 3...Photofixable thermosensitive recording layer.

Claims (1)

[Scope of utility model registration request] A paper support is provided with a magnetic recording layer on at least a portion of the back side thereof, and contains a diazosulfonate, a coupling agent, and a photocurable resin on at least a portion of the surface thereof, and is capable of photoactivation, thermal recording, and photofixing. A thermally printed magnetic soft note characterized by being provided with a recording layer.